JP6281217B2 - Radical polymerizable resin composition and civil engineering building material - Google Patents
Radical polymerizable resin composition and civil engineering building material Download PDFInfo
- Publication number
- JP6281217B2 JP6281217B2 JP2013186204A JP2013186204A JP6281217B2 JP 6281217 B2 JP6281217 B2 JP 6281217B2 JP 2013186204 A JP2013186204 A JP 2013186204A JP 2013186204 A JP2013186204 A JP 2013186204A JP 6281217 B2 JP6281217 B2 JP 6281217B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- radical polymerizable
- polymerizable resin
- acrylate
- resin composition
- 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.)
- Active
Links
- 239000011342 resin composition Substances 0.000 title claims description 28
- 239000004566 building material Substances 0.000 title claims description 4
- 229920005989 resin Polymers 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 28
- 229920000858 Cyclodextrin Polymers 0.000 claims description 26
- 229920000058 polyacrylate Polymers 0.000 claims description 22
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 74
- -1 laminates Substances 0.000 description 45
- 150000003254 radicals Chemical class 0.000 description 39
- 150000001875 compounds Chemical class 0.000 description 24
- 238000001035 drying Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- 239000004593 Epoxy Substances 0.000 description 17
- 239000004793 Polystyrene Substances 0.000 description 16
- 239000002253 acid Substances 0.000 description 16
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 16
- 229920002223 polystyrene Polymers 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- MHCLJIVVJQQNKQ-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O MHCLJIVVJQQNKQ-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 229920005862 polyol Polymers 0.000 description 9
- 229920006305 unsaturated polyester Polymers 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- 150000005846 sugar alcohols Polymers 0.000 description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- POYODSZSSBWJPD-UHFFFAOYSA-N 2-methylprop-2-enoyloxy 2-methylprop-2-eneperoxoate Chemical compound CC(=C)C(=O)OOOC(=O)C(C)=C POYODSZSSBWJPD-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 6
- 229920001228 polyisocyanate Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012169 petroleum derived wax Substances 0.000 description 5
- 235000019381 petroleum wax Nutrition 0.000 description 5
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- MOBNLCPBAMKACS-UHFFFAOYSA-N 2-(1-chloroethyl)oxirane Chemical compound CC(Cl)C1CO1 MOBNLCPBAMKACS-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229940080345 gamma-cyclodextrin Drugs 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- YZOUYRAONFXZSI-SBHWVFSVSA-N (1S,3R,5R,6R,8R,10R,11R,13R,15R,16R,18R,20R,21R,23R,25R,26R,28R,30R,31S,33R,35R,36R,37S,38R,39S,40R,41S,42R,43S,44R,45S,46R,47S,48R,49S)-5,10,15,20,25,30,35-heptakis(hydroxymethyl)-37,39,40,41,42,43,44,45,46,47,48,49-dodecamethoxy-2,4,7,9,12,14,17,19,22,24,27,29,32,34-tetradecaoxaoctacyclo[31.2.2.23,6.28,11.213,16.218,21.223,26.228,31]nonatetracontane-36,38-diol Chemical compound O([C@@H]([C@H]([C@@H]1OC)OC)O[C@H]2[C@@H](O)[C@@H]([C@@H](O[C@@H]3[C@@H](CO)O[C@@H]([C@H]([C@@H]3O)OC)O[C@@H]3[C@@H](CO)O[C@@H]([C@H]([C@@H]3OC)OC)O[C@@H]3[C@@H](CO)O[C@@H]([C@H]([C@@H]3OC)OC)O[C@@H]3[C@@H](CO)O[C@@H]([C@H]([C@@H]3OC)OC)O3)O[C@@H]2CO)OC)[C@H](CO)[C@H]1O[C@@H]1[C@@H](OC)[C@H](OC)[C@H]3[C@@H](CO)O1 YZOUYRAONFXZSI-SBHWVFSVSA-N 0.000 description 2
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000001116 FEMA 4028 Substances 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229960004853 betadex Drugs 0.000 description 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N butane-1,2,3,4-tetrol Chemical compound OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- JFZVSHAMRZPOPA-UHFFFAOYSA-N 1-[n-(2-hydroxypropyl)-4-methylanilino]propan-2-ol Chemical compound CC(O)CN(CC(C)O)C1=CC=C(C)C=C1 JFZVSHAMRZPOPA-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- RTSODCRZYKSCLO-UHFFFAOYSA-N 1-methylester malic acid Chemical compound COC(=O)C(O)CC(O)=O RTSODCRZYKSCLO-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- JUVSRZCUMWZBFK-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-4-methylanilino]ethanol Chemical compound CC1=CC=C(N(CCO)CCO)C=C1 JUVSRZCUMWZBFK-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- YXIKLBXSFOXIPR-UHFFFAOYSA-N 3-hydroxy-4-oxo-4-propoxybutanoic acid Chemical compound CCCOC(=O)C(O)CC(O)=O YXIKLBXSFOXIPR-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- JOCUIVLSLBBESN-UHFFFAOYSA-N 4-[2-hydroxyethyl(methyl)amino]benzaldehyde Chemical compound OCCN(C)C1=CC=C(C=O)C=C1 JOCUIVLSLBBESN-UHFFFAOYSA-N 0.000 description 1
- YSDDPNWGLSGZRC-UHFFFAOYSA-N 4-[bis(2-hydroxyethyl)amino]benzaldehyde Chemical compound OCCN(CCO)C1=CC=C(C=O)C=C1 YSDDPNWGLSGZRC-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- FHQRDEDZJIFJAL-UHFFFAOYSA-N 4-phenylmorpholine Chemical compound C1COCCN1C1=CC=CC=C1 FHQRDEDZJIFJAL-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- BWMONWDJCRUIOS-UHFFFAOYSA-N OCCN1C(N(C=2N(C(N(C(C1=2)=O)[N+]#[C-])=O)CCO)CCO)=O Chemical compound OCCN1C(N(C=2N(C(N(C(C1=2)=O)[N+]#[C-])=O)CCO)CCO)=O BWMONWDJCRUIOS-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- JVFGXECLSQXABC-UHFFFAOYSA-N ac1l3obq Chemical compound O1C(C(C2O)O)C(COCC(C)O)OC2OC(C(C2O)O)C(COCC(C)O)OC2OC(C(C2O)O)C(COCC(C)O)OC2OC(C(C2O)O)C(COCC(C)O)OC2OC(C(C2O)O)C(COCC(C)O)OC2OC(C(O)C2O)C(COCC(O)C)OC2OC(C(C2O)O)C(COCC(C)O)OC2OC2C(O)C(O)C1OC2COCC(C)O JVFGXECLSQXABC-UHFFFAOYSA-N 0.000 description 1
- RKSRGENQZGDZFN-UHFFFAOYSA-N acetyl acetate;cobalt Chemical compound [Co].CC(=O)OC(C)=O RKSRGENQZGDZFN-UHFFFAOYSA-N 0.000 description 1
- XNLPZZOCLLAQIM-UHFFFAOYSA-N acetyl acetate;vanadium Chemical compound [V].CC(=O)OC(C)=O XNLPZZOCLLAQIM-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- IZJDCINIYIMFGX-UHFFFAOYSA-N benzo[f][2]benzofuran-1,3-dione Chemical compound C1=CC=C2C=C3C(=O)OC(=O)C3=CC2=C1 IZJDCINIYIMFGX-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- JYVLIDXNZAXMDK-UHFFFAOYSA-N methyl propyl carbinol Natural products CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- GUYMMHOQXYZMJQ-UHFFFAOYSA-N n-ethyl-3-methylaniline Chemical compound CCNC1=CC=CC(C)=C1 GUYMMHOQXYZMJQ-UHFFFAOYSA-N 0.000 description 1
- KHARCSTZAGNHOT-UHFFFAOYSA-N naphthalene-2,3-dicarboxylic acid Chemical compound C1=CC=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 KHARCSTZAGNHOT-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ODLHGICHYURWBS-LKONHMLTSA-N trappsol cyclo Chemical compound CC(O)COC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)COCC(O)C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1COCC(C)O ODLHGICHYURWBS-LKONHMLTSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/16—Cyclodextrin; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Graft Or Block Polymers (AREA)
- Laminated Bodies (AREA)
Description
本発明は、表面乾燥性及び耐汚染性に優れる塗膜を与えるラジカル重合性樹脂組成物に関する。 The present invention relates to a radically polymerizable resin composition that gives a coating film excellent in surface drying property and stain resistance.
道路舗装等の土木建築業界では、工期短縮や施工時の臭気の改善に対応するため、不飽和ポリエステル、ポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート等のラジカル重合性樹脂及びラジカル重合性単量体を含有するラジカル重合性樹脂組成物が広く利用されている（例えば、特許文献１を参照。）。 In the civil engineering and construction industry such as road pavement, radical polymerizable resins such as unsaturated polyester, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, etc. in order to shorten the construction period and improve odor during construction In addition, radically polymerizable resin compositions containing radically polymerizable monomers are widely used (see, for example, Patent Document 1).
前記ラジカル重合性樹脂組成物は、優れた引張強度やスプレー適正を有するものの、塗膜の表面乾燥性や耐汚染性についてはより一層の改善が求められている。これは、前記ラジカル重合性樹脂組成物に含有されるラジカル重合性樹脂の反応性の低さに起因していると考えられ、未反応のラジカル重合性樹脂が塗膜表面に偏析し、塗膜の表面乾燥性及び耐汚染性の低下につながっているものと推測される。 Although the radical polymerizable resin composition has excellent tensile strength and sprayability, further improvement is required for the surface drying property and stain resistance of the coating film. This is considered to be due to the low reactivity of the radical polymerizable resin contained in the radical polymerizable resin composition, and the unreacted radical polymerizable resin segregates on the surface of the coating film. It is presumed that this has led to a decrease in the surface drying property and contamination resistance of the material.
本発明が解決しようとする課題は、表面乾燥性及び耐汚染性に優れる塗膜を与えるラジカル重合性樹脂組成物を提供することである。 The problem to be solved by the present invention is to provide a radically polymerizable resin composition that provides a coating film excellent in surface drying property and stain resistance.
本発明者等は、前記課題を解決すべく研究を進める中で、ラジカル重合性樹脂及びラジカル重合性単量体に添加する添加剤に着目し、鋭意研究を進めた。
その結果、ラジカル重合性樹脂及びラジカル重合性単量体に対し、シクロデキストリン及び／又はその誘導体とアクリル重合体とを添加することによって、前記課題を解決できることを見出し、本発明を完成するに至った。
While pursuing research to solve the above-mentioned problems, the inventors of the present invention focused on the additive added to the radical polymerizable resin and the radical polymerizable monomer, and conducted earnest research.
As a result, the inventors found that the above problems can be solved by adding cyclodextrin and / or a derivative thereof and an acrylic polymer to the radical polymerizable resin and the radical polymerizable monomer, and completed the present invention. It was.
即ち、本発明は、ラジカル重合性樹脂（Ａ）、ラジカル重合性単量体（Ｂ）、シクロデキストリン及び／又はその誘導体（Ｃ）、並びに、アクリル重合体（Ｄ）を含有することを特徴とするラジカル重合性樹脂組成物を提供するものである。 That is, the present invention is characterized by containing a radical polymerizable resin (A), a radical polymerizable monomer (B), a cyclodextrin and / or a derivative thereof (C), and an acrylic polymer (D). A radical polymerizable resin composition is provided.
また、本発明は、前記ラジカル重合性樹脂組成物を用いて得られた土木建築材料を提供するものである。 Moreover, this invention provides the civil engineering building material obtained using the said radically polymerizable resin composition.
本発明のラジカル重合性樹脂組成物は、表面乾燥性及び耐汚染性に優れる塗膜を与えることができる。従って、本発明のラジカル重合性樹脂組成物は、工場、倉庫、クリーンルーム等の床材；舗装材、防水材、塗料、プライマー、壁面コーティング材、道路マーキング材、注入材、シール材、注型品、積層品、接着剤、ライニング材、波平板等の土木建築材料の製造に好適に使用することができる。 The radically polymerizable resin composition of the present invention can provide a coating film excellent in surface drying property and stain resistance. Therefore, the radically polymerizable resin composition of the present invention is used for flooring materials such as factories, warehouses, and clean rooms; paving materials, waterproofing materials, paints, primers, wall coating materials, road marking materials, injection materials, sealing materials, and cast products. It can be suitably used for the production of civil engineering and building materials such as laminates, adhesives, lining materials and corrugated plates.
本発明のラジカル重合性樹脂組成物は、ラジカル重合性樹脂（Ａ）、ラジカル重合性単量体（Ｂ）、シクロデキストリン及び／又はその誘導体（Ｃ）、並びに、アクリル重合体（Ｄ）を必須成分として含有するものである。 The radical polymerizable resin composition of the present invention essentially comprises a radical polymerizable resin (A), a radical polymerizable monomer (B), cyclodextrin and / or a derivative thereof (C), and an acrylic polymer (D). It is contained as a component.
前記ラジカル重合性樹脂（Ａ）としては、例えば、不飽和ポリエステル、エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート、ウレタン（メタ）アクリレート等を用いることができる。これらの樹脂は単独で用いても２種以上を併用してもよい。 As said radically polymerizable resin (A), unsaturated polyester, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate etc. can be used, for example. These resins may be used alone or in combination of two or more.
これらの中でも、後述するシクロデキストリン及び／又はその誘導体（Ｃ）が有する水酸基と水素結合を形成してラジカル重合性樹脂（Ａ）が塗膜内部に沈降しやすくなるため、表面乾燥性及び耐汚染性をより一層向上できる点から、水酸基を有するラジカル重合性樹脂を用いることが好ましく、具体的には、不飽和ポリエステル、エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート及び水酸基を有するウレタン（メタ）アクリレートからなる群より選ばれる１種以上のラジカル重合性樹脂を用いることがより好ましい。 Among these, since the radical polymerizable resin (A) is likely to settle inside the coating film by forming a hydrogen bond with the hydroxyl group of cyclodextrin and / or its derivative (C) described later, surface drying and contamination resistance It is preferable to use a radically polymerizable resin having a hydroxyl group from the viewpoint of further improving the properties, and specifically, unsaturated polyester, epoxy (meth) acrylate, polyester (meth) acrylate, and urethane having a hydroxyl group (meth). It is more preferable to use one or more radically polymerizable resins selected from the group consisting of acrylates.
前記水酸基を有するラジカル重合性樹脂は、表面乾燥性及び耐汚染性をより一層向上できる点から、前記ラジカル重合性樹脂（Ａ）中４５質量％以上含有されていることが好ましい。 The radical polymerizable resin having a hydroxyl group is preferably contained in the radical polymerizable resin (A) in an amount of 45% by mass or more from the viewpoint that the surface drying property and the stain resistance can be further improved.
前記不飽和ポリエステルとしては、例えば、α，β−不飽和二塩基酸を含む二塩基酸と多価アルコールとを従来公知の方法で反応させて得られるものを用いることができる。 Examples of the unsaturated polyester include those obtained by reacting a dibasic acid containing an α, β-unsaturated dibasic acid with a polyhydric alcohol by a conventionally known method.
前記α，β−不飽和二塩基酸としては、例えば、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸等を用いることができる。これらの二塩基酸は単独で用いても２種以上を併用してもよい。 Examples of the α, β-unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, and the like. These dibasic acids may be used alone or in combination of two or more.
前記α，β−不飽和二塩基酸以外に用いることができる二塩基酸としては、飽和二塩基酸を用いることができ、例えば、フタル酸、無水フタル酸、ハロゲン化無水フタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロフタル酸、ヘキサヒドロ無水フタル酸、ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸、コハク酸、マロン酸、グルタル酸、アジピン酸、セバシン酸、１，１２−ドデカン２酸，２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、２，３−ナフタレンジカルボン酸、２，３−ナフタレンジカルボン酸無水物、４，４’−ビフェニルジカルボン酸、またこれらのジアルキルエステル等を用いることができる。これらの二塩基酸は単独で用いても２種以上を併用してもよい。 As the dibasic acid that can be used in addition to the α, β-unsaturated dibasic acid, a saturated dibasic acid can be used. For example, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, Terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12 -Dodecane diacid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,4'-biphenyldicarboxylic acid, and these The dialkyl ester or the like can be used. These dibasic acids may be used alone or in combination of two or more.
前記多価アルコールとしては、例えば、エチレングリコ−ル、ジエチレングリコ−ル、トリエチレングリコ−ル、ポリエチレングリコ−ル、プロピレングリコ−ル、ジプロピレングリコ−ル、ポリプロピレングリコ−ル、２−メチル−１，３−プロパンジオ−ル、１，３−ブタンジオ−ル、ネオペンチルグリコ−ル、水素化ビスフェノ−ルＡ、１，４−ブタンジオ−ル、ビスフェノ−ルＡのアルキレンオキサイド付加物、１，２，３，４−テトラヒドロキシブタン、グリセリン、トリメチロ−ルプロパン、１，３−プロパンジオ−ル、１，２−シクロヘキサングリコ−ル、１，３−シクロヘキサングリコ−ル、１，４−シクロヘキサングリコ−ル、１，４−シクロヘキサンジメタノ−ル、パラキシレングリコ−ル、ビシクロヘキシル−４，４’−ジオ−ル、２，６−デカリングリコ−ル、２，７−デカリングリコ−ル等を用いることができる。これらの多価アルコールは単独で用いても２種以上を併用してもよい。 Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and 2-methyl-1. 1,3-propanediol, 1,3-butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, alkylene oxide adduct of bisphenol A, 1,2 , 3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol 1,4-cyclohexanedimethanol, paraxylene glycol, bicyclohexyl-4,4 - Geo - le, 2,6-decalin glycolate - le, 2,7-decalin glyco - can be used Le like. These polyhydric alcohols may be used alone or in combination of two or more.
前記エポキシ（メタ）アクリレートとしては、ビスフェノール型エポキシ化合物又はビスフェノール型エポキシ化合物とノボラック型エポキシ化合物とを混合したエポキシ化合物と、不飽和一塩基酸とを従来公知の方法で反応して得られるものを用いることができる。 As the epoxy (meth) acrylate, a bisphenol type epoxy compound or an epoxy compound obtained by mixing a bisphenol type epoxy compound and a novolac type epoxy compound with an unsaturated monobasic acid by a conventionally known method is used. Can be used.
前記ビスフェノール型エポキシ化合物としては、例えば、エピクロルヒドリンとビスフェノールＡ又はビスフェノールＦとの反応により得られる１分子中に２個以上のエポキシ基を有するグリシジルエーテル型エポキシ化合物、メチルエピクロルヒドリンとビスフェノールＡ又はビスフェノールＦとを反応させて得られるジメチルグリシジルエーテル型エポキシ化合物、ビスフェノールＡのアルキレンオキサイド付加物とエピクロルヒドリン又はメチルエピクロルヒドリンとを反応させて得られるエポキ化合物等を用いることができる。これらのエポキシ化合物は単独で用いても２種以上を併用してもよい。 Examples of the bisphenol type epoxy compound include a glycidyl ether type epoxy compound having two or more epoxy groups in one molecule obtained by reaction of epichlorohydrin and bisphenol A or bisphenol F, methyl epichlorohydrin and bisphenol A or bisphenol F, and the like. A dimethyl glycidyl ether type epoxy compound obtained by reacting bisphenol A, an epoxy compound obtained by reacting an alkylene oxide adduct of bisphenol A with epichlorohydrin or methyl epichlorohydrin, and the like can be used. These epoxy compounds may be used alone or in combination of two or more.
前記ノボラックタイプ型エポキシ化合物としては、例えば、フェノールノボラック又はクレゾールノボラックと、エピクロルヒドリン又はメチルエピクロルヒドリンとを反応させて得られるエポキシ化合物等を用いることができる。これらのエポキシ化合物は単独で用いても２種以上を併用してもよい。 As the novolak type epoxy compound, for example, an epoxy compound obtained by reacting phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin can be used. These epoxy compounds may be used alone or in combination of two or more.
前記不飽和一塩基酸としては、例えば、（メタ）アクリル酸、桂皮酸、クロトン酸、モノメチルマレート、モノプロピルマレート、モノブテンマレート、ソルビン酸、モノ（２−エチルヘキシル）マレート等を用いることができる。これらの不飽和一塩基酸は単独で用いても２種以上を併用してもよい。 Examples of the unsaturated monobasic acid include (meth) acrylic acid, cinnamic acid, crotonic acid, monomethylmalate, monopropylmalate, monobutenemalate, sorbic acid, mono (2-ethylhexyl) malate, and the like. be able to. These unsaturated monobasic acids may be used alone or in combination of two or more.
前記ポリエステル（メタ）アクリレートとしては、例えば、１分子中に２個以上の（メタ）アクリロイル基を有する飽和ポリエステル又は不飽和ポリエステルを用いることができる。前記飽和ポリエステルは、飽和二塩基酸と多価アルコールとを縮合反応させたものであり、また、前記不飽和ポリエステルとは、α，β−不飽和二塩基酸と多価アルコールとを縮合反応させたものであり、いずれも末端に（メタ）アクリロイル基を有するものである。 As said polyester (meth) acrylate, the saturated polyester or unsaturated polyester which has a 2 or more (meth) acryloyl group in 1 molecule can be used, for example. The saturated polyester is a condensation reaction of a saturated dibasic acid and a polyhydric alcohol, and the unsaturated polyester is a condensation reaction of an α, β-unsaturated dibasic acid and a polyhydric alcohol. Each of them has a (meth) acryloyl group at the terminal.
前記飽和二塩基酸、α，β−不飽和二塩基酸及び多価アルコールは、前記不飽和ポリエステルの合成に用いるものと同様のものを用いることができる。 The saturated dibasic acid, α, β-unsaturated dibasic acid and polyhydric alcohol can be the same as those used for the synthesis of the unsaturated polyester.
前記ポリエステル（メタ）アクリレートの製造方法としては、飽和ポリエステル又は不飽和ポリエステルとグリシジル（メタ）アクリレートと公知の方法により反応する方法が挙げられる。 As a manufacturing method of the said polyester (meth) acrylate, the method of reacting a saturated polyester or unsaturated polyester, and glycidyl (meth) acrylate by a well-known method is mentioned.
前記ウレタン（メタ）アクリレートとしては、例えば、ポリオール、ポリイソシアネート及び水酸基を有する（メタ）アクリル化合物を従来公知の方法で反応させて得られるものを用いることができる。 As said urethane (meth) acrylate, what is obtained by making the (meth) acryl compound which has a polyol, polyisocyanate, and a hydroxyl group react by a conventionally well-known method can be used, for example.
前記ポリオールとしては、例えば、ポリエーテルポリオール、ポリカーボネートポリオール、ポリエステルポリオール、アクリルポリオール、カプロラクトンポリオール、ブタジエンポリオール等を用いることができる。これらのポリオールは単独で用いても２種以上を併用してもよい。 Examples of the polyol that can be used include polyether polyol, polycarbonate polyol, polyester polyol, acrylic polyol, caprolactone polyol, and butadiene polyol. These polyols may be used alone or in combination of two or more.
前記ポリイソシアネートとしては、例えば、フェニレンジイソシアネート、ジフェニルメタンジイソシアネート、トリレンジイソシアネート、ナフタレンジイソシアネート等の芳香族ジイソシアネート；、ヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキサンジイソシアネート、イソホロンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート等の脂肪族又は脂環式ジイソシアネート；キシリレンジイソシアネート、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、フェニレンジイソシアネート、ポリフェニレンポリメチレンポリイソシアネート、メチレンジフェニルジシソシアネートのホルマリン縮合体、４，４’−ジフェニルメタンジイソシアネートのカルボジイミド変性体等の芳香族系ポリイソシアネートなどを用いることができる。これらのポリイソシアネートは単独で用いても２種以上を併用してもよい。 Examples of the polyisocyanate include aromatic diisocyanates such as phenylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and xylylene. Aliphatic or cycloaliphatic diisocyanates such as diisocyanate, tetramethylxylylene diisocyanate; formalin condensation of xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polyphenylene polymethylene polyisocyanate, methylene diphenyl disissocyanate , 4,4'-carbodiimide-modified products such as diphenylmethane diisocyanate aromatic polyisocyanates can be used. These polyisocyanates may be used alone or in combination of two or more.
前記水酸基を有する（メタ）アクリル化合物としては、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等の水酸基を有する（メタ）アクリル酸アルキルエステル；ポリエチレングリコールモノアクリレート、ポリプロピレングリコールモノアクリレートなどを用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 Examples of the (meth) acrylic compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. (Meth) acrylic acid alkyl esters having the following hydroxyl groups; polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, and the like can be used. These compounds may be used alone or in combination of two or more.
なお、本発明において、「（メタ）アクリレート」とは、メタクリレートとアクリレートの一方又は両方をいい、「（メタ）アクリロイル基」とは、メタクリロイル基とアクリロイル基の一方又は両方をいい、「（メタ）アクリル酸」とは、メタクリル酸とアクリル酸の一方又は両方をいい、「（メタ）アクリル化合物」とは、アクリル化合物とメタクリル化合物の一方又は両方をいう。 In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and “(meth) acryloyl group” refers to one or both of methacryloyl group and acryloyl group. “Acrylic acid” refers to one or both of methacrylic acid and acrylic acid, and “(meth) acrylic compound” refers to one or both of an acrylic compound and a methacrylic compound.
また、前記ウレタン（メタ）アクリレートとして、水酸基を有するウレタン（メタ）アクリレートを用いる場合には、例えば、前記ウレタン（メタ）アクリレートの原料であるポリオール、ポリイソシアネート及び水酸基を有する（メタ）アクリル化合物と、更に多価アルコールとを従来公知の方法で反応させて得られるものを用いることができる。 Further, when a urethane (meth) acrylate having a hydroxyl group is used as the urethane (meth) acrylate, for example, a polyol, a polyisocyanate and a (meth) acrylic compound having a hydroxyl group, which are raw materials of the urethane (meth) acrylate, Further, those obtained by reacting with a polyhydric alcohol by a conventionally known method can be used.
前記多価アルコールは、前記不飽和ポリエステルの製造に用いるものと同様のものを用いることができる。 The said polyhydric alcohol can use the thing similar to what is used for manufacture of the said unsaturated polyester.
前記ラジカル重合性樹脂（Ａ）の数平均分子量としては、塗膜の引張物性、耐汚染性及び表面乾燥性をより一層向上できる点から、５００〜５，０００の範囲であることがより好ましく、１，０００〜３，０００の範囲であることがより好ましい。なお、前記ラジカル重合性樹脂（Ａ）の数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により、下記の条件で測定した値を示す。 The number average molecular weight of the radical polymerizable resin (A) is more preferably in the range of 500 to 5,000 from the viewpoint of further improving the tensile properties, stain resistance and surface drying properties of the coating film, More preferably, it is in the range of 1,000 to 3,000. In addition, the number average molecular weight of the said radical polymerizable resin (A) shows the value measured on condition of the following by the gel permeation chromatography (GPC) method.
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ−８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
「ＴＳＫｇｅｌ Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成した。
Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
（標準ポリスチレン）
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−１０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−２５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−５０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−１」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−２」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−４」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−１０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−２０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−４０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−８０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−１２８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−２８８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−５５０」
(Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation
前記ラジカル重合性単量体（Ｂ）としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、デシル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、β−エトキシエチル（メタ）アクリレート、２−シアノエチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、ポリカプロラクトン（メタ）アクリレート、ジエチレングリコールモノメチルエーテルモノ（メタ）アクリレート、ジプロピレングリコールモノメチルエーテルモノ（メタ）アクリレート、２−エチルヘキシルカルビトール（メタ）アクリレート、トリス（２−ヒドロキシエチル）イソシアヌル（メタ）アクリレート等の（メタ）アクリル単量体；ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等の沸点が１００℃以上の（メタ）アクリル単量体等を用いることできる。これらの単量体は単独で用いても２種以上を併用してもよい。 Examples of the radical polymerizable monomer (B) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and hexyl. (Meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, β-ethoxyethyl ( (Meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, polycaprolactone (meth) acrylate (Meth) acrylic such as dirate glycol monomethyl ether mono (meth) acrylate, dipropylene glycol monomethyl ether mono (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, tris (2-hydroxyethyl) isocyanuric (meth) acrylate Monomer: (Meth) acrylic monomers having a boiling point of 100 ° C. or higher, such as dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like can be used. These monomers may be used alone or in combination of two or more.
前記ラジカル重合性樹脂（Ａ）と前記ラジカル重合性単量体（Ｂ）との質量比［（Ａ）／（Ｂ）］としては、塗膜の引張物性、表面乾燥性、耐汚染性の点から、１０／９０〜９０／１０の範囲であることが好ましく、３０／７０〜８０／２０の範囲がより好ましい。 The mass ratio [(A) / (B)] of the radical polymerizable resin (A) and the radical polymerizable monomer (B) includes tensile properties of the coating film, surface drying properties, and contamination resistance. Therefore, the range of 10/90 to 90/10 is preferable, and the range of 30/70 to 80/20 is more preferable.
前記シクロデキストリン及び／又はその誘導体（Ｃ）は、反応性の低い前記ラジカル重合性樹脂（Ａ）を塗膜内部に沈降させやすくするものであり、塗膜に優れた表面乾燥性及び耐汚染性を付与する上で必須の成分である。 The cyclodextrin and / or its derivative (C) facilitates the precipitation of the radically polymerizable resin (A) having low reactivity inside the coating film, and has excellent surface drying and contamination resistance. Is an essential component for imparting.
前記シクロデキストリン及び／又はその誘導体（Ｃ）としては、例えば、シクロデキストリン；アルキル化シクロデキストリン、アセチル化シクロデキストリン、ヒドロキシアルキル化シクロデキストリン等のシクロデキストリンのグルコース単位の水酸基の水素原子を他の官能基で置換したものなどを用いることができる。また、シクロデキストリン及びシクロデキストリン誘導体におけるシクロデキストリン骨格としては、６個のグルコース単位からなるα−シクロデキストリン、７個のグルコース単位からなるβ−シクロデキストリン、８個のグルコース単位からなるγ−シクロデキストリンのいずれも用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。これらの中でも、前記ラジカル重合性樹脂（Ａ）及び前記ラジカル重合性単量体（Ｂ）との相溶性をより一層向上できる点から、シクロデキストリン誘導体を用いることが好ましく、アルキル化シクロデキストリンを用いることがより好ましい。 Examples of the cyclodextrin and / or its derivative (C) include, for example, cyclodextrin; the hydrogen atom of the hydroxyl group of the glucose unit of cyclodextrin such as alkylated cyclodextrin, acetylated cyclodextrin, and hydroxyalkylated cyclodextrin. Those substituted with a group can be used. The cyclodextrin skeleton in cyclodextrin and cyclodextrin derivatives includes α-cyclodextrin consisting of 6 glucose units, β-cyclodextrin consisting of 7 glucose units, and γ-cyclodextrin consisting of 8 glucose units. Any of these can be used. These compounds may be used alone or in combination of two or more. Among these, it is preferable to use a cyclodextrin derivative from the viewpoint that compatibility with the radical polymerizable resin (A) and the radical polymerizable monomer (B) can be further improved, and an alkylated cyclodextrin is used. It is more preferable.
前記シクロデキストリン誘導体における他の官能基の置換度としては、前記ラジカル重合性樹脂（Ａ）及び前記ラジカル重合性単量体（Ｂ）との相溶性の点から、０．３〜１４個／グルコースの範囲であることが好ましく、０．５〜８個／グルコースの範囲であることがより好ましい。 The substitution degree of other functional groups in the cyclodextrin derivative is 0.3 to 14 / glucose from the viewpoint of compatibility with the radical polymerizable resin (A) and the radical polymerizable monomer (B). It is preferable that it is the range of 0.5-8 pieces / glucose, and it is more preferable.
前記アルキル化シクロデキストリンとしては、例えば、メチル−α−シクロデキストリン、メチル−β−シクロデキストリン、メチル−γ−シクロデキストリン等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 Examples of the alkylated cyclodextrin include methyl-α-cyclodextrin, methyl-β-cyclodextrin, and methyl-γ-cyclodextrin. These compounds may be used alone or in combination of two or more.
前記アセチル化シクロデキストリンとしては、例えば、モノアセチル−α−シクロデキストリン、モノアセチル−β−シクロデキストリン、モノアセチル−γ−シクロデキストリン等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 Examples of the acetylated cyclodextrin include monoacetyl-α-cyclodextrin, monoacetyl-β-cyclodextrin, and monoacetyl-γ-cyclodextrin. These compounds may be used alone or in combination of two or more.
前記ヒドロキシアルキル化シクロデキストリンとしては、例えば、ヒドロキシプロピル−α−シクロデキストリン、ヒドロキシプロピル−β−シクロデキストリン、ヒドロキシプロピル−γ−シクロデキストリン等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 Examples of the hydroxyalkylated cyclodextrin include hydroxypropyl-α-cyclodextrin, hydroxypropyl-β-cyclodextrin, and hydroxypropyl-γ-cyclodextrin. These compounds may be used alone or in combination of two or more.
前記シクロデキストリン及び／又はその誘導体（Ｃ）の含有量としては、前記ラジカル重合性樹脂（Ａ）、前記ラジカル重合性単量体（Ｂ）及び後述するアクリル重合体（Ｄ）との相溶性、引張物性、表面乾燥性並びに耐汚染性をより一層向上できる点から、前記ラジカル重合性樹脂（Ａ）、前記ラジカル重合性単量体（Ｂ）及びアクリル重合体（Ｄ）の合計１００質量部に対して、０．５〜２０質量部の範囲であることが好ましく、１〜１５質量部の範囲がより好ましい。 As content of the said cyclodextrin and / or its derivative (C), compatibility with the said radically polymerizable resin (A), the said radically polymerizable monomer (B), and the acrylic polymer (D) mentioned later, From the point that tensile properties, surface drying properties and stain resistance can be further improved, the total amount of the radical polymerizable resin (A), the radical polymerizable monomer (B) and the acrylic polymer (D) is 100 parts by mass. On the other hand, it is preferable that it is the range of 0.5-20 mass parts, and the range of 1-15 mass parts is more preferable.
前記アクリル重合体（Ｄ）は、塗膜に優れた表面乾燥性及び耐汚染性を付与する上で必須の成分であり、例えば、（メタ）アクリル単量体を含む重合性化合物を従来公知の方法で重合して得られものを用いることができる。 The acrylic polymer (D) is an essential component for imparting excellent surface drying properties and stain resistance to the coating film. For example, a polymerizable compound containing a (meth) acrylic monomer is conventionally known. Those obtained by polymerization by the method can be used.
前記（メタ）アクリル単量体としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ネオペンチル（メタ）アクリレート、２−エチルへキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、セチル（メタ）アクリレート、ラウリル（メタ）アクリレート等の（メタ）アクリル酸アルキルエステル；２，２，２−トリフルオロエチル（メタ）アクリレート、２，２，３，３−テトラフルオロプロピル（メタ）アクリレート、１Ｈ，１Ｈ，５Ｈ−オクタフルオロペンチル（メタ）アクリレート、２−（パーフルオロオクチル）エチル（メタ）アクリレート等のフッ素原子を有する（メタ）アクリル単量体；イソボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、シジクロペンタニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート等の脂環構造を有する（メタ）アクリル単量体；ポリエチレングリコールモノ（メタ）アクリレート、メトキシエチル（メタ）アクリレート、メトキシブチル（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート等のエーテル基を有する（メタ）アクリル単量体；ベンジル（メタ）アクリレート、２−エチル−２−メチル−［１，３］−ジオキソラン−４−イル−メチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレートなどを用いることができる。これらの（メタ）アクリル単量体は、単独で用いても２種以上を併用してもよい。 Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, neopentyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cetyl (meth) acrylate, lauryl (meth) acrylate and other (meth) acrylic acids Alkyl ester; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 2- ( Perfluorooct (Meth) acrylic monomers having fluorine atoms such as ethyl (meth) acrylate; isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, sicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) (Meth) acrylic monomers having an alicyclic structure such as acrylate; polyethylene glycol mono (meth) acrylate, methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (Meth) acrylic monomers having an ether group such as (meth) acrylate; benzyl (meth) acrylate, 2-ethyl-2-methyl- [1,3] -dioxolan-4-yl-methyl (meth) acrylate Or the like can be used dimethylaminoethyl (meth) acrylate. These (meth) acrylic monomers may be used alone or in combination of two or more.
前記（メタ）アクリル単量体以外の重合性化合物としては、例えば、スチレン、α−メチルスチレン等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 As a polymerizable compound other than the (meth) acrylic monomer, for example, styrene, α-methylstyrene, or the like can be used. These compounds may be used alone or in combination of two or more.
前記アクリル重合体（Ｄ）を得る際には、必要に応じて有機溶剤を用いてもよい。前記有機溶剤としては、例えば、キシレン、トルエン、酢酸エチル、アセトン、メチルエチルケトン、ブタノール等を用いることができる。これらの有機溶剤は単独で用いても２種以上を併用してもよい。 When obtaining the said acrylic polymer (D), you may use an organic solvent as needed. As the organic solvent, for example, xylene, toluene, ethyl acetate, acetone, methyl ethyl ketone, butanol and the like can be used. These organic solvents may be used alone or in combination of two or more.
前記アクリル重合体（Ｄ）の重量平均分子量としては、前記ラジカル重合性樹脂（Ａ）が前記シクロデキストリン及び／又はその誘導体（Ｃ）と水素結合を形成して塗膜内部に沈降し、アクリル重合体（Ｄ）が塗膜表面に偏析して表面乾燥性及び耐汚染性をより一層向上しやすくなる点から、２０，０００以上であることが好ましく、３０，０００以上であることがより好ましい。なお、前記アクリル重合体（Ｄ）の重量平均分子量は、前記ラジカル重合性樹脂（Ａ）の数平均分子量と同様の測定により得られた値を示す。 The acrylic polymer (D) has a weight average molecular weight such that the radical polymerizable resin (A) forms a hydrogen bond with the cyclodextrin and / or its derivative (C) and settles inside the coating film. It is preferably 20,000 or more, more preferably 30,000 or more, from the viewpoint that the coalesced (D) is segregated on the surface of the coating film and the surface drying property and stain resistance are further improved. In addition, the weight average molecular weight of the said acrylic polymer (D) shows the value obtained by the same measurement as the number average molecular weight of the said radical polymerizable resin (A).
前記アクリル重合体（Ｄ）の含有量としては、表面乾燥性及び耐汚染性をより一層向上できる点から、前記ラジカル重合性樹脂（Ａ）、前記ラジカル重合性単量体（Ｂ）及び前記アクリル重合体（Ｄ）の合計中、０．５〜３０質量％の範囲であることが好ましく、１〜１０質量％の範囲であることがより好ましい。 As the content of the acrylic polymer (D), the radically polymerizable resin (A), the radically polymerizable monomer (B), and the acrylic are preferable because the surface drying property and stain resistance can be further improved. It is preferable that it is the range of 0.5-30 mass% in the sum total of a polymer (D), and it is more preferable that it is the range of 1-10 mass%.
本発明のラジカル重合性樹脂組成物は、前記ラジカル重合性樹脂（Ａ）、前記ラジカル重合性単量体（Ｂ）、前記シクロデキストリン及び／又はその誘導体（Ｃ）、並びに、前記アクリル重合体（Ｄ）を必須成分として含有するが、必要に応じてその他の添加剤を含有してもよい。 The radical polymerizable resin composition of the present invention comprises the radical polymerizable resin (A), the radical polymerizable monomer (B), the cyclodextrin and / or derivative (C), and the acrylic polymer ( D) is contained as an essential component, but may contain other additives as necessary.
前記その他の添加剤としては、例えば、硬化剤、硬化促進剤、重合禁止剤、顔料、チキソ性付与剤、酸化防止剤、溶剤、充填剤、補強材、骨材、難燃剤、石油ワックス等を１種以上用いることができる。 Examples of the other additives include a curing agent, a curing accelerator, a polymerization inhibitor, a pigment, a thixotropic agent, an antioxidant, a solvent, a filler, a reinforcing material, an aggregate, a flame retardant, and a petroleum wax. One or more can be used.
前記硬化剤としては、常温での表面乾燥性の点から有機過酸化物を用いることが好ましく、例えば、ジアシルパーオキサイド化合物、パーオキシエステル化合物、ハイドロパーオキサイド化合物、ジアルキルパーオキサイド化合物、ケトンパーオキサイド化合物、パーオキシケタール化合物、アルキルパーエステル化合物、パーカーボネート化合物等を用いることができる。これらの硬化剤は単独で用いても２種以上を併用してもよい。前記硬化剤の含有量としては、ラジカル重合性樹脂組成物中０．０１〜１０質量％の範囲であることが好ましい。 As the curing agent, an organic peroxide is preferably used from the viewpoint of surface dryness at room temperature. For example, a diacyl peroxide compound, a peroxy ester compound, a hydroperoxide compound, a dialkyl peroxide compound, a ketone peroxide. A compound, a peroxyketal compound, an alkyl perester compound, a carbonate compound, or the like can be used. These curing agents may be used alone or in combination of two or more. As content of the said hardening | curing agent, it is preferable that it is the range of 0.01-10 mass% in a radically polymerizable resin composition.
前記硬化促進剤は、前記硬化剤の有機過酸化物をレドックス反応によって分解し、活性ラジカルの発生を容易にする作用のある物質であり、例えば、ナフテン酸コバルト、オクチル酸コバルト等のコバルト有機酸塩、オクチル酸亜鉛、オクチル酸バナジウム、ナフテン酸銅、ナフテン酸バリウム等の金属石鹸、バナジウムアセチルアセテート、コバルトアセチルアセテート、鉄アセチルアセトネート等の金属キレート；アニリン、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジエチルアニリン、ｐ−トルイジン、Ｎ，Ｎ−ジメチル−ｐ−トルイジン、Ｎ，Ｎ−ジメチル−ｐ−トルイジンのエチレンオキサイド付加物、Ｎ，Ｎ−ビス（２-ヒドロキシエチル）−ｐ−トルイジン、４−（Ｎ，Ｎ−ジメチルアミノ）ベンズアルデヒド、４−［Ｎ，Ｎ−ビス（２-ヒドロキシエチル）アミノ］ベンズアルデヒド、４−（Ｎ−メチル−Ｎ−ヒドロキシエチルアミノ）ベンズアルデヒド、Ｎ，Ｎ−ビス（２−ヒドロキシプロピル）−ｐ−トルイジン、Ｎ−エチル−ｍ−トルイジン、トリエタノールアミン、ｍ−トルイジン、ジエチレントリアミン、ピリジン、フェニリモルホリン、ピペリジン、Ｎ，Ｎ−ビス（ヒドロキシエチル）アニリン、ジエタノールアニリン等のＮ，Ｎ−置換アニリン；Ｎ，Ｎ−置換−ｐ−トルイジン、４−（Ｎ，Ｎ−置換アミノ）ベンズアルデヒド等のアミン化合物などを用いることができる。これらの硬化促進剤は単独で用いても２種以上を併用してもよい。前記硬化促進剤の含有量としては、ラジカル重合性樹脂組成物中０．０１〜５質量％の範囲であることが好ましい。 The curing accelerator is a substance having an action of decomposing an organic peroxide of the curing agent by a redox reaction and facilitating generation of active radicals. For example, a cobalt organic acid such as cobalt naphthenate and cobalt octylate is used. Metal soaps such as salts, zinc octylate, vanadium octylate, copper naphthenate, barium naphthenate, metal chelates such as vanadium acetyl acetate, cobalt acetyl acetate, iron acetylacetonate; aniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, ethylene oxide adduct of N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine, 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, N, N-bis (2-hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine, tri N, N-substituted anilines such as ethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N, N-bis (hydroxyethyl) aniline, diethanolaniline; N, N-substituted-p-toluidine, 4 An amine compound such as-(N, N-substituted amino) benzaldehyde can be used. These curing accelerators may be used alone or in combination of two or more. As content of the said hardening accelerator, it is preferable that it is the range of 0.01-5 mass% in a radically polymerizable resin composition.
前記石油ワックスとしては、酸素による硬化阻害を防止するものであり、例えば、融点が３０〜８０℃の石油ワックスを用いることが好ましく、具体的には、パラフィンワックス、マイクロクリスタリンワックス、ペトロラクタム等を用いることができる。これらの石油ワックスは単独で用いても２種以上を併用してもよい。前記石油ワックスの含有量としては、ラジカル重合性樹脂組成物中０．０１〜５質量％の範囲であることが好ましい。 The petroleum wax is one that prevents curing inhibition by oxygen. For example, petroleum wax having a melting point of 30 to 80 ° C. is preferably used. Specifically, paraffin wax, microcrystalline wax, petrolactam, and the like are used. Can be used. These petroleum waxes may be used alone or in combination of two or more. As content of the said petroleum wax, it is preferable that it is the range of 0.01-5 mass% in a radically polymerizable resin composition.
以下、実施例を用いて、本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
［合成例１］ウレタンメタクリレート（Ａ−１）の合成
温度計、攪拌機、不活性ガス導入口、空気導入口及び還流冷却器を備えた四つ口フラスコに、数平均分子量１，０００のポリプロピレングリコールを５００質量部、トリレンジイソシアネートを１７４質量部仕込み、窒素気流下８０℃で４時間反応させた。イソシアネート基当量が６００とほぼ理論値となったのを確認して、５０℃まで冷却した。次いで、空気気流下でハイドロキノン０．０７質量部、２−ヒドロキシエチルメタクリレートを１３１質量部を加え、９０℃で５時間反応させた。イソシアネート％が０．１％以下となった時点でターシャリーブチルカテコールを０．０７質量部加え、数平均分子量；１５８４のウレタンメタクリレート（Ａ−１）を得た。
[Synthesis Example 1] Synthesis of urethane methacrylate (A-1) Polypropylene glycol having a number average molecular weight of 1,000 in a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet and a reflux condenser. Of 500 parts by mass and 174 parts by mass of tolylene diisocyanate were charged and reacted at 80 ° C. for 4 hours under a nitrogen stream. It was confirmed that the isocyanate group equivalent was 600, which was almost the theoretical value, and then cooled to 50 ° C. Next, 0.07 parts by mass of hydroquinone and 131 parts by mass of 2-hydroxyethyl methacrylate were added under an air stream and reacted at 90 ° C. for 5 hours. When the isocyanate% became 0.1% or less, 0.07 part by mass of tertiary butyl catechol was added to obtain urethane methacrylate (A-1) having a number average molecular weight of 1584.
［合成例２］ウレタンメタクリレート（Ａ−２）の合成
温度計、攪拌機、不活性ガス導入口、空気導入口及び還流冷却器を備えた四つ口フラスコに、数平均分子量１，０００のポリプロピレングリコールを５００質量部、トリレンジイソシアネートを１７４質量部仕込み、窒素気流下８０℃で４時間反応させた。イソシアネート基当量が６００とほぼ理論値となったのを確認して、５０℃まで冷却した。次いで、空気気流下でハイドロキノン０．０７質量部、２−ヒドロキシエチルメタクリレートを６６質量部とエチレングリコール６２質量部を加え、９０℃で５時間反応させた。イソシアネート％が０．１％以下となった時点でターシャリーブチルカテコールを０．０７質量部加え、数平均分子量；１５０６のウレタンメタクリレート（Ａ−２）を得た。
[Synthesis Example 2] Synthesis of urethane methacrylate (A-2) Polypropylene glycol having a number average molecular weight of 1,000 in a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet and a reflux condenser. Of 500 parts by mass and 174 parts by mass of tolylene diisocyanate were charged and reacted at 80 ° C. for 4 hours under a nitrogen stream. It was confirmed that the isocyanate group equivalent was 600, which was almost the theoretical value, and then cooled to 50 ° C. Next, 0.07 parts by mass of hydroquinone, 66 parts by mass of 2-hydroxyethyl methacrylate and 62 parts by mass of ethylene glycol were added under an air stream, and reacted at 90 ° C. for 5 hours. When the isocyanate% became 0.1% or less, 0.07 part by mass of tertiary butyl catechol was added to obtain urethane methacrylate (A-2) having a number average molecular weight of 1506.
［合成例３］エポキシメタクリレート（Ａ−３）の合成
温度計、攪拌機、不活性ガス導入口、空気導入口及び還流冷却器を備えた四つ口フラスコに、ビスフェノールＡとエピクロルヒドリンとの反応により得られたエポキシ化合物（ＤＩＣ株式会社製「エピクロン８５０」）を１，８５０質量部、メタクリル酸を８６０質量部、ハイドロキノンを１．３６質量部、トリエチルアミンを１０．８質量部仕込み、１２０まで昇温させ１０時間させて、酸価３．５ｍｇＫＯＨ／ｇのエポキシメタクリレート（Ａ−３）を得た。
[Synthesis Example 3] Synthesis of epoxy methacrylate (A-3) Obtained by reaction of bisphenol A and epichlorohydrin in a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, air inlet and reflux condenser. 1,850 parts by mass of the resulting epoxy compound (“Epiclon 850” manufactured by DIC Corporation), 860 parts by mass of methacrylic acid, 1.36 parts by mass of hydroquinone, and 10.8 parts by mass of triethylamine are charged to 120 ° C. After 10 hours, an epoxy methacrylate (A-3) having an acid value of 3.5 mgKOH / g was obtained.
［合成例４］アクリル重合体（Ｄ−１）の合成
温度計、攪拌機、不活性ガス導入口及び還流冷却器を備えた四つ口フラスコに、キシレン４５０質量部を加え、１１５℃にまで昇温して子の温度を維持した。次いで、メチルメタクリレートを２４０質量部、ｎ−ブチルメタクリレートを１６０質量部、ジーターシャリーブチルパーオキサイドを３質量部及びキシレンを１５０質量部を４時間に亘って滴下した。滴下終了後、１２０℃で８時間保持して、不揮発分が４０質量％、重量平均分子量が３５，０００のアクリル重合体（Ｄ−１）を得た。
[Synthesis Example 4] Synthesis of acrylic polymer (D-1) 450 parts by mass of xylene was added to a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, and the temperature was raised to 115 ° C. The child's temperature was maintained by heating. Next, 240 parts by mass of methyl methacrylate, 160 parts by mass of n-butyl methacrylate, 3 parts by mass of jettery butyl peroxide and 150 parts by mass of xylene were added dropwise over 4 hours. After completion of dropping, the mixture was held at 120 ° C. for 8 hours to obtain an acrylic polymer (D-1) having a nonvolatile content of 40% by mass and a weight average molecular weight of 35,000.
［実施例１］ラジカル重合性樹脂組成物の調製
合成例２で得られたウレタンメタクリレート（Ａ−２）を２０質量部、合成例３で得られたエポキシメタクリレート（Ａ−３）を３０質量部、メチルメタクリレートを４０質量部、「メチル−β−シクロデキストリン」（純正化学株式会社製）を５質量部、合成例４で得られたアクリル重合体（Ｄ−１）を１０質量部、融点が５４℃のパラフィンワックスを０．３質量部混合、撹拌してラジカル重合性樹脂組成物を得た。
[Example 1] Preparation of radical polymerizable resin composition 20 parts by mass of urethane methacrylate (A-2) obtained in Synthesis Example 2 and 30 parts by mass of epoxy methacrylate (A-3) obtained in Synthesis Example 3 40 parts by mass of methyl methacrylate, 5 parts by mass of “methyl-β-cyclodextrin” (manufactured by Junsei Chemical Co., Ltd.), 10 parts by mass of the acrylic polymer (D-1) obtained in Synthesis Example 4, and a melting point of A radically polymerizable resin composition was obtained by mixing and stirring 0.3 parts by mass of 54 ° C. paraffin wax.
［実施例２〜４、比較例１〜３］
用いるラジカル重合性樹脂（Ａ）の種類及び量、シクロデキストリン（Ｃ）の量及びアクリル重合体（Ｄ）の量を表１に示す通りに変更した以外は、実施例１と同様にしてラジカル重合性樹脂組成物を得た。
[Examples 2 to 4, Comparative Examples 1 to 3]
Radical polymerization in the same manner as in Example 1 except that the type and amount of the radical polymerizable resin (A) used, the amount of cyclodextrin (C) and the amount of the acrylic polymer (D) were changed as shown in Table 1. A functional resin composition was obtained.
［表面乾燥性の評価方法］
表面乾燥性は、ゲルタイム（ＧＴ）及びタックフリータイム（ＴＦ）の比［ＴＦ（分）／ＧＴ（分）］により以下のように評価した。
＜ゲルタイム（ＧＴ）＞
実施例及び比較例で得られたラジカル重合性樹脂組成物５０質量部を２５℃に調製した後、４０質量％ベンゾイルパーオキサイド溶液を２質量部添加し混合し試験片とした。これを２５℃の恒温槽に浸漬させ、この時点を基点として、ゲルが発生して糸切れ状態になるまでの時間（分）を測定しゲルタイムとした。
＜タックフリータイム（ＴＦ）＞
前記試験片を２５℃、湿度５０％の環境試験室内にて、ガラス板上に厚さ０．２５ｍｍとなるように、アプリケーターで塗布した。この時点を基点として、塗膜の表面状態を指触で確認し、指に樹脂が付かなくなるまでの時間（分）を測定しタックフリータイムとした。
＜表面乾燥性の評価＞
「Ａ」；２未満
「Ｂ」；２以上３未満
「Ｃ」；３以上
[Evaluation method of surface drying]
The surface drying property was evaluated as follows according to the ratio of gel time (GT) and tack free time (TF) [TF (min) / GT (min)].
<Geltime (GT)>
After preparing 50 parts by mass of the radical polymerizable resin compositions obtained in Examples and Comparative Examples at 25 ° C., 2 parts by mass of a 40% by mass benzoyl peroxide solution was added and mixed to obtain a test piece. This was immersed in a thermostatic bath at 25 ° C., and the time (minutes) from when the gel was generated until the yarn was broken was measured from this point in time as the gel time.
<Tack Free Time (TF)>
The test piece was applied with an applicator so as to have a thickness of 0.25 mm on a glass plate in an environmental test chamber at 25 ° C. and a humidity of 50%. Using this time as a base point, the surface state of the coating film was confirmed by finger touch, and the time (minutes) until the finger no longer adhered to the resin was measured to obtain a tack-free time.
<Evaluation of surface dryness>
“A”; less than 2 “B”; 2 or more and less than 3 “C”; 3 or more
［耐汚染性の評価方法］
前記＜タックフリータイム（ＴＦ）＞の評価において、タックフリータイムを測定直後、及びタックフリー測定後３０分毎に、塗膜にゴム栓を擦り付け、擦り付けたものが消しゴムで落とせるようになる時点を測定し、耐汚染性を以下のように評価した。
「Ａ」；ＴＦ測定後に汚れを消しゴムで落とせる。
「Ｂ」；ＴＦ測定後２時間以内に汚れを消しゴムで落とせる。
「Ｃ」；ＴＦ測定後２時間経過後４時間経過前までに消しゴムで落とせる。
「Ｄ」；ＴＦ測定後４時間経過しても汚れを消しゴムで落とせない。
[Contamination resistance evaluation method]
In the <tack free time (TF)> evaluation, immediately after measuring the tack free time and every 30 minutes after the tack free measurement, the rubber plug is rubbed against the coating film, and the rubbed material can be removed with an eraser. The contamination resistance was measured and evaluated as follows.
“A”: After the TF measurement, the dirt can be removed with an eraser.
“B”: Dirt can be removed with an eraser within 2 hours after TF measurement.
“C”: Can be removed with an eraser 2 hours after the TF measurement and 4 hours before the TF measurement.
“D”: Even after 4 hours have passed since the TF measurement, the dirt cannot be removed with an eraser.
本発明のラジカル重合性樹脂組成物である実施例１〜４は、表面乾燥性及び耐汚染性に優れる塗膜が得られることが分かった。 In Examples 1 to 4, which are the radical polymerizable resin compositions of the present invention, it was found that a coating film excellent in surface drying property and stain resistance was obtained.
一方、比較例１はシクロデキストリン及び／又はその誘導体（Ｃ）を含有しない態様であるが、塗膜の表面乾燥性及び耐汚染性が不良であった。 On the other hand, although the comparative example 1 is an aspect which does not contain cyclodextrin and / or its derivative (C), the surface drying property and stain resistance of the coating film were unsatisfactory.
比較例２及び３は、アクリル重合体（Ｄ）を含有しない態様であるが、塗膜の表面乾燥性及び耐汚染性が著しく不良であった。 Although the comparative examples 2 and 3 are the aspects which do not contain an acrylic polymer (D), the surface drying property and stain resistance of the coating film were remarkably bad.
Claims (7)
A radical polymerizable resin composition containing a radical polymerizable resin (A), a radical polymerizable monomer (B), cyclodextrin and / or a derivative thereof (C), and an acrylic polymer (D) , The radical polymerizable monomer (B) is (meth) acrylic acid ester, and the acrylic polymer (D) is one or more selected from the group consisting of (meth) acrylic acid ester, styrene and α-methylstyrene. A radically polymerizable resin composition characterized by being a polymer of a monomer.
ラジカル重合性樹脂組成物。 The radically polymerizable resin composition according to claim 1, wherein the acrylic polymer (D) has a weight average molecular weight of 20,000 or more.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013186204A JP6281217B2 (en) | 2013-09-09 | 2013-09-09 | Radical polymerizable resin composition and civil engineering building material |
| KR1020140090776A KR102163353B1 (en) | 2013-09-09 | 2014-07-18 | Radically polymerizable resin composition, and civil engineering and construction materilas |
| CN201410441404.4A CN104419300B (en) | 2013-09-09 | 2014-09-01 | Free-radical polymerised resin combination and civil construction material |
| TW103130426A TWI647274B (en) | 2013-09-09 | 2014-09-03 | Radical polymerizable resin composition and civil construction material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013186204A JP6281217B2 (en) | 2013-09-09 | 2013-09-09 | Radical polymerizable resin composition and civil engineering building material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015052080A JP2015052080A (en) | 2015-03-19 |
| JP6281217B2 true JP6281217B2 (en) | 2018-02-21 |
Family
ID=52701327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013186204A Active JP6281217B2 (en) | 2013-09-09 | 2013-09-09 | Radical polymerizable resin composition and civil engineering building material |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6281217B2 (en) |
| KR (1) | KR102163353B1 (en) |
| CN (1) | CN104419300B (en) |
| TW (1) | TWI647274B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6394077B2 (en) * | 2014-06-04 | 2018-09-26 | Dic株式会社 | Radical polymerizable composition, concrete repair material and road primer |
| JP6066027B1 (en) * | 2015-04-22 | 2017-01-25 | Dic株式会社 | Radical polymerizable resin composition and civil engineering primer |
| CN107400189A (en) * | 2016-10-27 | 2017-11-28 | 淮阴工学院 | A kind of free-radical polymerised resin combination and civil construction material |
| JP7208050B2 (en) * | 2019-02-14 | 2023-01-18 | 第一工業製薬株式会社 | civil engineering building materials |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04351660A (en) * | 1991-05-29 | 1992-12-07 | Dainippon Ink & Chem Inc | Actinic radiation-curable resin composition |
| JPH06329982A (en) * | 1993-05-26 | 1994-11-29 | Nippon Polyurethane Ind Co Ltd | Rapidly curing polyurethane coating composition |
| DE4440236A1 (en) | 1994-11-10 | 1996-05-15 | Wacker Chemie Gmbh | Redispersible polymer powder composition containing cyclodextrins or cyclodextrin derivatives |
| CN102449008B (en) * | 2009-06-18 | 2015-02-11 | Dic株式会社 | Air-drying polyester (meth)acrylate resin composition, structure and method for providing same |
| WO2011013532A1 (en) * | 2009-07-31 | 2011-02-03 | Dic株式会社 | Radical-curable resin composition, pavement materials using same, and paved structures |
| JP2011231231A (en) | 2010-04-28 | 2011-11-17 | Dic Corp | Radically curable unsaturated resin composition and coating material |
| JP6252019B2 (en) * | 2013-07-31 | 2017-12-27 | Dic株式会社 | Radical polymerizable resin composition and civil engineering building material |
-
2013
- 2013-09-09 JP JP2013186204A patent/JP6281217B2/en active Active
-
2014
- 2014-07-18 KR KR1020140090776A patent/KR102163353B1/en active IP Right Grant
- 2014-09-01 CN CN201410441404.4A patent/CN104419300B/en active Active
- 2014-09-03 TW TW103130426A patent/TWI647274B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015052080A (en) | 2015-03-19 |
| TW201512287A (en) | 2015-04-01 |
| CN104419300B (en) | 2018-12-11 |
| KR20150029527A (en) | 2015-03-18 |
| CN104419300A (en) | 2015-03-18 |
| KR102163353B1 (en) | 2020-10-08 |
| TWI647274B (en) | 2019-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW200906883A (en) | New urethane (meth)acrylates and their use in curable coating compositions | |
| JP6281217B2 (en) | Radical polymerizable resin composition and civil engineering building material | |
| KR20170120581A (en) | Cold hardened cross-sectional restoration material and method for repairing a cross-section using the same | |
| TW201233698A (en) | Radical curable resin composition | |
| JP5743043B1 (en) | Concrete repair material | |
| JP6394077B2 (en) | Radical polymerizable composition, concrete repair material and road primer | |
| JP6252019B2 (en) | Radical polymerizable resin composition and civil engineering building material | |
| JP5339171B1 (en) | Urethane (meth) acrylate resin composition and coating material | |
| JP2015048459A (en) | Radically polymerizable resin composition and civil engineering building material | |
| JP5867793B1 (en) | Radical polymerizable composition, concrete repair material and road primer | |
| JP5765605B1 (en) | Concrete repair material | |
| JP6066027B1 (en) | Radical polymerizable resin composition and civil engineering primer | |
| EP3858880A1 (en) | Radical polymerizable resin composition and structure repairing material | |
| JP2015052079A (en) | Evaluation method for curability of radical curable resin composition | |
| JP5927892B2 (en) | Composite covering structure | |
| JP5845935B2 (en) | Radical polymerizable resin composition | |
| JP6212892B2 (en) | Radical curable composition and civil engineering building material | |
| JP2022042660A (en) | Primer for concrete | |
| JP2022042661A (en) | Primer for concrete | |
| JP5979428B2 (en) | Radical curable resin composition | |
| JP2022048571A (en) | Concrete repair material | |
| JP2023005502A (en) | primer for concrete | |
| JP2021105093A (en) | Low-odor resin composition | |
| JP2014051633A (en) | Radical curable resin composition, covering material and waterproof material for floor slab |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160825 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170817 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20171011 |
|
| 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: 20171226 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180108 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 6281217 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |