JP2001145932A - Method for coating molding of crosslinked polymer - Google Patents
Method for coating molding of crosslinked polymerInfo
- Publication number
- JP2001145932A JP2001145932A JP33010099A JP33010099A JP2001145932A JP 2001145932 A JP2001145932 A JP 2001145932A JP 33010099 A JP33010099 A JP 33010099A JP 33010099 A JP33010099 A JP 33010099A JP 2001145932 A JP2001145932 A JP 2001145932A
- Authority
- JP
- Japan
- Prior art keywords
- paint
- solution
- metathesis
- crosslinked polymer
- weight
- 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
- 229920006037 cross link polymer Polymers 0.000 title claims abstract description 26
- 238000000576 coating method Methods 0.000 title claims description 30
- 239000011248 coating agent Substances 0.000 title claims description 27
- 238000000034 method Methods 0.000 title claims description 24
- 238000000465 moulding Methods 0.000 title abstract description 19
- 239000003973 paint Substances 0.000 claims description 57
- 239000000178 monomer Substances 0.000 claims description 29
- -1 cyclic olefin Chemical class 0.000 claims description 24
- 238000005649 metathesis reaction Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 16
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- 239000002685 polymerization catalyst Substances 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000012190 activator Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 39
- 238000007254 oxidation reaction Methods 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000004381 surface treatment Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 150000003658 tungsten compounds Chemical class 0.000 description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 6
- 239000005708 Sodium hypochlorite Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000005357 flat glass Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 239000002879 Lewis base Substances 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 150000007527 lewis bases Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 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
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010107 reaction injection moulding Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- AGQPHHBPENBBIO-UHFFFAOYSA-M iodo(dioctyl)alumane Chemical compound [I-].CCCCCCCC[Al+]CCCCCCCC AGQPHHBPENBBIO-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 2
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- VYVFQBFOMKEKBG-UHFFFAOYSA-L 3,3-dibutyl-2,4,3-benzodioxastannepine-1,5-dione Chemical compound O=C1O[Sn](CCCC)(CCCC)OC(=O)C2=CC=CC=C21 VYVFQBFOMKEKBG-UHFFFAOYSA-L 0.000 description 1
- YKZUNWLMLRCVCW-UHFFFAOYSA-N 4-[2-(4-bicyclo[2.2.1]hept-2-enyl)ethyl]bicyclo[2.2.1]hept-2-ene Chemical compound C1CC(C2)C=CC21CCC1(C=C2)CC2CC1 YKZUNWLMLRCVCW-UHFFFAOYSA-N 0.000 description 1
- KZDXMUNDVIUFPV-UHFFFAOYSA-N 4-ethylidenetricyclo[6.2.1.02,7]undec-9-ene Chemical compound C12CC(=CC)CCC2C2C=CC1C2 KZDXMUNDVIUFPV-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 102100033041 Carbonic anhydrase 13 Human genes 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 101000867860 Homo sapiens Carbonic anhydrase 13 Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- BWKCCRPHMILRGD-UHFFFAOYSA-N chloro hypochlorite;tungsten Chemical compound [W].ClOCl BWKCCRPHMILRGD-UHFFFAOYSA-N 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical group 0.000 description 1
- NOSWQDCFTDHNCM-UHFFFAOYSA-N cyclopenta-1,3-diene;1-methylcyclopenta-1,3-diene Chemical compound C1C=CC=C1.CC1=CC=CC1 NOSWQDCFTDHNCM-UHFFFAOYSA-N 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005323 electroforming Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- RIZMRRKBZQXFOY-UHFFFAOYSA-N ethion Chemical compound CCOP(=S)(OCC)SCSP(=S)(OCC)OCC RIZMRRKBZQXFOY-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 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
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- JFKBLKGQCUHUHJ-UHFFFAOYSA-N tricyclo[6.2.1.02,7]undec-9-ene Chemical compound C12CCCCC2C2CC1C=C2 JFKBLKGQCUHUHJ-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001291 vacuum drying Methods 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
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本願発明は、メタセシス重合
性モノマーをメタセシス重合触媒系の存在下で重合と同
時に成形を行って得た架橋重合体成形物に対し、塗料を
塗装する際の塗装方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating method for applying a coating to a crosslinked polymer molded product obtained by simultaneously polymerizing a metathesis polymerizable monomer in the presence of a metathesis polymerization catalyst system. Things.
【０００２】[0002]
【従来の技術】有歪環状オレフィンが、メタセシス重合
触媒系によって開環重合することは公知であり、ジシク
ロペンタジエンのような安価に得られるメタセシス重合
性モノマーを用い、メタセシス重合触媒系が触媒成分と
活性化剤成分との２成分とからなり、かかる２つの成分
を含有するモノマーの反応性溶液を混合後、直ちに成形
用鋳型に流し込み、その中でバルク重合を行い、重合と
成形を一段でおこなう方法が提案されている。（例えば
特開昭５８−１２９０１３号公報）このような方法によ
り、安価な成形用鋳型を用いて架橋重合体成形物が得ら
れるため、広範な用途に使用されている。2. Description of the Related Art It is known that ring-opening polymerization of a strained cyclic olefin is carried out by a metathesis polymerization catalyst system, and an inexpensive metathesis polymerizable monomer such as dicyclopentadiene is used. And an activator component. After mixing a reactive solution of a monomer containing these two components, the mixture is immediately poured into a molding mold, in which bulk polymerization is performed, and polymerization and molding are performed in one step. A method of doing this has been proposed. According to such a method, a crosslinked polymer molded product can be obtained using an inexpensive molding mold, and thus is used for a wide range of applications.
【０００３】このような架橋重合体成形物は、用途によ
り、外観上や耐久性の向上のために、あるいは成形物中
に残留する微量のモノマー成分が成形物外へ揮発するこ
とにより生じる臭気を減らすために、全体あるいは部分
の表面を塗装して用いられており、近年、より過酷な条
件での使用に耐えうるような、より耐久性に優れ、塗膜
剥れなどの不良の発生が少ない塗膜を有するこのような
架橋重合体成形物の塗装製品が望まれている。[0003] Such a crosslinked polymer molded article has an odor generated by improving the appearance and durability or by evaporating a small amount of a monomer component remaining in the molded article outside the molded article, depending on the use. In order to reduce it, the whole or part of the surface is painted and used.In recent years, it is more durable so that it can withstand use under more severe conditions, and the occurrence of defects such as coating film peeling is small. A coated product of such a crosslinked polymer molded article having a coating film is desired.
【０００４】このような架橋重合体成形物の表面は、一
般に成形直後には塗料や接着剤への密着性が低いが、架
橋重合体成形物中に炭素−炭素２重結合を含むために空
気、熱、光などの諸要因により酸化等の反応を受けやす
く、空気中に放置、もしくは後述するような方法などに
より表面処理を行うことで、塗料や接着剤の密着性が向
上することが知られている。[0004] The surface of such a crosslinked polymer molded article generally has low adhesion to paints and adhesives immediately after molding, but it contains air due to the carbon-carbon double bond contained in the crosslinked polymer molded article. It is known that the adhesiveness of paints and adhesives is improved by being easily susceptible to reactions such as oxidation due to various factors such as heat and light, and being left in the air or subjected to a surface treatment by a method as described later. Have been.
【０００５】上記表面処理の方法としては、特開平２−
６５２４号公報には、酸化により、酸化層が形成される
と表面の極性が大きくなり、塗料や接着剤との密着性が
向上することから、短時間に酸化層を形成せしめる方法
として、水溶性酸化剤を用いる表面処理方法が開示され
ている。また、特開平２−１８０９３７号公報には、次
亜塩素酸ナトリウムおよび／または過マンガン酸カリウ
ム水溶液を用いる表面処理方法が開示されている。As a method of the above-mentioned surface treatment, Japanese Patent Laid-Open No.
Japanese Patent No. 6524 discloses that a method of forming an oxide layer in a short time is a method for forming an oxide layer in a short time because the polarity of the surface increases when an oxide layer is formed by oxidation and the adhesion to a paint or an adhesive is improved. A surface treatment method using an oxidizing agent is disclosed. Further, Japanese Patent Application Laid-Open No. 2-180937 discloses a surface treatment method using an aqueous solution of sodium hypochlorite and / or potassium permanganate.
【０００６】かかる表面処理を行った製品は、表面処理
後、製造工程の都合により、空気中にて保管した後に、
塗装することがしばしば行われる。After the surface treatment, the product is stored in the air after the surface treatment due to the manufacturing process.
Painting is often done.
【０００７】しかしながら、本願発明者が検討した結
果、かかる架橋重合成形物を、成形後もしくは表面処理
を行った場合や、空気中にて放置した後塗装を行った場
合にも、密着不良が生じる場合があることが明らかにな
った。However, as a result of the study by the present inventors, poor adhesion occurs even when such a crosslinked polymer molded product is molded or subjected to a surface treatment, or when painted after being left in the air. It became clear that there were cases.
【０００８】[0008]
【発明が解決しようとする課題】本願発明は、かかるメ
タセシス架橋重合体成形物の優れた塗装製品を得るため
に鋭意検討を行った。その結果、塗装を行う際にこのよ
うなメタセシス架橋重合体成形物の表面を空気酸化せし
め、その表面張力をある一定範囲内にせしめることで、
種々の塗料に対し、耐久性の優れた塗装製品が得られる
ことを見出したものである。DISCLOSURE OF THE INVENTION The present invention has been studied diligently to obtain an excellent coated product of such a metathesis crosslinked polymer molded product. As a result, when performing the coating, the surface of such a metathesis crosslinked polymer molded article is air-oxidized, and the surface tension is controlled within a certain range.
It has been found that a coating product having excellent durability can be obtained for various paints.
【０００９】[0009]
【課題を解決するための手段】すなわち、本願発明は次
のとおりである。That is, the present invention is as follows.
【００１０】１． メタセシス重合触媒系の触媒成分を
含有するメタセシス重合性環状オレフィンからなるモノ
マー液（溶液Ａ）とメタセシス重合触媒系の活性化剤成
分を含有するメタセシス重合性環状オレフィンからなる
モノマー液（溶液Ｂ）とを混合し、金型内において架橋
重合せしめることによって得られた架橋重合体成形物を
空気酸化せしめ、その成形物の表面張力を３６×１０-3
ｋｇ／ｓ2以上５２×１０-3ｋｇ／ｓ2以下にした後塗装
することを特徴とする架橋重合体成形物の塗装方法。[0010] 1. A monomer liquid composed of a metathesis polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst system (solution A) and a monomer liquid composed of a metathesis polymerizable cyclic olefin containing a activator component of a metathesis polymerization catalyst system (solution B); , And then subjected to air oxidation to obtain a crosslinked polymer molded product in a mold. The surface tension of the molded product is 36 × 10 −3.
A method for coating a crosslinked polymer molded article, wherein the coating is carried out after adjusting the pressure to not less than kg / s 2 and not more than 52 × 10 −3 kg / s 2 .
【００１１】２． 塗装に使用する塗料がウレタン塗
料、アクリル塗料、アクリルウレタン塗料、エポキシ塗
料から選択される塗料のいずれかであるかあるいはその
いずれかを含有する塗料であることを特徴とする上記１
記載の架橋重合体成形物の塗装方法。2. Wherein the paint used for coating is any one of a paint selected from urethane paint, acrylic paint, acrylic urethane paint, and epoxy paint, or a paint containing any of them.
A method for coating the crosslinked polymer molded article according to the above.
【００１２】本願発明における架橋重合体成形物は、メ
タセシス重合触媒系の触媒成分を含有するメタセシス重
合性環状オレフィンからなるモノマー液Ａ（溶液Ａ）と
メタセシス重合触媒系の活性化剤成分を含有するメタセ
シス重合性環状オレフィンからなるモノマー液Ｂ（溶液
Ｂ）とを混合し、その原料混合液を金型内に注入し、そ
の金型内において重合および架橋反応せしめることによ
って得られる。もしくは、溶液Ａと溶液Ｂとにさらにメ
タセシス重合性環状オレフィンからなるモノマー液Ｃを
第三成分として混合してもよい。The molded article of the crosslinked polymer in the present invention contains a monomer liquid A (solution A) comprising a metathesis polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst and an activator component of the metathesis polymerization catalyst. It is obtained by mixing a monomer solution B (solution B) composed of a metathesis polymerizable cyclic olefin, injecting the raw material mixture into a mold, and causing a polymerization and crosslinking reaction in the mold. Alternatively, the monomer liquid C composed of a metathesis polymerizable cyclic olefin may be further mixed with the solution A and the solution B as a third component.
【００１３】なお、ここで、「空気酸化」とは空気を利
用した酸化を意味し、具体的には空中に放置することに
よって達成されるが、光、温度等この空気酸化を促進す
る要素を組み合わせ使用することも可能である。[0013] Here, "air oxidation" means oxidation using air, which is specifically achieved by leaving it in the air. Elements such as light and temperature which promote this air oxidation are referred to as "air oxidation". It is also possible to use a combination.
【００１４】かかるメタセシス重合性環状オレフィンと
しては、メタセシス重合性シクロアルケン基を分子中に
１〜２個含有するものが使用される。好ましくはノルボ
ルネン骨格を分子中に少なくとも１つ有する化合物であ
る。As the metathesis-polymerizable cyclic olefin, those containing one or two metathesis-polymerizable cycloalkene groups in the molecule are used. Preferred are compounds having at least one norbornene skeleton in the molecule.
【００１５】これらの具体例としては、ジシクロペンタ
ジエン、トリシクロペンタジエン、シクロペンタジエン
−メチルシクロペンタジエン共二量体、５−エチリデン
ノルボルネン、ノルボルネン、ノルボルナジエン、５−
シクロヘキセニルノルボルネン、１,４,５,８−ジメタ
ノ−１,４,４ａ,５,６,７,８,８ａ−オクタヒドロナフ
タレン、１,４−メタノ−１,４,４ａ,５,６,７,８,８ａ
−オクタヒドロナフタレン、６−エチリデン−１,４,
５,８−ジメタノ−１,４,４ａ,５,６,７,８,８ａ−オク
タヒドロナフタレン、６−エチリデン−１,４−メタノ
−１,４,４ａ,５,６,７,８,８ａ−オクタヒドロナフタ
レン、１,４,５,８−ジメタノ−１,４,４ａ,５,８,８ａ
−ヘキサヒドロナフタレン、エチレンビス（５−ノルボ
ルネン）などを挙げることができこれらの混合物も使用
することができる。特にジシクロペンタジエンまたはそ
れを５０モル％以上、好ましくは７０モル％以上含む混
合物が好適に用いられる。また、必要に応じて、酸素、
窒素などの異種元素を含有する極性基を有するメタセシ
ス重合性環状オレフィンを共重合モノマーとして用いる
ことができる。Specific examples of these include dicyclopentadiene, tricyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer, 5-ethylidene norbornene, norbornene, norbornadiene,
Cyclohexenyl norbornene, 1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4-methano-1,4,4a, 5,6, 7,8,8a
-Octahydronaphthalene, 6-ethylidene-1,4,
5,8-Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4-methano-1,4,4a, 5,6,7,8, 8a-octahydronaphthalene, 1,4,5,8-dimethano-1,4,4a, 5,8,8a
-Hexahydronaphthalene, ethylenebis (5-norbornene) and the like, and mixtures thereof can also be used. In particular, dicyclopentadiene or a mixture containing 50 mol% or more, preferably 70 mol% or more thereof is suitably used. Also, if necessary, oxygen,
A metathesis polymerizable cyclic olefin having a polar group containing a different element such as nitrogen can be used as a copolymerization monomer.
【００１６】モノマー液Ａ（溶液Ａ）中に含有する触媒
成分としては、タングステン、レニウム、タンタル、モ
リブデンなどの金属のハライドやアンモニウムなどの塩
類が用いられるが、特にタングステン化合物が好まし
い。As the catalyst component contained in the monomer solution A (solution A), salts of metals such as tungsten, rhenium, tantalum and molybdenum, and salts of ammonium are used, and a tungsten compound is particularly preferable.
【００１７】かかるタングステン化合物としては、タン
グステンヘキサハライド、タングステンオキシハライド
などが好ましく、より具体的にはタングステンヘキサク
ロライド、タングステンオキシクロライドなどが好まし
い。また、有機アンモニウムタングステン酸塩なども用
いることができる。As such a tungsten compound, tungsten hexahalide, tungsten oxyhalide and the like are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride and the like are preferable. Further, an organic ammonium tungstate or the like can be used.
【００１８】かかるタングステン化合物は、直接モノマ
ーに添加すると、直ちにカチオン重合を開始することが
分かっており好ましくない。従って、かかるタングステ
ン化合物は不活性溶媒、例えばベンゼン、トルエン、ク
ロロベンゼンなどに予め懸濁し、少量のアルコール系化
合物および／またはフェノール系化合物を添加すること
によって可溶化させて使用するのが好ましい。さらに上
述した如き好ましくない重合を予防するために、タング
ステン化合物１モルに対し、約１〜５モルのルイス塩基
またはキレート化剤を添加することが好ましい。かかる
添加剤としてはアセチルアセトン、アセト酢酸アルキル
エステル類、テトラヒドロフラン、ベンゾニトリルなど
を挙げることができる。It has been found that such a tungsten compound immediately starts cationic polymerization when added directly to a monomer, which is not preferable. Therefore, it is preferable that the tungsten compound is used by suspending it in an inert solvent such as benzene, toluene, chlorobenzene or the like in advance and solubilizing by adding a small amount of an alcohol compound and / or a phenol compound. Further, in order to prevent the undesirable polymerization as described above, it is preferable to add about 1 to 5 mol of a Lewis base or a chelating agent per 1 mol of the tungsten compound. Examples of such additives include acetylacetone, alkyl acetoacetates, tetrahydrofuran, and benzonitrile.
【００１９】極性モノマーを用いる場合には、前述の如
く、そのものがルイス塩基である場合があり、上記の如
き化合物を特に加えなくてもその作用を有している場合
もある。When a polar monomer is used, as described above, the polar monomer itself may be a Lewis base, and in some cases, the above-mentioned compound may have its action without adding any of the above compounds.
【００２０】前述の如くして、触媒成分を含むモノマー
液Ａ（溶液Ａ）は、実質上充分な安定性を有することに
なる。As described above, the monomer liquid A containing the catalyst component (solution A) has substantially sufficient stability.
【００２１】一方、モノマー液Ｂ（溶液Ｂ）中に含有す
る活性化剤成分としては、周期律表第Ｉ〜第ＩＩＩ族の
金属のアルキル化物を中心とする有機金属化合物、特に
テトラアルキル錫、アルキルアルミニウム化合物、アル
キルアルミニウムハライド化合物が好ましく、具体的に
は塩化ジエチルアルミニウム、ジ塩化エチルアルミニウ
ム、トリエチルアルミニウム、トリオクチルアルミニウ
ム、ジオクチルアルミニウムアイオダイド、テトラブチ
ル錫などを挙げることができる。これら活性化剤成分と
しての有機金属化合物をモノマーに溶解することによ
り、モノマー液Ｂ（溶液Ｂ）が形成される。On the other hand, as the activator component contained in the monomer liquid B (solution B), an organic metal compound mainly composed of an alkylated metal of Group I to Group III of the periodic table, especially tetraalkyltin, Alkyl aluminum compounds and alkyl aluminum halide compounds are preferable, and specific examples thereof include diethyl aluminum chloride, ethyl aluminum dichloride, triethyl aluminum, trioctyl aluminum, dioctyl aluminum iodide, and tetrabutyl tin. By dissolving the organometallic compound as an activator component in the monomer, a monomer liquid B (solution B) is formed.
【００２２】基本的には前記溶液Ａおよび溶液Ｂを混合
し、金型内に注入することによって、架橋重合体成形物
を得ることができるが、上記組成のままでは、重合反応
が非常に速く開始されるので、成形金型に十分流れ込ま
ない間に硬化が起こることもあり、問題となる場合が多
い。従って、活性調節剤を用いることが好ましい。Basically, a crosslinked polymer molded product can be obtained by mixing the solution A and the solution B and injecting the mixture into a mold. However, if the above composition is maintained, the polymerization reaction is extremely fast. Since it is started, curing may occur while not sufficiently flowing into the molding die, which often causes a problem. Therefore, it is preferable to use an activity regulator.
【００２３】かかる調節剤としては、ルイス塩基類が一
般に用いられ、なかんずく、エーテル類、エステル類、
ニトリル類などが用いられる。具体例としては安息香酸
エチル、ブチルエーテル、ジグライムなどを挙げること
ができる。As such a regulator, Lewis bases are generally used, and above all, ethers, esters,
Nitriles and the like are used. Specific examples include ethyl benzoate, butyl ether, diglyme and the like.
【００２４】かかる調節剤は一般的に、有機金属化合物
の活性化剤の成分の溶液（溶液Ｂ）の側に添加して用い
られる。前述と同様にルイス塩基を有するモノマーを使
用する場合には、それに調節剤の役目を兼ねさせること
ができる。Such a regulator is generally used by adding it to the solution (solution B) of the component of the activator of the organometallic compound. When a monomer having a Lewis base is used as described above, it can also serve as a regulator.
【００２５】メタセシス重合触媒系の使用量は、例えば
触媒成分としてタングステン化合物を用いる場合は、上
記原料モノマーに対するタングステン化合物の比率は、
モル基準で約１,０００対１〜１５，０００対１、好ま
しくは１,５００対１〜２，５００対１であり、また、
活性化剤成分はアルキルアルミニウム類を用いる場合に
は、上記原料モノマーに対するアルミニウム化合物の比
率は、モル基準で約１００対１〜１０,０００対１、好
ましくは２００対１〜１，０００対１が用いられる。The amount of the metathesis polymerization catalyst system used is, for example, when a tungsten compound is used as a catalyst component, the ratio of the tungsten compound to the raw material monomer is as follows:
About 1,000 to 1 to 15,000, preferably 1,500 to 1, 2500 to 1 on a molar basis;
When an alkyl aluminum is used as the activator component, the ratio of the aluminum compound to the raw material monomer is about 100: 1 to 10,000: 1, preferably 200: 1 to 1,000: 1 on a molar basis. Used.
【００２６】さらに上述した如き、マスク剤や調節剤に
ついては、実験によって上記触媒系の使用量に応じて、
適宜、調節して用いることができる。Further, as described above, with respect to the masking agent and the adjusting agent, the amount of the above-mentioned catalyst system is determined by experiments.
It can be used after being appropriately adjusted.
【００２７】この架橋重合体の成形物には、実用に当っ
てその特性を改良または維持するために更にその目的に
応じた各種添加剤を配合することができる。かかる添加
剤としては、エラストマー、充填剤、強化剤、酸化防止
剤、熱安定剤、顔料、光安定剤、紫外線吸収剤、滑剤、
帯電防止剤、難燃化剤、発泡剤、軟化剤、粘着付与剤、
可塑剤、離型剤、防臭剤、香料または増量剤が挙げら
れ、これらは単独のみならず２種以上を組み合せて使用
することもできる。In order to improve or maintain the properties in practical use, various additives depending on the purpose can be further added to the molded product of the crosslinked polymer. Such additives include elastomers, fillers, reinforcing agents, antioxidants, heat stabilizers, pigments, light stabilizers, ultraviolet absorbers, lubricants,
Antistatic agent, flame retardant, foaming agent, softener, tackifier,
Plasticizers, release agents, deodorants, fragrances and extenders can be mentioned, and these can be used alone or in combination of two or more.
【００２８】添加の方法としては、予め原料液に混ぜる
ことも、また第３液として重合直前に混合することも、
またあるいは予め成形金型内に充填して置くこともで
き、添加剤の種類により適した方法が選択される。特に
ガラス繊維などの補強剤は、金型内に予めセットしそこ
に混合した液を注入するのが一般的である。As a method of addition, it is possible to mix the raw material liquid in advance, or as the third liquid immediately before the polymerization,
Alternatively, it can be filled in a molding die in advance, and a method suitable for the type of additive is selected. In particular, a reinforcing agent such as glass fiber is generally set in a mold in advance, and a mixed liquid is poured into the mold.
【００２９】また、環状オレフィンの反応射出成形法に
よる成形物は、他の重合体をモノマー溶液状態の時に添
加しておいて得ることができる。かかる重合体添加剤と
してはエラストマーが、成形物の耐衝撃性を高めること
および溶液の粘度を調節する上で効果がある。かかる目
的に用いられるエラストマーとしては、スチレン−ブタ
ジエン−スチレントリブロックゴム、スチレン−イソプ
レン−スチレントリブロックゴム、ポリブタジエン、ポ
リイソプレン、ブチルゴム、エチレンプロピレン−ジエ
ン−ポリマー、ニトリルゴムなど広範なエラストマーを
挙げることができる。A molded product of the cyclic olefin obtained by the reaction injection molding method can be obtained by adding another polymer in a monomer solution state. As such a polymer additive, an elastomer is effective in increasing the impact resistance of a molded product and adjusting the viscosity of a solution. Examples of the elastomer used for this purpose include a wide range of elastomers such as styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene propylene-diene-polymer, and nitrile rubber. Can be.
【００３０】本願発明の成形物を成形するための金型の
材質としては、スチール、鋳造あるいは鍛造のアルミニ
ウム、亜鉛合金などの鋳造や溶射、ニッケルや銅などの
電鋳および樹脂などが挙げられる。また、型の構造は成
形時に型内に発生する圧力が数ｋｇ／ｃｍ2と他の成形
方法に比べて極めて低いので簡単なもので十分であり、
従って他の成形方法に比べて安価に作ることができる。Examples of the material of the mold for molding the molded article of the present invention include steel, cast or forged aluminum and zinc alloys, and spraying, electroforming of nickel and copper, and resin. In addition, since the pressure generated in the mold during molding is several kg / cm 2 , which is extremely low as compared with other molding methods, a simple structure is sufficient.
Therefore, it can be manufactured at lower cost than other molding methods.
【００３１】本願発明における成形物表面の表面張力
は、ＪＩＳＫ６７６８に記載されたホルムアミド／エチ
レングリコールモノエチルエーテル混合液による評価方
法により評価される。あるいは液滴の接触角を測定して
評価する液滴法などの方法が挙げられる。これら諸法の
中で、ホルムアミド／エチレングリコールモノエチルエ
ーテル混合液による評価方法が簡便であり好ましい。本
願発明に言う表面張力は、この方法で測定したものであ
る。The surface tension of the molded product surface in the present invention is evaluated by the evaluation method using a formamide / ethylene glycol monoethyl ether mixed solution described in JIS K6768. Alternatively, a method such as a droplet method of measuring and evaluating the contact angle of a droplet may be used. Among these methods, an evaluation method using a formamide / ethylene glycol monoethyl ether mixed solution is simple and preferable. The surface tension referred to in the present invention is measured by this method.
【００３２】研究の結果、かかる表面張力の好適な範囲
としては、３６×１０-3ｋｇ／ｓ2以上５２×１０-3ｋ
ｇ／ｓ2以下であることが好ましいことが判明した。よ
り好ましくは、４０×１０-3ｋｇ／ｓ2以上５０×１０
-3ｋｇ／ｓ2以下である。As a result of the study, a suitable range of the surface tension is 36 × 10 −3 kg / s 2 or more and 52 × 10 −3 k or more.
g / s 2 or less was found to be preferable. More preferably, it is 40 × 10 −3 kg / s 2 or more and 50 × 10 −3 kg / s 2 or more.
-3 kg / s 2 or less.
【００３３】これ未満である場合はもちろん、これを超
えた場合には、塗料の成形物表面への密着性が悪いため
に、塗装剥れ等の不良が発生しやすいという意外な結果
が判明した。It is surprisingly found that not only when the value is less than this value but also when the value exceeds this value, the adhesion of the paint to the surface of the molded product is poor, so that defects such as paint peeling are likely to occur. .
【００３４】また、従来の水溶性酸化剤や次亜塩素酸ナ
トリウムや過マンガン酸カリウム水溶液を用い、表面処
理を行った場合に、時として塗料の成形物表面への密着
性不良、塗装剥れ等が生じており、このような「時とし
て生じる異常」は、万一製品で生じた場合には、製品の
イメージを大きく傷付けることから、生産工程における
過剰な検査作業を余儀なくされていた。Further, when the surface treatment is performed using a conventional water-soluble oxidizing agent, an aqueous solution of sodium hypochlorite or potassium permanganate, poor adhesion of the paint to the surface of the molded product, peeling of the paint sometimes occurs. If the "occasionally occurring abnormality" occurs in a product, it would greatly damage the image of the product, so that an excessive inspection work in the production process had to be performed.
【００３５】今回の研究の結果、これは、部分的には、
上記のごとく、適正な表面張力を越える場合があったた
めと推察されたが、検討の結果、従来の水溶性酸化剤や
次亜塩素酸ナトリウムや過マンガン酸カリウム水溶液を
用い表面処理を行った場合には、表面張力の範囲に関係
せず、依然塗装剥れ等が時折生じること、本願発明に係
る「空気酸化」を採用した場合には、そのような時折生
じる異常が排除できることが判明した。As a result of this study, this was partially due to
As described above, it was presumed that the surface tension exceeded the appropriate value, but as a result of the examination, the case where the surface treatment was performed using a conventional water-soluble oxidizing agent or an aqueous solution of sodium hypochlorite or potassium permanganate It has been found that, regardless of the range of the surface tension, paint peeling still occurs occasionally, and when the “air oxidation” according to the present invention is employed, such an occasional abnormality can be eliminated.
【００３６】かかる範囲に表面張力がなるように空気酸
化せしめる場合には、温度や光量などの諸条件などによ
り、その空気酸化の速度は異なる。より短時間に行うに
は、より高温下で、より強い光を照射した方が良いが、
酸化速度が速いために制御が難しいことが多く、温度や
光量を適宜制限して行うことが好ましい。In the case where the air is oxidized so that the surface tension is in such a range, the speed of the air oxidization varies depending on various conditions such as temperature and light amount. In order to perform in a shorter time, it is better to irradiate stronger light at higher temperature,
Since the oxidation rate is high, control is often difficult, and it is preferable that the temperature and the amount of light be appropriately restricted.
【００３７】また、水溶性酸化剤や次亜塩素酸ナトリウ
ムや過マンガン酸カリウム水溶液を用い、表面処理を行
った後、空気酸化せしめても良い。この場合、空気酸化
の効果を得るには、後の空気酸化によって表面張力を１
×１０-3ｋｇ／ｓ2以上あげるのが好ましく、この空気
酸化によって「時として生じる異常」も防止できること
が判明した。表面張力は３×１０-3ｋｇ／ｓ2以上あげ
るのがさらに好ましい。After surface treatment using a water-soluble oxidizing agent, an aqueous solution of sodium hypochlorite or potassium permanganate, air oxidation may be performed. In this case, in order to obtain the effect of air oxidation, the surface tension is reduced to 1 by air oxidation later.
It is preferable to increase the pressure by at least × 10 −3 kg / s 2 , and it has been found that this air oxidation can also prevent “sometimes abnormalities”. The surface tension is more preferably raised to 3 × 10 −3 kg / s 2 or more.
【００３８】上述のごとく、空気酸化せしめた後に、架
橋重合体成形物の表面に対し、塗料の塗布を行う。As described above, after air oxidation, a paint is applied to the surface of the crosslinked polymer molded product.
【００３９】本願発明の架橋重合体成形物の表面を被覆
する塗料としては、ウレタン塗料、アクリル塗料、アク
リルウレタン塗料、エポキシ塗料、アミノアルキッド塗
料、フェノール塗料、アルキッド塗料、ウレア塗料、シ
リコーン塗料等の架橋型塗料や、ラッカーやビニル系の
非架橋型、またはこれらの混合物などが使われる。これ
らの塗料は、主成分となる樹脂成分に対し、顔料や染料
などの着色成分、溶剤、さらには可塑剤、分散安定剤、
紫外線吸収剤、防かび剤、増粘剤などの副資材を含有す
ることができる。これらの中で、ウレタン塗料、アクリ
ル塗料、アクリルウレタン塗料、エポキシ塗料は、耐久
性がありかつ本願発明の架橋重合体との密着性が良好な
ために好ましい。Examples of paints for coating the surface of the crosslinked polymer molded product of the present invention include urethane paints, acrylic paints, acrylic urethane paints, epoxy paints, aminoalkyd paints, phenol paints, alkyd paints, urea paints, silicone paints and the like. A crosslinked paint, a non-crosslinked lacquer or vinyl paint, or a mixture thereof is used. These coatings, for the resin component as the main component, coloring components such as pigments and dyes, solvents, further plasticizers, dispersion stabilizers,
Secondary materials such as an ultraviolet absorber, a fungicide, and a thickener can be contained. Among these, urethane paints, acrylic paints, acrylic urethane paints, and epoxy paints are preferable because they have durability and good adhesion to the crosslinked polymer of the present invention.
【００４０】かかる塗料の塗布方法は使用する塗料の通
常の塗布方法によれば良く、一般にはローラーや刷毛塗
りあるいはスプレー塗布であり、場合によっては塗料中
に浸漬し、塗布することもできる。また、使用する塗料
によっては加熱硬化させる場合も有るが、素材の耐熱性
から通常は１３０℃以下で行われる。かかる塗料は場合
により溶剤の除去のため乾燥を行うが、その方法は使用
する塗料の通常の方法によれば良く、一般には自然乾
燥、加熱乾燥、熱風乾燥、真空乾燥などが例示される。The method of applying such a paint may be a usual method of applying the paint to be used. Generally, it is a roller, a brush or a spray, and in some cases, the paint can be applied by dipping in the paint. Further, depending on the paint used, it may be cured by heating. However, it is usually performed at 130 ° C. or lower due to the heat resistance of the material. Such a paint is optionally dried to remove the solvent, and the method may be a usual method of the paint to be used, and generally includes natural drying, heat drying, hot air drying, vacuum drying and the like.
【００４１】[0041]
【実施例】以下実施例を挙げて本願発明を説明する。な
お、実施例は説明のためのものであって、本願発明はこ
れらに限定されない。EXAMPLES The present invention will be described below with reference to examples. It should be noted that the examples are for explanation, and the present invention is not limited to these.
【００４２】［参考例１］ （モノマー液） （溶液Ａの調製）六塩化タングステン２８重量部を窒素
気流中下で乾燥トルエン８０重量部に添加し、次いでｔ
−ブタノール１．３重量部をトルエン１重量部に溶解し
た溶液を加え１時間撹拌し、次いでノニルフェノール１
８重量部およびトルエン１４重量部よりなる溶液を添加
して５時間窒素パージ下撹拌した。さらにアセチルアセ
トン１４重量部を加えた。副生する塩化水素ガスを追い
出しながら窒素パージ下に一晩撹拌を継続し、重合用触
媒溶液を調製した。REFERENCE EXAMPLE 1 (Monomer liquid) (Preparation of solution A) 28 parts by weight of tungsten hexachloride was added to 80 parts by weight of dry toluene under a nitrogen stream, and then t
A solution of 1.3 parts by weight of butanol dissolved in 1 part by weight of toluene was added and stirred for 1 hour.
A solution consisting of 8 parts by weight and 14 parts by weight of toluene was added, and the mixture was stirred for 5 hours under a nitrogen purge. Further, 14 parts by weight of acetylacetone was added. The stirring was continued overnight under a nitrogen purge while expelling the by-produced hydrogen chloride gas to prepare a polymerization catalyst solution.
【００４３】次いで、精製ジシクロペンタジエン（純度
９９．７重量％、以下同様）９５重量部、精製エチリデ
ンノルボルネン（純度９９．５重量％、以下同様）５重
量部よりなるモノマー混合物に対し、エチレン含有７０
モル％のエチレン−プロピレン−エチリデンノルボルネ
ン重合ゴム３重量部、酸化安定剤としてエチル社製エタ
ノックス７０２を２重量部加えた溶液に上記重合用触媒
溶液をタングステン含量が０．０１Ｍ／リットルになる
ように加えて触媒成分を含有するモノマー液（溶液Ａ）
を調製した。Next, a monomer mixture consisting of 95 parts by weight of purified dicyclopentadiene (purity: 99.7% by weight, the same applies hereinafter) and 5 parts by weight of purified ethylidene norbornene (purity: 99.5% by weight, the same applies hereinafter) was mixed with ethylene containing 70
The polymerization catalyst solution was added to a solution obtained by adding 3 parts by weight of an ethylene-propylene-ethylidene norbornene polymerized rubber of 2 mol% and 2 parts by weight of Ethanox 702 manufactured by Ethyl as an oxidation stabilizer so that the tungsten content became 0.01 M / liter. In addition, a monomer solution containing a catalyst component (solution A)
Was prepared.
【００４４】（溶液Ｂの調製）精製ジシクロペンタジエ
ン９５重量部、精製エチリデンノルボルネン５重量部よ
りなるモノマー混合物に対し、エチレン含有７０モル％
のエチレンープロピレンーエチリデンノルボルネン重合
ゴム３重量部を溶解した溶液に、トリオクチルアルミニ
ウム８５、ジオクチルアルミニウムアイオダイド１５、
ジグライム１００のモル割合で混合調製した重合用活性
化剤混合液をアルミニウム含有が０．０３Ｍ／リットル
になる割合で添加し、活性化剤成分を含有するモノマー
液Ｂ（溶液Ｂ）を調製した。(Preparation of solution B) 70% by mole of ethylene was contained in a monomer mixture consisting of 95 parts by weight of purified dicyclopentadiene and 5 parts by weight of purified ethylidene norbornene.
In a solution prepared by dissolving 3 parts by weight of ethylene-propylene-ethylidene norbornene polymerized rubber, was added trioctyl aluminum 85, dioctyl aluminum iodide 15,
A mixture of activators for polymerization prepared by mixing at a molar ratio of 100 diglyme was added at a ratio of 0.03 M / liter of aluminum to prepare a monomer solution B containing the activator component (solution B).
【００４５】［参考例２］ （成形）成形用アルミニウム金型により厚さ３ｍｍX５
００ｍｍX５００ｍｍの成形板を作成した。この金型を
使用し、キャビティー型を９０℃、コア型を６０℃に加
熱し型を閉じた後、この中へＲＩＭ（反応射出成形）成
形機を利用してミキシングヘッド中で溶液Ａと溶液Ｂと
を５０：５０の重量比で衝突混合し注入した。液注入充
填後５分で型を開き架橋重合品を取り出した。REFERENCE EXAMPLE 2 (Molding) A 3 mm × 5 mm thick aluminum mold was used for molding.
A molded plate of 00 mm × 500 mm was prepared. Using this mold, the cavity mold is heated to 90 ° C., the core mold is heated to 60 ° C., and the mold is closed. Then, the solution A is mixed with the solution A in a mixing head using a RIM (reaction injection molding) molding machine. The solution B and the solution B were impact-mixed at a weight ratio of 50:50 and injected. Five minutes after the liquid injection and filling, the mold was opened and the crosslinked polymer product was taken out.
【００４６】［実施例１］ （空気酸化）参考例２で得られた平板を窓ガラス越しに
直射日光があたらないやや薄暗い場所に１４日間放置し
た。得られた成形板の表面をＪＩＳＫ６７６８に記載さ
れたホルムアミド／エチレングリコールモノエチルエー
テル混合液による評価方法により評価した結果、表面張
力は４６×１０-3ｋｇ／ｓ2であった。Example 1 (Air Oxidation) The flat plate obtained in Reference Example 2 was allowed to stand for 14 days in a slightly dim place without direct sunlight through a window glass. The surface of the obtained molded plate was evaluated by the evaluation method using a mixed solution of formamide and ethylene glycol monoethyl ether described in JIS K6768. As a result, the surface tension was 46 × 10 −3 kg / s 2 .
【００４７】（ウレタン塗料による塗布）エチレンジア
ミンの酸化プロピレン付加物５０重量部とポリエチレン
グリコール５０重量部、ジブチルフタレート１０重量
部、ジブチル錫フタレート０．０５重量部からなるＡ液
の１００重量部とポリメチレンポリフェニレンポリイソ
シアネートからなるＢ液７０重量部を混合しシンナーで
希釈し塗料を調製し、この塗料を、上記表面が酸化され
た平板に対し、スプレー塗布し、風乾の後、７０℃で５
時間乾燥した。(Application with urethane paint) 100 parts by weight of solution A comprising 50 parts by weight of propylene oxide adduct of ethylenediamine, 50 parts by weight of polyethylene glycol, 10 parts by weight of dibutyl phthalate and 0.05 parts by weight of dibutyl tin phthalate, and polymethylene 70 parts by weight of a liquid B composed of polyphenylene polyisocyanate was mixed and diluted with a thinner to prepare a paint. The paint was spray-coated on the flat plate having the oxidized surface, air-dried, and dried at 70 ° C. for 5 hours.
Dried for hours.
【００４８】（塗膜特性評価）得られた塗膜の膜厚は５
６μｍであった。得られた塗膜の耐久性の評価は、塗
装後７日間経過したサンプル、および５０℃の温水に
７日間浸漬後、取り出し、表面に付着した水分を拭き取
った後２５℃湿度５０％で１時間放置したサンプル、の
２種類のサンプルを用い、塗膜に１ｍｍ2の桝目１００
個の格子パターンの切り込みを入れた後、透明付着テー
プを押し付け、これを剥がす際の塗膜の剥れの有無によ
り、評価を行った（以下これを碁盤目テストと呼ぶ）。
また、温水に４日間浸漬したサンプルについては塗膜の
膨れの有無についても評価を行った。(Evaluation of coating film characteristics) The thickness of the obtained coating film was 5
It was 6 μm. Evaluation of the durability of the obtained coating film was performed on a sample that had passed for 7 days after coating, and after immersion in warm water of 50 ° C. for 7 days, taken out, wiped off moisture adhering to the surface, and then at 25 ° C. and a humidity of 50% for 1 hour. Using two types of samples, a left sample, a 1 mm 2 square 100
After making the cuts of the individual grid patterns, the transparent adhesive tape was pressed and evaluated by the presence or absence of peeling of the coating film when the transparent adhesive tape was peeled off (hereinafter referred to as a grid test).
The samples immersed in warm water for 4 days were also evaluated for the presence or absence of swelling of the coating.
【００４９】碁盤目テストの評価の結果、塗装後７日間
経過したサンプル、温水に４日間浸漬したサンプルのい
ずれもはがれ無しであった。また、温水に４日間浸漬し
たサンプルの塗膜の膨れも無かった。As a result of the cross-cut test, neither the sample 7 days after coating nor the sample immersed in warm water for 4 days did not peel off. In addition, there was no swelling of the coating film of the sample immersed in warm water for 4 days.
【００５０】［実施例２］この例においては表１のごと
く塗料としてアクリルウレタン塗料を用い塗布を行った
他は、実施例１と同様に処理を行った。その評価結果を
表１に示す。Example 2 In this example, the treatment was performed in the same manner as in Example 1 except that the application was performed using an acrylic urethane paint as shown in Table 1. Table 1 shows the evaluation results.
【００５１】（アクリルウレタン塗料による塗布）２−
ヒドロキシルエチルメタクリレート２０重量部、ポリプ
ロピレングリコール７５重量部、メチルメタクリレート
５重量部、ジブチルフタレート１０重量部、ジブチル錫
ジウラレート０．０５重量部、ｔ−ブチルパーオキシ−
２−エチルヘキサレート０．１重量部からなるＡ液の１
００重量部とポリメチレンポリフェニレンポリイソシア
ネートからなるＢ液６５重量部とを混合しシンナーで希
釈し塗料を調製し、この塗料を、上記表面が酸化された
平板に対し、スプレー塗布し、風乾の後、７０℃で５時
間乾燥した。(Application with acrylic urethane paint)
20 parts by weight of hydroxylethyl methacrylate, 75 parts by weight of polypropylene glycol, 5 parts by weight of methyl methacrylate, 10 parts by weight of dibutyl phthalate, 0.05 part by weight of dibutyltin diurarate, t-butyl peroxy-
Solution 1 consisting of 0.1 part by weight of 2-ethylhexarate
00 parts by weight and 65 parts by weight of the liquid B composed of polymethylene polyphenylene polyisocyanate were mixed and diluted with a thinner to prepare a paint. The paint was spray-coated on the flat plate having the oxidized surface, and then air-dried. And dried at 70 ° C. for 5 hours.
【００５２】［実施例３、４］これらの例においては表
１のごとく参考例２にて作成した平板を成形後、窓ガラ
ス越しに直射日光があたる場所に５日間放置したものを
用いた他は、それぞれ実施例１と同様に処理を行った。
その評価結果を表１に示す。[Examples 3 and 4] In these examples, the flat plate prepared in Reference Example 2 was molded as shown in Table 1 and then left for 5 days in a place exposed to direct sunlight through a window glass. Were processed in the same manner as in Example 1.
Table 1 shows the evaluation results.
【００５３】［実施例５、６］この例においては表１、
２のごとく参考例２にて作成した平板を成形後、窓ガラ
ス越しに直射日光があたらないやや薄暗い場所に７日間
放置したものを用いた他は、それぞれ実施例１，２と同
様に処理を行った。その評価結果をそれぞれ表１、２に
示す。Embodiments 5 and 6 In this embodiment, Table 1
After processing the flat plate created in Reference Example 2 as in Example 2, the same processing as in Examples 1 and 2 was performed except that the plate was left for 7 days in a slightly dark place where direct sunlight did not shine through the window glass. went. The evaluation results are shown in Tables 1 and 2, respectively.
【００５４】［比較例１、２］この例においては表２の
ごとく参考例２にて作成した平板を成形直後に用いた他
は、それぞれ実施例１，２と同様に処理を行った。その
評価結果を表２に示す。[Comparative Examples 1 and 2] In this example, the treatment was performed in the same manner as in Examples 1 and 2, except that the flat plate prepared in Reference Example 2 was used immediately after molding as shown in Table 2. Table 2 shows the evaluation results.
【００５５】［比較例３、４］これらの例においては表
２のごとく参考例２にて作成した平板を成形後、窓ガラ
ス越しに直射日光があたる場所に１０日間放置したもの
を用いた他は、それぞれ実施例１，２と同様に処理を行
った。その評価結果を表２に示す。[Comparative Examples 3 and 4] In these examples, the flat plate prepared in Reference Example 2 was molded as shown in Table 2 and then left for 10 days in a place exposed to direct sunlight through a window glass. Were processed in the same manner as in Examples 1 and 2, respectively. Table 2 shows the evaluation results.
【００５６】実施例１〜６では、塗料の耐久性が良く、
塗装乾燥後および温水浸漬後のいずれも密着性が良好で
あり、温水浸漬によっても塗膜の膨れは発生しなかっ
た。一方、比較例１〜４では塗装乾燥後および／または
温水浸漬後に密着不良や塗膜の膨れが生じ、耐久性に劣
っていた。In Examples 1 to 6, the durability of the paint was good.
Adhesion was good both after coating drying and after immersion in warm water, and no swelling of the coating film occurred even after immersion in warm water. On the other hand, in Comparative Examples 1 to 4, poor adhesion and swelling of the coating film occurred after coating and drying and / or immersion in warm water, resulting in poor durability.
【００５７】［比較例５］この例においては、参考例２
にて作成した平板を成形後、ただちに次亜塩素酸ナトリ
ウムの０．５重量％溶液に１０分間浸漬し、その後水洗
したものを用い、実施例１の空気酸化は行なわなかった
他は、実施例１と同様に処理を行い、これを５回繰り返
した。その評価結果を表３に示す。Comparative Example 5 In this example, reference example 2
Immediately after forming the flat plate prepared in the above, the plate was immersed in a 0.5% by weight solution of sodium hypochlorite for 10 minutes and then washed with water. The same processing as in No. 1 was performed, and this was repeated five times. Table 3 shows the evaluation results.
【００５８】［実施例７］比較例５と同様に次亜塩素酸
ナトリウムの０．５重量％溶液に１０分間浸漬し、その
後水洗したものを、さらに窓ガラス越しに直射日光があ
たらないやや薄暗い場所に３日間放置したものを用い、
実施例１の空気酸化は行なわなかった他は、実施例１と
同様に処理を行い、これを５回繰り返した。その評価結
果を表３に示す。表３に示すごとく、比較例５の場合
は、良好な塗装結果が得られる場合もあるが、不良な場
合も発生した。一方実施例７では、このような不良は発
生しなかった。Example 7 As in Comparative Example 5, the product was immersed in a 0.5% by weight solution of sodium hypochlorite for 10 minutes, and then washed with water, and further slightly dim without being exposed to direct sunlight through a window glass. Using what was left in place for 3 days,
The same treatment as in Example 1 was performed except that the air oxidation of Example 1 was not performed, and this was repeated five times. Table 3 shows the evaluation results. As shown in Table 3, in the case of Comparative Example 5, good coating results could be obtained in some cases, but in other cases, poor coatings occurred. On the other hand, in Example 7, such a defect did not occur.
【００５９】[0059]
【表１】 [Table 1]
【００６０】[0060]
【表２】 [Table 2]
【００６１】[0061]
【表３】 [Table 3]
【００６２】[0062]
【発明の効果】本願発明によれば、メタセシス架橋重合
体成形物に塗装を行う際にこのようなメタセシス架橋重
合体成形物の表面を空気酸化せしめ、その表面張力をあ
る一定範囲内にせしめることで、種々の塗料に対し、従
来品に比べ耐久性に優れた塗装製品が提供される。According to the present invention, when a metathesis crosslinked polymer molded article is coated, the surface of such a metathesis crosslinked polymer molded article is oxidized with air and the surface tension is kept within a certain range. Thus, for various paints, a coated product having higher durability than conventional products is provided.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 井口 紀夫 山口県岩国市日の出町２番１号 帝人メト ン株式会社テクニカルセンター内 Ｆターム(参考） 4D075 AA01 CA01 CA13 DA23 DA29 DB31 EB22 EB33 EB38 4F206 AA03L AB04 AC05 JA01 JW31 JW41 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Norio Iguchi 2-1 Hinodecho, Iwakuni-shi, Yamaguchi F-term in Technical Center Teijin Meton Co., Ltd. 4D075 AA01 CA01 CA13 DA23 DA29 DB31 EB22 EB33 EB38 4F206 AA03L AB04 AC05 JA01 JW31 JW41
Claims (2)
するメタセシス重合性環状オレフィンからなるモノマー
液（溶液Ａ）とメタセシス重合触媒系の活性化剤成分を
含有するメタセシス重合性環状オレフィンからなるモノ
マー液（溶液Ｂ）とを混合し、金型内において架橋重合
せしめることによって得られた架橋重合体成形物を空気
酸化せしめ、その成形物の表面張力を３６×１０-3ｋｇ
／ｓ2以上５２×１０-3ｋｇ／ｓ2以下にした後塗装する
ことを特徴とする架橋重合体成形物の塗装方法。1. A monomer liquid comprising a metathesis-polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst (solution A) and a monomer liquid comprising a metathesis-polymerizable cyclic olefin containing an activator component of a metathesis polymerization catalyst (Solution B) and subjected to cross-linking polymerization in a mold to air-oxidize the obtained cross-linked polymer molded product. The surface tension of the molded product is 36 × 10 −3 kg.
/ S 2 or more and 52 × 10 −3 kg / s 2 or less, and then coating.
クリル塗料、アクリルウレタン塗料、エポキシ塗料から
選択される塗料のいずれかであるかあるいはそのいずれ
かを含有する塗料であることを特徴とする請求項１記載
の架橋重合体成形物の塗装方法。2. A paint used for coating is any one of a paint selected from urethane paint, acrylic paint, acrylic urethane paint, and epoxy paint, or a paint containing any of the paints. Item 6. A method for coating a crosslinked polymer molded article according to Item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33010099A JP2001145932A (en) | 1999-11-19 | 1999-11-19 | Method for coating molding of crosslinked polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33010099A JP2001145932A (en) | 1999-11-19 | 1999-11-19 | Method for coating molding of crosslinked polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001145932A true JP2001145932A (en) | 2001-05-29 |
Family
ID=18228803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33010099A Pending JP2001145932A (en) | 1999-11-19 | 1999-11-19 | Method for coating molding of crosslinked polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001145932A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007130936A (en) * | 2005-11-11 | 2007-05-31 | Nippon Plast Co Ltd | Method for manufacturing interior parts for automobile and interior material for automobile |
-
1999
- 1999-11-19 JP JP33010099A patent/JP2001145932A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007130936A (en) * | 2005-11-11 | 2007-05-31 | Nippon Plast Co Ltd | Method for manufacturing interior parts for automobile and interior material for automobile |
| JP4698391B2 (en) * | 2005-11-11 | 2011-06-08 | 日本プラスト株式会社 | Manufacturing method of interior parts for automobile and interior material for automobile |
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