JP2001181421A - Method for forming coating film on molded article of crosslinked polymer - Google Patents
Method for forming coating film on molded article of crosslinked polymerInfo
- Publication number
- JP2001181421A JP2001181421A JP36643599A JP36643599A JP2001181421A JP 2001181421 A JP2001181421 A JP 2001181421A JP 36643599 A JP36643599 A JP 36643599A JP 36643599 A JP36643599 A JP 36643599A JP 2001181421 A JP2001181421 A JP 2001181421A
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- crosslinked polymer
- metathesis
- solution
- 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.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 77
- 239000011248 coating agent Substances 0.000 title claims abstract description 74
- 229920006037 cross link polymer Polymers 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 20
- -1 cyclic olefin Chemical class 0.000 claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 28
- 239000004743 Polypropylene Substances 0.000 claims abstract description 25
- 229920001155 polypropylene Polymers 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000012190 activator Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 16
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- 238000000465 moulding Methods 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 239000003973 paint Substances 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 11
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 150000003658 tungsten compounds Chemical class 0.000 description 7
- 230000008961 swelling Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- 238000007605 air drying Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 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
- 239000000806 elastomer Substances 0.000 description 4
- 150000007527 lewis bases Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005507 spraying Methods 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
- 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
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 229920000642 polymer Polymers 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 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
- 238000007598 dipping method Methods 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
- 238000011049 filling Methods 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- AGQPHHBPENBBIO-UHFFFAOYSA-M iodo(dioctyl)alumane Chemical compound [I-].CCCCCCCC[Al+]CCCCCCCC AGQPHHBPENBBIO-UHFFFAOYSA-M 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 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
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 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
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 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
- 238000001291 vacuum drying Methods 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
- KXYDGGNWZUHESZ-UHFFFAOYSA-N 4-(2,2,4-trimethyl-3h-chromen-4-yl)phenol Chemical compound C12=CC=CC=C2OC(C)(C)CC1(C)C1=CC=C(O)C=C1 KXYDGGNWZUHESZ-UHFFFAOYSA-N 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
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 101000701286 Pseudomonas aeruginosa (strain ATCC 15692 / DSM 22644 / CIP 104116 / JCM 14847 / LMG 12228 / 1C / PRS 101 / PAO1) Alkanesulfonate monooxygenase Proteins 0.000 description 1
- 101000983349 Solanum commersonii Osmotin-like protein OSML13 Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002390 adhesive tape Substances 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
- 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
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 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
- 230000007547 defect Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004070 electrodeposition Methods 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
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000005357 flat glass 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
- 125000004435 hydrogen atom Chemical group [H]* 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
- 239000000976 ink Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 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
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000007639 printing Methods 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
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 239000000725 suspension Substances 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
- 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
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 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
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Paints Or Removers (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代表される塗膜形成方法に関す
るものである。[0001] 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. The present invention relates to a representative coating film forming method.
【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主触媒成分
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. After mixing a reactive solution of a monomer containing the two components, the mixture is immediately poured into a molding mold, and bulk polymerization is performed therein, and polymerization and molding are performed in one step. Has been proposed. According to such a method, a crosslinked polymer molded product can be obtained using an inexpensive mold for molding, 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不十分で塗
膜が剥がれやすいが、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、空気中に放置すると、塗料
や接着剤の密着性が十分高められることが知られてい
る。[0004] The surface of such a crosslinked polymer molded product generally has insufficient adhesion to paints and adhesives immediately after molding, and the coating film is easily peeled off. It is known that, due to the presence of a heavy bond, it is susceptible to reactions such as oxidation due to various factors such as air, heat, and light, and that when left in air, the adhesion of paints and adhesives is sufficiently enhanced.
【０００５】従って、かかる架橋重合成形体を塗装して
満足すべき塗膜密着性を得るには、成形後に空気中にし
かるべき期間にわたって保管した後に、塗装することが
必須条件と考えられている。保管する時間は、光の当た
り具合などにもよるが、一般には１〜２日間を要する。[0005] Therefore, in order to apply such a crosslinked polymer molded article to obtain satisfactory coating film adhesion, it is considered essential to store the article in the air after molding for an appropriate period of time and then apply it. . The storage time depends on the condition of the light, but generally requires 1 to 2 days.
【０００６】しかしながら、生産現場に於いて、十分満
足できる塗装を施した架橋重合成形体を得るために、こ
のように長時間にわたって成形体を保管することが難し
く、市場からは成形直後すぐにでも塗装を行ないたいと
いう要望が強い。However, in order to obtain a crosslinked polymer molded article having a sufficiently satisfactory coating at the production site, it is difficult to store the molded article for such a long period of time. There is a strong demand for painting.
【０００７】[0007]
【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膜形成製品を得る
ために鋭意検討を行った。その結果、塗膜形成を行う際
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
酸化させないでも、すなわち成形直後にでも、耐久性の
優れた塗膜形成製品を得ることができる塗膜形成材料を
見出したものである。DISCLOSURE OF THE INVENTION The present invention has been intensively studied in order to obtain an excellent film-forming product of such a metathesis crosslinked polymer molded product. As a result, even when the surface of such a metathesis crosslinked polymer molded article is not air-oxidized when forming a film, that is, immediately after molding, a film-forming product having excellent durability can be obtained. I found the material.
【０００８】[0008]
【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.
【０００９】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に
対し、塗膜を形成する際に、その塗膜が塩素化ポリプロ
ピレンを主成分とするものである、架橋重合体成形物の
塗膜形成方法。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 forming a coating film on the crosslinked polymer molded product obtained by crosslinking and polymerizing in a mold, the coating film is mainly composed of chlorinated polypropylene. A method for forming a coating film of a united molded product.
【００１０】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 crosslinked polymer molded article of the present invention contains a monomer solution A (solution A) composed of 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.
【００１１】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.
【００１２】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 codimer, 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, 5,5
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 a mixture 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. Further, if necessary, a metathesis polymerizable cyclic olefin having a polar group containing a different element such as oxygen or nitrogen can be used as a copolymer monomer.
【００１３】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 and the like are used, and a tungsten compound is particularly preferable.
【００１４】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.
【００１５】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.
【００１６】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 compound may have its action without adding any of the above compounds.
【００１７】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.
【００１８】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, the activator component contained in the monomer solution B (solution B) includes an organometallic compound mainly composed of an alkylated metal of a metal of Groups I to 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.
【００１９】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. 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.
【００２０】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, among others, ethers, esters,
Nitriles and the like are used. Specific examples include ethyl benzoate, butyl ether, diglyme and the like.
【００２１】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.
【００２２】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: 1 to 15,000: 1 on a molar basis, preferably 1,500: 1 to 2,500: 1, and
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.
【００２３】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。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.
【００２４】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.
【００２５】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 a third liquid immediately before 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.
【００２６】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 prepared 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.
【００２７】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.
【００２８】本願発明における成形品表面の表面張力
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とホルムアミ
ド／水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あるいはホルム
アミド／水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 surface of the molded article in the present invention is evaluated by an evaluation method using a formamide / ethylene glycol monoethyl ether mixture and a formamide / water mixture 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 mixture or a formamide / water mixture is simple and preferable. The surface tension referred to in the present invention is measured by this method.
【００２９】研究の結果、本願発明に係る塩素化ポリプ
ロピレンを主成分とする塗膜を形成させた場合には、成
形直後の架橋重合体成形物上に塗膜を形成させた場合に
も優れた密着力が得られることが判明した。As a result of the study, when the coating film containing the chlorinated polypropylene according to the present invention as a main component was formed, it was excellent also when the coating film was formed on the crosslinked polymer molded product immediately after molding. It has been found that adhesion can be obtained.
【００３０】この理由は定かでないが、本願発明に係る
架橋重合体成形物に存在する二重結合が塩素ガスと常温
で直接容易に反応することから知られるように、塩素を
含む特定構造の塗膜形成物質が、本願発明に係る架橋重
合体成形物と特殊な親和性を有していることが原因であ
ろうと推測されている。The reason for this is not clear, but as is known from the fact that the double bond present in the crosslinked polymer molded product according to the present invention easily reacts directly with chlorine gas at normal temperature, coating with a specific structure containing chlorine is performed. It is presumed that the cause is that the film-forming substance has a special affinity for the crosslinked polymer molded article according to the present invention.
【００３１】一般に本願発明の架橋重合体成形物は、成
形直後の表面張力は３２×１０-3Ｎ／ｍを示す。しか
し、溶液Ａと溶液Ｂとの組成を種々変更した場合には、
この値よりも小さい表面張力を示すこともあり得る。そ
して、本願発明に係る架橋重合体成形物がこのような３
２×１０-3Ｎ／ｍやそれより低い表面張力を有する場合
においても、本願発明に係る塩素化ポリプロピレンを主
成分とする塗膜は優れた密着力が得られることが明らか
になった。Generally, the crosslinked polymer molded article of the present invention has a surface tension of 32 × 10 −3 N / m immediately after molding. However, when the compositions of the solution A and the solution B are variously changed,
A surface tension lower than this value may be exhibited. And the crosslinked polymer molded product according to the present invention is such a 3
It became clear that even when the surface tension is 2 × 10 −3 N / m or lower, the coating film containing chlorinated polypropylene as the main component according to the present invention can obtain excellent adhesion.
【００３２】なお、かかる表面張力の好適な範囲として
は、５２×１０-3Ｎ／ｍ以下であることがより好まし
い。５２×１０-3Ｎ／ｍを超える場合には、塗膜の成形
品表面への密着性が悪化し、塗膜剥れ等の不良が発生す
る傾向が認めらる場合があるからである。成形後、本願
発明の架橋重合体成形物を空気中に長時間にわたって保
管するとこの値に到達する場合がある。ただし、通常の
場合には空気酸化は密着性悪化の原因にはならない。The preferable range of the surface tension is more preferably 52 × 10 −3 N / m or less. If it exceeds 52 × 10 −3 N / m, the adhesiveness of the coating film to the surface of the molded product may be deteriorated, and a tendency such as peeling of the coating film may occur. This value may be reached when the crosslinked polymer molded product of the present invention is stored in air for a long time after molding. However, in normal cases, air oxidation does not cause deterioration of adhesion.
【００３３】なお、ここで、本願で言う「塗膜」とは、
一般的に塗装、スプレー、電着等公知の方法で形成され
る膜を意味し、通常の塗装によって得られる塗料による
膜のほか、プライマーとし塗布される場合、消臭のため
等の目的で形成されるコーティング膜を含むものであ
る。Here, the “coating film” referred to in the present application is:
Generally means a film formed by a known method such as painting, spraying, electrodeposition, etc., and in addition to a film made of a paint obtained by ordinary painting, when applied as a primer, formed for the purpose of deodorization, etc. It includes a coating film to be formed.
【００３４】本願発明の架橋重合体成形物の表面を被覆
する塗膜形成のためには、塩素化ポリプロピレンを主成
分とする塗料に代表される、塗膜形成材料が使われる。For forming a coating film for covering the surface of the crosslinked polymer molded product of the present invention, a coating film forming material represented by a coating material containing chlorinated polypropylene as a main component is used.
【００３５】これらの塗膜形成材料には、主成分となる
塩素化ポリプロピレン樹脂成分に対し、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させる
ことができる。These coating film forming materials include a coloring component such as a pigment and a dye, a solvent, a plasticizer, a dispersion stabilizer, an ultraviolet absorber, a fungicide, and a chlorinated polypropylene resin component as a main component. And a secondary material such as a thickener.
【００３６】塩素化ポリプロピレンの塩素含有率は１０
重量％以上が望ましく、１５重量％以上がより望まし
い。The chlorine content of the chlorinated polypropylene is 10
% By weight or more, more preferably 15% by weight or more.
【００３７】代表的な塩素化ポリプロピレンとしては、
塩素含有率が３５重量％以下のものが有利に使用でき、
ポリプロピレンを四塩化炭素などの溶液または懸濁液と
し、均一にこの範囲の塩素含有率まで塩素化して製造さ
れる。通常、多少のゴム弾性を示し、ほぼ透明で有機溶
剤に良く溶ける熱可塑性樹脂である。主として、ポリプ
ロピレンの接着剤、貼り合わせ剤、印刷インキ、ペイン
ト用ビヒクルなどに使われている。Representative chlorinated polypropylenes include:
Those having a chlorine content of 35% by weight or less can be advantageously used,
It is produced by preparing polypropylene as a solution or suspension such as carbon tetrachloride and chlorinating uniformly to a chlorine content in this range. Usually, it is a thermoplastic resin which shows some rubber elasticity, is almost transparent and is well soluble in organic solvents. It is mainly used for polypropylene adhesives, laminating agents, printing inks, paint vehicles, and the like.
【００３８】なお、ここで言う塩素含有率とはポリプロ
ピレン中の水素原子を塩素原子で置換した割合いを意味
し、塩素化ポリプロピレンの全重量に対する当該置換塩
素原子の重量割合い（重量％）で表わされるものであ
る。The chlorine content as used herein means the proportion of hydrogen atoms in polypropylene replaced by chlorine atoms, and is the weight percentage (% by weight) of the substituted chlorine atoms with respect to the total weight of chlorinated polypropylene. It is represented.
【００３９】また、「塩素化ポリプロピレンを主成分と
する」とは、塗膜形成成分にある固形分中において当該
塩素化ポリプロピレンが４０重量％以上であることを意
味する。６０重量％以上であることがより望ましい。The phrase "having chlorinated polypropylene as a main component" means that the chlorinated polypropylene is at least 40% by weight in the solid content of the coating film forming component. More preferably, it is 60% by weight or more.
【００４０】塩素化ポリプロピレンは、例えば、我国で
は、日本製紙株式会社、東洋化成株式会社、山陽化成株
式会社から市販されている。Chlorinated polypropylene is commercially available in Japan, for example, from Nippon Paper Industries Co., Ltd., Toyo Kasei Co., Ltd., and Sanyo Kasei Co., Ltd.
【００４１】そして、この塩素化ポリプロピレンを主成
分とする塗膜形成材料としては大日本塗料（株）のプラ
ニットＬ＃５４３、Ｌ＃４５やプラニットＴＳが知られ
ている。As a coating film forming material containing chlorinated polypropylene as a main component, Planit L # 543, L # 45 and Planit TS manufactured by Dainippon Paint Co., Ltd. are known.
【００４２】本願発明の塩素化ポリプロピレンを主成分
とする塗膜形成材料は、プライマー塗料として使い、架
橋重合体成形物の表面に５〜２０μｍの厚みに被覆する
だけで十分に本願発明の効果を発揮することができる。
この上を被覆するトップコート塗料としては、一般に良
く使われるウレタン系塗料などが良い。The coating film-forming material containing chlorinated polypropylene of the present invention as a main component is used as a primer paint, and the effect of the present invention can be sufficiently obtained only by coating the surface of a crosslinked polymer molded product with a thickness of 5 to 20 μm. Can be demonstrated.
As a top coat paint which covers this, a commonly used urethane paint is preferred.
【００４３】かかる塗膜形成材料の塗膜形成方法は使用
する塗膜形成材料の通常の塗布方法によれば良く、一般
にはスプレー塗布あるいはローラーや刷毛塗りであり、
場合によっては塗膜形成材料中に浸漬し、塗布すること
もできる。The method for forming the coating film-forming material may be a conventional coating method for the coating film-forming material to be used, and is generally spray coating or roller or brush coating.
In some cases, it can be applied by dipping in a film-forming material.
【００４４】なお、塗膜形成に先立って、本願発明に係
る架橋重合体成形物の表面を洗剤やアルコール等の液状
有機物で清拭することも本願発明の範囲に含まれる。It is to be noted that wiping the surface of the crosslinked polymer molded product according to the present invention with a liquid organic substance such as a detergent or alcohol prior to the formation of a coating film is also included in the scope of the present invention.
【００４５】本願発明の塗膜形成材料をプライマーとし
て使用する場合は、塗布後、５〜１０分自然乾燥させた
後、トップコートを塗布するのが良い。When the coating film forming material of the present invention is used as a primer, it is preferable to apply a top coat after air-drying for 5 to 10 minutes after application.
【００４６】これ以上長い乾燥時間を取っても本願発明
のプライマーの性能を発揮させるためには支障はない
が、乾燥時間は塗膜形成工程の生産性を考えて決められ
るので、時間を長くすることは好まれない。There is no hindrance to exhibiting the performance of the primer of the present invention even if a longer drying time is used, but the drying time is determined in consideration of the productivity of the coating film forming step, so that the drying time is increased. I don't like that.
【００４７】また、加熱乾燥、熱風乾燥、真空乾燥など
を行っても良い。塗膜形成架橋重合体成形物のユーザー
への出荷形態として、プライマーを塗布するだけで出荷
する場合がある。この時も溶剤の除去が主たる目的で乾
燥を行うが、その方法は使用する塗膜形成材料の通常の
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。Further, heat drying, hot air drying, vacuum drying and the like may be performed. As a shipping form of the coating film-forming crosslinked polymer molded product to a user, there is a case where it is shipped simply by applying a primer. At this time, drying is carried out mainly for the purpose of removing the solvent, and the method may be a usual method of the coating film forming material to be used, and generally includes natural drying, heat drying, hot air drying, vacuum drying and the like. You.
【００４８】[0048]
【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。なお、以下の例では塗膜形成材料
による塗膜形成の例として、塗料による塗装を採用し
た。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. In the following examples, coating with a paint was adopted as an example of the coating film formation with the coating film forming material.
【００４９】［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 in 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.
【００５０】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 mixture. 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.
【００５１】（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−プロピレン−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) Ethylene content of 70 mol% was based on 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 an ethylene-propylene-ethylidene norbornene polymerized rubber of above, 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).
【００５２】［参考例２］ （成形）成形用アルミニウム金型を使用し、キャビティ
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、
厚さ３ｍｍｘ幅５００ｍｍｘ長さ５００ｍｍの架橋重合
品成形板を作成した。Reference Example 2 (Molding) Using an aluminum mold for molding, heating the cavity mold to 90 ° C. and the core mold to 60 ° C. and closing the mold, then RIM (reaction injection molding) molding. The solution A and the solution B were collision-mixed and injected at a weight ratio of 50:50 in a mixing head using a mixer. Open the mold 5 minutes after filling and filling,
A crosslinked polymer product molded plate having a thickness of 3 mm x a width of 500 mm x a length of 500 mm was prepared.
【００５３】［実施例１］ （成形直後の架橋重合品成形板の表面張力評価）参考例
２で得られた成形板の表面を、成形直後に、ＪＩＳＫ６
７６８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３２×１０-3Ｎ／ｍであった。Example 1 (Evaluation of Surface Tension of Cross-Linked Polymerized Molded Sheet Immediately after Molding) The surface of the molded sheet obtained in Reference Example 2 was subjected to JIS K6 immediately after molding.
As a result of evaluation by the evaluation method using a formamide / ethylene glycol monoethyl ether mixed solution described in 768, the surface tension was 32 × 10 −3 N / m.
【００５４】（塩素化ポリプロピレンを主成分とする塗
料による塗布）その後、直ちに、塩素含有率が２３重量
％の塩素化ポリプロピレンを主成分とする塗料である大
日本塗料（株）のプラニットＬ＃５４３をシンナーＰ２
０で６０重量％に希釈し、塗料を調製した。この塗料を
スプレー塗布し、風乾の後、８０℃で３０分間乾燥し
た。(Coating with paint containing chlorinated polypropylene as a main component) Immediately thereafter, Planit L # 543 manufactured by Dainippon Paint Co., Ltd., which is a paint containing chlorinated polypropylene having a chlorine content of 23% by weight as a main component. To thinner P2
0 to 60% by weight to prepare a paint. This paint was applied by spraying, air-dried, and then dried at 80 ° C. for 30 minutes.
【００５５】（塗膜特性評価）得られた塗膜の膜厚は１
５μｍであった。得られた塗膜の耐久性の評価は、塗
装後３日間経過したサンプル、および４０℃の温水に
１０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、ＪＩＳＫ５４００に記載さ
れた方法に準じて塗膜に１ｍｍ2の桝目１００個の格子
パターンの切り込みを入れた後、粘着テープを押し付
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（以下碁盤目テストと呼ぶ）。また、温水に１０
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 1
It was 5 μm. Evaluation of the durability of the obtained coating film was performed on a sample 3 days after coating, and after dipping in warm water of 40 ° C. for 10 days, taking out and wiping off moisture adhering to the surface, and then 1 hour at 25 ° C. and 50% humidity 50%. Samples left alone,
Using the two types of samples, a cut of 100 lattices of 1 mm 2 was cut into the coating film according to the method described in JIS K5400, and then an adhesive tape was pressed. An evaluation was made based on the presence or absence of this (hereinafter referred to as a grid test). In addition, 10
The samples immersed for days were also evaluated for the presence or absence of swelling of the coating film.
【００５６】碁盤目テープ法の評価の結果、塗装後３日
間経過したサンプル、温水に１０日間浸漬したサンプ
ル、いずれもＪＩＳＫ５４００に準じた評価で、はがれ
無しで、１０点であった。また、温水に１０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 evaluation by the cross-cut tape method, a sample 3 days after coating and a sample immersed in warm water for 10 days were evaluated according to JIS K5400, and each of them was 10 points without peeling. In addition, there was no swelling of the coating film of the sample immersed in warm water for 10 days.
【００５７】［実施例２］大日本塗料（株）のプラニッ
トＬ＃５４３の代わりに、塩素含有率が２０重量％の塩
素化ポリプロピレンを主成分とする塗料であるプラニッ
トＴＳを使った以外は実施例１と同様に行った。得られ
た塗膜の膜厚は１５μｍであった。塗膜特性評価を実施
例１と同様に行った結果、碁盤目テストは１０点であ
り、塗膜の膨れもなかった。Example 2 The procedure was carried out except that in place of Planit L # 543 manufactured by Dainippon Paint Co., Ltd., Planit TS, which was a coating mainly composed of chlorinated polypropylene having a chlorine content of 20% by weight, was used. It carried out like Example 1. The thickness of the obtained coating film was 15 μm. The coating film properties were evaluated in the same manner as in Example 1. As a result, the grid test was 10 points, and the coating film did not swell.
【００５８】［実施例３］参考例２で得られた成形板を
窓ガラス越しに直射日光があたる場所に５日間放置し、
表面張力が５３×１０-3Ｎ／ｍのサンプルを得た。その
後、実施例１と同様の塗装を行った。ただし、得られた
塗膜の膜厚は９μｍであった。実施例１と同様の塗膜特
性評価を行った結果、碁盤目テストは１０点であり、塗
膜の膨れもなかった。Example 3 The molded plate obtained in Reference Example 2 was left over a window glass in a place exposed to direct sunlight for 5 days.
A sample having a surface tension of 53 × 10 −3 N / m was obtained. Thereafter, the same coating as in Example 1 was performed. However, the thickness of the obtained coating film was 9 μm. The coating film properties were evaluated in the same manner as in Example 1. As a result, the grid test showed 10 points, and there was no swelling of the coating film.
【００５９】［実施例４］実施例１と同様の成形板に実
施例１と同様の塩素化ポリプロピレンを主成分とする塗
料を、実施例１と同様にして、塗布し１分間の風乾の
後、ウレタン系塗料である大橋化学（株）のポリナール
＃８００をスプレー塗布した。２分間の風乾の後、８０
℃で３０分間乾燥した。なお、得られた塩素化ポリプロ
ピレン系塗料の塗膜の膜厚は９μｍ、ウレタン系塗料の
塗膜の膜厚は３５μｍになった。塗膜特性評価を実施例
１と同様に行った結果、碁盤目テストは１０点であり、
塗膜の膨れもなかった。Example 4 The same chlorinated polypropylene-based paint as in Example 1 was applied to the same molded plate as in Example 1 in the same manner as in Example 1, and after air-drying for 1 minute. , A urethane-based paint, Polynal # 800, manufactured by Ohashi Chemical Co., Ltd. was spray applied. After air drying for 2 minutes, 80
Dry at 30 ° C. for 30 minutes. The thickness of the obtained chlorinated polypropylene coating was 9 μm, and the thickness of the urethane coating was 35 μm. As a result of performing the evaluation of the coating film properties in the same manner as in Example 1, the grid test was 10 points,
There was no swelling of the coating film.
【００６０】［実施例５］実施例１と同様の成形直後の
成形板を使った。塩素含有率が２５重量％の塩素化ポリ
プロピレンをトルエン中に２０重量％含む日本製紙
（株）のスーパークロン８２２をさらにキシレンで１０
重量％にまで希釈した。この溶液をスプレー塗布し、１
分間風乾の後、８０℃で３０分間乾燥した。得られた塗
膜の膜厚は１０μｍであった。塗膜特性評価を実施例１
と同様に行った結果、碁盤目テストは１０点であり、塗
膜の膨れもなかった。Example 5 A molded plate immediately after molding similar to that in Example 1 was used. Nippon Paper Industries Co., Ltd.'s Supercron 822 containing 20% by weight of chlorinated polypropylene having a chlorine content of 25% by weight in toluene is further added with xylene.
Diluted to% by weight. Spray this solution and apply
After air drying for 30 minutes, it was dried at 80 ° C. for 30 minutes. The film thickness of the obtained coating film was 10 μm. Evaluation of coating film properties in Example 1
As a result, the grid test showed 10 points and there was no swelling of the coating film.
【００６１】［比較例１］参考例２で得られた成形板を
成形直後に、ウレタン系塗料の大橋化学（株）のポリナ
ール＃８００をスプレー塗布した。２分間風乾の後、８
０℃で３０分間乾燥した。得られた塗膜の膜厚は３５μ
ｍであった。塗膜特性評価を実施例１と同様に行った結
果、塗装後３日間経過したサンプルの碁盤目テストは４
点であった。また、温水に１０日間浸漬したサンプルで
は、碁盤目テストは０点であり、多数の塗膜の膨れが観
察された。[Comparative Example 1] Immediately after molding the molded plate obtained in Reference Example 2, a urethane-based paint, Polynal # 800, manufactured by Ohashi Chemical Co., Ltd. was spray applied. After air drying for 2 minutes, 8
Dry at 0 ° C. for 30 minutes. The thickness of the obtained coating film is 35 μm.
m. The coating film properties were evaluated in the same manner as in Example 1. As a result, the cross-cut test of the sample 3 days after coating was 4
Was a point. In addition, in the sample immersed in warm water for 10 days, the cross-cut test was 0 point, and swelling of many coating films was observed.
【００６２】[0062]
【発明の効果】本願発明によれば、メタセシス架橋重合
体成形物に塗膜を形成する際に、塩素化ポリプロピレン
を主成分とする塗料を塗布することにより、従来の成形
・塗装工程の生産性を上げ、従来品に比べ耐久性に優れ
た塗装製品を短期間に提供できる。According to the present invention, when a coating film is formed on a metathesis crosslinked polymer molded product, a coating material containing chlorinated polypropylene as a main component is applied to improve the productivity of the conventional molding and coating process. To provide coating products with excellent durability compared to conventional products in a short period of time.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山田 建孔 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） 4F006 AA31 AB13 BA01 DA04 4J038 CB081 CB171 NA03 NA12 PA13 PC08 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Yamada Kenko No.2-1 Hinode-cho, Iwakuni-shi, Yamaguchi Prefecture Teijin Metho Co., Ltd. Technical Center F-term (reference) 4F006 AA31 AB13 BA01 DA04 4J038 CB081 CB171 NA03 NA12 PA13 PC08
Claims (1)
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に対
し、塗膜を形成する際に、その塗膜が塩素化ポリプロピ
レンを主成分とするものである、架橋重合体成形物の塗
膜形成方法。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 a crosslinked polymer molded product obtained by cross-linking and polymerization in a mold. When a coating film is formed, the coating film mainly contains chlorinated polypropylene. A method for forming a coating film of a crosslinked polymer molded product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36643599A JP4198290B2 (en) | 1999-12-24 | 1999-12-24 | Method for forming coating film of crosslinked polymer molded product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36643599A JP4198290B2 (en) | 1999-12-24 | 1999-12-24 | Method for forming coating film of crosslinked polymer molded product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001181421A true JP2001181421A (en) | 2001-07-03 |
| JP4198290B2 JP4198290B2 (en) | 2008-12-17 |
Family
ID=18486783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36643599A Expired - Lifetime JP4198290B2 (en) | 1999-12-24 | 1999-12-24 | Method for forming coating film of crosslinked polymer molded product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4198290B2 (en) |
-
1999
- 1999-12-24 JP JP36643599A patent/JP4198290B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP4198290B2 (en) | 2008-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW593466B (en) | Contact metathesis polymerization | |
| US4818325A (en) | Method of bonding non-polar or highly crystalline resin substrates employing a primer and a cyanoacrylate adhesive | |
| CA1099428A (en) | Curable systems containing epoxy resin | |
| US5292364A (en) | Primer composition | |
| US20070148354A1 (en) | Methods for improving coating adhesion | |
| JPH0229308A (en) | Reaction injection molding method | |
| JP2001181421A (en) | Method for forming coating film on molded article of crosslinked polymer | |
| US8790753B2 (en) | Rubber material with barrier material made of cycloolefin copolymers | |
| JP2001145932A (en) | Method for coating molding of crosslinked polymer | |
| JPH10182513A (en) | Non-ozone depleting auxiliary solvent composition | |
| US3926895A (en) | Liquid plastic repair composition and method | |
| JP5907995B2 (en) | Rubber material having a barrier material from cycloolefin copolymer | |
| JP2001071345A (en) | In-mold coating method | |
| US5958509A (en) | Coating of molded plastics articles | |
| JP3133042B2 (en) | Polyurethane lacquers, spray diluents for polyurethane lacquers and methods for spraying lacquers on polystyrene-containing substrates | |
| Beach | Parylene Coating | |
| JPS59166534A (en) | Coating agent | |
| JP2002128873A (en) | Molded article of crosslinked polymer | |
| JP2003094454A (en) | Coating method for norbornene crossilinked polymer molded article, and coated molded article | |
| JPS63199771A (en) | Coating composition | |
| JP2004123898A (en) | Method for manufacturing coated molded subject | |
| JP2001031788A (en) | Plated crosslinked polymer molding | |
| JPH0120660B2 (en) | ||
| KR920007661B1 (en) | Primer composition of polypropylene | |
| JP2676538B2 (en) | Manufacturing method of molded products with improved resistance to oxidative deterioration |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20051215 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20071206 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080909 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20081001 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111010 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111010 Year of fee payment: 3 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111010 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121010 Year of fee payment: 4 |