JP2006298962A - Coating material containing low-molecular-weight polyphenylene ether and having excellent adhesion - Google Patents
Coating material containing low-molecular-weight polyphenylene ether and having excellent adhesion Download PDFInfo
- Publication number
- JP2006298962A JP2006298962A JP2005118127A JP2005118127A JP2006298962A JP 2006298962 A JP2006298962 A JP 2006298962A JP 2005118127 A JP2005118127 A JP 2005118127A JP 2005118127 A JP2005118127 A JP 2005118127A JP 2006298962 A JP2006298962 A JP 2006298962A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- molecular weight
- low molecular
- weight polyphenylene
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 97
- 238000000576 coating method Methods 0.000 title claims abstract description 41
- 239000011248 coating agent Substances 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 25
- 239000003822 epoxy resin Substances 0.000 claims abstract description 24
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 239000003973 paint Substances 0.000 claims description 36
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- -1 phenol compound Chemical class 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229920000180 alkyd Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 229920001225 polyester resin Polymers 0.000 claims description 5
- 239000004645 polyester resin Substances 0.000 claims description 5
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 5
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 5
- 125000003107 substituted aryl group Chemical group 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 239000004640 Melamine resin Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 150000002689 maleic acids Chemical class 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 3
- 229920005749 polyurethane resin Polymers 0.000 claims description 3
- 229920002050 silicone resin Polymers 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 abstract description 18
- 239000010959 steel Substances 0.000 abstract description 18
- 229910001335 Galvanized steel Inorganic materials 0.000 abstract description 9
- 239000008397 galvanized steel Substances 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 29
- 239000002904 solvent Substances 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 230000002265 prevention Effects 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004173 biogeochemical cycle Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000012673 precipitation polymerization Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- ATGFTMUSEPZNJD-UHFFFAOYSA-N 2,6-diphenylphenol Chemical compound OC1=C(C=2C=CC=CC=2)C=CC=C1C1=CC=CC=C1 ATGFTMUSEPZNJD-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- CIRRFAQIWQFQSS-UHFFFAOYSA-N 6-ethyl-o-cresol Chemical compound CCC1=CC=CC(C)=C1O CIRRFAQIWQFQSS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- PXPHPCSQPDHQNI-UHFFFAOYSA-N 2,6-bis(2-methylphenyl)phenol Chemical class CC1=CC=CC=C1C1=CC=CC(C=2C(=CC=CC=2)C)=C1O PXPHPCSQPDHQNI-UHFFFAOYSA-N 0.000 description 1
- METWAQRCMRWDAW-UHFFFAOYSA-N 2,6-diethylphenol Chemical compound CCC1=CC=CC(CC)=C1O METWAQRCMRWDAW-UHFFFAOYSA-N 0.000 description 1
- NAILKKRDWBJCNH-UHFFFAOYSA-N 2,6-dipropylphenol Chemical compound CCCC1=CC=CC(CCC)=C1O NAILKKRDWBJCNH-UHFFFAOYSA-N 0.000 description 1
- BIAWAXVRXKIUQB-UHFFFAOYSA-N 2-(2-phenylethenyl)pyridine Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=N1 BIAWAXVRXKIUQB-UHFFFAOYSA-N 0.000 description 1
- KTIRRDOBTNZKNL-UHFFFAOYSA-N 2-bromo-6-ethylphenol Chemical compound CCC1=CC=CC(Br)=C1O KTIRRDOBTNZKNL-UHFFFAOYSA-N 0.000 description 1
- YXZPTVOCJLCMRO-UHFFFAOYSA-N 2-bromo-6-methylphenol Chemical compound CC1=CC=CC(Br)=C1O YXZPTVOCJLCMRO-UHFFFAOYSA-N 0.000 description 1
- KUNNUNBSGQSGDY-UHFFFAOYSA-N 2-butyl-6-methylphenol Chemical compound CCCCC1=CC=CC(C)=C1O KUNNUNBSGQSGDY-UHFFFAOYSA-N 0.000 description 1
- XNJCFOQHSHYSLG-UHFFFAOYSA-N 2-chloro-6-ethylphenol Chemical compound CCC1=CC=CC(Cl)=C1O XNJCFOQHSHYSLG-UHFFFAOYSA-N 0.000 description 1
- YPNZJHFXFVLXSE-UHFFFAOYSA-N 2-chloro-6-methylphenol Chemical compound CC1=CC=CC(Cl)=C1O YPNZJHFXFVLXSE-UHFFFAOYSA-N 0.000 description 1
- AKZFZHNJLYDHKN-UHFFFAOYSA-N 2-ethyl-6-propylphenol Chemical compound CCCC1=CC=CC(CC)=C1O AKZFZHNJLYDHKN-UHFFFAOYSA-N 0.000 description 1
- PGJXFACHLLIKFG-UHFFFAOYSA-N 2-methyl-6-phenylphenol Chemical compound CC1=CC=CC(C=2C=CC=CC=2)=C1O PGJXFACHLLIKFG-UHFFFAOYSA-N 0.000 description 1
- KFETUQFRWIVAMU-UHFFFAOYSA-N 2-methyl-6-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(C)=C1O KFETUQFRWIVAMU-UHFFFAOYSA-N 0.000 description 1
- NXSQQKKFGJHACS-UHFFFAOYSA-N 2-methyl-6-propylphenol Chemical compound CCCC1=CC=CC(C)=C1O NXSQQKKFGJHACS-UHFFFAOYSA-N 0.000 description 1
- 229940061334 2-phenylphenol Drugs 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VVUJBFUHEWGKAZ-UHFFFAOYSA-N 4-(2-aminoethoxy)benzonitrile Chemical compound NCCOC1=CC=C(C#N)C=C1 VVUJBFUHEWGKAZ-UHFFFAOYSA-N 0.000 description 1
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-UHFFFAOYSA-N 0.000 description 1
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- VRMIIYFFNBDUFU-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu].[Cu] VRMIIYFFNBDUFU-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- DVUVKWLUHXXIHK-UHFFFAOYSA-N tetraazanium;tetrahydroxide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[OH-].[OH-].[OH-].[OH-] DVUVKWLUHXXIHK-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Polyethers (AREA)
Abstract
Description
本発明は特定のポリフェニレンエーテルの新規な用途に関するものである。さらに詳しくは自動車の車体及びバンパーや、建築材料の構造物などに使われる亜鉛メッキ鋼板、アルミ鋼板などの鋼板に対する塗膜密着性に優れた塗料に関するものである。 The present invention relates to novel uses of certain polyphenylene ethers. More specifically, the present invention relates to a paint having excellent coating film adhesion to steel sheets such as galvanized steel sheets and aluminum steel sheets used for automobile bodies and bumpers, structures of building materials, and the like.
電気亜鉛メッキ鋼板や溶融亜鉛メッキ鋼板、アルミ鋼板等の剛材は自動車、家電、構造物などに広く用いられており、優れた防錆性を有する表面処理鋼板に対する要求が強い。一般に防錆を目的とする表面処理鋼板は、亜鉛メッキを施した後に６価クロム酸塩等の水溶液処理により防錆被膜を形成する手法がとられている。この処理を施した、いわゆるクロメート処理層は、それ自身で高度の防錆性及び塗膜密着性を有するものである。
しかし、近年６価クロムによる作業環境や設置場所のクロム汚染の問題、製品が廃棄される段階での６価クロムの溶出の懸念が指摘されており、６価クロム酸塩等の水溶液処理によるクロメート処理を省略する動きがある。
Rigid materials such as electrogalvanized steel sheets, hot-dip galvanized steel sheets, and aluminum steel sheets are widely used in automobiles, home appliances, structures, and the like, and there is a strong demand for surface-treated steel sheets having excellent rust prevention properties. In general, a surface-treated steel sheet for the purpose of preventing rust is formed by galvanizing and then forming a rust-preventing film by treatment with an aqueous solution such as hexavalent chromate. The so-called chromate treatment layer subjected to this treatment itself has a high degree of rust prevention and coating film adhesion.
However, in recent years, there are concerns about chromium contamination in the work environment and installation location due to hexavalent chromium, and concerns about elution of hexavalent chromium at the stage of product disposal. There is a move to skip processing.
一方、塗装による防錆は、金属表面の酸素との接触を遮断する技術とした手法が一般的で、エポキシ塗料、アクリル塗料、ウレタン塗料などの高分子塗装被膜を形成する手法が当業者に公知である。
しかし、クロメート処理を行わない亜鉛メッキ鋼板などの鋼板の場合、塗装膜と鋼板との密着性が低下し、その結果防錆性能が低下することが懸念される。
塗膜密着性を向上させるため、樹脂骨格中に含まれる水酸基に注目した塗料組成物が特許文献１に提案されている。樹脂骨格中に水酸基を多く含むエポキシ樹脂を用いることで、金属板との塗膜密着性の向上に有効であるが、クロメート処理を行わない亜鉛メッキ鋼板の鋼板との密着性は充分とはいえない。従ってさらに密着性を向上させるには、樹脂組成物中に含まれる水酸基の濃度を高めることが必要と考えられる。
On the other hand, rust prevention by painting is generally a technique that blocks the contact with oxygen on the metal surface, and those skilled in the art know how to form a polymer coating film such as epoxy paint, acrylic paint, urethane paint, etc. It is.
However, in the case of a steel plate such as a galvanized steel plate that is not subjected to the chromate treatment, there is a concern that the adhesion between the coating film and the steel plate is lowered, and as a result, the rust prevention performance is lowered.
In order to improve the adhesion of the coating film, Patent Document 1 proposes a coating composition paying attention to a hydroxyl group contained in the resin skeleton. Using an epoxy resin containing many hydroxyl groups in the resin skeleton is effective in improving the adhesion of the coating film to the metal plate, but the adhesion to the steel plate of the galvanized steel plate without chromate treatment is sufficient. Absent. Therefore, in order to further improve the adhesion, it is considered necessary to increase the concentration of the hydroxyl group contained in the resin composition.
ポリフェニレンエーテルは加工性・生産性に優れ、溶融射出成形法や溶融押出成形法などの成形方法により所望の形状の製品、部品を効率良く生産できるため、電気・電子分野、自動車分野、その他の各種工業材料分野、包装分野の製品、部品用の材料として幅広く用いられている。
ポリフェニレンエーテルは、フェノール性化合物の水酸基を酸化カップリングすることで重合体として得られることから推察されるに、高分子鎖の分子鎖末端は水酸基であり、鋼板との密着性があると考えられる。しかし、溶融射出成形法や溶融押出成形法などの成形方法で用いられるポリフェニレンエーテルは比較的分子量の高いことから水酸基の量が少なく、鋼板との密着性が不十分である。
Polyphenylene ether is excellent in processability and productivity, and it can efficiently produce products and parts of desired shape by molding methods such as melt injection molding and melt extrusion molding. It is widely used as a material for products and parts in the industrial materials and packaging fields.
Polyphenylene ether is presumed to be obtained as a polymer by oxidative coupling of the hydroxyl group of the phenolic compound, but the molecular chain terminal of the polymer chain is a hydroxyl group and is considered to have adhesiveness to the steel sheet. . However, polyphenylene ethers used in molding methods such as the melt injection molding method and the melt extrusion molding method have a relatively high molecular weight, so that the amount of hydroxyl groups is small and the adhesion to the steel sheet is insufficient.
さらなる密着性向上を望むなら分子鎖末端の水酸基の濃度を高めればよい、すなわち分子量を下げポリマー単位重量当たりの分子鎖数を増やすのが有効との類推は難しくはない。このように低分子量化は密着性の向上に有効であるが、一方で単に分子量を小さくするだけでは塗膜の強度は低下するため、低分子量のポリフェニレンエーテル自体の塗料としての性能は必ずしも十分ではない。なお、低分子量のポリフェニレンエーテル自体は、特許文献２、特許文献３及び特許文献４などに開示されている。
本発明は、亜鉛メッキ鋼板、アルミ鋼板などの剛材に対し、密着性に優れた塗料を提供することを目的とする。
一般に防錆を目的とした表面処理鋼板は亜鉛メッキを施した後に６価クロム酸水溶液処理により防錆被膜を形成する手法がとられている。しかし、６価クロムによる作業環境や設置場所のクロム汚染の問題、製品を廃棄する段階での６価クロムの溶出の懸念が指摘され、クロム水溶液処理などのクロメート処理を省略する動きがある。
一方、塗装による防錆は、エポキシ塗料、アクリル塗料、ウレタン塗料など高分子塗装被膜を形成することにより金属表面の大気中の酸素や水分との接触を遮断することが一般的である。しかし、クロメート処理を行わない場合、塗装膜との密着性が低下し、その結果防錆性能が必ずしも十分とはいえなく、より密着性の良好な塗料が望まれる。
本発明は、クロメート処理を行わない亜鉛メッキ鋼板などの剛材に対する塗膜密着性に優れた塗料を提供することである。
An object of this invention is to provide the coating material excellent in adhesiveness with respect to rigid materials, such as a galvanized steel plate and an aluminum steel plate.
In general, a surface-treated steel sheet for the purpose of rust prevention is formed by galvanizing and forming a rust-preventive film by treatment with a hexavalent chromic acid aqueous solution. However, there are concerns about chromium contamination in the work environment and installation location due to hexavalent chromium, and concerns about elution of hexavalent chromium at the stage of product disposal, and there is a move to omit chromate treatment such as chromium aqueous solution treatment.
On the other hand, as for rust prevention by painting, it is common to block contact of metal surface with oxygen and moisture in the atmosphere by forming a polymer coating film such as epoxy paint, acrylic paint, urethane paint. However, when the chromate treatment is not performed, the adhesion with the coating film is lowered, and as a result, the rust prevention performance is not necessarily sufficient, and a paint having better adhesion is desired.
This invention is providing the coating material excellent in the coating-film adhesiveness with respect to rigid materials, such as a galvanized steel plate which does not perform a chromate process.
本発明者は、前記課題を解決するため鋭意検討した結果、低分子量ポリフェニレンエーテルは密着性向上に必要だが、一方で分子量を低下させることにより塗膜の強度及び密着性の低下、さらにはクロメート処理を行わない鋼板とのの密着性が低下することが懸念される。しかし密着性はポリフェニレンエーテル鎖に複数の水酸基を導入することで補えること、さらに低分子量ポリフェニレンエーテルを塗料として用いられる樹脂と混合して用いることが密着性を向上するに好ましいこと等が明らかとなった。
その結果、低分子量、さらに分子量あたり複数の水酸基を有する低分子量ポリフェニレンエーテルは、ポリフェニレンエーテルを含まない塗料、特にエポキシ樹脂、アクリル樹脂、フェノール樹脂等の塗料用樹脂と併用して使用することにより、亜鉛メッキ鋼板などの剛材に対する塗膜密着性に優れた塗料として適することを見出し本発明をなすに至った。
As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that low molecular weight polyphenylene ether is necessary for improving adhesion, but on the other hand, decreasing the molecular weight reduces the strength and adhesion of the coating film, and further chromate treatment. There is a concern that the adhesiveness with the steel sheet which does not perform is lowered. However, it has become clear that adhesion can be compensated by introducing a plurality of hydroxyl groups into the polyphenylene ether chain, and that low molecular weight polyphenylene ether is preferably mixed with a resin used as a paint to improve adhesion. It was.
As a result, low molecular weight, low molecular weight polyphenylene ether having a plurality of hydroxyl groups per molecular weight, by using in combination with paint resins not containing polyphenylene ether, especially epoxy resins, acrylic resins, phenol resins, etc. The present inventors have found that it is suitable as a paint having excellent coating film adhesion to a rigid material such as a galvanized steel sheet.
即ち、本発明は、
１．３０℃において濃度０．５ｇ／ｄｌのクロロホルム溶液中で測定した還元粘度が０．０４〜０．１８ｄｌ／ｇ であることを特徴とする低分子量ポリフェニレンエーテルを含有する塗料。
２．該低分子量ポリフェニレンエーテルが、１分子鎖当たりの水酸基が１．１ヶ以上２．０ヶ以下であることを特徴とする上記１記載の低分子量ポリフェニレンエーテルを含有する塗料。
３．該低分子量ポリフェニレンエーテルの一部又は全部が、低分子量ポリフェニレンエーテルとエポキシ化合物、又はフマル酸、マレイン酸、イタコン酸、ハロゲン化マレイン酸から選ばれるジカルボン酸又はこれらの酸無水物、又はアクリル酸、メタクリル酸から選ばれるモノカルボン酸とを反応させて得られる官能化されたポリフェニレンエーテルであることを特徴とする上記1又は２記載の低分子ポリフェニレンエーテルを含有する塗料。
４．該低分子量ポリフェニレンエーテルが、２，６−ジメチルフェノール、または２，６−ジメチルフェノールと２，３，６−トリメチルフェノールの混合物から得られる重合体であることを特徴とする上記１〜３のいずれかに記載の低分子量ポリフェニレンエーテルを含有する塗料。
５．該低分子量ポリフェニレンエーテルが、下記の一般式（１）で表される２価フェノール化合物を用いた重合体であることを特徴とする上記１〜４のいずれかに記載の低分子量ポリフェニレンエーテルを含有する塗料。
That is, the present invention
1. A paint containing a low molecular weight polyphenylene ether having a reduced viscosity of 0.04 to 0.18 dl / g measured in a chloroform solution having a concentration of 0.5 g / dl at 30 ° C.
2. 2. The coating material containing the low molecular weight polyphenylene ether according to the above 1, wherein the low molecular weight polyphenylene ether has 1.1 to 2.0 hydroxyl groups per molecular chain.
3. A part or all of the low molecular weight polyphenylene ether is a low molecular weight polyphenylene ether and an epoxy compound, or a dicarboxylic acid selected from fumaric acid, maleic acid, itaconic acid, halogenated maleic acid, or an acid anhydride thereof, or acrylic acid, 3. A paint containing a low molecular weight polyphenylene ether according to the above 1 or 2, which is a functionalized polyphenylene ether obtained by reacting with a monocarboxylic acid selected from methacrylic acid.
4). Any of the above 1 to 3, wherein the low molecular weight polyphenylene ether is a polymer obtained from 2,6-dimethylphenol or a mixture of 2,6-dimethylphenol and 2,3,6-trimethylphenol. A paint containing the low molecular weight polyphenylene ether according to claim 1.
5. The low molecular weight polyphenylene ether according to any one of 1 to 4 above, wherein the low molecular weight polyphenylene ether is a polymer using a divalent phenol compound represented by the following general formula (1): Paint.
（式中、Ｑ１、Ｑ２は各々同一または異なる置換基を表し、水素、アルキル基、置換アルキル基、アラルキル基、置換アラルキル基、アリール基、置換アリール基、アルコキシ基、置換アルコキシ基又はハロゲンを表し、各々同一でも異なってもよい。：Ｘは脂肪族炭化水素残基及びそれらの置換誘導体、酸素、イオウまたはスルホニル基を表し、Ｑ２、Ｘの結合位置はフェノール水酸基に対してオルソ位またはパラ位である。）
６．上記１〜５のいずれかに記載の該低分子量ポリフェニレンエーテルを含有する塗料が、該低分子量ポリフェニレンエーテル（ａ）と、エポキシ樹脂、フェノール樹脂、アルキド樹脂、メラミン樹脂、ポリエステル樹脂、アクリル樹脂、シリコーン樹脂、ポリウレタン樹脂、塩化ビニル樹脂、フッ素樹脂から選ばれる少なくとも1種の樹脂（ｂ）からなり、かつ（ａ）と（ｂ）の重量比（ａ）／（ｂ）が０．５／９９．５〜２０／８０からなることを特徴とする低分子量ポリフェニレンエーテルを含有する塗料。
(In the formula, Q1 and Q2 each represent the same or different substituents, and each represents hydrogen, an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, a substituted aryl group, an alkoxy group, a substituted alkoxy group or a halogen. May be the same or different from each other: X represents an aliphatic hydrocarbon residue and a substituted derivative thereof, oxygen, sulfur or a sulfonyl group, and the bonding position of Q2 and X is an ortho position or a para position with respect to the phenol hydroxyl group. .)
6). The coating material containing the low molecular weight polyphenylene ether according to any one of the above 1 to 5 includes the low molecular weight polyphenylene ether (a), an epoxy resin, a phenol resin, an alkyd resin, a melamine resin, a polyester resin, an acrylic resin, and silicone. It comprises at least one resin (b) selected from resins, polyurethane resins, vinyl chloride resins and fluororesins, and the weight ratio (a) / (b) between (a) and (b) is 0.5 / 99. A paint containing low molecular weight polyphenylene ether, characterized in that it comprises 5-20 / 80.
本発明に基づけば、塗膜の強度が高く、かつ金属鋼板との密着性に優れた塗料の製造が可能である。 Based on the present invention, it is possible to produce a paint having high coating strength and excellent adhesion to a metal steel plate.
本発明における低分子量ポリフェニレンエーテルの還元粘度は０．０４〜０．１８ｄｌ／ｇ、好ましくは０．０４〜０．１５ｄｌ／ｇ、さらに好ましくは０．０５〜０．１３ｄｌ／ｇである。還元粘度は０．５ｇ／ｄｌの濃度のクロロホルム溶液とし、ウベローデ粘度管を用いて３０℃において測定することにより測定できる。本発明の低分子量ポリフェニレンエーテルの密着性は水酸基が多いほど、換言すれば分子量が小さいほど優れるが、塗膜の密着性及び塗膜の強度に関しては、分子量が小さすぎると低下の傾向にある。
本発明に用いられる低分子量ポリフェニレンエーテル原料となるフェノール化合物は次のような一般式（２）の構造を持つ化合物である。
The reduced viscosity of the low molecular weight polyphenylene ether in the present invention is 0.04 to 0.18 dl / g, preferably 0.04 to 0.15 dl / g, and more preferably 0.05 to 0.13 dl / g. The reduced viscosity can be measured by preparing a chloroform solution having a concentration of 0.5 g / dl and measuring it at 30 ° C. using an Ubbelohde viscosity tube. The adhesiveness of the low molecular weight polyphenylene ether of the present invention is better as the number of hydroxyl groups is increased, in other words, the smaller the molecular weight, but the adhesiveness of the coating film and the strength of the coating film tend to decrease when the molecular weight is too small.
The phenol compound used as the raw material for the low molecular weight polyphenylene ether used in the present invention is a compound having the following general formula (2).
（式中、Ｒ１、Ｒ２、Ｒ３は各々独立の置換基を表し、Ｒ１はアルキル基、置換アルキル基、アラルキル基、置換アラルキル基、アリール基、置換アリール基、アルコキシ基、置換アルコキシ基であり、Ｒ２、Ｒ３はＲ１について定義されたものと同一の基に加え、更に水素、ハロゲンであっても良い。） (Wherein R1, R2 and R3 each represents an independent substituent, R1 is an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, a substituted aryl group, an alkoxy group, or a substituted alkoxy group; R2 and R3 may be hydrogen or halogen in addition to the same groups defined for R1.)
該化合物の例としては例えば、ｏ−クレゾール、２，６−ジメチルフェノール、２，３，６−トリメチルフェノール、２−エチルフェノール、２−メチル−６−エチルフェノール、２，６−ジエチルフェノール、２−ｎ−プロピルフェノール、２−エチル−６−ｎ−プロピルフェノール、２−メチル−６−クロルフェノール、２−メチル−６−ブロモフェノール、２−メチル−６−イソプロピルフェノール、２−メチル−６−ｎ−プロピルフェノール、２−エチル−６−ブロモフェノール、２−メチル−６−ｎ−ブチルフェノール、２，６−ジ−ｎ−プロピルフェノール、２−エチル−６−クロルフェノール、２−メチル−６−フェニルフェノール、２−フェニルフェノール、２，６−ジフェニルフェノール、２，６−ビス−（４−フルオロフェニル）フェノール、２−メチル−６−トリルフェノール、２，６−ジトリルフェノール等が挙げられる。これらの化合物はそれぞれ単独で用いても良いし、２種以上併用しても良い。また少量のｍ−クレゾール、ｐ−クレゾール、２，４−ジメチルフェノール、２，４，６−トリメチルフェノール等を含んでいても実質上差し支えない。これらの中で２，６−ジメチルフェノールは工業上重要である。また２，６−ジメチルフェノールと２，３，６−トリメチルフェノールとの組み合わせ、あるいは２，６−ジメチルフェノールと２，６−ジフェニルフェノールとの組み合わせも好ましく用いられる。 Examples of the compound include o-cresol, 2,6-dimethylphenol, 2,3,6-trimethylphenol, 2-ethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, -N-propylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-isopropylphenol, 2-methyl-6- n-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6 Phenylphenol, 2-phenylphenol, 2,6-diphenylphenol, 2,6-bis- (4-fluoro Eniru) phenol, 2-methyl-6-tolyl, 2,6-di-tolyl phenols, and the like. These compounds may be used alone or in combination of two or more. Moreover, even if it contains a small amount of m-cresol, p-cresol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, etc., it does not matter. Among these, 2,6-dimethylphenol is industrially important. A combination of 2,6-dimethylphenol and 2,3,6-trimethylphenol or a combination of 2,6-dimethylphenol and 2,6-diphenylphenol is also preferably used.
本発明の低分子量ポリフェニレンエーテルは分子鎖あたり１．０ケ以上，より好ましくは１．５ケ以上の水酸基を持つことが好ましい。通常ポリフェニレンエーテルは，分子鎖の片末端に水酸基を有する。さらに水酸基数を増やすには，ジフェノキノンに代表されるキノン類とカップリングさせる方法が知られている。更により多くの水酸基を導入するには，フェノール化合物として前記一般式（１）で表される二価フェノール化合物を共重合させることは好ましい。 The low molecular weight polyphenylene ether of the present invention preferably has 1.0 or more, more preferably 1.5 or more hydroxyl groups per molecular chain. Usually, polyphenylene ether has a hydroxyl group at one end of the molecular chain. In order to increase the number of hydroxyl groups, a method of coupling with quinones represented by diphenoquinone is known. In order to introduce more hydroxyl groups, it is preferable to copolymerize the dihydric phenol compound represented by the general formula (1) as a phenol compound.
（式中、Ｑ１、Ｑ２は水素、アルキル基、置換アルキル基、アラルキル基、置換アラルキル基、アリール基、置換アリール基、アルコキシ基、置換アルコキシ基またはハロゲンであり、各々同一でも異なっていてもよい：Ｘは脂肪族炭化水素残基またはそれらの置換誘導体、酸素、イオウまたはスルホニル基を表し、Ｑ２，Ｘの結合位置はフェノール水酸基に対してオルソ位またはパラ位である。）
該化合物の例としては例えば、下記一般式（１−ａ）、（１−ｂ）、（１−ｃ）の各々の構造に挙げる化合物群がある。
(Wherein Q1 and Q2 are hydrogen, an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, a substituted aryl group, an alkoxy group, a substituted alkoxy group or a halogen, which may be the same or different. : X represents an aliphatic hydrocarbon residue or a substituted derivative thereof, oxygen, sulfur or a sulfonyl group, and the bonding position of Q2 and X is an ortho position or a para position with respect to the phenol hydroxyl group.
As an example of this compound, there exists a compound group quoted in each structure of the following general formula (1-a), (1-b), (1-c), for example.
（式中、Ｑ１、Ｑ２は水素、アルキル基，置換アルキル基，アラルキル基，置換アラルキル基，アリール基，置換アリール基，アルコキシ基，置換アルコキシ基またはハロゲンを表し、各々同一でも異なっていてもよい：Ｘは脂肪族炭化水素残基またはそれらの置換誘導体、酸素、イオウまたはスルホニル基である。） (In the formula, Q1 and Q2 represent hydrogen, an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, a substituted aryl group, an alkoxy group, a substituted alkoxy group, or a halogen, which may be the same or different. : X is an aliphatic hydrocarbon residue or a substituted derivative thereof, oxygen, sulfur or sulfonyl group.)
上記一般式の構造を持つもので代表的なものは、Ｑ１、Ｑ２がメチル基でＸがイソプロピリデンである化合物、Ｑ１とＱ２がメチル基でＸがメチレンである化合物、Ｑ１とＱ２がメチル基でＸがチオである化合物、Ｑ１とＱ２がメチル基でＸがシクロヘキシリデンである化合物等であるがこれらの例に限定されないことはいうまでもない。
これらの二価フェノール性化合物は一種類でも用いられるし、２種以上組み合わせて用いても良い。二価フェノール性化合物を含有される量は特に限定されないが、一価フェノール類に対して０．１〜３０モル％とするのが好ましい。
低分子量ポリフェニレンエーテル分子鎖中に存在する水酸基の数は，塗膜の密着性の向上に重要である。詳細は明らかではないが、水酸基が地金の金属やトップコート塗膜成分と相互作用を持つと推定され、分子鎖あたり複数個の水酸基、具体的には１．０ケ〜２．０ケ、好ましくは１．１ヶ〜２．０ヶの水酸基を有することがより好ましい。水酸基の数は、ＮＭＲ法または、ＧＰＣとＵＶ分光光度計を併用する方法などにより定量できる。
A typical compound having the structure of the above general formula is a compound in which Q1 and Q2 are methyl groups and X is isopropylidene, a compound in which Q1 and Q2 are methyl groups and X is methylene, Q1 and Q2 are methyl groups And X is thio, Q1 and Q2 are methyl groups, and X is cyclohexylidene. However, it goes without saying that these examples are not limiting.
These dihydric phenolic compounds may be used alone or in combination of two or more. Although the amount containing the dihydric phenolic compound is not particularly limited, it is preferably 0.1 to 30 mol% with respect to the monohydric phenol.
The number of hydroxyl groups present in the low molecular weight polyphenylene ether molecular chain is important for improving the adhesion of the coating film. Although details are not clear, it is presumed that the hydroxyl group interacts with the metal of the bare metal and the top coat film component, and a plurality of hydroxyl groups per molecular chain, specifically 1.0 to 2.0, Preferably, it has 1.1 to 2.0 hydroxyl groups. The number of hydroxyl groups can be quantified by NMR method or a method using GPC and UV spectrophotometer in combination.
一般にポリフェニレンエーテルを得る方法としては、ポリフェニレンエーテルの貧溶媒を重合溶媒として用い、重合の進行に伴ってポリフェニレンエーテルが粒子として析出する沈殿重合法と、良溶媒を重合溶媒として用い、ポリフェニレンエーテルが溶媒中に溶解している溶液重合法が知られているが、本発明の低分子量ポリフェニレンエーテルは、どちらの方法を用いても得ることができる。
析出重合法，即ちポリフェニレンエーテルの貧溶媒を重合溶媒として用い、重合の進行に伴ってポリフェニレンエーテルを析出させる沈殿重合法を用いる場合には、貧溶媒と良溶媒を組み合わせて用いることが好ましい。貧溶媒としては、炭素数１〜１０のアルコールが好ましく，メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、エチレングリコールが例示できる。複数のアルコールを併用することも任意である。この貧溶媒は水を含んでいないことが好ましい。良溶媒は，低分子量ポリフェニレンエーテルを溶解させない範囲で用いられる。
Generally, polyphenylene ether is obtained by using a poor polymerization solvent of polyphenylene ether as a polymerization solvent, a precipitation polymerization method in which polyphenylene ether is precipitated as particles as the polymerization proceeds, a good solvent as a polymerization solvent, and polyphenylene ether as a solvent. Solution polymerization methods are known which are dissolved therein, but the low molecular weight polyphenylene ether of the present invention can be obtained by either method.
In the case of using a precipitation polymerization method, that is, a precipitation polymerization method in which a polyphenylene ether is used as a polymerization solvent and polyphenylene ether is precipitated as the polymerization proceeds, it is preferable to use a combination of a poor solvent and a good solvent. As the poor solvent, alcohol having 1 to 10 carbon atoms is preferable, and methanol, ethanol, propanol, butanol, pentanol, hexanol, and ethylene glycol can be exemplified. A combination of a plurality of alcohols is also optional. It is preferable that this poor solvent does not contain water. The good solvent is used as long as the low molecular weight polyphenylene ether is not dissolved.
一方、ポリフェニレンエーテルの良溶媒を重合溶媒として用い、得られた低分子量ポリフェニレンエーテルを含む溶液に貧溶媒を添加して低分子量ポリフェニレンエーテルを析出させる溶液重合法を用いることもできる。
良溶媒としてはベンゼン、トルエン、キシレン（ｏ−、ｍ−、ｐ−の各異性体を含む）、エチルベンゼン、スチレン等の芳香族炭化水素、クロロホルム、塩化メチレン、１，２−ジクロロエタン、クロロベンゼン、ジクロロベンゼン等のハロゲン化炭化水素、ニトロベンゼンのようなニトロ化合物が挙げられる。好ましい良溶媒はトルエンである。溶液中の低分子量ポリフェニレンエーテルの濃度は特に制限されないが、２５〜７０重量％が好ましい。重合溶液は、そのまま塗料原料として用いることが可能であるが、重合時に用いたものと異なる溶剤系の塗料を得るには析出操作が必要である。
On the other hand, it is also possible to use a solution polymerization method in which a good solvent of polyphenylene ether is used as a polymerization solvent and a poor solvent is added to the resulting solution containing low molecular weight polyphenylene ether to precipitate low molecular weight polyphenylene ether.
Good solvents include benzene, toluene, xylene (including o-, m-, and p-isomers), ethylbenzene, styrene and other aromatic hydrocarbons, chloroform, methylene chloride, 1,2-dichloroethane, chlorobenzene, di- Examples thereof include halogenated hydrocarbons such as chlorobenzene and nitro compounds such as nitrobenzene. A preferred good solvent is toluene. The concentration of the low molecular weight polyphenylene ether in the solution is not particularly limited, but is preferably 25 to 70% by weight. The polymerization solution can be used as a raw material for the coating as it is, but a precipitation operation is required to obtain a solvent-based coating different from that used in the polymerization.
低分子量ポリフェニレンエーテルの析出操作は、攪拌機を有する適当な大きさの槽に連続的に低分子量ポリフェニレンエーテルを含む溶液と貧溶媒を添加する方法、低分子量ポリフェニレンエーテルを含む溶液が入った槽に貧溶媒を添加する方法、貧溶媒が入った槽に低分子量ポリフェニレンエーテルを含む溶液を添加する方法、管型スタティックミキサーに連続的に低分子量ポリフェニレンエーテルを含む溶液と貧溶媒を添加する方法等が例示できる。貧溶媒としてはエーテル類、ケトン類またはアルコール類が挙げられる。好ましくは炭素数１〜１０のアルコールであり、さらに好ましくはメタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノールおよびエチレングリコールから選ばれる少なくとも１種である。これらには水が含まれていても良い。析出温度は−８０〜＋２０℃が好ましい。 The low molecular weight polyphenylene ether is precipitated by a method of continuously adding a solution containing a low molecular weight polyphenylene ether and a poor solvent to a suitably sized tank having a stirrer, and a tank containing a solution containing a low molecular weight polyphenylene ether. Examples include a method of adding a solvent, a method of adding a solution containing low molecular weight polyphenylene ether to a tank containing a poor solvent, a method of continuously adding a solution containing low molecular weight polyphenylene ether and a poor solvent to a tubular static mixer, and the like. it can. Examples of the poor solvent include ethers, ketones, and alcohols. Preferably it is C1-C10 alcohol, More preferably, it is at least 1 sort (s) chosen from methanol, ethanol, propanol, butanol, pentanol, hexanol, and ethylene glycol. These may contain water. The precipitation temperature is preferably -80 to + 20 ° C.
又、低分子量ポリフェニレンエーテルを塗料の１成分として用いるに際し、本発明の目的を損なわない範囲でポリスチレン系樹脂を混合してもよい。ポリスチレン系樹脂の好ましい添加量は、低分子量ポリフェニレンエーテル１００重量部につき１〜４５重量部である。
塗料としての総合的性能、即ち塗膜の強度、塗膜硬度、耐傷つき性、外観、密着性及び耐光性が求められることから、ポリフェニレンエーテルを含まない塗料と混合して用いる手法は好ましい実施形態の一つである。低分子量ポリフェニレンエーテルと混合することのできるポリフェニレンエーテルを含まない塗料としては、例えばエポキシ樹脂、アルキド樹脂、ポリエステル樹脂、ビニルエステル樹脂、ジアリルフタレート樹脂、シアネートエステル樹脂、キシレン樹脂、トリアジン樹脂、フェノール樹脂、ユリア樹脂、メラミン樹脂、ベンゾグアナミン樹脂、ウレタン樹脂、ケトン樹脂、フラン樹脂、スチリルピリジン樹脂、シリコーン樹脂、合成ゴムなどからなる塗料が好ましい。中でも、エポキシ樹脂、アルキド樹脂、ポリエステル樹脂からなる塗料が好適である。特に、エポキシ樹脂からなる塗料はポリフェニレンエーテル鎖の水酸基と相溶性が良く、最も好ましい選択である。
Moreover, when using low molecular weight polyphenylene ether as one component of a coating material, you may mix a polystyrene resin in the range which does not impair the objective of this invention. A preferable addition amount of the polystyrene-based resin is 1 to 45 parts by weight per 100 parts by weight of the low molecular weight polyphenylene ether.
Since the overall performance as a paint, that is, the strength of the paint film, the paint film hardness, the scratch resistance, the appearance, the adhesion and the light resistance, is required, the method used by mixing with a paint not containing polyphenylene ether is a preferred embodiment. one of. Examples of paints that do not contain polyphenylene ether that can be mixed with low molecular weight polyphenylene ether include epoxy resins, alkyd resins, polyester resins, vinyl ester resins, diallyl phthalate resins, cyanate ester resins, xylene resins, triazine resins, phenol resins, A paint made of urea resin, melamine resin, benzoguanamine resin, urethane resin, ketone resin, furan resin, styrylpyridine resin, silicone resin, synthetic rubber, or the like is preferable. Of these, paints composed of epoxy resins, alkyd resins, and polyester resins are suitable. In particular, a coating made of an epoxy resin is most preferable because it has good compatibility with the hydroxyl group of the polyphenylene ether chain.
本発明において、好適に用いられるエポキシ樹脂は、分子中に少なくとも２個の、エポキシ基を有する化合物であればよく、特に制限されるものではない。一例として、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、レゾルシノール型エポキシ樹脂、ノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、多官能型エポキシ樹脂等を挙げることができ、これらのエポキシ樹脂は単独又は二種以上を混合して用いることができる。
これら塗料の好ましい混合比率は、低分子量ポリフェニレンエーテル（ａ）とポリフェニレンエーテルを含まない塗料、つまりエポキシ樹脂、フェノール樹脂、アルキド樹脂、メラミン樹脂、ポリエステル樹脂、アクリル樹脂、シリコーン樹脂、ポリウレタン樹脂、塩化ビニル樹脂、フッ素樹脂から選ばれる少なくとも1種の樹脂（ｂ）との重量比（ａ）／（ｂ）において、（ａ）が０．５以上であれば本発明の密着性を向上させることができ、好ましくは２以上、より好ましくは５以上であり、また、塗膜の強度及び密着性を低下させないためには（ａ）が２０以下であり、好ましくは１８以下、より好ましくは１５以下である。
In the present invention, the epoxy resin suitably used may be any compound having at least two epoxy groups in the molecule, and is not particularly limited. Examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, resorcinol type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, polyfunctional type epoxy resin, etc. An epoxy resin can be used individually or in mixture of 2 or more types.
The preferred mixing ratio of these paints is a paint not containing low molecular weight polyphenylene ether (a) and polyphenylene ether, that is, epoxy resin, phenol resin, alkyd resin, melamine resin, polyester resin, acrylic resin, silicone resin, polyurethane resin, vinyl chloride. In the weight ratio (a) / (b) with at least one resin (b) selected from resins and fluororesins, the adhesiveness of the present invention can be improved if (a) is 0.5 or more. In order not to lower the strength and adhesion of the coating film, (a) is 20 or less, preferably 18 or less, more preferably 15 or less. .
本発明における分子鎖当たりの水酸基が１．０ヶ以上２．０以下、好ましくは１．１ヶ以上２．０以下の範囲を満足する限り、ポリフェニレンエーテルを含まない塗料との相性を高める目的で、ポリフェニレンエーテルの一部又は全部を予めエポキシ化合物やフマル酸、マレイン酸、イタコン酸、ハロゲン化マレイン酸などのカルボン酸又はこれらの酸無水物、アクリル酸、メタクリル酸などのモノカルボン酸を用いて変性することも可能である。反応して得られる官能化されたポリフェニレンエーテルの量は、低分子量ポリフェニレンエーテルと官能化されたポリフェニレンエーテルの合計量に対し２０重量％以下が好ましく、さらに好ましくは１０重量％以下である。また、変性方法は特に制限はなく、押出機や反応器を用い、当業者公知の方法で実施できる。好適な変性率は、塗料の使用目的や条件に応じて変化するため、用途毎に適宜設定すれば良い。 As long as the hydroxyl group per molecular chain in the present invention satisfies the range of 1.0 to 2.0, preferably 1.1 to 2.0, for the purpose of enhancing the compatibility with the paint not containing polyphenylene ether. In addition, a part or all of the polyphenylene ether is previously prepared using an epoxy compound, a carboxylic acid such as fumaric acid, maleic acid, itaconic acid, a halogenated maleic acid, or a monocarboxylic acid such as an acid anhydride, acrylic acid or methacrylic acid. It is also possible to denature. The amount of the functionalized polyphenylene ether obtained by the reaction is preferably 20% by weight or less, more preferably 10% by weight or less, based on the total amount of the low molecular weight polyphenylene ether and the functionalized polyphenylene ether. The modification method is not particularly limited, and can be carried out by a method known to those skilled in the art using an extruder or a reactor. A suitable modification rate varies depending on the purpose and conditions of use of the paint, and therefore may be set as appropriate for each application.
本発明における上記低分子量ポリフェニレンエーテルの平均粒径は、特に制限はないが、ポリフェニレンエーテルを含まない塗料に対する溶解性を向上させるために、３００μｍ以下にすることが好ましく、より好ましくは該平均粒径を１００μｍ以下、更に好ましくは該平均粒径を５０μｍ以下にすることが好適に用いられる。上記平均粒径が３００μｍ以下、より好ましくは１００μｍ以下、更に好ましくは５０μｍ以下の低分子量ポリフェニレンエーテルを得るには、機械的に粉砕する方法、或いは機械的に粉砕した後、分粒する方法等を用いることができる。 The average particle diameter of the low molecular weight polyphenylene ether in the present invention is not particularly limited, but is preferably 300 μm or less, more preferably the average particle diameter in order to improve the solubility in a paint not containing polyphenylene ether. Is preferably 100 μm or less, more preferably 50 μm or less. In order to obtain a low molecular weight polyphenylene ether having an average particle size of 300 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less, a mechanical pulverization method, a mechanical pulverization method, and a sizing method are used. Can be used.
上記の機械的粉砕には、任意の粉砕機を使用できるが、例えば、高速回転式衝撃粉砕機（ハンマーミル、ピンミル、ディスクミル、遠心分級ミル等）、ローラーミル、エロフォールミル、ボールミル（転動ミル、振動ミル等）、媒体撹拌型粉砕機（塔式粉砕機、撹拌槽型粉砕機、流通管型粉砕機等）、ジェットミル、コロイドミル等を挙げることができる。また、液体窒素等を利用して該ポリフェニレンエーテル及び粉砕機容器内を冷却した上で上記粉砕機等を用いて粉砕する（凍結粉砕）方法も適宜用いられる。また、粉砕後の分級には、乾式分粒器、湿式分粒器、フィルター分粒器等を用いて、重量方式、遠心力方式、慣性力方式等で所望の粒径を得ることができる。
本塗料に許される範囲で亜鉛系、鉛系防錆成分を配合することも任意にできる。粘度調節剤、顔料、染料、熱安定剤、光安定剤の配合も任意に添加できる。塗装方法については特に制限することはなく、公知の方法で可能である。
以下、実施例に基づき、本発明を説明する。
For the mechanical pulverization, any pulverizer can be used. For example, a high-speed rotary impact pulverizer (hammer mill, pin mill, disc mill, centrifugal classification mill, etc.), roller mill, erotic fall mill, ball mill (roller) A dynamic mill, a vibration mill, etc.), a medium agitation type pulverizer (a tower type pulverizer, an agitation tank type pulverizer, a flow pipe type pulverizer, etc.), a jet mill, a colloid mill and the like. Moreover, after cooling the inside of the polyphenylene ether and the pulverizer container using liquid nitrogen or the like, pulverization (freeze pulverization) using the pulverizer or the like is also used as appropriate. Further, for the classification after pulverization, a desired particle size can be obtained by a weight method, a centrifugal force method, an inertial force method, or the like using a dry sizer, a wet sizer, a filter sizer, or the like.
Zinc-based and lead-based anticorrosive components can be optionally blended within the range allowed for this paint. Viscosity modifiers, pigments, dyes, heat stabilizers, and light stabilizers can be optionally added. The coating method is not particularly limited and can be performed by a known method.
Hereinafter, the present invention will be described based on examples.
＜ポリフェニレンエーテルの合成方法＞
[合成例１]
反応器底部に酸素含有ガス導入の為のスパージャー、攪拌タービン翼及びバッフル、反応器上部のベントガスラインに還流冷却器を備えた１．５リットルのジャケット付き反応器に、０．２５１２ｇの塩化第二銅２水和物、１．１０６２ｇの３５％塩酸、３．６１７９ｇのジ−ｎ−ブチルアミン、９．５９３７ｇのＮ，Ｎ，Ｎ‘，Ｎ’−テトラメチルプロパンジアミン、２１１．６３ｇのメタノール及び４９３．８０ｇのｎ−ブタノールおよび１８０．０ｇの２，６−ジメチルフェノールを入れた。溶媒の組成重量比はｎ−ブタノール：メタノール＝７０：３０である。次いで激しく攪拌しながら反応器へ１８０ｍｌ／ｍｉｎの速度で酸素をスパージャーより導入を始めると同時に、重合温度は４０℃を保つようにジャケットに熱媒を通して調節した。重合液は次第にスラリーの様態を呈した。重合中、反応器に付着は観測されなかった。酸素を導入し始めてから１２０分後、酸素の通気をやめ、得られた重合混合物にエチレンジアミン四酢酸３カリウム塩（同仁化学研究所製試薬）の１０％水溶液を添加し、５０℃に温めた。次いでハイドロキノン（和光純薬社製試薬）を少量ずつ添加し、スラリー状のポリフェニレンエーテルが白色となるまで、５０℃での保温を続けた。終了後、濾過して、濾残の湿潤ポリフェニレンエーテルを５０％の水を含むメタノール洗浄溶媒に投入し、６０℃で攪拌を行った。続いて再び濾過し、濾残に５０％の水を含むメタノールをふりかけ洗浄し湿潤ポリフェニレンエーテルを得た。次いで１１０℃で真空乾燥し乾燥ポリフェニレンエーテルを得た。
<Synthesis Method of Polyphenylene Ether>
[Synthesis Example 1]
A reactor with a jacket of 1.5 liters equipped with a sparger for introducing an oxygen-containing gas at the bottom of the reactor, a stirring turbine blade and a baffle, and a reflux condenser in the vent gas line at the top of the reactor was added with 0.2512 g of chloride chloride. Dicopper dihydrate, 1.1062 g of 35% hydrochloric acid, 3.6179 g of di-n-butylamine, 9.5937 g of N, N, N ′, N′-tetramethylpropanediamine, 211.63 g of methanol and 493.80 g n-butanol and 180.0 g 2,6-dimethylphenol were charged. The composition weight ratio of the solvent is n-butanol: methanol = 70: 30. Subsequently, oxygen was introduced from the sparger into the reactor at a rate of 180 ml / min with vigorous stirring, and at the same time, the polymerization temperature was adjusted by passing a heating medium through the jacket so as to maintain 40 ° C. The polymerization solution gradually became a slurry. No adhesion was observed in the reactor during the polymerization. After 120 minutes from the start of oxygen introduction, the ventilation of oxygen was stopped, and a 10% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) was added to the resulting polymerization mixture, and the mixture was warmed to 50 ° C. Subsequently, hydroquinone (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little, and the temperature was kept at 50 ° C. until the slurry polyphenylene ether became white. After completion, the mixture was filtered, and the residual wet polyphenylene ether was put into a methanol washing solvent containing 50% water and stirred at 60 ° C. Subsequently, the mixture was filtered again and washed with a 50% water-containing methanol to obtain a wet polyphenylene ether. Then, it was vacuum dried at 110 ° C. to obtain dry polyphenylene ether.
[合成例２]
使用した溶媒の全量は変えずに組成重量比をｎ−ブタノール：メタノール＝３０：７０とし，フェノール化合物を２．５モル％の２，２−ビス（３，５−ジメチル−４−ヒドロキシフェニル）プロパンを含む２，６−ジメチルフェノールを用いた以外は実施例１と同様の方法でポリフェニレンエーテルを得た。
[Synthesis Example 2]
Without changing the total amount of the solvent used, the composition weight ratio was n-butanol: methanol = 30: 70, and the phenol compound was 2.5 mol% of 2,2-bis (3,5-dimethyl-4-hydroxyphenyl). Polyphenylene ether was obtained in the same manner as in Example 1 except that 2,6-dimethylphenol containing propane was used.
[合成例３]
使用した溶媒の全量は変えずに組成重量比をキシレン：ｎ−ブタノール：メタノール＝６０：２０：２０とし、洗浄溶媒として、メタノールを用いた以外は実施例１の方法でポリフェニレンエーテルを得た。
[Synthesis Example 3]
The polyphenylene ether was obtained by the method of Example 1 except that the composition weight ratio was xylene: n-butanol: methanol = 60: 20: 20 and methanol was used as the washing solvent without changing the total amount of the solvent used.
＜ポリフェニレンエーテルの分析方法＞
[還元粘度（ηｓｐ／ｃ）]
ポリフェニレンエーテルを０．５ｇ／ｄｌのクロロホルム溶液として、ウベローデ粘度管を用いて３０℃で測定した。単位はｄｌ／ｇである。
<Analytical method of polyphenylene ether>
[Reduced viscosity (ηsp / c)]
The polyphenylene ether was measured as a 0.5 g / dl chloroform solution at 30 ° C. using an Ubbelohde viscosity tube. The unit is dl / g.
[分子量]
昭和電工（株）製ゲルパーミエーションクロマトグラフィーＳＨＯＤＥＸ・ＧＰＣｓｙｓｔｅｍ２１でエチルベンゼンと標準ポリスチレンを用いて検量線を作成し測定した。標準ポリスチレンの分子量は５５０、１３００、９６８０、２８６００、６５９００、１７２０００、６２９０００、９９６０００、１９６００００、３９０００００のものを用いた。カラムはＳＨＯＤＥＸ製Ｋ−８０２．５を直列に２本つないで使用した。また、溶媒はクロロホルム、溶媒の流量は１．０ｍｌ／ｍｉｎ、カラムの温度は４０℃で測定した。検出部にはＵＶ検出器を用い、波長は標準ポリスチレンの検量線作成にあたっては２５４ｎｍ、測定対象のポリフェニレンエーテルにあたっては２８３ｎｍで測定した。サンプルをクロロホルムに溶かし、メンブランフィルターで不溶液を除去し溶液を測定した。
[Molecular weight]
A calibration curve was prepared and measured using ethylbenzene and standard polystyrene by Showa Denko Co., Ltd. gel permeation chromatography SHODEX / GPC system 21. The molecular weight of standard polystyrene was 550, 1300, 9680, 28600, 65900, 172000, 629000, 996000, 1960000, 390000. As the column, two K-802.5 manufactured by SHODEX were connected in series. The solvent was chloroform, the solvent flow rate was 1.0 ml / min, and the column temperature was 40 ° C. A UV detector was used for the detection part, and the wavelength was measured at 254 nm when preparing a standard polystyrene calibration curve, and at 283 nm when measuring polyphenylene ether. The sample was dissolved in chloroform, the non-solution was removed with a membrane filter, and the solution was measured.
[水酸基数]
高分子論文集、ｖｏｌ．５１、Ｎｏ．７（１９９４）、４８０ページ記載の方法に従い、ポリフェニレンエーテルの塩化メチレン溶液にテトラアンモニウムハイドロオキシド溶液を加えたときの３１８ｎｍにおける吸光度変化を紫外可視吸光光度計で測定した値と先の分子量測定で得られた数平均分子量の値から算出した。
[Number of hydroxyl groups]
Polymer Papers, vol. 51, no. 7 (1994), according to the method described on page 480, the change in absorbance at 318 nm when a tetraammonium hydroxide solution was added to a methylene chloride solution of polyphenylene ether was obtained by a value measured with an ultraviolet-visible spectrophotometer and the previous molecular weight measurement. It was calculated from the obtained number average molecular weight value.
＜塗膜の評価方法＞
試験片の下地として０．９５％炭素綱板、亜鉛鉄板（ＪＩＳ Ｇ ３３０２）を用い、メチルエチルケトンを用いて表面を洗浄した。
ポリフェニレンエーテル以外の樹脂（ｂ）としてビスフェノールＡ型液状エポキシ樹脂を用いた（以下エポキシ樹脂と略）。
実施例１〜４、比較例３、４、５は、合成例１、２、３で得たポリフェニレンエーテル（ａ）をエポキシ樹脂に、表１の示す通り配合させた後、エポキシ樹脂の硬化剤としてトリエチレンテトラミンをエポキシ樹脂のエポキシ当量に対し、１．２倍の活性水素当量相当分を添加させた。得られた液をバーコーターで塗布し、室温で１０時間放置後、１００℃、３０分間乾燥し塗膜試験片を得た。比較例１は実施例で用いたエポキシ樹脂を用いて同様の操作を行い、塗膜試験片を得た。また、比較例２、は合成例２で得たポリフェニレンエーテル（ａ）をトルエンに溶解させ５重量％とした溶液を、同じくバーコーターで塗布し、室温で５分間乾燥させた後、比較例２は１７０℃で乾燥し塗膜試験片を得た。また、比較例５は合成例３で得たポリフェニレンエーテル（ａ）をエポキシ樹脂に配合したが、溶解せず評価できなかった。
<Evaluation method of coating film>
A 0.95% carbon steel plate and a zinc iron plate (JIS G 3302) were used as the base of the test piece, and the surface was cleaned with methyl ethyl ketone.
A bisphenol A liquid epoxy resin was used as the resin (b) other than polyphenylene ether (hereinafter abbreviated as epoxy resin).
In Examples 1 to 4 and Comparative Examples 3, 4, and 5, the polyphenylene ether (a) obtained in Synthesis Examples 1, 2, and 3 was blended in an epoxy resin as shown in Table 1, and then a curing agent for the epoxy resin. Triethylenetetramine was added in an amount equivalent to an active hydrogen equivalent of 1.2 times the epoxy equivalent of the epoxy resin. The obtained liquid was applied with a bar coater, allowed to stand at room temperature for 10 hours, and then dried at 100 ° C. for 30 minutes to obtain a coating film test piece. The comparative example 1 performed the same operation using the epoxy resin used in the Example, and obtained the coating-film test piece. In Comparative Example 2, a solution obtained by dissolving polyphenylene ether (a) obtained in Synthesis Example 2 in toluene to 5% by weight was similarly applied with a bar coater and dried at room temperature for 5 minutes. Was dried at 170 ° C. to obtain a coating film test piece. Moreover, although the comparative example 5 mix | blended the polyphenylene ether (a) obtained by the synthesis example 3 with the epoxy resin, it did not melt | dissolve but evaluation was not possible.
（塗膜剥離評価）
上記で得られた各試験片の塗膜に１ｍｍ間隔で、縦、横のクロスカットを施し、セロハンテープを密着させ、強く剥離した時の塗膜の状態を下記の基準により評価した。その結果を表２に示した。
◎：剥離が認められない、○：僅かに剥離が認められる、△：かなりの剥離が認められる、×：著しい剥離が認められる。
（環境サイクル試験後の密着性評価）
上記で得られた試験片を試料とし、ＪＩＳ−Ｚ−２３７１に規定されている環境サイクル試験を実施した。即ち、塩水噴霧（２時間）−乾燥（６０℃、湿度１５〜２０％）−湿潤（５０℃、湿度５０％以上）を１サイクルとし、環境サイクル試験を３サイクル行った。試験後の試験片を取り出し、表面を乾燥させた時の塗膜の状態を下記の基準により評価した。その結果を表２に示した。
◎：剥離が認められない、○：僅かな剥離が認められる、△：かなりの剥離が認められる、×：著しい剥離が認められる。
(Coating peeling evaluation)
The coating film of each test piece obtained above was subjected to vertical and horizontal crosscuts at 1 mm intervals, the cellophane tape was brought into close contact, and the state of the coating film when strongly peeled was evaluated according to the following criteria. The results are shown in Table 2.
(Double-circle): Peeling is not recognized, (circle): Slight peeling is recognized, (triangle | delta): Considerable peeling is recognized, X: Remarkable peeling is recognized.
(Adhesion evaluation after environmental cycle test)
Using the test piece obtained above as a sample, an environmental cycle test defined in JIS-Z-2371 was performed. That is, salt spray (2 hours) -drying (60.degree. C., humidity 15-20%)-wetting (50.degree. C., humidity 50% or more) was set as one cycle, and the environmental cycle test was performed three cycles. The test piece after the test was taken out, and the state of the coating film when the surface was dried was evaluated according to the following criteria. The results are shown in Table 2.
(Double-circle): Peeling is not recognized, (circle): Slight peeling is recognized, (triangle | delta): Considerable peeling is recognized, X: Remarkable peeling is recognized.
本発明の塗料は、電気亜鉛メッキ鋼板や溶融亜鉛メッキ鋼板などの鋼板との塗膜密着性に優れ、自動車部品の車体及びバンパー、建築材料の構造物、家電等の塗装に好適である。 The coating material of the present invention is excellent in coating film adhesion with steel sheets such as electrogalvanized steel sheets and hot-dip galvanized steel sheets, and is suitable for coating automobile parts such as car bodies and bumpers, building material structures, and home appliances.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005118127A JP2006298962A (en) | 2005-04-15 | 2005-04-15 | Coating material containing low-molecular-weight polyphenylene ether and having excellent adhesion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005118127A JP2006298962A (en) | 2005-04-15 | 2005-04-15 | Coating material containing low-molecular-weight polyphenylene ether and having excellent adhesion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2006298962A true JP2006298962A (en) | 2006-11-02 |
Family
ID=37467654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005118127A Pending JP2006298962A (en) | 2005-04-15 | 2005-04-15 | Coating material containing low-molecular-weight polyphenylene ether and having excellent adhesion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2006298962A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009518521A (en) * | 2005-12-08 | 2009-05-07 | ゼネラル・エレクトリック・カンパニイ | Poly (arylene ether) copolymer |
| JP2014005468A (en) * | 2007-07-02 | 2014-01-16 | Kaneka Corp | Polymer electrolyte, polymer electrolyte membrane, catalyst layer binder for fuel cell, and use thereof |
| JP2018531819A (en) * | 2015-10-16 | 2018-11-01 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ． ＫＧａＡ | Joining two different plastics |
| CN114350150A (en) * | 2019-04-18 | 2022-04-15 | 重庆市智翔铺道技术工程有限公司 | High-strength light steel bridge deck pavement material based on polymer alloy and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS506520B2 (en) * | 1972-05-29 | 1975-03-14 | ||
| JPS6239628A (en) * | 1985-08-14 | 1987-02-20 | バイエル・アクチエンゲゼルシヤフト | Production of mono- and di- functional oligophenylene oxide |
| JPH0491111A (en) * | 1990-08-07 | 1992-03-24 | Asahi Chem Ind Co Ltd | Electrically conductive resin composition and curable resin composition thereof |
| JPH08236906A (en) * | 1995-03-01 | 1996-09-13 | Asahi Chem Ind Co Ltd | Overcoating material |
| JPH11269428A (en) * | 1998-01-22 | 1999-10-05 | Inst Fr Petrole | Use of polymer composition for surface coating and surface coating material containing same |
| JP2002536476A (en) * | 1999-02-05 | 2002-10-29 | ゼネラル・エレクトリック・カンパニイ | Method for producing low molecular weight polyphenylene ether resin |
| JP2003527462A (en) * | 1999-10-05 | 2003-09-16 | ゼネラル・エレクトリック・カンパニイ | Powder coating composition |
-
2005
- 2005-04-15 JP JP2005118127A patent/JP2006298962A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS506520B2 (en) * | 1972-05-29 | 1975-03-14 | ||
| JPS6239628A (en) * | 1985-08-14 | 1987-02-20 | バイエル・アクチエンゲゼルシヤフト | Production of mono- and di- functional oligophenylene oxide |
| JPH0491111A (en) * | 1990-08-07 | 1992-03-24 | Asahi Chem Ind Co Ltd | Electrically conductive resin composition and curable resin composition thereof |
| JPH08236906A (en) * | 1995-03-01 | 1996-09-13 | Asahi Chem Ind Co Ltd | Overcoating material |
| JPH11269428A (en) * | 1998-01-22 | 1999-10-05 | Inst Fr Petrole | Use of polymer composition for surface coating and surface coating material containing same |
| JP2002536476A (en) * | 1999-02-05 | 2002-10-29 | ゼネラル・エレクトリック・カンパニイ | Method for producing low molecular weight polyphenylene ether resin |
| JP2003527462A (en) * | 1999-10-05 | 2003-09-16 | ゼネラル・エレクトリック・カンパニイ | Powder coating composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009518521A (en) * | 2005-12-08 | 2009-05-07 | ゼネラル・エレクトリック・カンパニイ | Poly (arylene ether) copolymer |
| JP2014005468A (en) * | 2007-07-02 | 2014-01-16 | Kaneka Corp | Polymer electrolyte, polymer electrolyte membrane, catalyst layer binder for fuel cell, and use thereof |
| JP2018531819A (en) * | 2015-10-16 | 2018-11-01 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ． ＫＧａＡ | Joining two different plastics |
| CN114350150A (en) * | 2019-04-18 | 2022-04-15 | 重庆市智翔铺道技术工程有限公司 | High-strength light steel bridge deck pavement material based on polymer alloy and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2705069B1 (en) | Multifunctional primary amine, process for its preparation, and use thereof | |
| CN106164171B (en) | Polyester coating compositions comprising polymers derived from cyclic carbonates | |
| US11104762B2 (en) | Silicone-modified polyester coating | |
| US8445573B2 (en) | Polyphenylene ether resin composition having narrow molecular weight distribution | |
| JP2006298962A (en) | Coating material containing low-molecular-weight polyphenylene ether and having excellent adhesion | |
| JPH07500123A (en) | thermosetting coating composition | |
| WO2008045894A1 (en) | Soluble polymers with low conversion of acids from aromatic epoxy resins and diacids and crosslinked coatings prepared therefrom | |
| Torlakoğlu et al. | Alkyd–amino resins based on waste PET for coating applications | |
| WO2008045889A1 (en) | Process for preparing soluble polymers with low conversion of acid from aromatic epoxy resins and diacids and process for preparing crosslinked coatings therefrom | |
| JP6985285B2 (en) | Methods for Improving Freezing / Thawing Stability of Compositions, Aqueous Coating Compositions, and Aqueous Coating Compositions | |
| JP6724921B2 (en) | Copolyester and metal primer coating using the same | |
| Zafar et al. | Water‐borne melamine–formaldehyde‐cured epoxy–acrylate corrosion resistant coatings | |
| JP4906049B2 (en) | Epoxy resin powder coating composition | |
| Büyükyonga et al. | The usage of novel acrylic-modified water-reducible alkyd resin obtained from post-consumer PET bottles in water-based paint formulation | |
| Tahmaz et al. | Synthesis and film properties of long oil alkyd resin/organo clay nanocomposite coatings | |
| Wang et al. | Preparation and application of a waterborne acrylic copolymer-siloxane composite: improvement on the corrosion resistance of zinc-coated NdFeB magnets | |
| JP2010132910A (en) | Coating resin composition and coated metal plate | |
| CN114341229B (en) | Coating composition with easy-to-clean performance | |
| JPH0362818A (en) | Epoxy resin and water-base paint | |
| JP2001508491A (en) | Stabilized non-polymeric acetoacetate esters that promote adhesion to metallic and oxidized substrates | |
| CN1831208B (en) | Multilayer film forming method | |
| JP2010189548A (en) | Process for producing polyphenylene ether | |
| JPS625467B2 (en) | ||
| KR100644767B1 (en) | Thermosetting Polyester Resin Composition For Pre-Coated Metal Primer Paints And Pre-Coated Metal Primer Paints Comprising The Same | |
| KR102322661B1 (en) | Aqueous PCM Coating Composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080404 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110830 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20120110 |