JP5915251B2 - Curable resin composition and cured product thereof - Google Patents
Curable resin composition and cured product thereof Download PDFInfo
- Publication number
- JP5915251B2 JP5915251B2 JP2012038752A JP2012038752A JP5915251B2 JP 5915251 B2 JP5915251 B2 JP 5915251B2 JP 2012038752 A JP2012038752 A JP 2012038752A JP 2012038752 A JP2012038752 A JP 2012038752A JP 5915251 B2 JP5915251 B2 JP 5915251B2
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- JP
- Japan
- Prior art keywords
- fluorine
- curable resin
- weight
- segment
- 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.)
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- 239000011342 resin composition Substances 0.000 title claims description 34
- 229910052731 fluorine Inorganic materials 0.000 claims description 113
- 239000011737 fluorine Substances 0.000 claims description 109
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 104
- 229920005989 resin Polymers 0.000 claims description 56
- 239000011347 resin Substances 0.000 claims description 56
- 239000000178 monomer Substances 0.000 claims description 55
- 229920001400 block copolymer Polymers 0.000 claims description 43
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 239000004793 Polystyrene Substances 0.000 claims description 29
- 229920002223 polystyrene 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 16
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 8
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 230000008602 contraction Effects 0.000 claims 1
- 238000003856 thermoforming Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000000465 moulding Methods 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- -1 perfluoro group Chemical group 0.000 description 14
- 150000002978 peroxides Chemical class 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000004925 Acrylic resin Substances 0.000 description 11
- 229920000178 Acrylic resin Polymers 0.000 description 11
- 239000003822 epoxy resin Substances 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229920006337 unsaturated polyester resin Polymers 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000003373 anti-fouling effect Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000001771 impaired effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 150000004812 organic fluorine compounds Chemical class 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 229920001567 vinyl ester resin Polymers 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 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
- 239000003112 inhibitor Substances 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 229920002689 polyvinyl acetate Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 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 3
- 102100026735 Coagulation factor VIII Human genes 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 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
- 229930003836 cresol Natural products 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000002928 artificial marble Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229920001519 homopolymer Polymers 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
- 239000004579 marble Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 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 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000004729 acetoacetic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 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
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910021538 borax Inorganic materials 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
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
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- CPZVJYPXOWWFSW-VAWYXSNFSA-N dibenzyl (e)-but-2-enedioate Chemical compound C=1C=CC=CC=1COC(=O)/C=C/C(=O)OCC1=CC=CC=C1 CPZVJYPXOWWFSW-VAWYXSNFSA-N 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、表面外観および防汚性に優れた硬化性樹脂組成物およびその硬化成形物に関するものである。 The present invention relates to a curable resin composition excellent in surface appearance and antifouling property and a cured molded product thereof.
人工大理石とは、一般に、樹脂、無機充填剤、低収縮剤、触媒、架橋剤および顔料などからなる樹脂組成物を硬化したものであり、比較的安価でありながら加工性、施工性、強度などに優れ、外観が天然大理石に近い樹脂成形物である。その為、浴槽、洗い場、カウンタートップ、キッチン天板およびサニタリー用途等に適した防汚材料として広く用いられてきた。しかし、用途が主に水回りということで水垢を始めとした種々の汚れ付着が大きな問題となり、これらの問題を解決するために多くの検討がなされてきた。 Artificial marble is generally a cured resin composition composed of resin, inorganic filler, low shrinkage agent, catalyst, cross-linking agent, pigment, etc., and it is relatively inexpensive, while its workability, workability, strength, etc. It is a resin molded product that is excellent in appearance and close in appearance to natural marble. For this reason, it has been widely used as an antifouling material suitable for bathtubs, washing places, countertops, kitchen top plates, sanitary applications, and the like. However, since the application is mainly used for water, adhesion of various types of dirt such as scale becomes a big problem, and many studies have been made to solve these problems.
例えば、特許文献1では、硬化性樹脂、無機充填剤および有機フッ素化合物を含む樹脂組成物を硬化させた樹脂成形物が開示されている。そこで使用されている有機フッ素化合物とはフッ素系単独重合体、フッ素系ランダム共重合体、フッ素系オイルや低分子フッ素系界面活性剤である。また、特許文献2では、骨材、低分子フッ素系化合物および硬化性樹脂を含む樹脂組成物を硬化させた樹脂成形物が開示されている。 For example, Patent Document 1 discloses a resin molded product obtained by curing a resin composition containing a curable resin, an inorganic filler, and an organic fluorine compound. The organic fluorine compound used there is a fluorine homopolymer, a fluorine random copolymer, a fluorine oil or a low molecular fluorine surfactant. Patent Document 2 discloses a resin molded product obtained by curing a resin composition containing an aggregate, a low-molecular fluorine-based compound, and a curable resin.
しかしながら特許文献1や特許文献2に開示された樹脂成形物では、有機フッ素化合物ないし低分子フッ素化合物と硬化性樹脂との相容性が非常に乏しいことから、両者を均質に混合させることは困難であり、また、成形後においても有機フッ素化合物や低分子フッ素化合物が表面に遊離し易い状態にある。そのため表面の有機フッ素化合物や低分子フッ素化合物が容易に脱落してしまう為、目的とする撥水撥油性を持続させることは困難であった。 However, in the resin molded products disclosed in Patent Document 1 and Patent Document 2, since compatibility between the organic fluorine compound or the low molecular fluorine compound and the curable resin is very poor, it is difficult to mix the two uniformly. In addition, even after molding, the organic fluorine compound and the low molecular fluorine compound are easily released on the surface. Therefore, since the organic fluorine compound and low molecular fluorine compound on the surface easily fall off, it has been difficult to maintain the desired water and oil repellency.
さらに、有機フッ素化合物としてフッ素系ランダム共重合体を用いた場合、フッ素量が多いと合成樹脂との相容性が減少するため前記したと同じような現象となり、撥水撥油性を持続させることは困難である。また、合成樹脂との相容性を上げる為にフッ素量を下げるとフッ素系ランダム共重合体の表面への配向性が乏しくなり目的とする撥水撥油性を確保することが困難となる。 Furthermore, when a fluorine-based random copolymer is used as the organic fluorine compound, the compatibility with the synthetic resin decreases if the amount of fluorine is large, so that the same phenomenon as described above occurs, and the water and oil repellency is maintained. It is difficult. Further, if the amount of fluorine is lowered in order to increase the compatibility with the synthetic resin, the orientation of the fluorine-based random copolymer on the surface becomes poor and it becomes difficult to ensure the desired water and oil repellency.
本発明は、上記問題点に鑑みて成されたものであり、本発明の目的は、撥水撥油性を確保するとともに、表面外観および防汚性に優れた硬化性樹脂組成物およびその硬化成形物を提供することである。 The present invention has been made in view of the above problems, and an object of the present invention is to ensure water and oil repellency, and to provide a curable resin composition excellent in surface appearance and antifouling property and cured molding thereof. Is to provide things.
即ち、第1の発明は、含フッ素セグメントと非フッ素セグメントからなるフッ素系ブロック共重合体と、硬化性樹脂と、低収縮剤と、を含む硬化性樹脂組成物であって、前記含フッ素セグメントを構成する含フッ素単量体が、炭素数6のパーフルオロアルキル基を有する下記一般式(I)に示される含フッ素単量体であり、
前記非フッ素セグメントは、メタクリル酸メチル40〜41.1重量%、メタクリル酸ブチル40〜41.1重量%、メタクリル酸2−ヒドロキシエチル16.7重量%、及びメタクリル酸1.1〜3.3重量%の合計100重量%からなる共重合体であり、
前記低収縮剤はポリスチレン系であり、前記硬化性樹脂100重量部に対して1〜150重量部含有されていることを特徴とする硬化性樹脂組成物である。
(一般式(I)において、R1は、水素原子、メチル基、フッ素原子又は塩素原子であり、R2は、炭素数1以上の脂肪族基である。)
第2の発明は、含フッ素セグメントと非フッ素セグメントからなるフッ素系ブロック共重合体と、硬化性樹脂と、を含む硬化性樹脂組成物であって、前記含フッ素セグメントを構成する含フッ素単量体が、炭素数6のパーフルオロアルキル基を有する上記一般式(I)に示される含フッ素単量体であり、
前記非フッ素セグメントは、メタクリル酸メチル40〜41.1重量%、メタクリル酸ブチル40〜41.1重量%、メタクリル酸2−ヒドロキシエチル16.7重量%、及びメタクリル酸1.1〜3.3重量%の合計100重量%からなる共重合体であり、
低収縮剤を含まないことを特徴とする硬化性樹脂組成物である。
第3の発明は、含フッ素セグメントと非フッ素セグメントからなるフッ素系ブロック共重合体の前記含フッ素セグメントが5〜95重量%であることを特徴とする第1又は第2の発明に記載の硬化性樹脂組成物である。
第4の発明は、前記硬化性樹脂100重量部に対して、前記フッ素系ブロック共重合体0.01〜50重量部を含有することを特徴とする第1から第3の発明のうちいずれかの硬化性樹脂組成物である。
第5の発明は、第1から第4の発明のうちのいずれかの硬化性樹脂組成物を硬化させて得られることを特徴とする硬化性樹脂の硬化成形物である。
第6の発明は、硬化時に加熱成形して得られることを特徴とする第5の発明の硬化性樹脂の硬化成形物である。
That is, the first invention is a curable resin composition comprising a fluorine-based block copolymer comprising a fluorine-containing segment and a non-fluorine segment, a curable resin, and a low shrinkage agent, wherein the fluorine-containing segment Is a fluorine-containing monomer represented by the following general formula (I) having a C6 perfluoroalkyl group,
The non-fluorine segment comprises 40 to 41.1 wt% methyl methacrylate, 40 to 41.1 wt% butyl methacrylate, 16.7 wt% 2-hydroxyethyl methacrylate, and 1.1 to 3.3 methacrylic acid. A copolymer consisting of 100% by weight in total,
The low shrinkage agent is a polystyrene-based resin, and is contained in an amount of 1 to 150 parts by weight with respect to 100 parts by weight of the curable resin.
(In the general formula (I), R1 is a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom, and R2 is an aliphatic group having 1 or more carbon atoms.)
The second invention is a curable resin composition comprising a fluorine-based block copolymer comprising a fluorine-containing segment and a non-fluorine segment, and a curable resin, wherein the fluorine-containing single monomer constituting the fluorine-containing segment Is a fluorine-containing monomer represented by the above general formula (I) having a perfluoroalkyl group having 6 carbon atoms,
The non-fluorine segment comprises 40 to 41.1 wt% methyl methacrylate, 40 to 41.1 wt% butyl methacrylate, 16.7 wt% 2-hydroxyethyl methacrylate, and 1.1 to 3.3 methacrylic acid. A copolymer consisting of 100% by weight in total,
It is a curable resin composition characterized by not containing a low shrinkage agent.
The third invention is the curing according to the first or second invention, characterized in that the fluorine-containing segment of the fluorine-based block copolymer comprising a fluorine-containing segment and a non-fluorine segment is 5 to 95% by weight. It is an adhesive resin composition.
4th invention contains 0.01-50 weight part of said fluorine-type block copolymers with respect to 100 weight part of said curable resin, Any one of 1st-3rd invention characterized by the above-mentioned. The curable resin composition.
A fifth invention is a curable resin cured product obtained by curing the curable resin composition of any of the first to fourth inventions.
A sixth invention is a cured molded product of the curable resin according to the fifth invention, which is obtained by heat molding at the time of curing.
本発明によれば、撥水撥油性を確保するとともに、表面外観および防汚性に優れた硬化性樹脂成形物およびその硬化成形物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, while ensuring water and oil repellency, the curable resin molding excellent in surface appearance and antifouling property, and its cured molding can be provided.
以下に、この発明の実施の形態について、より詳細に説明する。本発明の硬化性樹脂組成物(以下、単に樹脂組成物と称することがある)は、フッ素系ブロック共重合体と、硬化性樹脂とを含有する樹脂組成物である。また、硬化成形物とは、樹脂組成物を硬化させて得られるものである。その形態としては、それ単独で成り立つものに加え、物品の表面を被覆するものや、基材に含浸させて硬化させたもの等も含む。 Hereinafter, embodiments of the present invention will be described in more detail. The curable resin composition of the present invention (hereinafter sometimes simply referred to as a resin composition) is a resin composition containing a fluorine-based block copolymer and a curable resin. The cured molded product is obtained by curing a resin composition. As the form, in addition to what is formed by itself, the form which covers the surface of an article | item, the thing which impregnated the base material and hardened | cured are included.
[フッ素系ブロック共重合体]
フッ素系ブロック共重合体とは、含フッ素セグメントと、非フッ素セグメントとからなるブロック共重合体(ブロックポリマー)である。
[Fluoro-based block copolymer]
The fluorine-based block copolymer is a block copolymer (block polymer) composed of a fluorine-containing segment and a non-fluorine segment.
含フッ素セグメントは、含フッ素単量体の単独重合体、または含フッ素単量体と非フッ素系単量体との共重合体のいずれかで構成される。含フッ素セグメントを構成する含フッ素単量体は、炭素数6のパーフルオロ基を有し、下記一般式(I)で示される。 The fluorine-containing segment is composed of either a homopolymer of a fluorine-containing monomer or a copolymer of a fluorine-containing monomer and a non-fluorine monomer. The fluorine-containing monomer constituting the fluorine-containing segment has a C6 perfluoro group and is represented by the following general formula (I).
上記一般式(I)において、R1は水素原子、メチル基、フッ素原子、塩素原子である。 In the general formula (I), R 1 is a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom.
上記一般式(I)において、R2は、炭素数1以上の脂肪族基である。好ましくは炭素数1〜50のアルキレン基、さらに好ましくは炭素数1〜4、18〜24のアルキレン基である。 In the general formula (I), R 2 is an aliphatic group having 1 or more carbon atoms. An alkylene group having 1 to 50 carbon atoms is preferable, and an alkylene group having 1 to 4 carbon atoms and 18 to 24 carbon atoms is more preferable.
また、含フッ素セグメントとして、含フッ素単量体と非フッ素系単量体との共重合体を形成するために使用される非フッ素系単量体は、公知のフッ素を含有しないラジカル重合可能な単量体の全てが含まれる。含フッ素単量体と非フッ素系単量体との共重合体で構成される含フッ素セグメントの場合、含フッ素セグメント中に占める含フッ素単量体に基づく重合部分の割合は、80重量%以上、好ましくは85重量%以上、更に好ましくは95重量%以上である。80重量%未満では、十分な撥水撥油性を発現するのは困難となる傾向にある。 Further, as a fluorine-containing segment, a non-fluorine monomer used for forming a copolymer of a fluorine-containing monomer and a non-fluorine monomer can be radically polymerized without containing a known fluorine. All of the monomers are included. In the case of a fluorinated segment composed of a copolymer of a fluorinated monomer and a non-fluorinated monomer, the proportion of the polymerized portion based on the fluorinated monomer in the fluorinated segment is 80% by weight or more. It is preferably 85% by weight or more, more preferably 95% by weight or more. If it is less than 80% by weight, it tends to be difficult to develop sufficient water and oil repellency.
非フッ素セグメントは、非フッ素系単量体のみ、あるいは非フッ素系単量体を主体として形成される。非フッ素セグメントの形成に用いられる非フッ素系単量体は、公知のフッ素を含有しないラジカル重合可能な単量体の全てが含まれる。また含フッ素セグメントとして構成される含フッ素単量体と非フッ素系単量体との共重合体を形成するために使用された非フッ素系単量体と同一のものが使用可能である。 The non-fluorine segment is formed mainly of a non-fluorine monomer alone or a non-fluorine monomer. Non-fluorinated monomers used for forming the non-fluorine segment include all known radically polymerizable monomers not containing fluorine. Moreover, the same thing as the non-fluorine-type monomer used in order to form the copolymer of the fluorine-containing monomer comprised as a fluorine-containing segment and a non-fluorine-type monomer can be used.
これらの中では、十分な重合転化率が得られ、かつ、硬化性樹脂成分との相容性を確保し、そして硬化成形物の撥水性を損なわない単量体として、下記一般式(A)の化合物やその他の非フッ素系単量体がある。これらの一種又は二種以上を組み合わせて使用される。 Among these, as a monomer that provides a sufficient polymerization conversion rate, ensures compatibility with the curable resin component, and does not impair the water repellency of the cured molded product, the following general formula (A) And other non-fluorinated monomers. These are used alone or in combination of two or more.
上記一般式(A)のR3は水素原子、またはメチル基である。R4は炭素数1〜22のアルキル基若しくは置換アルキル基、炭素数3〜15のシクロアルキル基若しくは置換シクロアルキル基またはフェニル基若しくは置換フェニル基を表す。 R3 in the general formula (A) is a hydrogen atom or a methyl group. R4 represents an alkyl group or substituted alkyl group having 1 to 22 carbon atoms, a cycloalkyl group or substituted cycloalkyl group having 3 to 15 carbon atoms, a phenyl group or a substituted phenyl group.
上記一般式(A)の具体例として、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n−ブチル、(メタ)アクリル酸t−ブチル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸ヘキサデシル、(メタ)アクリル酸オクタデシル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸ヒドロキシエチル、(メタ)アクリル酸ヒドロキシプロピル、(メタ)アクリル酸グリシジル、(メタ)アクリル酸ベンジル、(メタ)アクリルアミド、(メタ)アクリル酸アミドN,N−ジメチル、N−メチロール(メタ)アクリルアミド、N−(メタ)アクリロイルモルホリン、(メタ)アクリル酸、(メタ)アクリルニトリル、酢酸ビニル、スチレン、メトキシスチレン、N−メチルマレイミド、N−エチルマレイミド、N−フェニルマレイミド、フマル酸ジイソプロピル、フマル酸ジt−ブチル、フマル酸ジシクロヘキシル、フマル酸ジベンジル、イタコン酸ジメチル等が好ましいものとして挙げられる。 Specific examples of the general formula (A) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, dodecyl (meth) acrylate, (Meth) acrylic acid hexadecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid hydroxyethyl, (meth) acrylic acid hydroxypropyl, (meth) acrylic Glycidyl acid, benzyl (meth) acrylate, (meth) acrylamide, (meth) acrylic acid amide N, N-dimethyl, N-methylol (meth) acrylamide, N- (meth) acryloylmorpholine, (meth) acrylic acid, ( (Meth) acrylonitrile, vinyl acetate, styrene, methoxystyrene, - methyl maleimide, N- ethylmaleimide, N- phenylmaleimide, diisopropyl fumarate, di-t- butyl, dicyclohexyl fumarate, dibenzyl fumarate, be mentioned as dimethyl itaconate and the like are preferable.
フッ素系ブロック共重合体中の含フッ素セグメントの割合は5〜95重量%、好ましくは10〜70重量%、更に好ましくは20〜50重量%である。含フッ素セグメントが5重量%未満では含フッ素セグメントとしての性能、即ち、撥水撥油性が十分に得られない。また95重量%を超えると、硬化性樹脂成分との相容性を確保することが困難になる傾向にある。 The proportion of the fluorine-containing segment in the fluorine-based block copolymer is 5 to 95% by weight, preferably 10 to 70% by weight, and more preferably 20 to 50% by weight. When the fluorine-containing segment is less than 5% by weight, the performance as the fluorine-containing segment, that is, water / oil repellency cannot be sufficiently obtained. If it exceeds 95% by weight, it tends to be difficult to ensure compatibility with the curable resin component.
フッ素系ブロック共重合体の分子量に関しては、数平均分子量で5,000〜1,000,000が良く、好ましくは10,000〜300,000、更に好ましくは10,000〜100,000である。5,000未満では、フッ素の性能、即ち、撥水撥油性が十分には発揮されなくなり、また1,000,000を超えると製造することそのものが困難となる傾向にある。 Regarding the molecular weight of the fluorine-based block copolymer, the number average molecular weight is preferably 5,000 to 1,000,000, preferably 10,000 to 300,000, and more preferably 10,000 to 100,000. If it is less than 5,000, the performance of fluorine, that is, water / oil repellency, is not sufficiently exhibited, and if it exceeds 1,000,000, it tends to be difficult to produce.
次に、フッ素系ブロック共重合体の製造方法について説明する。フッ素系ブロック共重合体は、例えば、塊状重合法、懸濁重合法、溶液重合法又はエマルション重合法等により、含フッ素セグメントを構成する含フッ素単量体、又は含フッ素単量体と非フッ素系単量体と、非フッ素セグメントを構成する非フッ素系単量体とを混合し、重合開始剤を添加して合成することができる。重合開始剤としては、有機過酸化物や無機過酸化物、アゾ化合物等を用いることができる。なかでも、ポリメリックペルオキシド用いると、触媒等を用いることなく、パーオキサイド結合含有共重合体中のパーオキサイド結合の開裂を制御することで効率よくブロック共重合体を得ることができるという点で好ましい。例えば、このフッ素系ブロック共重合体は、ポリメリックペルオキシドを重合開始剤とした公知の製造プロセス(例えば特公平5−41668号公報、特公平5−59942号公報)により製造することができる。 Next, the manufacturing method of a fluorine-type block copolymer is demonstrated. The fluorine-based block copolymer is, for example, a fluorine-containing monomer constituting a fluorine-containing segment or a fluorine-containing monomer and a non-fluorine by a bulk polymerization method, a suspension polymerization method, a solution polymerization method or an emulsion polymerization method. It can be synthesized by mixing a monomer and a non-fluorine monomer constituting a non-fluorine segment, and adding a polymerization initiator. As the polymerization initiator, an organic peroxide, an inorganic peroxide, an azo compound, or the like can be used. Among these, the use of polymeric peroxide is preferable in that a block copolymer can be efficiently obtained by controlling the cleavage of the peroxide bond in the peroxide bond-containing copolymer without using a catalyst or the like. For example, this fluorine-based block copolymer can be produced by a known production process using, for example, polymeric peroxide as a polymerization initiator (for example, Japanese Patent Publication Nos. 5-41668 and 5-59942).
上記フッ素系ブロック共重合体の製造時に用いられるポリメリックペルオキシドとは1分子中に2個以上のペルオキシ結合を持つ化合物である。ポリメリックペルオキシドとしては、特公平5−59942号公報に記載されている各種ポリメリックペルオキシドの一種または二種以上を使用することができる。下記式(1)、(2)および(3)で示されるものは好ましい例として使用できる。 The polymeric peroxide used in the production of the above-mentioned fluorine-based block copolymer is a compound having two or more peroxy bonds in one molecule. As the polymer peroxide, one or more of various polymer peroxides described in JP-B-5-59942 can be used. Those represented by the following formulas (1), (2) and (3) can be used as preferred examples.
(式中nは1〜10の整数、mは2〜20の整数で表されるポリメリックペルオキシド。) (In the formula, n is an integer of 1 to 10, and m is a polymeric peroxide represented by an integer of 2 to 20.)
(式中nは2〜20の整数で表されるポリメリックペルオキシド。) (In the formula, n is a polymeric peroxide represented by an integer of 2 to 20.)
(式中nは3〜20の整数で表されるジアシル型ポリメリックペルオキシド。) (Wherein n is a diacyl polymeric peroxide represented by an integer of 3 to 20)
フッ素系ブロック共重合体は、前記のポリメリックペルオキシドを用いて、通常の塊状重合法、懸濁重合法、溶液重合法そしてエマルション重合法によって容易に得られる。例えば、溶液重合法の場合、第1工程としてまずポリメリックペルオキシドを重合開始剤として用い、非フッ素系セグメントを形成する前記非フッ素系単量体を溶液中で重合することにより、連鎖中にパーオキサイド結合が導入されたパーオキサイド結合含有非フッ素系重合体を得る。 The fluorine-based block copolymer can be easily obtained by the usual bulk polymerization method, suspension polymerization method, solution polymerization method and emulsion polymerization method using the above-mentioned polymeric peroxide. For example, in the case of a solution polymerization method, as a first step, first, a polymer peroxide is used as a polymerization initiator, and the non-fluorine monomer that forms a non-fluorine segment is polymerized in a solution, whereby a peroxide is introduced into the chain. A peroxide bond-containing non-fluorinated polymer into which bonds are introduced is obtained.
次に、第2工程において、第1工程で得られた溶液中にフッ素系単量体を加えて重合を行うと、パーオキサイド結合含有非フッ素系重合体中のパーオキサイド結合が開裂し、効率よくブロック共重合体を得ることができる。なお、上記のような二段階重合において、第1工程の非フッ素系単量体を第2工程に、そして第2工程のフッ素系単量体を第1工程に用いても良い。 Next, in the second step, when the polymerization is carried out by adding a fluorine monomer to the solution obtained in the first step, the peroxide bond in the peroxide bond-containing non-fluorine polymer is cleaved, and the efficiency A block copolymer can be obtained well. In the two-stage polymerization as described above, the non-fluorine monomer in the first step may be used in the second step, and the fluorine monomer in the second step may be used in the first step.
[硬化性樹脂]
硬化性樹脂とは公知の全ての硬化性樹脂が対象であり、例えば、人工大理石、塗料やゲルコート剤に用いられる公知の全ての樹脂等が対象である。用いられる硬化性樹脂の具体例として、不飽和ポリエステル樹脂、ビニルエステル樹脂、及び硬化性(メタ)アクリル系樹脂等の樹脂を挙げることができる。なお、硬化性樹脂は単独でも、また、二種類以上を混合して用いても良い。
[Curable resin]
The curable resin includes all known curable resins, and includes, for example, all known resins used for artificial marble, paints, and gel coating agents. Specific examples of the curable resin used include resins such as unsaturated polyester resins, vinyl ester resins, and curable (meth) acrylic resins. The curable resin may be used alone or in combination of two or more.
前記不飽和ポリエステル樹脂とは、不飽和二塩基酸、飽和二塩基酸、および多価アルコールを特定の割合で加熱・脱水縮合させて得られる不飽和ポリエステルをラジカル重合性単量体に溶解させた液状樹脂であり、公知のものがいずれも使用できる。 The unsaturated polyester resin is obtained by dissolving an unsaturated polyester obtained by heating and dehydrating condensation of an unsaturated dibasic acid, a saturated dibasic acid, and a polyhydric alcohol at a specific ratio in a radical polymerizable monomer. Any known resin can be used.
不飽和二塩基酸としては例えば無水マレイン酸、マレイン酸、フマル酸、イタコン酸等が挙げられ、これらの一種または二種以上より選択される。飽和二塩基酸としては、例えば無水フタル酸、オルトフタル酸、イソフタル酸、テレフタル酸等の芳香族二塩基酸、アジピン酸、コハク酸、セバシン酸等の脂肪族二塩基酸等が挙げられ、これら群の一種または二種以上より選択される。 Examples of the unsaturated dibasic acid include maleic anhydride, maleic acid, fumaric acid, itaconic acid and the like, and are selected from one or more of these. Examples of the saturated dibasic acid include aromatic dibasic acids such as phthalic anhydride, orthophthalic acid, isophthalic acid, and terephthalic acid, and aliphatic dibasic acids such as adipic acid, succinic acid, and sebacic acid. Selected from one or more of the following.
多価アルコールとしては、例えばエチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、1,4−ブタンジオール、1,6−ヘキサンジオール、ネオペンチルグリコール、ビスフェノールA、水素化ビスフェノールA、水素化ビスフェノールAのエチレンオキサイドまたはプロピレンオキサイド付加物等が挙げられ、これら群の一種または二種以上より選択される。 Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, bisphenol A, hydrogenated bisphenol A, and hydrogenated bisphenol A. An ethylene oxide or a propylene oxide adduct is mentioned, It selects from 1 type, or 2 or more types of these groups.
ラジカル重合性単量体としては、前記一般式(A)の単量体やその他の非フッ素系単量体やフッ素系単量体等が挙げられ、これら群の一種または二種以上より選択される。不飽和ポリエステル樹脂中の不飽和ポリエステルの配合割合は30〜80重量%が好ましい。30重量%未満では硬化物の機械的特性が低下する傾向にある。また、80重量%を超えると不飽和ポリエステル樹脂の粘度が高くなり、作業性が低下する傾向にある。 Examples of the radical polymerizable monomer include the monomer of the general formula (A), other non-fluorine monomers, fluorine monomers, and the like, and are selected from one or more of these groups. The The blending ratio of the unsaturated polyester in the unsaturated polyester resin is preferably 30 to 80% by weight. If it is less than 30% by weight, the mechanical properties of the cured product tend to deteriorate. Moreover, when it exceeds 80 weight%, the viscosity of unsaturated polyester resin will become high, and it exists in the tendency for workability | operativity to fall.
ビニルエステル樹脂とは、1分子中に2個以上のエポキシ基を有するエポキシ樹脂のエポキシ基にアクリル酸やメタクリル酸等の不飽和一塩基酸またはマレイン酸やフマル酸等の不飽和二塩基酸のモノエステルを開環付加させた反応生成物をラジカル重合性単量体に溶解させた液状樹脂であり、公知のものがいずれも使用できる。 The vinyl ester resin is an epoxy group of an epoxy resin having two or more epoxy groups in one molecule and an unsaturated monobasic acid such as acrylic acid or methacrylic acid or an unsaturated dibasic acid such as maleic acid or fumaric acid. It is a liquid resin in which a reaction product obtained by ring-opening addition of a monoester is dissolved in a radical polymerizable monomer, and any known resin can be used.
前記エポキシ樹脂の具体例としては、例えばビスフェノールA、ビスフェノールFまたはビスフェノールSとエピクロルヒドリンとから合成されるビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂またはビスフェノールS型エポキシ樹脂等のビスフェノール型エポキシ樹脂;フェノールとホルムアルデヒドを酸性触媒存在下反応させて得られるいわゆるフェノールノボラック樹脂とエピクロルヒドリンとから合成されるフェノールノボラック型エポキシ樹脂;及びクレゾールとホルムアルデヒドとを酸性触媒存在下で反応させて得られるいわゆるクレゾールノボラック樹脂とエピクロルヒドリンとから合成されるクレゾールノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂等が挙げられる。 Specific examples of the epoxy resin include, for example, bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin or bisphenol S type epoxy resin synthesized from bisphenol A, bisphenol F or bisphenol S and epichlorohydrin; phenol A phenol novolac-type epoxy resin synthesized from a so-called phenol novolak resin and epichlorohydrin obtained by reacting aldehyde with formaldehyde in the presence of an acidic catalyst; and a so-called cresol novolak resin obtained by reacting cresol and formaldehyde in the presence of an acidic catalyst Examples thereof include novolak-type epoxy resins such as cresol novolak-type epoxy resins synthesized from epichlorohydrin.
前記ラジカル重合性単量体としては、前記不飽和ポリエステル樹脂における単量体がいずれも使用でき、これらの群の一種又は二種以上より選択される。ビニルエステル樹脂中の不飽和エポキシ樹脂の配合割合は30〜90重量%であるのが好ましい。30重量%未満では、これより得られるビニルエステル樹脂の硬化物の耐蝕性や耐熱性が悪化する傾向にある。一方、90重量%を越える場合には、これより得られるビニルエステル樹脂の粘度が高くなり、作業性が悪化する傾向にある。 As the radical polymerizable monomer, any of the monomers in the unsaturated polyester resin can be used, and the monomer is selected from one or more of these groups. The blending ratio of the unsaturated epoxy resin in the vinyl ester resin is preferably 30 to 90% by weight. If it is less than 30% by weight, the corrosion resistance and heat resistance of the cured vinyl ester resin obtained therefrom tend to deteriorate. On the other hand, when it exceeds 90% by weight, the viscosity of the vinyl ester resin obtained from this increases, and the workability tends to deteriorate.
硬化性(メタ)アクリル系樹脂とは、通常(メタ)アクリル樹脂と1分子中に不飽和基を2個以上有するラジカル重合性単量体(以下、架橋剤と略記する。)を溶媒としてのラジカル重合性単量体に溶解させた(メタ)アクリルシラップを指し、公知のものがいずれも使用できる。
(メタ)アクリル樹脂は、(メタ)アクリル酸エステルを有機過酸化物あるいはアゾ化合物で重合することにより得られる。(メタ)アクリル酸エステルとしては、公知の(メタ)アクリル酸エステルがいずれも使用できるが、具体的には、例えば上記一般式(A)の単量体等が挙げられる。これらの(メタ)アクリル酸エステルは、通常一種または二種以上を選択して用いるが、特にメタクリル酸メチルを50重量%以上含有することが好ましい。メタクリル酸メチルを50重量%以上含有することにより、耐候性や透明性、表面光沢に優れる硬化成形物が得られる。
The curable (meth) acrylic resin is usually a (meth) acrylic resin and a radical polymerizable monomer having two or more unsaturated groups in one molecule (hereinafter abbreviated as a crosslinking agent) as a solvent. It refers to (meth) acrylic syrup dissolved in a radical polymerizable monomer, and any known one can be used.
The (meth) acrylic resin is obtained by polymerizing (meth) acrylic acid ester with an organic peroxide or an azo compound. As the (meth) acrylic acid ester, any known (meth) acrylic acid ester can be used. Specific examples include the monomer represented by the general formula (A). These (meth) acrylic acid esters are usually used by selecting one or two or more kinds, and it is particularly preferable to contain 50% by weight or more of methyl methacrylate. By containing 50% by weight or more of methyl methacrylate, a cured molded article having excellent weather resistance, transparency, and surface gloss can be obtained.
また、(メタ)アクリル樹脂の他の構成成分として、例えば(メタ)アクリル酸、クロトン酸等の不飽和一塩基酸、マレイン酸、フマル酸、イタコン酸等の不飽和二塩基酸、これら不飽和二塩基酸のモノエステル、スチレン、ビニルトルエン、α−メチルスチレン、t−ブチルスチレン、クロルスチレン等のスチレン誘導体、酢酸ビニル、プロピオン酸ビニル等のビニルエステル類を30重量%以下の範囲で含有させることもできる。 Further, as other components of the (meth) acrylic resin, for example, unsaturated monobasic acids such as (meth) acrylic acid and crotonic acid, unsaturated dibasic acids such as maleic acid, fumaric acid and itaconic acid, these unsaturated A monoester of dibasic acid, styrene derivatives such as styrene, vinyl toluene, α-methyl styrene, t-butyl styrene, chlorostyrene, and vinyl esters such as vinyl acetate and vinyl propionate are included in an amount of 30% by weight or less. You can also.
溶媒としてのラジカル重合性単量体としては、前記不飽和ポリエステル樹脂における単量体がいずれも使用でき、これらの群の一種又は二種以上より選択される。 As the radical polymerizable monomer as the solvent, any of the monomers in the unsaturated polyester resin can be used, and it is selected from one or more of these groups.
前記架橋剤の具体例としては、例えばエチレングリコールジ(メタ)アクリレート、1,3−プロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート等のアルキレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジビニルベンゼン、アリル(メタ)アクリレート、フタル酸ジアリル、(メタ)アクリル酸ビニル、クロトン酸ビニル等が挙げられ、これらの群より一種または二種以上が選択される。 Specific examples of the crosslinking agent include, for example, ethylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, alkylene glycol di (meth) acrylate such as neopentyl glycol di (meth) acrylate, and diethylene glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, divinylbenzene, allyl (meth) acrylate, diallyl phthalate, vinyl (meth) acrylate, vinyl crotonate, etc., one or two of these groups The above is selected.
溶媒としてのラジカル重合性単量体及び架橋剤の総量中における架橋剤の含有量は、好ましくは1〜20重量%であり、より好ましくは3〜15重量%である。架橋剤の含有量が1重量%未満の場合には、これより得られる硬化成形物の耐熱性が悪化する傾向にある。一方、架橋剤の含有量が20重量%を越える場合には、これより得られる硬化成形物が脆くなる傾向にある。 The content of the crosslinking agent in the total amount of the radical polymerizable monomer and the crosslinking agent as a solvent is preferably 1 to 20% by weight, more preferably 3 to 15% by weight. When the content of the crosslinking agent is less than 1% by weight, the heat resistance of a cured molded product obtained therefrom tends to deteriorate. On the other hand, when the content of the crosslinking agent exceeds 20% by weight, the cured molded product obtained therefrom tends to be brittle.
硬化性(メタ)アクリル系樹脂中の(メタ)アクリル樹脂の配合割合は10〜50重量%であることが好ましい。(メタ)アクリル樹脂が10重量%未満の場合には、これより得られる硬化物にクラックが入り易くなる傾向にある。(メタ)アクリル樹脂が50重量%を越える場合には、熱硬化性(メタ)アクリル系樹脂の粘度が高くなり、作業性が悪化する傾向にある。 The blending ratio of the (meth) acrylic resin in the curable (meth) acrylic resin is preferably 10 to 50% by weight. When the (meth) acrylic resin is less than 10% by weight, the cured product obtained from this tends to crack. When the (meth) acrylic resin exceeds 50% by weight, the viscosity of the thermosetting (meth) acrylic resin increases, and the workability tends to deteriorate.
本発明の樹脂組成物では、フッ素系ブロック共重合体の一種または二種類以上を混ぜ合わせて使用することができる。ただし、このフッ素系ブロック共重合体の使用量は硬化性樹脂100重量部に対して0.01〜50重量部とするのが好ましい。0.01重量部未満では撥水撥油性の発現が困難となり、また、50重量部を超えると樹脂成形物の強度を損なう傾向にある。より好ましくは0.1〜10重量部、更に好ましくは0.1〜5重量部である。 In the resin composition of the present invention, one type or two or more types of fluorine-based block copolymers can be mixed and used. However, the amount of the fluorine-based block copolymer used is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the curable resin. If it is less than 0.01 part by weight, it is difficult to develop water and oil repellency, and if it exceeds 50 parts by weight, the strength of the resin molded product tends to be impaired. More preferably, it is 0.1-10 weight part, More preferably, it is 0.1-5 weight part.
硬化性樹脂の使用量は、樹脂組成物中10〜85重量%であるのが好ましく、より好ましくは15〜45重量%、更に好ましくは20〜40重量%である。10重量%未満では硬化成形物の強度を損なう傾向にあり、また、60重量%を超えると成形時の収縮が大きくなることから成形そのものが困難になる傾向にある。 The amount of the curable resin used is preferably 10 to 85% by weight in the resin composition, more preferably 15 to 45% by weight, and still more preferably 20 to 40% by weight. If it is less than 10% by weight, the strength of the cured molded product tends to be impaired, and if it exceeds 60% by weight, shrinkage during molding tends to be large, and molding itself tends to be difficult.
樹脂組成物中には、用途等に応じて、本発明の効果を阻害しない範囲で、各種添加物を添加することもできる。 Various additives can also be added to the resin composition within a range that does not impair the effects of the present invention, depending on the application.
例えば、低収縮剤を添加することができる。低収縮剤とは、熱硬化性樹脂組成物を熱硬化する際の成形収縮を抑制するための添加剤である。低収縮剤としては、ポリスチレン系低収縮剤、アクリル系低収縮剤などが挙げられる。中でもポリスチレン系低収縮剤は、フッ素系ブロック共重合体の含フッ素セグメントが硬化成形物表面に配向しやすくなる。そのため、撥水撥油性が発現しやすいという点でポリスチレン系低収縮剤が好ましい。ポリスチレン系低収縮剤としては、ポリスチレン、セグメントとしてポリスチレンを10〜99.9重量部含んだブロック共重合体、架橋ポリスチレン、これらの混合物が挙げられる。これらの低収縮剤はいずれも反応性基を有していてもよい。また、上記ポリスチレン系低収縮剤にポリスチレン分離防止剤を0.1〜50重量%含有した混合物も含まれる。上記ポリスチレン分離防止剤とは、ポリスチレンの凝集を抑えて硬化性樹脂組成物中にポリスチレンを均一に分散させるものであり、硬化性樹脂とポリスチレンの相容性に優れたブロック共重合体やグラフト共重合体などが挙げられる。また、低収縮剤の配合比は、硬化性樹脂100重量部に対して好ましくは1〜150重量部、より好ましくは5〜100重量部である。1重量部以下では成形収縮を抑制することが困難となり、また、150重量部を超えると成形物の強度を損なう傾向にある。 For example, a low shrinkage agent can be added. The low shrinkage agent is an additive for suppressing molding shrinkage when thermosetting the thermosetting resin composition. Examples of the low shrinkage agent include polystyrene low shrinkage agents and acrylic low shrinkage agents. Among them, the polystyrene-based low shrinkage agent tends to orient the fluorine-containing segment of the fluorine-based block copolymer on the surface of the cured molded product. Therefore, a polystyrene-based low shrinkage agent is preferable in that water and oil repellency is easily exhibited. Examples of the polystyrene-based low shrinkage agent include polystyrene, a block copolymer containing 10 to 99.9 parts by weight of polystyrene as a segment, crosslinked polystyrene, and a mixture thereof. Any of these low shrinkage agents may have a reactive group. Moreover, the mixture which contains 0.1-50 weight% of polystyrene separation inhibitors in the said polystyrene-type low shrinkage agent is also contained. The above-mentioned polystyrene separation inhibitor is an agent that suppresses aggregation of polystyrene and uniformly disperses polystyrene in the curable resin composition, and is a block copolymer or graft copolymer having excellent compatibility between the curable resin and polystyrene. A polymer etc. are mentioned. Moreover, the compounding ratio of the low shrinkage agent is preferably 1 to 150 parts by weight, more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the curable resin. If it is 1 part by weight or less, it is difficult to suppress molding shrinkage, and if it exceeds 150 parts by weight, the strength of the molded product tends to be impaired.
また、成形物の機械的強度、熱伝導性、耐熱性などの物性向上のために、充填剤を添加することもできる。充填剤としては公知の全ての無機ないし有機の充填剤が使用可能であり、特に限定はされない。例えば、水酸化アルミニウム、ケイ酸アルミニウム、ガラスフリット、シリカ、水酸化カルシウム、ケイ酸カルシウム、炭酸カルシウム、亜硫酸カルシウム、硫酸カルシウム、水酸化マグネシウム、硫酸バリウム、酸化チタン、三酸化アンチモン、粉末タルク、粉末石英、方解石、珪藻土、粘土鉱物質、粉末チョーク、大理石、石灰岩、ホウ砂等を好ましい充填剤として挙げることができる。なお、充填剤は単独でも良いし、また、二種類以上を混合して用いても良い。粒径は、1〜200μmであるのが好ましく、より好ましくは5〜150μm、更に好ましくは10〜80μmである。1μm未満では、耐熱水性が低下する傾向にあり、200μmを越えると硬化成形物の表面平滑性が損なわれる傾向にある。 In addition, a filler can be added to improve physical properties such as mechanical strength, thermal conductivity, and heat resistance of the molded product. As the filler, all known inorganic or organic fillers can be used and are not particularly limited. For example, aluminum hydroxide, aluminum silicate, glass frit, silica, calcium hydroxide, calcium silicate, calcium carbonate, calcium sulfite, calcium sulfate, magnesium hydroxide, barium sulfate, titanium oxide, antimony trioxide, powder talc, powder Quartz, calcite, diatomaceous earth, clay minerals, powdered chalk, marble, limestone, borax and the like can be mentioned as preferred fillers. In addition, a filler may be individual and may be used in mixture of 2 or more types. The particle size is preferably 1 to 200 μm, more preferably 5 to 150 μm, and still more preferably 10 to 80 μm. If it is less than 1 μm, the hot water resistance tends to decrease, and if it exceeds 200 μm, the surface smoothness of the cured molded product tends to be impaired.
この無機充填剤の使用量は樹脂組成物中35〜85重量%であるのが好ましく、より好ましくは50〜80重量%、更に好ましくは55〜75重量%である。35重量%未満では成形時の収縮が大きくなることから成形そのものが困難となり、また、85重量%を超えると樹脂成形物の強度を損なう傾向にある。 The amount of the inorganic filler used is preferably 35 to 85% by weight in the resin composition, more preferably 50 to 80% by weight, and still more preferably 55 to 75% by weight. If it is less than 35% by weight, the shrinkage at the time of molding increases, so that molding itself becomes difficult. If it exceeds 85% by weight, the strength of the resin molded product tends to be impaired.
その他、例えば、抗菌剤、染料、顔料、紫外線吸収剤、架橋剤、酸化防止剤、増粘剤、内部離型剤、ガラス繊維、樹脂系繊維等を加えることもできる。 In addition, for example, antibacterial agents, dyes, pigments, ultraviolet absorbers, crosslinking agents, antioxidants, thickeners, internal mold release agents, glass fibers, resin fibers, and the like can be added.
以上の各成分を含有する樹脂組成物は、硬化剤を用いて硬化させて硬化成形物を得ることができる。その場合の硬化剤とは、例えばケトンペルオキシド類、ペルオキシケタール類、ヒドロペルオキシド類、ジアルキルペルオキシド類、ジアシルペルオキシド類、ペルオキシジカーボネート類、ペルオキシエステル類等の各種公知の有機過酸化物である。 The resin composition containing each of the above components can be cured using a curing agent to obtain a cured molded product. Examples of the curing agent in this case include various known organic peroxides such as ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters.
硬化の条件は用いられる有機過酸化物により異なるが通常70〜180℃で0.5〜60分である。また、過酸化物化合物を分解させるための触媒、例えば、N,N−ジブチルアニリンやトリブチルアミン等の第三級アミン、アセト酢酸エチルやアセト酢酸プロピル等のアセト酢酸エステル、ナフテン酸コバルトやオクチル酸コバルトなどのコバルト塩等を用いる場合は、室温付近でも充分に硬化させることができる。具体的には0〜80℃の条件で硬化させることが可能である。この触媒の使用量としては樹脂組成物全量に対し0.005〜0.2重量%が適当である。 The curing conditions vary depending on the organic peroxide used, but are usually 70 to 180 ° C. and 0.5 to 60 minutes. Catalysts for decomposing peroxide compounds, for example, tertiary amines such as N, N-dibutylaniline and tributylamine, acetoacetates such as ethyl acetoacetate and propylacetoacetate, cobalt naphthenate and octylic acid When a cobalt salt such as cobalt is used, it can be sufficiently cured even near room temperature. Specifically, it can be cured under conditions of 0 to 80 ° C. The amount of the catalyst used is suitably 0.005 to 0.2% by weight based on the total amount of the resin composition.
硬化させる具体的な方法としては、目的の硬化成形物を得られれば特に限定されるものではないが、例えば、室温におけるハンドレイアップ成形法、スプレーアップ成形法、SMC・BMCプレス法、室温またはそれ以上の温度におけるレジントランスファーモールディング法、波板・平板の室温以上の温度における連続成形法等のFRP製品を製造するための成形法、室温またはそれ以上の温度における注型法、そしてゲルコート、ライニング、化粧板を製造するためのフローコート法を挙げることができる。 The specific method of curing is not particularly limited as long as the desired cured molded product can be obtained. For example, hand lay-up molding method at room temperature, spray-up molding method, SMC / BMC press method, room temperature or Molding method for manufacturing FRP products such as resin transfer molding at higher temperatures, continuous molding of corrugated plates and flat plates at temperatures above room temperature, casting at room temperature or above, gel coating, lining And a flow coating method for producing a decorative board.
本発明を実施例により更に詳しく説明するが、本発明はこれら実施例により何ら制限を受けるものではない。 The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
まず、表1に示される各製造例のフッ素系ブロック共重合体分散液を得た。製造例1では、はじめに、温度計、撹拌機及び還流冷却管を備えた5リットルの4つ口フラスコに、メチルエチルケトン600gを仕込み、窒素ガスを吹き込みながら70℃に加熱し、それに、メタクリル酸メチル〈MMA〉200g、メタクリル酸ブチル〈BMA〉200g、メタクリル酸2−ヒドロキシエチル〈HEMA〉83gおよびメタクリル酸〈MAA〉17gから成る混合液と、メチルエチルケトン400gおよびポリメリックペルオキシド110gから成る混合液の両液を同時に2時間かけて仕込み、更に4時間重合反応を行った。これにより、非フッ素セグメントを構成するMMA、BMA、HEMA及びMAAの重合体の分散液を得た。得られた非フッ素セグメント中の各単量体の組成比(MMA/BMA/HEMA/MAA)は、表1に示されるとおりである。 First, the fluorine-type block copolymer dispersion liquid of each manufacture example shown by Table 1 was obtained. In Production Example 1, first, 600 g of methyl ethyl ketone was charged into a 5-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, heated to 70 ° C. while blowing nitrogen gas, and methyl methacrylate < MMA> 200 g, butyl methacrylate <BMA> 200 g, 2-hydroxyethyl methacrylate <HEMA> 83 g and methacrylic acid <MAA> 17 g mixed liquid and methylethylketone 400 g and polymeric peroxide 110 g simultaneously. The mixture was charged over 2 hours, and the polymerization reaction was further carried out for 4 hours. Thereby, the dispersion liquid of the polymer of MMA, BMA, HEMA, and MAA which comprises a non-fluorine segment was obtained. The composition ratio (MMA / BMA / HEMA / MAA) of each monomer in the obtained non-fluorine segment is as shown in Table 1.
続いて、メチルエチルケトン850g、フッ素単量体CH2=CHCOO(CH2)2(CF2)5CF3〈FA(C6)〉317g、メタクリル酸メチル〈MMA〉17gの混合液を40分かけて仕込み、1.5時間重合反応を行い、更に80℃で3時間重合反応を行うことで、フッ素系ブロック共重合体(Mw=44000)を含む分散液を得た。得られたフッ素系ブロック共重合体中の非フッ素セグメントと含フッ素セグメントとの組成比は、表1に示されるように、60:40であり、含フッ素セグメントにおけるFA(C6)とNMAの比(FA(C6)/MMA)は、表に示されるように38/2である。 Subsequently, 850 g of methyl ethyl ketone, 317 g of fluorine monomer CH 2 ═CHCOO (CH 2 ) 2 (CF 2 ) 5 CF 3 <FA (C 6 )>, and 17 g of methyl methacrylate <MMA> are taken over 40 minutes. The mixture was charged and subjected to a polymerization reaction for 1.5 hours, and further a polymerization reaction was performed at 80 ° C. for 3 hours to obtain a dispersion containing a fluorine-based block copolymer (Mw = 44000). The composition ratio of the non-fluorine segment and the fluorine-containing segment in the obtained fluorine-based block copolymer is 60:40 as shown in Table 1, and FA (C 6 ) and NMA in the fluorine-containing segment are The ratio (FA (C 6 ) / MMA) is 38/2 as shown in the table.
同様に、製造例1−2〜1−6、2−1〜2−3についても、表1に示させる組成のフッ素系ブロック共重合体を含む分散液を得た。尚、各製造例で用いた含フッ素系単量体は、下記一般式(II)で示され、R1、R2、Rfは表1に示されているとおりである。 Similarly, with respect to Production Examples 1-2 to 1-6 and 2-1 to 2-3, dispersions containing a fluorine-based block copolymer having the composition shown in Table 1 were obtained. The fluorine-containing monomer used in each production example is represented by the following general formula (II), and R1, R2, and Rf are as shown in Table 1.
次に、得られた製造例1−1〜1−6、2−1〜2−3に係るフッ素系ブロック共重合体を含む分散液と以下の硬化性樹脂及び以下の低収縮剤等を用いて、表2に示される組成の実施例及び比較例の各硬化成形物を得た。なお、表2にて示されるフッ素系ブロック共重合体及び低収縮剤の配合量は、硬化性樹脂100重量部に対する重量比で示されている。
なお、フッ素系ブロック共重合体の配合量は分散液の配合量ではなく、フッ素系ブロック共重合体としての配合量である。
Next, using the obtained dispersion containing the fluorine-based block copolymer according to Production Examples 1-1 to 1-6 and 2-1 to 2-3, the following curable resin, the following low shrinkage agent, and the like Thus, each cured molded product of Examples and Comparative Examples having the compositions shown in Table 2 was obtained. In addition, the compounding quantity of the fluorine-type block copolymer shown in Table 2 and a low shrinkage agent is shown by the weight ratio with respect to 100 weight part of curable resin.
In addition, the compounding quantity of a fluorine-type block copolymer is not the compounding quantity of a dispersion liquid but the compounding quantity as a fluorine-type block copolymer.
[硬化性樹脂]
UP(1)不飽和ポリエステル樹脂(ジャパンコンポジット株式会社製、ポリホープ(登録商標)R100AP)
UP(2)不飽和ポリエステル樹脂(ジャパンコンポジット株式会社製、ポリホープ(登録商標)6619)
アクリル アクリル樹脂(日本ユピカ株式会社製、ネオポール(登録商標)8101)
[Curable resin]
UP (1) unsaturated polyester resin (manufactured by Japan Composite Co., Ltd., Polyhope (registered trademark) R100AP)
UP (2) unsaturated polyester resin (manufactured by Japan Composite Co., Ltd., Polyhope (registered trademark) 6619)
Acrylic Acrylic resin (Nippon Iupika Co., Ltd., Neopol (registered trademark) 8101)
[低収縮剤]
PS系(A) PVAc−b−PS=10/90(ポリ酢酸ビニルのセグメント10重量部とポリスチレンのセグメント90重量部から成るブロック共重合体)(日油株式会社製、モディパー(登録商標)SV10B-30)
PS系(B) ポリスチレン95重量部とポリスチレン分離防止剤(BYK製)5重量部の混合物
PS系(C) ポリスチレン70重量部と低収縮剤A30重量部の混合物
PS系(D) PVAc-b-PS=50/50(ポリ酢酸ビニルのセグメント50重量部とポリスチレンのセグメント50重量部から成るブロック共重合体)(日油株式会社製、モディパー(登録商標)SV501)
PS系(E) 反応性基含有架橋ポリスチレン
PVAc ポリ酢酸ビニル
[Low shrinkage agent]
PS system (A) PVAc-b-PS = 10/90 (block copolymer consisting of 10 parts by weight of polyvinyl acetate and 90 parts by weight of polystyrene) (manufactured by NOF Corporation, Modiper (registered trademark) SV10B) -30)
PS system (B) Mixture of 95 parts by weight of polystyrene and 5 parts by weight of polystyrene separation inhibitor (by BYK) PS system (C) Mixture of 70 parts by weight of polystyrene and 30 parts by weight of low shrinkage agent PS system (D) PVAc-b- PS = 50/50 (a block copolymer comprising 50 parts by weight of a polyvinyl acetate segment and 50 parts by weight of a polystyrene segment) (manufactured by NOF Corporation, MODIPER (registered trademark) SV501)
PS (E) Reactive group-containing crosslinked polystyrene PVAc Polyvinyl acetate
[実施例1−1〜1−3、2−1、比較例1−1〜1−3]
実施例1−1、2−1、比較例1−1では、硬化性樹脂100重量部に対して、フッ素系ブロック共重合体、低収縮剤を表2に示される配合比で配合するとともに、硬化剤としてメチルエチルケトンパーオキサイド(日油株式会社製、商品名:パーメックN)2.0重量部、硬化促進剤としてナフテン酸コバルト0.5重両部を加え、撹拌機で15分間混合して液状の硬化性樹脂組成物を得た。そして、PETフィルムを貼付したガラス板上で、調整した樹脂組成物を♯450のチョップドストランドマットに含浸させ、25℃の恒温槽内で30分放置して硬化成形物を得た。
[Examples 1-1 to 1-3, 2-1 and Comparative Examples 1-1 to 1-3]
In Examples 1-1 and 2-1, Comparative Example 1-1, the fluorine-based block copolymer and the low shrinkage agent are blended at a blending ratio shown in Table 2 with respect to 100 parts by weight of the curable resin. Add 2.0 parts by weight of methyl ethyl ketone peroxide (trade name: Permec N, manufactured by NOF Corporation) as a curing agent, and add 0.5 double parts of cobalt naphthenate as a curing accelerator, and mix for 15 minutes with a stirrer to form a liquid A curable resin composition was obtained. Then, the prepared resin composition was impregnated with a chopped strand mat of # 450 on a glass plate on which a PET film was attached, and left in a thermostatic bath at 25 ° C. for 30 minutes to obtain a cured molded product.
[実施例2−2〜2−21、比較例2−1〜2−8]
実施例2−2〜2−21、比較例2−1〜2−8では、硬化性樹脂100重量部に対して、フッ素系ブロック共重合体、低収縮剤を表2に示される配合比で配合するとともに、充填材として炭酸カルシウム粉末(日東粉化工業株式会社製、商品名:NS-100)200重量部、硬化剤としてt−ブチルパーオキシイソプロピルカーボネート(日油株式会社製、商品名:パーブチルI−75)2.0重量部、重合禁止剤としてパラベンゾキノン0.05重量部、内部離型剤としてステアリン酸亜鉛5.0重量部、増粘剤として酸化マグネシウム2.0重量部を加え、撹拌機で15分間混合してペーストを得た。その後、そのペーストをニーダーに移し、ガラス繊維(6mmチョップドストランドマット;日本ガラス繊維株式会社製、商品名:EM450G−1)を内割りで10重量%となるように添加し、ニーダーで5分間混練して硬化性樹脂組成物を得た。得られた硬化性樹脂組成物をポリエチレンフィルムでシート状にはさみ、ロールにて押圧一体化した。この一体化物を40℃の雰囲気下に24時間放置し、SMC(FRP作成過程の複合体)を作製した。得られたSMCを100トンプレスを用い、金型温度145℃/130℃(下型/上型)、10MPaの成形圧力で4分間圧縮成形し、150mm×100mm×4mmの平板状の硬化成形物を得た。
[Examples 2-2 to 2-21, Comparative Examples 2-1 to 2-8]
In Examples 2-2 to 2-21 and Comparative Examples 2-1 to 2-8, with respect to 100 parts by weight of the curable resin, the fluorine-based block copolymer and the low shrinkage agent are mixed at the compounding ratio shown in Table 2. While blended, 200 parts by weight of calcium carbonate powder (manufactured by Nitto Flour Chemical Co., Ltd., trade name: NS-100) as a filler, and t-butylperoxyisopropyl carbonate (manufactured by NOF Corporation, trade name: as a curing agent) Perbutyl I-75) 2.0 parts by weight, 0.05 parts by weight of parabenzoquinone as a polymerization inhibitor, 5.0 parts by weight of zinc stearate as an internal mold release agent, and 2.0 parts by weight of magnesium oxide as a thickener The mixture was mixed for 15 minutes with a stirrer to obtain a paste. Thereafter, the paste was transferred to a kneader, glass fiber (6 mm chopped strand mat; manufactured by Nippon Glass Fiber Co., Ltd., trade name: EM450G-1) was added so as to be 10% by weight, and kneaded with a kneader for 5 minutes. Thus, a curable resin composition was obtained. The obtained curable resin composition was sandwiched with a polyethylene film in a sheet shape and pressed and integrated with a roll. This integrated product was allowed to stand in an atmosphere of 40 ° C. for 24 hours to produce SMC (complex of FRP preparation process). The obtained SMC was compression-molded for 4 minutes at a molding temperature of 10 MPa using a mold temperature of 145 ° C./130° C. (lower mold / upper mold) using a 100 ton press, and a flat cured product of 150 mm × 100 mm × 4 mm Got.
得られた各硬化成形物について、下記の方法にて外観及び防汚姓について評価した。また、撥水撥油性の指標として水の接触角とn−ドデカンの接触角を液滴法にて測定した。その結果を表2に併記する。 About each obtained hardening molded object, the external appearance and antifouling last name were evaluated by the following method. Moreover, the contact angle of water and the contact angle of n-dodecane were measured by a droplet method as an index of water and oil repellency. The results are also shown in Table 2.
[外観の評価方法]
目視にて判断し、表面にツヤ・光沢があり、平滑性に優れる場合を◎、表面にツヤ・光沢があり、平滑性が良好である場合を○、表面にくすみがあり、平滑性が不良である場合を×とした。
[Appearance evaluation method]
Judging by visual inspection, the surface is glossy and glossy, and the smoothness is excellent. The case where it is is set as x.
[防汚性の評価]
オレイン酸の液滴を試料表面に載せ、シャワーで流した際の液滴の除去性を目視で判断し、液滴の除去性良好(少量のシャワーで流れる)を○、液滴の除去性不良(液滴が広がる)を×とした。
[Evaluation of antifouling properties]
Droplet of oleic acid is placed on the surface of the sample and the removability of the droplet is judged visually when it is flowed in the shower. Good removability of the droplet (flowing with a small amount of shower) ○, poor removability of the droplet (The droplet spreads) was set as x.
上記一般式(I)に示される含フッ素単量体中の炭素数が7以上のパーフルオロアルキル基は結晶性をもつので、フッ素系ブロック共重合体が表面に配向する際に結晶化してドメインを形成するため、表面がミクロ相分離のような状態になり表面外観を損ねる。また、含フッ素単量体中の炭素数5以下のパーフルオロアルキル基では防汚性を付与することができない。これに対し、炭素数6のパーフルオロアルキル基は結晶性を持たないので、フッ素系ブロック共重合体が表面に配向する際に均一に分散し、優れた表面外観を得ることができ、さらに十分な撥水撥油性を確保することもできる。
また、低収縮剤を併用しない場合でも含フッ素系ブロック共重合体による撥水撥油性は発現するが、低収縮剤を併用して表面の平滑性をさらに良好にすることで、より撥水撥油性が向上する。この低収縮剤としてポリスチレン系低収縮剤などの低極性のものが有効な理由として、フッ素系ブロック共重合体には、エステル基に起因する極性により、不飽和ポリエステル樹脂などの硬化性樹脂とは親和性を有するが、低極性のポリスチレン系低収縮剤を併用することにより、この親和性が低減され、フッ素系ブロック共重合体が表面に偏析しやすくなるためである。
Since the perfluoroalkyl group having 7 or more carbon atoms in the fluorine-containing monomer represented by the general formula (I) has crystallinity, it is crystallized when the fluorine-based block copolymer is oriented on the surface. Therefore, the surface becomes in a state like microphase separation and the surface appearance is impaired. Moreover, antifouling property cannot be imparted with a perfluoroalkyl group having 5 or less carbon atoms in the fluorinated monomer. On the other hand, since the perfluoroalkyl group having 6 carbon atoms does not have crystallinity, it can be uniformly dispersed when the fluorine-based block copolymer is oriented on the surface, and an excellent surface appearance can be obtained. Water and oil repellency can be secured.
In addition, the water / oil repellency of the fluorine-containing block copolymer is exhibited even when a low shrinkage agent is not used in combination, but the use of the low shrinkage agent together with the surface smoothness further improves the water repellency and water repellency. Oiliness is improved. The reason why a low polarity such as a polystyrene based low shrinkage agent is effective as this low shrinkage agent is that the fluorine-based block copolymer has a curable resin such as an unsaturated polyester resin due to the polarity due to the ester group. This is because the affinity is reduced and the fluorine-based block copolymer is easily segregated on the surface by using a low-polarity polystyrene-based low-shrink agent in combination with an affinity.
Claims (6)
前記含フッ素セグメントを構成する含フッ素単量体が、炭素数6のパーフルオロアルキル基を有する下記一般式(I)に示される含フッ素単量体であり、
前記非フッ素セグメントは、メタクリル酸メチル40〜41.1重量%、メタクリル酸ブチル40〜41.1重量%、メタクリル酸2−ヒドロキシエチル16.7重量%、及びメタクリル酸1.1〜3.3重量%の合計100重量%からなる共重合体であり、
前記低収縮剤はポリスチレン系であり、前記硬化性樹脂100重量部に対して1〜150重量部含有されていることを特徴とする硬化性樹脂組成物。
(一般式(I)において、R1は、水素原子、メチル基、フッ素原子又は塩素原子であり、R2は、炭素数1以上の脂肪族基である。) A curable resin composition comprising a fluorine-based block copolymer comprising a fluorine-containing segment and a non-fluorine segment, a curable resin, and a low shrinkage agent,
The fluorine-containing monomer constituting the fluorine-containing segment is a fluorine-containing monomer represented by the following general formula (I) having a C6 perfluoroalkyl group,
The non-fluorine segment comprises 40 to 41.1 wt% methyl methacrylate, 40 to 41.1 wt% butyl methacrylate, 16.7 wt% 2-hydroxyethyl methacrylate, and 1.1 to 3.3 methacrylic acid. A copolymer consisting of 100% by weight in total,
The said low shrinkage | contraction agent is a polystyrene type, 1-150 weight part is contained with respect to 100 weight part of said curable resins, The curable resin composition characterized by the above-mentioned.
(In the general formula (I), R1 is a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom, and R2 is an aliphatic group having 1 or more carbon atoms.)
前記含フッ素セグメントを構成する含フッ素単量体が、炭素数6のパーフルオロアルキル基を有する下記一般式(I)に示される含フッ素単量体であり、
前記非フッ素セグメントは、メタクリル酸メチル40〜41.1重量%、メタクリル酸ブチル40〜41.1重量%、メタクリル酸2−ヒドロキシエチル16.7重量%、及びメタクリル酸1.1〜3.3重量%の合計100重量%からなる共重合体であり、
低収縮剤を含まないことを特徴とする硬化性樹脂組成物。
(一般式(I)において、R1は、水素原子、メチル基、フッ素原子又は塩素原子であり、R2は、炭素数1以上の脂肪族基である。) A curable resin composition comprising a fluorinated block copolymer comprising a fluorinated segment and a non-fluorinated segment, and a curable resin,
The fluorine-containing monomer constituting the fluorine-containing segment is a fluorine-containing monomer represented by the following general formula (I) having a C6 perfluoroalkyl group,
The non-fluorine segment comprises 40 to 41.1 wt% methyl methacrylate, 40 to 41.1 wt% butyl methacrylate, 16.7 wt% 2-hydroxyethyl methacrylate, and 1.1 to 3.3 methacrylic acid. A copolymer consisting of 100% by weight in total,
A curable resin composition containing no low shrinkage agent.
(In the general formula (I), R1 is a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom, and R2 is an aliphatic group having 1 or more carbon atoms.)
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