JP6195702B2 - Fiber reinforced plastic composition and water product - Google Patents
Fiber reinforced plastic composition and water product Download PDFInfo
- Publication number
- JP6195702B2 JP6195702B2 JP2012227484A JP2012227484A JP6195702B2 JP 6195702 B2 JP6195702 B2 JP 6195702B2 JP 2012227484 A JP2012227484 A JP 2012227484A JP 2012227484 A JP2012227484 A JP 2012227484A JP 6195702 B2 JP6195702 B2 JP 6195702B2
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- JP
- Japan
- Prior art keywords
- resin
- reinforced plastic
- fiber
- silicone compound
- water
- 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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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 86
- 239000000203 mixture Substances 0.000 title claims description 81
- 229920002430 Fibre-reinforced plastic Polymers 0.000 title claims description 74
- 239000011151 fibre-reinforced plastic Substances 0.000 title claims description 74
- 229920005989 resin Polymers 0.000 claims description 101
- 239000011347 resin Substances 0.000 claims description 101
- 229920001296 polysiloxane Polymers 0.000 claims description 83
- 150000001875 compounds Chemical class 0.000 claims description 82
- 239000000178 monomer Substances 0.000 claims description 49
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 36
- 239000000835 fiber Substances 0.000 claims description 19
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 239000012779 reinforcing material Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 description 48
- -1 polysiloxane Polymers 0.000 description 37
- 230000003373 anti-fouling effect Effects 0.000 description 21
- 238000005096 rolling process Methods 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 239000003365 glass fiber Substances 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 12
- 125000001424 substituent group Chemical group 0.000 description 11
- 229920006337 unsaturated polyester resin Polymers 0.000 description 10
- 238000000465 moulding Methods 0.000 description 9
- 239000003677 Sheet moulding compound Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 6
- 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 6
- 239000011521 glass Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 229920002545 silicone oil Polymers 0.000 description 6
- 239000004412 Bulk moulding compound Substances 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- 239000011152 fibreglass Substances 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000004386 diacrylate group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000009428 plumbing Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- ZODNDDPVCIAZIQ-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C=C ZODNDDPVCIAZIQ-UHFFFAOYSA-N 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- 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
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 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
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 102100029538 Structural maintenance of chromosomes protein 1A Human genes 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 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
- 238000009826 distribution Methods 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 108010004731 structural maintenance of chromosome protein 1 Proteins 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-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
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- IQGIEMYBDGDBMR-UHFFFAOYSA-N (3-methyl-5-prop-2-enoyloxypentyl) prop-2-enoate Chemical compound C=CC(=O)OCCC(C)CCOC(=O)C=C IQGIEMYBDGDBMR-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- UHLWGJNVYHBNBV-UHFFFAOYSA-N 1-(1-hydroxypropan-2-yloxy)-3-methoxypropan-2-ol;prop-2-enoic acid Chemical compound OC(=O)C=C.COCC(O)COC(C)CO UHLWGJNVYHBNBV-UHFFFAOYSA-N 0.000 description 1
- NQUXRXBRYDZZDL-UHFFFAOYSA-N 1-(2-prop-2-enoyloxyethyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCOC(=O)C=C)C(O)=O NQUXRXBRYDZZDL-UHFFFAOYSA-N 0.000 description 1
- YUTHQCGFZNYPIG-UHFFFAOYSA-N 1-[2-(2-methylprop-2-enoyloxy)ethyl]cyclohexane-1,2-dicarboxylic acid Chemical compound CC(=C)C(=O)OCCC1(C(O)=O)CCCCC1C(O)=O YUTHQCGFZNYPIG-UHFFFAOYSA-N 0.000 description 1
- IFWOFRICKCJBGV-UHFFFAOYSA-N 1-butoxy-2-(2-hydroxyethoxy)ethanol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCCCOC(O)COCCO IFWOFRICKCJBGV-UHFFFAOYSA-N 0.000 description 1
- OBNIRVVPHSLTEP-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(O)COCCO OBNIRVVPHSLTEP-UHFFFAOYSA-N 0.000 description 1
- SDNFLDFYNSORLN-UHFFFAOYSA-N 1-ethylcyclohexane-1,2-dicarboxylic acid Chemical compound CCC1(C(O)=O)CCCCC1C(O)=O SDNFLDFYNSORLN-UHFFFAOYSA-N 0.000 description 1
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
- IFSLSXUHNIVHPB-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OCC(C)(C)CO.OCC(C)(C)C(O)=O IFSLSXUHNIVHPB-UHFFFAOYSA-N 0.000 description 1
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 1
- IAMASUILMZETHW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOCC(O)OC1=CC=CC=C1 IAMASUILMZETHW-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- COORVRSSRBIIFJ-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]-1-methoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(O)COCCOCCO COORVRSSRBIIFJ-UHFFFAOYSA-N 0.000 description 1
- LBNDGEZENJUBCO-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethyl]butanedioic acid Chemical compound CC(=C)C(=O)OCCC(C(O)=O)CC(O)=O LBNDGEZENJUBCO-UHFFFAOYSA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- RVHOBHMAPRVOLO-UHFFFAOYSA-N 2-ethylbutanedioic acid Chemical compound CCC(C(O)=O)CC(O)=O RVHOBHMAPRVOLO-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-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
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 description 1
- DRIGZYJEJBTAII-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;2-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCO.CC(O)COC(=O)C(C)=C DRIGZYJEJBTAII-UHFFFAOYSA-N 0.000 description 1
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
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- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- QISZCVLALJOROC-UHFFFAOYSA-N 3-(2-hydroxyethyl)-4-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OCCC1=C(CCOC(=O)C=C)C=CC(C(O)=O)=C1C(O)=O QISZCVLALJOROC-UHFFFAOYSA-N 0.000 description 1
- UXTGJIIBLZIQPK-UHFFFAOYSA-N 3-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(CCOC(=O)C=C)=C1C(O)=O UXTGJIIBLZIQPK-UHFFFAOYSA-N 0.000 description 1
- NMGBFVPQUCLJGM-UHFFFAOYSA-N 3-ethylphthalic acid Chemical compound CCC1=CC=CC(C(O)=O)=C1C(O)=O NMGBFVPQUCLJGM-UHFFFAOYSA-N 0.000 description 1
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- OIRWCSXDSJUCJN-UHFFFAOYSA-N 4-ethyl-1-(2-hydroxyethoxy)octan-2-ol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCC(CC)CC(O)COCCO OIRWCSXDSJUCJN-UHFFFAOYSA-N 0.000 description 1
- RWOBPFXXSSWQBF-UHFFFAOYSA-N 4-ethyl-3-(2-hydroxyethyl)phthalic acid Chemical compound C(C)C=1C(=C(C(C(=O)O)=CC1)C(=O)O)CCO RWOBPFXXSSWQBF-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
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- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- NGEXKJMKBNDRQH-UHFFFAOYSA-N C(C(=C)C)(=O)OC1=CC=CC=2OC3=CC(=CC=C3CC12)OC(C(=C)C)=O Chemical compound C(C(=C)C)(=O)OC1=CC=CC=2OC3=CC(=CC=C3CC12)OC(C(=C)C)=O NGEXKJMKBNDRQH-UHFFFAOYSA-N 0.000 description 1
- BIVUTUUWZHMKOD-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.CC(CO)CCCCCCO Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.CC(CO)CCCCCCO BIVUTUUWZHMKOD-UHFFFAOYSA-N 0.000 description 1
- 0 CC*O[N+]([N+](*=C)[N-])[O-] Chemical compound CC*O[N+]([N+](*=C)[N-])[O-] 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-BREBYQMCSA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C=C)C[C@@H]1C2(C)C PSGCQDPCAWOCSH-BREBYQMCSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
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- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
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- 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
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- DIDDVZFHORVZMG-UHFFFAOYSA-N methyl 2-methylprop-2-eneperoxoate Chemical compound COOC(=O)C(C)=C DIDDVZFHORVZMG-UHFFFAOYSA-N 0.000 description 1
- BSDQITJYKQHXQR-UHFFFAOYSA-N methyl prop-2-eneperoxoate Chemical compound COOC(=O)C=C BSDQITJYKQHXQR-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
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- 239000012778 molding material Substances 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 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
- 239000003921 oil Substances 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- CSVRUJBOWHSVMA-UHFFFAOYSA-N oxolan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCO1 CSVRUJBOWHSVMA-UHFFFAOYSA-N 0.000 description 1
- FEUIEHHLVZUGPB-UHFFFAOYSA-N oxolan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC1CCCO1 FEUIEHHLVZUGPB-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- QKNZNUNCDJZTCH-UHFFFAOYSA-N pentyl benzoate Chemical compound CCCCCOC(=O)C1=CC=CC=C1 QKNZNUNCDJZTCH-UHFFFAOYSA-N 0.000 description 1
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- 230000035699 permeability Effects 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- GRDVGGZNFFBWTM-UHFFFAOYSA-N phenyl 2-methylprop-2-eneperoxoate Chemical compound CC(=C)C(=O)OOC1=CC=CC=C1 GRDVGGZNFFBWTM-UHFFFAOYSA-N 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WZESLRDFSNLECD-UHFFFAOYSA-N phenyl prop-2-eneperoxoate Chemical compound C=CC(=O)OOC1=CC=CC=C1 WZESLRDFSNLECD-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
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- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
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- 239000004926 polymethyl methacrylate Substances 0.000 description 1
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- 238000012805 post-processing Methods 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 230000002787 reinforcement Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 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 1
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- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
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- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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Landscapes
- Reinforced Plastic Materials (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、繊維強化プラスチック組成物、及び水まわり製品に関する。 The present invention relates to a fiber reinforced plastic composition and a water product.
繊維強化プラスチック（Fiber Reinforced Plastics；FRP）は、加工成形されることにより多種多様の製品とされ、住宅設備機器等として用いられることが多い。特に、浴室内、洗面化粧台、台所などの、水まわり製品、例えば、ユニットバスの床、浴槽、壁や洗面化粧台のパネルなどに使用される。
水や湿気に晒される水まわり製品では、環境状況に応じて、ピンク色や褐色を呈したぬるぬるした付着物が発生し、また浴室の壁、床、天井などでは黒色又は褐色のカビが発生し易い。
Fiber Reinforced Plastics (FRP) are processed and molded into a wide variety of products and are often used as housing equipment. In particular, it is used for water-related products such as bathrooms, vanities and kitchens, for example, floors of unit baths, bathtubs, walls and vanities.
Water-based products that are exposed to water or moisture may generate slimy deposits that appear pink or brown, depending on the environmental conditions, and black or brown mold on bathroom walls, floors, ceilings, etc. easy.
近年、台所の壁やタイルなどの汚れを防止するために、樹脂表面をフッ素コーティング加工したり、防汚機能を有する機能性部材を積層する技術が開示されている（例えば、特許文献１参照）。また、反応性基を有しないシリコーンオイルと樹脂とを含む樹脂組成物や、反応性基を有するシリコーンオイルと樹脂とを含む樹脂組成物等も開示されている（例えば、特許文献２参照）。 In recent years, in order to prevent stains on kitchen walls, tiles, and the like, a technique for fluorine coating the resin surface or laminating functional members having an antifouling function has been disclosed (for example, see Patent Document 1). . In addition, a resin composition containing a silicone oil having no reactive group and a resin, a resin composition containing a silicone oil having a reactive group and a resin, and the like are also disclosed (for example, see Patent Document 2).
しかしながら、基材となる樹脂表面をコーティング加工したり、機能性部材を樹脂に積層するには、専門の設備を必要とし、樹脂表面の形状が複雑である場合には、均一なコーティングが困難であり、樹脂表面との機能性部材の接着性が弱くなることがある。
また、樹脂組成物に含まれるシリコーンオイルが反応性基を有していない場合、樹脂組成物を成形加工した水まわり製品の使用と共に、シリコーンオイルが取り除かれ、防汚性等の効果が、経時と共に弱くなることがある。
これに対し、反応性基を有するシリコーンオイルを含有する樹脂組成物は、経時による性能の低下を抑制し得るものの、未だ防汚性能には改善の余地があった。
However, in order to coat the resin surface that is the base material or to laminate functional members on the resin, specialized equipment is required, and uniform coating is difficult if the resin surface shape is complicated. Yes, the adhesion of the functional member to the resin surface may be weakened.
In addition, when the silicone oil contained in the resin composition does not have a reactive group, the silicone oil is removed along with the use of the water-based product obtained by molding the resin composition, and the effects such as antifouling properties are improved over time. It may become weak with it.
On the other hand, although the resin composition containing the silicone oil having a reactive group can suppress deterioration in performance over time, there is still room for improvement in antifouling performance.
本発明は、撥水性および水の転がり性に優れ、良好な防汚効果を発揮し得る成形体を製造可能な繊維強化プラスチック組成物、並びに、水まわり製品を提供することを目的とする。 An object of the present invention is to provide a fiber-reinforced plastic composition capable of producing a molded article that is excellent in water repellency and water rolling property and can exhibit a good antifouling effect, and a water-based product.
＜１＞ 少なくとも不飽和樹脂を含む基体樹脂と、前記基体樹脂１００質量部に対して、１質量部〜４質量部の、数平均分子量が５，０００〜２０，０００であり、片末端に反応性基を有するシリコーン化合物と、（メタ）アクリルモノマーと、（メタ）アクリルモノマー以外の架橋剤と、を含有する繊維強化プラスチック組成物である。
＜２＞ 少なくとも不飽和樹脂を含む基体樹脂と、前記基体樹脂１００質量部に対して、１質量部〜４質量部の、数平均分子量が５，０００〜２０，０００であり、片末端に反応性基を有するシリコーン化合物と、（メタ）アクリルモノマーと、（メタ）アクリルモノマー以外の架橋剤と、補強材として、シート形状でない、長さ１５ｍｍ以上１００ｍｍ以下の長繊繊及び長さ３ｍｍ以上１５ｍｍ未満の短繊維の少なくとも一方と、を含有する繊維強化プラスチック組成物である。
＜３＞ 前記（メタ）アクリルモノマーの含有量が、前記基体樹脂１００質量部に対して、０．１質量部〜１．２質量部である前記＜１＞または＜２＞に記載の繊維強化プラスチック組成物である。
＜４＞ 前記＜１＞〜＜３＞のいずれか１に記載の繊維強化プラスチック組成物を用いて成形された水まわり製品である。
<1> A number average molecular weight of 5,000 to 20,000 of 1 to 4 parts by mass with respect to a base resin containing at least an unsaturated resin and 100 parts by mass of the base resin, and reacts at one end It is a fiber reinforced plastic composition containing a silicone compound having a functional group, a (meth) acrylic monomer, and a crosslinking agent other than the (meth) acrylic monomer.
<2> The number average molecular weight of 5,000 to 20,000 of 1 to 4 parts by mass with respect to 100 parts by mass of the base resin containing at least unsaturated resin and the base resin, and reacts at one end A silicone compound having a functional group, a (meth) acrylic monomer, a cross-linking agent other than the (meth) acrylic monomer, and a reinforcing material that is not in sheet form, a long fiber with a length of 15 mm to 100 mm and a length of 3 mm to 15 mm And a fiber reinforced plastic composition containing at least one of less short fibers.
<3> The fiber reinforcement according to <1> or <2>, wherein the content of the (meth) acrylic monomer is 0.1 part by mass to 1.2 parts by mass with respect to 100 parts by mass of the base resin. It is a plastic composition.
<4> A water product molded using the fiber-reinforced plastic composition according to any one of <1> to <3>.
本発明によれば、撥水性および水の転がり性に優れ、良好な防汚効果を発揮し得る成形体を製造可能な繊維強化プラスチック組成物、並びに、水まわり製品を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the fiber reinforced plastic composition which can manufacture the molded object which is excellent in water repellency and the rolling property of water, and can exhibit the favorable antifouling effect, and a water product can be provided.
＜繊維強化プラスチック組成物＞
本発明の繊維強化プラスチック組成物は、少なくとも不飽和樹脂を含む基体樹脂と、前記基体樹脂１００質量部に対して、１質量部〜４質量部の、数平均分子量が５，０００〜２０，０００であり、片末端に反応性基を有するシリコーン化合物と、（メタ）アクリルモノマーと、を含有して構成される。
数平均分子量が５，０００〜２０，０００であり、片末端に反応性基を有するシリコーン化合物を、以下、「特定シリコーン化合物」とも称する。また、繊維強化プラスチックは、ＦＲＰ（Ｆｉｂｅｒ Ｒｅｉｎｆｏｒｃｅｄ Ｐｌａｓｔｉｃｓ）とも略称され、繊維強化プラスチック組成物を「ＦＲＰ組成物」と称することがある。
<Fiber-reinforced plastic composition>
The fiber-reinforced plastic composition of the present invention has a number average molecular weight of 5,000 to 20,000 with respect to 100 parts by mass of the base resin containing at least an unsaturated resin and 100 parts by mass of the base resin. It is configured to contain a silicone compound having a reactive group at one end and a (meth) acrylic monomer.
A silicone compound having a number average molecular weight of 5,000 to 20,000 and having a reactive group at one end is hereinafter also referred to as “specific silicone compound”. The fiber reinforced plastic is also abbreviated as FRP (Fiber Reinforced Plastics), and the fiber reinforced plastic composition may be referred to as “FRP composition”.
繊維強化プラスチック組成物を上記構成とすることで、繊維強化プラスチック組成物を成形加工等して水まわり製品を製造したとき、水まわり製品の撥水性および水の転がり性を高め、良好な防汚効果を発揮することができる。この理由は定かではないが、次の理由によるものと推測される。 By making the fiber reinforced plastic composition as described above into a water-based product by molding or processing the fiber-reinforced plastic composition, the water repellency and water rolling property of the water-based product are improved and good antifouling property is obtained. The effect can be demonstrated. The reason for this is not clear, but is presumed to be due to the following reason.
特定シリコーン化合物は、分子の片末端に、反応性基を有することから、不飽和樹脂を含む基体樹脂と共に用いられることで、不飽和樹脂の二重結合部分と、特定シリコーン化合物の反応性基との間で反応が生じ、基体樹脂と特定シリコーン化合物とが結合すると考えられる。
但し、特定シリコーン化合物の中には、不飽和樹脂の二重結合部分と反応せずにそのまま残存するものも存在すると考えられ、この反応せずに残存した特定シリコーン化合物による撥水性と水の転がり性の向上への寄与は低いと思われる。
Since the specific silicone compound has a reactive group at one end of the molecule, it is used together with a base resin containing an unsaturated resin, so that the double bond portion of the unsaturated resin, the reactive group of the specific silicone compound, and It is considered that a reaction occurs between the base resin and the specific silicone compound.
However, it is considered that some of the specific silicone compounds remain as they are without reacting with the double bond portion of the unsaturated resin, and the water repellency due to the specific silicone compounds remaining without this reaction and the rolling of water. The contribution to the improvement of sex seems to be low.
これに対し、本発明に係る繊維強化プラスチック組成物では更に（メタ）アクリルモノマーを含有しており、（メタ）アクリルモノマーの二重結合部分の一端が不飽和樹脂の二重結合部分と反応し、且つもう一端が特定シリコーン化合物と反応することで、両者の間に介在する形で反応効率を高める効果をもたらすものと考えられる。
その結果、反応せずにそのまま残存する特定シリコーン化合物が減り、反応した特定シリコーン化合物が撥水性と水の転がり性の向上に効率的に寄与することで、繊維強化プラスチック組成物の成型品である水まわり製品の撥水性と水の転がり性がより向上し、良好な防汚効果を発揮し得るものと考えられる。
In contrast, the fiber-reinforced plastic composition according to the present invention further contains a (meth) acrylic monomer, and one end of the double bond portion of the (meth) acrylic monomer reacts with the double bond portion of the unsaturated resin. And, it is thought that the other end reacts with the specific silicone compound, thereby bringing about an effect of increasing the reaction efficiency in a form interposed between the two.
As a result, the specific silicone compound remaining as it is without reacting is reduced, and the reacted specific silicone compound contributes efficiently to the improvement of water repellency and water rolling property, thereby being a molded product of a fiber reinforced plastic composition. It is considered that the water repellency and water rolling property of water-related products are further improved, and a good antifouling effect can be exhibited.
尚、本発明に係る繊維強化プラスチック組成物は、（メタ）アクリルモノマーを含有させることで、上記の通り反応せずに残存する特定シリコーン化合物の割合を減らし、添加した特定シリコーン化合物を効率的に反応させることができる。そのため、含有させる特定シリコーン化合物がより少ない量であっても撥水性と水の転がり性が得られ、良好な防汚効果を発揮し得るものと考えられる。 The fiber-reinforced plastic composition according to the present invention contains a (meth) acrylic monomer, thereby reducing the proportion of the specific silicone compound remaining without reacting as described above, and efficiently adding the added specific silicone compound. Can be reacted. Therefore, even if the specific silicone compound is contained in a smaller amount, it is considered that water repellency and water rolling property can be obtained and a good antifouling effect can be exhibited.
このように、本発明の繊維強化プラスチック組成物は、未反応状態の不飽和樹脂と、特定シリコーン化合物と、（メタ）アクリルモノマーと、を含有する組成物であり、組成物中の不飽和樹脂と特定シリコーン化合物とが（メタ）アクリルモノマーを介して反応し、ポリシロキサン複合樹脂としたものを、成形し、水まわり製品とする。
その結果、撥水性のみならず、水の転がり性にも優れた水まわり製品を製造することができ、長期的な防汚性を発現することができると考えられる。
Thus, the fiber-reinforced plastic composition of the present invention is a composition containing an unreacted unsaturated resin, a specific silicone compound, and a (meth) acrylic monomer, and the unsaturated resin in the composition And a specific silicone compound react through a (meth) acrylic monomer to form a polysiloxane composite resin, which is then molded into a water product.
As a result, it is considered that not only water repellency but also water-related products having excellent water rolling property can be produced, and long-term antifouling properties can be exhibited.
尚、水の転がり性は、水滴を載せた水まわり製品の表面を傾けて、水滴が転がり始める角度（転落角）を測定することにより評価され、水の接触角が大きく撥水性が高い製品でも、転落角が大きくなる（水が転がりにくい）ことがある。つまり、一般に、水の転がり性評価は、撥水性ないし防汚性の評価指標となる接触角評価よりも厳しい防汚性の評価基準であると考えられる。本発明の水まわり製品は、高い撥水性のみならず、高い水の転がり性をも併せもつため、優れた防汚性を実現し得る。
なお、転落角は、接触角同様、各種接触角測定装置（例えば、協和界面科学社製の全自動接触角計など）で測定することができる。
The rolling property of water is evaluated by inclining the surface of the water product on which water droplets are placed and measuring the angle at which the water droplets begin to roll (falling angle). Even if the product has a large water contact angle and high water repellency. , The falling angle may become large (water is difficult to roll). That is, in general, the water rolling property evaluation is considered to be a stricter antifouling evaluation criterion than the contact angle evaluation which is an evaluation index of water repellency or antifouling property. Since the water product of the present invention has not only high water repellency but also high water rolling property, it can realize excellent antifouling property.
The sliding angle can be measured by various contact angle measuring devices (for example, a fully automatic contact angle meter manufactured by Kyowa Interface Science Co., Ltd.) as well as the contact angle.
以下、（メタ）アクリルモノマー、特定シリコーン化合物、基体樹脂、その他繊維強化プラスチック組成物を構成する成分、及び水まわり製品について説明する。 Hereinafter, the (meth) acryl monomer, the specific silicone compound, the base resin, other components constituting the fiber-reinforced plastic composition, and the water product will be described.
〔（メタ）アクリルモノマー〕
本発明の繊維強化プラスチック組成物は、（メタ）アクリルモノマーを含有する。（メタ）アクリルモノマーとは、具体的には下記一般式（Ｉ）で表される化合物を表す。
[(Meth) acrylic monomer]
The fiber-reinforced plastic composition of the present invention contains a (meth) acrylic monomer. The (meth) acryl monomer specifically represents a compound represented by the following general formula (I).
一般式（Ｉ）中、Ｒ１１は水素原子またはメチル基を、Ｒ１２は水素原子または１価の有機基を表す。 In general formula (I), R 11 represents a hydrogen atom or a methyl group, and R 12 represents a hydrogen atom or a monovalent organic group.
尚、Ｒ１２で表される１価の有機基としては、例えばアルキル基、アリール基、複素環基、アルコキシ基、アリールオキシ基等が挙げられ、特にアルキル基が好ましい。 Examples of the monovalent organic group represented by R 12 include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, and an aryloxy group, and an alkyl group is particularly preferable.
Ｒ１２で表されるアルキル基は、直鎖状、分枝鎖状、環状のいずれでもよく、また更に置換基を有していてもよい。
置換基を有していない直鎖状または分枝鎖状のアルキル基の例としては、例えばメチル、エチル、ｎ−ブチル、イソブチル、ｔｅｒｔ−ブチル、ペンチル、オクチル、デシル、ラウリル、トリデシル、ステアリル等が挙げられ、また環状のアルキル基の例としては、例えばシクロヘキシル、イソボルニル等が挙げられる。
The alkyl group represented by R 12 may be linear, branched, or cyclic, and may further have a substituent.
Examples of linear or branched alkyl groups having no substituent include, for example, methyl, ethyl, n-butyl, isobutyl, tert-butyl, pentyl, octyl, decyl, lauryl, tridecyl, stearyl and the like. Examples of the cyclic alkyl group include cyclohexyl, isobornyl and the like.
Ｒ１２で表されるアルキル基に置換する置換基としては、例えばアリール、複素環、アルコキシ、アリールオキシ、水酸基、アミノ基、エポキシ、リン酸、ハロゲン原子等が挙げられる。また、置換基を有するアルキル基は、アルキルエステルや、エチレングリコール、ポリエチレングリコール等の態様であってもよく、またこれらの置換基が更に置換基を有していてもよい。尚、上記アルキル基はこれらの置換基を１種有していても２種以上有していてもよい。
上記置換基を有するアルキル基としては、例えばベンジル、テトラヒドロフルフリル、フェノキシエチル、ヒドロキシエチル、ヒドロキシプロピル、ヒドロキシブチル、ジメチルアミノエチル、ジエチルアミノエチル、トリメチルアミノエチル（四級化物）、エチルコハク酸、エチルヘキサヒドロフタル酸、エチルフタル酸、エチル−２−ヒドロキシエチル−フタル酸、メタクリル酸ブチル、メタクリル酸ペンチル、メタクリル酸ヘキシル、メタクリル酸ノニル、安息香酸ペンチル、グリシジル、エチルアシッドホスフェート、トリフロロエチル、２−ヒドロキシ−３−メタクリロイロキシプロピル、２−ヒドロキシ−３−アクリロイロキシプロピル、２−ヒドロキシ−３−フェノキシプロピル等が挙げられる。
Examples of the substituent substituted on the alkyl group represented by R 12 include aryl, heterocyclic ring, alkoxy, aryloxy, hydroxyl group, amino group, epoxy, phosphoric acid, halogen atom and the like. The alkyl group having a substituent may be an alkyl ester, ethylene glycol, polyethylene glycol or the like, and these substituents may further have a substituent. In addition, the said alkyl group may have 1 type or 2 types or more of these substituents.
Examples of the alkyl group having the above substituent include benzyl, tetrahydrofurfuryl, phenoxyethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, dimethylaminoethyl, diethylaminoethyl, trimethylaminoethyl (quaternized product), ethyl succinic acid, ethyl hexa Hydrophthalic acid, ethylphthalic acid, ethyl-2-hydroxyethyl-phthalic acid, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, nonyl methacrylate, pentyl benzoate, glycidyl, ethyl acid phosphate, trifluoroethyl, 2-hydroxy -3-Methacryloyloxypropyl, 2-hydroxy-3-acryloyloxypropyl, 2-hydroxy-3-phenoxypropyl and the like.
一般式（Ｉ）で表される（メタ）クリルモノマーとしては、例えばメタクリレート、アクリレート、エチルメタクリレート、ｎ−ブチルメタクリレート、イソブチルメタクリレート、ｔｅｒｔ−ブチルメタクリレート、２−エチルヘキシルメタクリレート、イソデシルメタクリレート、ｎ−ラウリルメタクリレート、トリデシルメタクリレート、ｎ−ステアリルメタクリレート、ブトキシジエチレングリコールメタクリレート、メトキシポリエチレングリコールメタクリレート、メトキシポリエチレングリコールメタクリレート、シクロヘキシルメタクリレート、テトラヒドロフルフリルメタクリレート、ベンジルメタクリレート、フェノキシエチルメタクリレート、イソボルニルメタクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレート、２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、２−ヒドロキシブチルメタクリレート、ジメチルアミノエチルメタクリレート、ジエチルアミノエチルメタクリレート、ジメチルアミノエチルメタクリレート／四級化物、２−メタクリロイロキシエチルコハク酸、２−メタクリロイロキシエチルヘキサヒドロフタル酸、グリシジルメタクリレート、２−メタクロイロキシエチルアシッドホスフェート、エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチエレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、１，４−ブタンジオールジメタクリレート、ネオペンチルグリコールジメタクリレート、１，６−ヘキサンジオールジメタクリレート、１，９−ノナンジオールジメタクリレート、グリセリンジメタクリレート、２−ヒドロキシ−３−アクリロイロキシプロピルメタクリレート、ビスフェノールＡのＥＯ付加物ジメタクリレート、トリメチロールプロパントリメタクリレート、トリフロロエチルメタクリレート、イソアミルアクリレート、ラウリルアクリレート、ステアリルアクリレート、エトキシジエチレングリコールアクリレート、メトキシトリエチレングリコールアクリレート、２−エチルヘキシルジエチレングリコールアクリレート、メトキシポリエチレングリコールアクリレート、メトキシジプロピレングリコールアクリレート、フェノキシエチルアクリレート、フェノキシジエチレングリコールアクリレート、フェノキシポリエチレングリコールアクリレート、ノニルフェノールＥＯ付加物アクリレート、テトラヒドロフルフリルアクリレート、イソボルニルアクリレート、２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、２−ヒドロキシブチルアクリレート、２−ヒドロキシ−３−フェノキシプロピルアクリレート、２−アクリロイロキシエチルコハク酸、２−アクリロイロキシエチルヘキサヒドロフタル酸、２−アクリロイロキシエチルフタル酸、２−アクリロイロキシエチル−２−ヒドロキシエチルフタル酸、ネオペンチルグリコールアクリル酸安息香酸エステル、２−アクリロイルオキシエチルアシッドフォスフェート、トリエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、ポリテトラメチレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、３−メチル−１，５ペンタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、１，９−ノナンジオールジアクリレート、２−メチル−１，８オクタンジオールジアクリレート、ジメチロールトリシクロデカンジアクリレート、ビスフェノールＡのＥＯ付加物ジアクリレート、ビスフェノールＡのＰＯ付加物ジアクリレート、ヒドロキシピバリン酸ネオペンチルグリコールアクリル酸付加物、２−ヒドロキシ−３−アクリロイロキシプロピルメタクリレート、トリメチロルプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート等が挙げられる。 Examples of the (meth) acrylic monomer represented by the general formula (I) include methacrylate, acrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, and n-lauryl. Methacrylate, tridecyl methacrylate, n-stearyl methacrylate, butoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate 2 Hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate / quaternized product, 2-methacryloyloxyethyl succinic acid, 2 -Methacryloyloxyethyl hexahydrophthalic acid, glycidyl methacrylate, 2-methacryloyl ethyl acetate phosphate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol di Methacrylate, neopentyl glycol dimethacrylate, 1,6- Xanthdiol dimethacrylate, 1,9-nonanediol dimethacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO adduct dimethacrylate of bisphenol A, trimethylolpropane trimethacrylate, trifluoroethyl methacrylate, Isoamyl acrylate, lauryl acrylate, stearyl acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, 2-ethylhexyl diethylene glycol acrylate, methoxypolyethylene glycol acrylate, methoxydipropylene glycol acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxypolyethylene Tylene glycol acrylate, nonylphenol EO adduct acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2- Acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, neopentyl glycol acrylic acid benzoate, 2-acryloyloxyethyl acid phosphate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polytetramethylene glycol Diacrylate, neopentyl glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 2-methyl-1,8 octanediol diacrylate Acrylate, dimethylol tricyclodecane diacrylate, bisphenol A EO adduct diacrylate, bisphenol A PO adduct diacrylate, hydroxypivalate neopentyl glycol acrylic acid adduct, 2-hydroxy-3-acryloyloxypropyl methacrylate , Trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate and the like.
また、一般式（Ｉ）で表される（メタ）クリルモノマーとしては、フェニルメタクリレート、フェニルアクリレート、テトラヒドロフリルメタクリレート、テトラヒドロフリルアクリレート、メトキシメタクリレート、メトキシアクリレート、エトキシメタクリレート、エトキシアクリレート、フェノキシメタクリレート、フェノキシアクリレート等も挙げられる。
これらの中でも、ｔｅｒｔ−ブチルメタクリレート、イソボルニルアクリレートが更に好ましい。
The (meth) acrylic monomer represented by the general formula (I) includes phenyl methacrylate, phenyl acrylate, tetrahydrofuryl methacrylate, tetrahydrofuryl acrylate, methoxy methacrylate, methoxy acrylate, ethoxy methacrylate, ethoxy acrylate, phenoxy methacrylate, phenoxy acrylate. And so on.
Among these, tert-butyl methacrylate and isobornyl acrylate are more preferable.
また、本発明の繊維強化プラスチック組成物中の（メタ）アクリルモノマーの含有量は、基体樹脂１００質量部に対して、０．１質量部〜１．２質量部であることが好ましい。０．１質量部以上であることにより、撥水性と水の転がり性がより向上し良好な防汚効果を発揮し得る。一方１．２質量部以下であることにより、繊維強化プラスチック組成物を水まわり製品としたときに生じる（メタ）アクリルモノマーの浮き出しが抑制され、また水まわり製品において好適な表面性状が得られる。
なお、繊維強化プラスチック組成物が含有する（メタ）アクリルモノマーは、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
Moreover, it is preferable that content of the (meth) acryl monomer in the fiber reinforced plastic composition of this invention is 0.1 mass part-1.2 mass parts with respect to 100 mass parts of base resin. By being 0.1 mass part or more, water repellency and the rolling property of water improve more, and it can exhibit the favorable antifouling effect. On the other hand, when the amount is 1.2 parts by mass or less, the (meth) acrylic monomer raised when the fiber-reinforced plastic composition is used as a swirl product is suppressed, and a suitable surface property can be obtained in a swirl product.
In addition, the (meth) acryl monomer which a fiber reinforced plastic composition contains may be used individually by 1 type, and may be used in combination of 2 or more type.
〔シリコーン化合物〕
本発明の繊維強化プラスチック組成物は、数平均分子量が５，０００〜２０，０００であり、片末端に反応性基を有するシリコーン化合物（特定シリコーン化合物）を、基体樹脂１００質量部に対して１質量部〜４質量部の範囲で含有する。
シリコーン化合物の化学構造の詳細については、後述するが、片末端とは、例えば、シロキサン部位を繰り返し単位として有する分子鎖（主鎖）を有するシリコーン化合物の一方の末端を意味し、主鎖の途中、すなわち、側鎖に反応性基を有することは含まれない。
[Silicone compound]
The fiber reinforced plastic composition of the present invention has a number average molecular weight of 5,000 to 20,000, and a silicone compound having a reactive group at one end (specific silicone compound) is added in an amount of 1 to 100 parts by mass of the base resin. It contains in the range of 4 mass parts to 4 mass parts.
The details of the chemical structure of the silicone compound will be described later. One end means, for example, one end of a silicone compound having a molecular chain (main chain) having a siloxane moiety as a repeating unit, and is in the middle of the main chain. That is, it does not include a reactive group in the side chain.
尚、繊維強化プラスチック組成物の成型品である水まわり製品の撥水性と水の転がり性を向上するには、基体樹脂とシリコーン化合物とが結合して得られるポリシロキサン分子のシロキサン部分が、基体樹脂から離脱することなく表面側に偏在していることが必要と考えられる。
このとき、シリコーン化合物の分子鎖が長過ぎると、基体樹脂に含まれる不飽和樹脂とシリコーン化合物とが相溶しにくいため、シリコーン化合物が不飽和樹脂と結合し難いと考えられる。一方、シリコーン化合物の分子鎖が短すぎると、逆に、シリコーン化合物が、基体樹脂と混ざり合いすぎて、シリコーン化合物と不飽和樹脂とが反応しても、シリコーン化合物由来のシロキサン部分が基体樹脂の表面に偏在し難いと考えられる。
また、基体樹脂に対するシリコーン化合物の割合も、基体樹脂の表面へのシロキサン部分の偏在に大きく関わり、シリコーン化合物の基体樹脂に対するシリコーン化合物の割合が少ないと、撥水性や水の転がり性を発現できないと考えられる。一方、シリコーン化合物の基体樹脂に対するシリコーン化合物の割合が多いと、水まわり製品を得たときに、不飽和樹脂と反応せずに残ったシリコーン化合物が浮き出し、表面性状に支障をきたし、撥水性や水の転がり性を損ねると考えられる。
In addition, in order to improve the water repellency and water rolling property of the water product that is a molded product of the fiber reinforced plastic composition, the siloxane portion of the polysiloxane molecule obtained by bonding the base resin and the silicone compound is It is considered necessary to be unevenly distributed on the surface side without leaving the resin.
At this time, if the molecular chain of the silicone compound is too long, the unsaturated resin and the silicone compound contained in the base resin are difficult to be compatible with each other, so that it is considered that the silicone compound is difficult to bind to the unsaturated resin. On the other hand, if the molecular chain of the silicone compound is too short, conversely, even if the silicone compound is too mixed with the base resin and the silicone compound and the unsaturated resin react with each other, the siloxane portion derived from the silicone compound does not react with the base resin. It is thought that it is hard to be unevenly distributed on the surface.
In addition, the ratio of the silicone compound to the base resin is greatly related to the uneven distribution of the siloxane portion on the surface of the base resin, and if the ratio of the silicone compound to the base resin of the silicone compound is small, the water repellency and the water rolling property cannot be expressed. Conceivable. On the other hand, when the ratio of the silicone compound to the base resin of the silicone compound is large, when a water-based product is obtained, the silicone compound that remains without reacting with the unsaturated resin is raised, causing a problem in surface properties, It is thought that the rolling property of water is impaired.
一般に高分子化合物の分子鎖の長さは、化合物の分子量と関連し、シリコーン化合物の数平均分子量が、５，０００〜２０，０００であり、基体樹脂１００質量部に対するシリコーン化合物を１質量部〜４質量部の割合とすることで、片末端に反応性基を有するシリコーン化合物と基体樹脂に含まれる不飽和樹脂とが（メタ）アクリルモノマーを介して反応し結合した部分においても、（メタ）アクリルモノマーを介さずに反応し結合した部分においても、基体樹脂の表面にシロキサン部分が偏在するものと考えられる。 In general, the molecular chain length of the polymer compound is related to the molecular weight of the compound, the number average molecular weight of the silicone compound is 5,000 to 20,000, and 1 part by mass of the silicone compound to 100 parts by mass of the base resin. By setting the ratio of 4 parts by mass, even in the part where the silicone compound having a reactive group at one end and the unsaturated resin contained in the base resin react and bond via a (meth) acrylic monomer, (meth) It is considered that the siloxane portion is unevenly distributed on the surface of the base resin even in the portion that reacts and binds without passing through the acrylic monomer.
反応性基を有する特定シリコーン化合物は、不飽和樹脂をマトリックス樹脂とし且つ（メタ）アクリルモノマーを含有する繊維強化プラスチック組成物に配合されて硬化すると、反応性基が、（メタ）アクリルモノマーを介して不飽和樹脂の二重結合と反応する部分や、（メタ）アクリルモノマーを介さずに不飽和樹脂の二重結合と反応する部分が生じるが、この際、非反応性のポリシロキサン部分が残ると推定される。この残ったポリシロキサン部分は不飽和樹脂と非相溶なため、得られる成形品の最表面において選択的に非反応性のポリシロキサン部分の濃度が高くなると考えられる。このポリシロキサン部分が高い撥水性および水の転がり性を示すため、水まわり製品の表面に汚れや菌が付き難く、また、付着した汚れや菌が取れ易くなると考えられる。 When the specific silicone compound having a reactive group is blended with a fiber reinforced plastic composition containing an unsaturated resin as a matrix resin and containing a (meth) acrylic monomer and cured, the reactive group passes through the (meth) acrylic monomer. Part that reacts with the double bond of the unsaturated resin and part that reacts with the double bond of the unsaturated resin without going through the (meth) acrylic monomer, but at this time, the non-reactive polysiloxane part remains It is estimated to be. Since the remaining polysiloxane portion is incompatible with the unsaturated resin, it is considered that the concentration of the non-reactive polysiloxane portion is selectively increased on the outermost surface of the obtained molded product. Since this polysiloxane part exhibits high water repellency and water rolling property, it is considered that dirt and bacteria are difficult to adhere to the surface of the water product, and the attached dirt and bacteria are easily removed.
本発明では、不飽和樹脂の二重結合と特定シリコーン化合物の反応性基とが、上記の通り（メタ）アクリルモノマーを介して反応した部分でも、介さずに反応した部分でも、成形品表面に非反応性で撥水性の高いポリシロキサン部分を生成させることにより、防汚性を得ることから、反応性基を持たない非反応性のポリシロキサンのみからなるストレートシリコーンオイルでは、これを繊維強化プラスチックに配合しても配合部数を相当量増加しないと撥水性は得られない。 In the present invention, the double bond of the unsaturated resin and the reactive group of the specific silicone compound are formed on the surface of the molded product, either as a part reacted through the (meth) acrylic monomer as described above, or as a part reacted without the intervention. By creating a non-reactive and highly water-repellent polysiloxane part, antifouling properties are obtained, so in straight silicone oils consisting only of non-reactive polysiloxanes that do not have reactive groups, this is a fiber-reinforced plastic. Even if it is blended, water repellency cannot be obtained unless the number of blended parts is increased by a considerable amount.
本発明の繊維強化プラスチック組成物は、通常の繊維強化プラスチック組成物に更に特定シリコーン化合物および（メタ）アクリルモノマーを配合するのみであり、材料コストの高騰の問題はなく、しかも、成形工程や後加工工程の増加の問題もなく、安価に提供される。しかも、成形性に影響を及ぼすような多量配合の必要もなく、複雑形状品にも十分に適用し得る。更に、コーティング被膜のような後加工によるものではないため、防汚性の耐久性にも優れ、また、紫外線等の外部環境に何ら関係を受けることなく、良好な防汚性を得ることができる。 The fiber-reinforced plastic composition of the present invention is obtained by only adding a specific silicone compound and a (meth) acrylic monomer to a normal fiber-reinforced plastic composition, and there is no problem of an increase in material cost. There is no problem of increase in processing steps, and it is provided at a low cost. In addition, there is no need for a large amount of blending that affects the moldability, and it can be sufficiently applied to complex shaped products. Furthermore, since it is not by post-processing like a coating film, it is excellent also in antifouling durability, and good antifouling properties can be obtained without being affected by the external environment such as ultraviolet rays. .
特定シリコーン化合物が有する反応性基としては、例えば、二重結合を含む官能基（エチレン性不飽和結合基）、イソシアナート基、ブロックイソシアナート基、エポキシ基、オキセタニル基、アミノ基、カルボキシ基等が挙げられる。中でも、二重結合を含む官能基が好ましく、より具体的には、下記一般式（１）に示されるアクリロイル基を含む基、及び、下記一般式（２）に示されるメタクリロイル基を含む基の少なくとも一方が挙げられる。 Examples of the reactive group possessed by the specific silicone compound include a functional group containing a double bond (ethylenically unsaturated bond group), an isocyanate group, a block isocyanate group, an epoxy group, an oxetanyl group, an amino group, and a carboxy group. Is mentioned. Among them, a functional group containing a double bond is preferable, and more specifically, a group containing an acryloyl group represented by the following general formula (1) and a group containing a methacryloyl group represented by the following general formula (2). At least one is mentioned.
一般式（１）のＲａ、および一般式（２）中のＲｂは、各々独立に、単結合、または、２価の連結基を表す。ＲａまたはＲｂで表される２価の連結基としては、アルキレン基、アルケニレン基、アリーレン基、及びこれらの組み合わせ等が挙げられる。
中でも、アルキレン基が好ましく、炭素数は１〜６が好ましい。例えば、メチレン基、エチレン基、プロピレン基、ブチレン基等が挙げられ、中でもプロピレン基が好ましい。２価の連結基がさらに置換可能な場合は、２価の連結基は、炭化水素基、ハロゲン原子、ヒドロキシ基などの１価の置換基を有していてもよい。
Ra in the general formula (1) and Rb in the general formula (2) each independently represent a single bond or a divalent linking group. Examples of the divalent linking group represented by Ra or Rb include an alkylene group, an alkenylene group, an arylene group, and combinations thereof.
Among these, an alkylene group is preferable, and 1 to 6 carbon atoms are preferable. For example, a methylene group, an ethylene group, a propylene group, a butylene group, and the like can be given. When the divalent linking group can be further substituted, the divalent linking group may have a monovalent substituent such as a hydrocarbon group, a halogen atom, or a hydroxy group.
特定シリコーン化合物は、上記のような反応性基を、シロキサン部位を繰り返し単位として有する分子鎖（主鎖）の片末端に有する。
分子鎖の片末端に反応性基を有するシリコーン化合物としては、例えば、下記一般式（３）で表されるものが挙げられる。
The specific silicone compound has a reactive group as described above at one end of a molecular chain (main chain) having a siloxane moiety as a repeating unit.
Examples of the silicone compound having a reactive group at one end of the molecular chain include those represented by the following general formula (3).
一般式（３）中、Ｒ１〜Ｒ７は、各々独立に、１価の非反応性の置換基を表し、ｎは繰り返し単位の量を表し〔ただし、一般式（３）で表される化合物の数平均分子量が５，０００〜２０，０００のとなる範囲で選択される量を表す〕、Ｑは反応性基を表す。 In general formula (3), R 1 to R 7 each independently represents a monovalent non-reactive substituent, and n represents the amount of the repeating unit [wherein, represented by general formula (3) Q represents a reactive group, which represents an amount selected within a range where the number average molecular weight of the compound is 5,000 to 20,000.
一般式（３）中のＲ１〜Ｒ７で表される１価の非反応性の置換基としては、水素原子、アルキル基、アルケニル基、アリール基等が挙げられる。Ｒ１〜Ｒ７は全て同じであっていても、異なっていてもよい。また、繰り返し単位中の複数のＲ４同士、およびＲ５同士は、同じであっても異なっていてもよい。
中でも、水素原子またはアルキル基が好ましい。
アルキル基としては、直鎖、分岐、又は環状のアルキル基が好ましく、例えば、メチル基、エチル基、イソプロピル基、ブチル基、ｔｅｒｔ−ブチル基、ヘキシル基、シクロヘキシル基等が挙げられる。アルキル基の炭素数は１〜６が好ましく、より好ましくは１〜４である。
Examples of the monovalent non-reactive substituent represented by R 1 to R 7 in the general formula (3) include a hydrogen atom, an alkyl group, an alkenyl group, and an aryl group. R 1 to R 7 may all be the same or different. Moreover, several R < 4 > in a repeating unit and R < 5 > may be same or different.
Among these, a hydrogen atom or an alkyl group is preferable.
The alkyl group is preferably a linear, branched, or cyclic alkyl group, and examples thereof include a methyl group, an ethyl group, an isopropyl group, a butyl group, a tert-butyl group, a hexyl group, and a cyclohexyl group. As for carbon number of an alkyl group, 1-6 are preferable, More preferably, it is 1-4.
一般式（３）中のＱは、反応性基を表し、例えば、一般式（１）に示されるアクリロイル基を含む基、一般式（２）に示されるメタクリロイル基を含む基等が挙げられる。
本発明において、特定シリコーン化合物が有する反応性基は、分子鎖の片末端に位置し、分子鎖の側鎖や、分子鎖の両末端に反応性基を有するシリコーン化合物は、特定シリコーン化合物に含まれない。なお、分子鎖の側鎖に反応性基を有するものとしては、例えばシリコーン化合物が一般式（３）で表される場合、Ｒ４およびＲ５の少なくとも一方が反応性基である場合をいう。また、分子鎖の両末端に反応性基を有するものとしては、シリコーン化合物が一般式（３）で表される場合、Ｑのほかに、Ｒ１〜Ｒ３の少なくとも１つが反応性基である場合をいう。
Q in the general formula (3) represents a reactive group, and examples thereof include a group containing an acryloyl group represented by the general formula (1) and a group containing a methacryloyl group represented by the general formula (2).
In the present invention, the reactive group possessed by the specific silicone compound is located at one end of the molecular chain, and the silicone compound having a reactive group at the side chain of the molecular chain or both ends of the molecular chain is included in the specific silicone compound. I can't. Incidentally, those having a reactive group in the side chain of the molecular chain, for example, if the silicone compound is represented by the general formula (3), refers to the case at least one of R 4 and R 5 is a reactive group. Further, those having a reactive group at both ends of the molecular chain, if the silicone compound is represented by the general formula (3), in addition to Q, at least one of R 1 to R 3 is a reactive group Refers to cases.
特定シリコーン化合物としては、上記の中でも、一般式（３）で表され、Ｒ１〜Ｒ７が全てメチル基であり、Ｑが一般式（１）または一般式（２）で表される化合物であることが好ましい。 Among the above, the specific silicone compound is a compound represented by the general formula (3), wherein R 1 to R 7 are all methyl groups, and Q is a compound represented by the general formula (1) or the general formula (2). Preferably there is.
特定シリコーン化合物の数平均分子量（Ｍｎとも称する）は、基体樹脂に含まれる不飽和樹脂との反応性、および、基体樹脂表面に特定シリコーン化合物が偏在する観点から、５，０００〜２０，０００であり、６，０００〜１５，０００であることが好ましい。既述のように、特定シリコーン化合物の数平均分子量（Ｍｎ）が２０，０００を超えると、基体樹脂に含まれる不飽和樹脂とシリコーン化合物とが相溶せずに分離し、表面へ選択的に集まらなくなり、分子量が５，０００未満であると、シリコーン化合物が相溶しすぎて、基体樹脂表面にシリコーン化合物が偏在しないため、優れた撥水性と水の転がり性を発現することができない。 The number average molecular weight (also referred to as Mn) of the specific silicone compound is 5,000 to 20,000 from the viewpoint of the reactivity with the unsaturated resin contained in the base resin and the uneven distribution of the specific silicone compound on the base resin surface. Yes, it is preferably 6,000 to 15,000. As described above, when the number average molecular weight (Mn) of the specific silicone compound exceeds 20,000, the unsaturated resin and the silicone compound contained in the base resin are separated from each other without being compatible with each other, and selectively to the surface. When the molecular weight is less than 5,000, the silicone compound is too compatible and the silicone compound is not unevenly distributed on the surface of the base resin, so that excellent water repellency and water rollability cannot be expressed.
上記の数平均分子量を有する特定シリコーン化合物の性状は、特に制限されず、室温で固体状態であっても、オイル状態であってもよいが、基体樹脂との反応で生成するポリシロキサン分子の成形品の最表面への移行のし易さの観点からは、室温（例えば、２５℃）でオイル状であることが好ましい。 The property of the specific silicone compound having the above number average molecular weight is not particularly limited, and may be in a solid state or an oil state at room temperature, but may be a polysiloxane molecule formed by reaction with a base resin. From the viewpoint of easy transfer to the outermost surface of the product, it is preferably oily at room temperature (for example, 25 ° C.).
また、本発明の繊維強化プラスチック組成物中の特定シリコーン化合物の含有量は、基体樹脂１００質量部に対して、１質量部〜４質量部である。１質量部未満であると、撥水性の付与効果が十分に得られず、防汚が劣るものとなり、４質量部を超えると、繊維強化プラスチック組成物を水まわり製品としたときに、シリコーン化合物が浮き出したり、水まわり製品の表面性状を損ねる。 Moreover, content of the specific silicone compound in the fiber reinforced plastic composition of this invention is 1 mass part-4 mass parts with respect to 100 mass parts of base resin. When the amount is less than 1 part by mass, the effect of imparting water repellency cannot be sufficiently obtained, and the antifouling property is inferior. Will be raised or the surface properties of water-related products will be damaged.
〔基体樹脂〕
本発明の繊維強化プラスチック組成物は、少なくとも不飽和樹脂を含む基体樹脂を含有する。
基体樹脂は、マトリックス樹脂として少なくとも不飽和樹脂を含み、本発明の繊維強化プラスチック組成物を後述するＳＭＣ、ＴＭＣ、ＢＭＣにより成形加工する場合には、さらに、低収縮剤等を含んで構成されていてもよい。従って、基体樹脂が不飽和樹脂のみを含む場合は、本発明の繊維強化プラスチック組成物中の特定シリコーン化合物および（メタ）アクリルモノマーの含有量は、不飽和樹脂１００質量部に対しての割合となり、基体樹脂が不飽和樹脂と低収縮剤とを含む樹脂組成物である場合には、本発明の繊維強化プラスチック組成物中の特定シリコーン化合物および（メタ）アクリルモノマーの含有量は、不飽和樹脂と低収縮剤との合計１００質量部に対しての割合となる。
[Base resin]
The fiber-reinforced plastic composition of the present invention contains a base resin containing at least an unsaturated resin.
The base resin contains at least an unsaturated resin as a matrix resin. When the fiber reinforced plastic composition of the present invention is molded by SMC, TMC, or BMC, which will be described later, it further includes a low shrinkage agent. May be. Therefore, when the base resin contains only an unsaturated resin, the content of the specific silicone compound and (meth) acrylic monomer in the fiber-reinforced plastic composition of the present invention is a ratio with respect to 100 parts by mass of the unsaturated resin. When the base resin is a resin composition containing an unsaturated resin and a low shrinkage agent, the content of the specific silicone compound and (meth) acrylic monomer in the fiber-reinforced plastic composition of the present invention is And the ratio of the total amount of the low shrinkage agent to 100 parts by mass.
−不飽和樹脂−
基体樹脂に含まれる不飽和樹脂としては、分子内に二重結合を含む樹脂であれば特に制限されず、例えば、不飽和ポリエステル樹脂、ビニルエステル樹脂、ポリアミド樹脂、フェノール樹脂などの単独あるいは混合物よりなる不飽和樹脂が挙げられる。
中でも、不飽和ポリエステル樹脂が好ましく用いられる。
不飽和ポリエステル樹脂は、不飽和ジカルボン酸を含むジカルボン酸成分とグリコール成分とをエステル化反応することによって得られる。不飽和ポリエステル樹脂は、数平均分子量５００〜５０００程度のポリマーであることが好ましい。
-Unsaturated resin-
The unsaturated resin contained in the base resin is not particularly limited as long as the resin contains a double bond in the molecule. For example, from unsaturated polyester resin, vinyl ester resin, polyamide resin, phenol resin alone or a mixture thereof. The unsaturated resin which becomes.
Of these, unsaturated polyester resins are preferably used.
The unsaturated polyester resin can be obtained by esterifying a dicarboxylic acid component containing an unsaturated dicarboxylic acid and a glycol component. The unsaturated polyester resin is preferably a polymer having a number average molecular weight of about 500 to 5,000.
マトリックス樹脂は、不飽和ポリエステル樹脂を含有する液状体を用いてもよい。
不飽和ポリエステル樹脂を含有する液状体は、不飽和ジカルボン酸を含むジカルボン酸成分とグリコール成分とをエステル化反応することによって得られた不飽和ポリエステル樹脂を液状のビニルモノマーに溶解したものとして得られる。
不飽和ジカルボン酸としては、通常無水マレイン酸又はフマル酸が用いられる。また、液状のビニルモノマーは、不飽和ポリエステル樹脂の溶媒として働くと共に、架橋剤として機能する。この液状のビニルモノマーとしては、一般にスチレンモノマーが用いられるが、その他メタクリル酸メチル、ビニルトルエン、α−メチルスチレンなどのモノマーや、ジビニルベンゼン、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）アクリレートなどの多官能性モノマーなどを、目的に応じて用いることができる。
この液状のビニルモノマーは一種を単独で用いてもよく、二種以上を組み合わせて用いてもよく、またその配合量は特に制限はなく、状況に応じて適宜選定されるが、一般に樹脂成分の合計量、すなわち前記不飽和ポリエステル樹脂と、後述の低収縮剤との合計１００質量部に対し、１０〜１５０質量部、好ましくは１５〜８０質量部の範囲で選ばれる。
As the matrix resin, a liquid containing an unsaturated polyester resin may be used.
A liquid containing an unsaturated polyester resin is obtained by dissolving an unsaturated polyester resin obtained by esterifying a dicarboxylic acid component containing an unsaturated dicarboxylic acid and a glycol component in a liquid vinyl monomer. .
As the unsaturated dicarboxylic acid, maleic anhydride or fumaric acid is usually used. The liquid vinyl monomer functions as a solvent for the unsaturated polyester resin and functions as a crosslinking agent. As the liquid vinyl monomer, a styrene monomer is generally used, but other monomers such as methyl methacrylate, vinyl toluene, α-methyl styrene, divinylbenzene, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meta ) A polyfunctional monomer such as acrylate can be used depending on the purpose.
This liquid vinyl monomer may be used singly or in combination of two or more, and the blending amount thereof is not particularly limited and is appropriately selected according to the situation. It is selected in the range of 10 to 150 parts by mass, preferably 15 to 80 parts by mass with respect to the total amount, that is, 100 parts by mass in total of the unsaturated polyester resin and the low shrinkage agent described later.
−低収縮剤−
低収縮剤としては、例えば、ポリメタクリル酸メチル樹脂や、ポリスチレン樹脂、ポリ酢酸ビニル樹脂、粉末ポリエチレン樹脂、飽和ポリエステル、スチレン−ブタジエン共重合体、スチレン−メタクリル酸共重合体、ポリカプロラクトン、ポリブタジエン等の熱可塑性樹脂などが挙げられ、中でも、ポリスチレン樹脂が好ましい。これらは一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
低収縮剤は、基体樹脂１００質量部に対して、０．５質量部〜１０質量部が好ましい。
低収縮剤の配合量は、得られる繊維強化プラスチックの収縮率や表面平滑性、表面光沢などを考慮して選定してもよく、前記マトリックス樹脂と該低収縮剤との質量比が、通常９０：１０〜５０：５０、好ましくは８０：２０〜６０：４０の範囲で選ばれる。
-Low shrinkage agent-
Examples of the low shrinkage agent include polymethyl methacrylate resin, polystyrene resin, polyvinyl acetate resin, powdered polyethylene resin, saturated polyester, styrene-butadiene copolymer, styrene-methacrylic acid copolymer, polycaprolactone, polybutadiene and the like. The thermoplastic resin of these is mentioned, Among these, a polystyrene resin is preferable. These may be used individually by 1 type, and may be used in combination of 2 or more types.
The low shrinkage agent is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the base resin.
The amount of the low shrinkage agent may be selected in consideration of the shrinkage rate, surface smoothness, surface gloss, etc. of the fiber-reinforced plastic obtained, and the mass ratio of the matrix resin to the low shrinkage agent is usually 90. : 10-50: 50, preferably 80: 20-60: 40.
〔他の添加成分〕
なお、本発明の繊維強化プラスチック組成物は、基体樹脂に対して特定シリコーン化合物および（メタ）アクリルモノマーを配合すること以外は、従来の一般的な繊維強化プラスチック組成物と同様の配合とすることができる。なお、繊維強化プラスチック組成物が含有する各添加成分は、いずれも一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
繊維強化プラスチックは、基体樹脂に補強材として繊維（好ましくはガラス繊維）が配合されたものである。繊維としては、ガラス繊維のほかに、炭素繊維、さらにはポリエステル繊維、ナイロン繊維、アラミド繊維などの有機繊維などが挙げられる。
一般に、補強材としてのガラス繊維は、Ｅ−ガラス（無アルカリガラス）、Ｓ−ガラス（Ｈｉｇｈ Ｓｔｒｅｎｇｔｈガラス）などに分類され、その形状としてはガラスロービング、チョップトストランドマット、ロービングクロスなどが使用される。
[Other additive components]
The fiber reinforced plastic composition of the present invention should have the same composition as the conventional general fiber reinforced plastic composition, except that the specific silicone compound and the (meth) acrylic monomer are blended with the base resin. Can do. In addition, as for each additive component which a fiber reinforced plastic composition contains, all may be used individually by 1 type, and may be used in combination of 2 or more types.
The fiber reinforced plastic is obtained by blending fibers (preferably glass fibers) as a reinforcing material in a base resin. Examples of the fiber include carbon fiber, and organic fiber such as carbon fiber, polyester fiber, nylon fiber, and aramid fiber.
Generally, glass fibers as a reinforcing material are classified into E-glass (non-alkali glass), S-glass (High Strength glass), and the like, and glass roving, chopped strand mat, roving cloth, etc. are used. The
ガラス繊維としてロービング形状の繊維を用いる場合は、通常、ロービングを切断した長繊維及び短繊維が用いられる。長繊維は、長さが、通常１５〜１００ｍｍ、好ましくは２０〜５０ｍｍの範囲のものであり、短繊維は、長さが、通常３ｍｍ以上１５ｍｍ未満、好ましくは６〜１３ｍｍの範囲のものである。
上記ロービングは、通常、繊維径５〜２５μｍの単繊維５０〜４０００本程度をポリ酢酸ビニル系、ポリエステル系、エポキシ樹脂系、ポリウレタン系などの集束剤で集束することにより得られたものである。
その他の添加成分としては、例えば、硬化触媒、内部離型剤、充填材等、次に示す各種成分が挙げられる。
When a roving-shaped fiber is used as the glass fiber, a long fiber and a short fiber obtained by cutting the roving are usually used. The long fiber has a length of usually 15 to 100 mm, preferably 20 to 50 mm, and the short fiber has a length of usually 3 mm or more and less than 15 mm, preferably 6 to 13 mm. .
The roving is usually obtained by bundling about 50 to 4000 single fibers having a fiber diameter of 5 to 25 μm with a bundling agent such as polyvinyl acetate, polyester, epoxy resin or polyurethane.
Examples of other additive components include the following various components such as a curing catalyst, an internal mold release agent, and a filler.
硬化触媒としては、例えば、ｔ−ブチルパーオキシベンゾエート、ｔ−ブチルパーオキシ−２−ヘキサノエート、メチルエチルケトンパーオキシド、アセチルアセトンパーオキシド、ベンゾイルパーオキシド、ジクミルパーオキシド、クメンハイドロパーオキシドなどの有機過酸化物が用いられる。硬化触媒は、いわゆる重合開始剤として慣用されているものである。 Examples of the curing catalyst include organic peroxidation such as t-butyl peroxybenzoate, t-butyl peroxy-2-hexanoate, methyl ethyl ketone peroxide, acetylacetone peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, and the like. Things are used. The curing catalyst is commonly used as a so-called polymerization initiator.
内部離型剤としては、例えば、ステアリン酸亜鉛等が用いられる。 As the internal release agent, for example, zinc stearate is used.
充填材としては、例えば、炭酸カルシウム、水酸化アルミニウム、シリカ、タルク、硫酸バリウム、レー、マイカ、中空バルーン（ガラス、シラス、セメント）、フェライト、亜鉛華などの無機化合物などが挙げられるが、これらの中で、炭酸カルシウムが好ましい。前記充填材は、分散性をよくするために、表面処理を施すことができる。 Examples of the filler include inorganic compounds such as calcium carbonate, aluminum hydroxide, silica, talc, barium sulfate, leh, mica, hollow balloon (glass, shirasu, cement), ferrite, and zinc white. Of these, calcium carbonate is preferred. The filler can be subjected to a surface treatment in order to improve dispersibility.
増粘剤として、例えば、不飽和ポリエステル樹脂中のカルボキシル基と反応し得るＭｇＯ、Ｍｇ（ＯＨ）２といったアルカリ土類金属の酸化物や水酸化物、Ｋ２Ｏ、ＫＯＨといったアルカリ金属の酸化物や水酸化物などが挙げられるが、一般的には酸化マグネシウムが用いられる。 As a thickener, for example, an oxide or hydroxide of an alkaline earth metal such as MgO or Mg (OH) 2 that can react with a carboxyl group in an unsaturated polyester resin, or an oxide of an alkali metal such as K 2 O or KOH In general, magnesium oxide is used.
着色剤としては、例えば、トナー、顔料等が挙げられる。 Examples of the colorant include toner and pigment.
硬化促進剤としては、例えば、ナフテン酸コバルト；オクトエ酸コバルト；Ｎ，Ｎ−ジメチルアニリン；Ｎ，Ｎ−ジエチルアニリン；Ｎ，Ｎ−ジメチル−ｐ−トルイジン；アセチルアセトン；アセト酢酸エチルなどが挙げられる。 Examples of the curing accelerator include cobalt naphthenate; cobalt octoate; N, N-dimethylaniline; N, N-diethylaniline; N, N-dimethyl-p-toluidine; acetylacetone; ethyl acetoacetate.
重合禁止剤としては、例えば、ハイドロキノン；ｐ−ベンゾキノン；メチルハイドロキノン；トリメチルハイドロキノン；ｔ−ブチルハイドロキノン；カテコール；ｔ−ブチルカテコール；２，６−ジ−ｔ−ブチル−４−メチルフェノールなどが挙げられる。 Examples of the polymerization inhibitor include hydroquinone; p-benzoquinone; methylhydroquinone; trimethylhydroquinone; t-butylhydroquinone; catechol; t-butylcatechol; 2,6-di-t-butyl-4-methylphenol. .
（添加成分の配合量）
本発明の繊維強化プラスチック組成物において、特定シリコーン化合物および（メタ）アクリルモノマー以外の添加成分の好適配合は、成形方法や用途等によっても異なるが、一般的に次のような配合割合とされ、繊維（好ましくはガラス繊維）は、これらを含む繊維強化プラスチック組成物中に２０〜５０質量％程度の割合で配合される。
本発明の繊維強化プラスチック組成物に含み得る他の添加成分の含有量は、基体樹脂（マトリックス樹脂および低収縮剤）１００質量部に対して、次の範囲が好ましい。
硬化触媒 ：０．２〜 ２質量部
内部離型剤：１．０〜１０質量部
充填材 ：１０〜２００質量部
増粘剤 ：０．５〜１０質量部
(Amount of additive component)
In the fiber reinforced plastic composition of the present invention, the preferred blending of the additive components other than the specific silicone compound and the (meth) acrylic monomer varies depending on the molding method, the use, etc., but is generally the following blending ratio, Fibers (preferably glass fibers) are blended in a proportion of about 20 to 50% by mass in a fiber reinforced plastic composition containing them.
The content of other additive components that can be included in the fiber-reinforced plastic composition of the present invention is preferably in the following range with respect to 100 parts by mass of the base resin (matrix resin and low shrinkage agent).
Curing catalyst: 0.2-2 parts by weight Internal mold release agent: 1.0-10 parts by weight Filler: 10-200 parts by weight Thickener: 0.5-10 parts by weight
以上例示したもののほか、従来から繊維強化プラスチック組成物に使用されているその他添加剤、例えば、酸化防止剤、紫外線吸収剤、消泡剤、揺変性付与剤などを、所望により配合することができる。 In addition to those exemplified above, other additives conventionally used in fiber reinforced plastic compositions, such as antioxidants, ultraviolet absorbers, antifoaming agents, thixotropic agents, and the like can be blended as desired. .
＜水まわり製品＞
本発明の水まわり製品は、本発明の繊維強化プラスチック組成物を用いて成形される。繊維強化プラスチックには多くの成形法があり、成形材料によりＳＭＣ（Ｓｈｅｅｔ Ｍｏｌｄｉｎｇ Ｃｏｍｐｏｕｎｄ）、ＢＭＣ（Ｂｕｌｋ Ｍｏｌｄｉｎｇ Ｃｏｍｐｏｕｎｄ）、ＴＭＣ（Ｔｈｉｃｋ Ｍｏｌｄｉｎｇ Ｃｏｍｐｏｕｎｄ）などに分類される。
<Water products>
The water product of the present invention is molded using the fiber reinforced plastic composition of the present invention. There are many molding methods for fiber reinforced plastics, which are classified into SMC (Sheet Molding Compound), BMC (Bulk Molding Compound), TMC (Thick Molding Compound), etc., depending on the molding material.
ＳＭＣは、基体樹脂に充填材、離型剤、硬化触媒などを混練した混合物に、増粘剤を混合した組成物をポリエチレンフィルム上に塗布し、この上に繊維（例えば、ガラス繊維）を敷き、両者を圧縮含浸させてシート状としてロール巻きし、タックフリーとしたものである。ＢＭＣは上述のベース樹脂に離型剤、硬化触媒などを混合した混合物に、充填材をニーダーで混練し、次いで増粘剤を混合した後、ガラス繊維を均一に分散混合し、ニーダー取り出して所定の大きさや形状となして熟成したものである。ＴＭＣは、基体樹脂に充填材、離型剤、硬化触媒などを混練した混合物に、増粘剤を混合した組成物と、繊維（例えば、ガラス繊維）とを、相対する少なくとも一対のローラーの間を通過させた後、当該ローラーに近接し、かつ間隙を設けて配置された回転体の高速回転により、生成混合物をかき落とし、棒状、塊状、シート状等の所望の形状にする方法である。 In SMC, a composition in which a thickener is mixed with a mixture obtained by kneading a base resin with a filler, a release agent, a curing catalyst, and the like is applied onto a polyethylene film, and fibers (for example, glass fibers) are laid on the polyethylene film. Both are compression impregnated and rolled into a sheet to make it tack free. BMC is a mixture of the above-mentioned base resin mixed with a release agent, a curing catalyst, etc., and a filler is kneaded with a kneader, then a thickener is mixed, and then glass fibers are uniformly dispersed and mixed, and the kneader is taken out and predetermined. Aged in the size and shape. TMC is a mixture of a base resin mixed with a filler, a release agent, a curing catalyst, etc., and a composition in which a thickener is mixed, and a fiber (for example, glass fiber) between at least a pair of opposed rollers. Is passed, and the product mixture is scraped off into a desired shape such as a rod shape, a lump shape, or a sheet shape by high-speed rotation of a rotating body that is arranged close to the roller and provided with a gap.
なお、ＳＭＣ成形やＴＭＣ成形において、シート状のＳＭＣないしＴＭＣを得る場合は、当該シートの厚みは、基体樹脂を含む混合物のガラス繊維への浸透性などの面から、通常、１〜１０ｍｍ、好ましくは１〜５ｍｍとする。 In the SMC molding or TMC molding, when obtaining sheet-like SMC or TMC, the thickness of the sheet is usually 1 to 10 mm, preferably from the viewpoint of the permeability of the mixture containing the base resin to the glass fiber. Is 1 to 5 mm.
本発明の水まわり製品は、常法に従って、本発明の繊維強化プラスチック組成物をＳＭＣ、ＢＭＣ、ＴＭＣ成形等により製造することができる。例えば、既述のシート状のＳＭＣとした本発明の繊維強化プラスチック組成物を、硬化成形することで、不飽和樹脂と、反応性基を有する特定シリコーン化合物と、が（メタ）アクリルモノマーを介さずに反応する部分に加え、更に（メタ）アクリルモノマーを介して反応する部分が生じることで、ポリシロキサン分子がより効率的に成型品の表面に発現する。ポリシロキサン分子は、基体樹脂の表面にシロキサン部分が偏在しているため、成形品（水まわり製品）は高い撥水性と高い水の転がり性を有し、優れた防汚性を長期に亘り維持することができる。 The water-based product of the present invention can be produced by SMC, BMC, TMC molding or the like of the fiber reinforced plastic composition of the present invention according to a conventional method. For example, the fiber-reinforced plastic composition of the present invention, which is the sheet-like SMC described above, is cured and molded so that the unsaturated resin and the specific silicone compound having a reactive group are interposed via a (meth) acrylic monomer. In addition to the reactive part, a part that reacts via the (meth) acrylic monomer is generated, so that the polysiloxane molecules are more efficiently expressed on the surface of the molded product. Since the polysiloxane molecule has a siloxane portion unevenly distributed on the surface of the base resin, the molded product (water product) has high water repellency and high water rolling property, and maintains excellent antifouling properties over a long period of time. can do.
水まわり製品としては、特に制限されず、浴室、洗面化粧台、台所などで用いられ、水が付着する物が挙げられ、具体的には、例えば、ユニットバスの床、浴槽、壁や洗面化粧台のパネル、洗面器等が挙げられる。
本発明の水まわり製品は、本発明の繊維強化プラスチック組成物を成形加工して得られるので、高い防汚性を示し、防汚効果の耐久性にも優れる。また、本発明の水まわり製品は、安価に製造でき、また、水まわり製品の形状が複雑形状でも適用可能である。
The product around the water is not particularly limited, and is used in bathrooms, vanity tables, kitchens, etc., and can be attached to water. Specifically, for example, a floor of a unit bath, a bathtub, a wall, and a toilet. A panel of a stand, a basin, etc. are mentioned.
Since the water product of the present invention is obtained by molding the fiber reinforced plastic composition of the present invention, it exhibits high antifouling properties and excellent antifouling durability. Moreover, the water product of the present invention can be manufactured at low cost, and can be applied even if the shape of the water product is complicated.
以下に実施例及び比較例を挙げて本発明をより具体的に説明する。なお、以下において、特に記載しない限り、「部」および「％」は質量基準である。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the following, “part” and “%” are based on mass unless otherwise specified.
〔実施例１〕
＜ＦＲＰ組成物の調製＞
表１に示す成分を混合し、ＦＲＰ組成物１を調製した。
具体的には、基体樹脂１００部に対し、特定シリコーン化合物（ＪＮＣ(株)社製、ＦＭ０７２５）を１．００部、およびメタクリルモノマー（１）（共栄社化学製、ライトエステルＴＢ、ｔｅｒｔ−ブチルメタクリレート）を表３に示す割合で配合した。これに、表１に示す成分のうち、基体樹脂、シリコーン化合物、メタクリルモノマー（１）及びガラス繊維以外の他の成分を添加して混練したものを、ガラス繊維のチョップドストランドマットに含浸させて、実施例１のＦＲＰ組成物１（ガラス繊維強化プラスチック組成物）を得た。なお、表１中、ガラス繊維の量（％）は、ＦＲＰ組成物１（ガラス繊維強化プラスチック組成物）の全質量に対する割合を示す。
[Example 1]
<Preparation of FRP composition>
The components shown in Table 1 were mixed to prepare FRP composition 1.
Specifically, with respect to 100 parts of the base resin, 1.00 part of a specific silicone compound (manufactured by JNC Corporation, FM0725) and methacryl monomer (1) (manufactured by Kyoeisha Chemical Co., Ltd., light ester TB, tert-butyl methacrylate) ) Were blended in the proportions shown in Table 3. To this, a glass fiber chopped strand mat is impregnated with a base resin, a silicone compound, a methacrylic monomer (1), and other components other than glass fiber among the components shown in Table 1, and kneaded. The FRP composition 1 (glass fiber reinforced plastic composition) of Example 1 was obtained. In Table 1, the amount (%) of glass fiber represents a ratio to the total mass of FRP composition 1 (glass fiber reinforced plastic composition).
尚、前記特定シリコーン化合物（ＪＮＣ(株)社製、ＦＭ０７２５）のＭｎ（数平均分子量）＝１４，９７２、Ｍｗ（重量平均分子量）＝１６，０８９、Ｍｐ（ピークトップ分子量）＝１６，１７６であり、室温でオイル状であった。ここで、特定シリコーン化合物のＭｎ（数平均分子量）、Ｍｗ（重量平均分子量）、Ｍｐ（ピークトップ分子量）は、下記条件によるＧＰＣ測定により測定したポリスチレン換算の値である。
・測定器；Ｗａｔｅｒｓ社製、ゲルパーミエーションクロマトグラフ（ＧＰＣ）
・カラム；東ソー社製、TSKgelSuperH2000+TSKgelSuperH3000
・溶剤 ；テトラヒドロフラン（ＴＨＦ）
・カラム温度；４０℃
・流量 ；０．５ｍｌ／ｍｉｎ
In addition, Mn (number average molecular weight) of the specific silicone compound (manufactured by JNC Corporation, FM0725) = 14,972, Mw (weight average molecular weight) = 16,089, Mp (peak top molecular weight) = 16,176 Yes, it was oily at room temperature. Here, Mn (number average molecular weight), Mw (weight average molecular weight), and Mp (peak top molecular weight) of the specific silicone compound are values in terms of polystyrene measured by GPC measurement under the following conditions.
・ Measuring instrument: Water perm, gel permeation chromatograph (GPC)
・ Column: Tosoh Corporation, TSKgelSuperH2000 + TSKgelSuperH3000
・ Solvent: Tetrahydrofuran (THF)
Column temperature: 40 ° C
・ Flow rate: 0.5ml / min
＜水まわり製品の作製＞
得られたＦＲＰ組成物１を、シート状に成形してＳＭＣ１とした。
次いで、得られたＳＭＣ１を、硬化温度１４０℃で硬化させて、実施例１のガラス繊維強化プラスチックの板状試料（水まわり製品１）を作製した。
<Production of water products>
The obtained FRP composition 1 was formed into a sheet shape to obtain SMC1.
Next, the obtained SMC1 was cured at a curing temperature of 140 ° C. to produce a glass fiber reinforced plastic plate sample (water product 1) of Example 1.
＜評価＞
−水の転がり性評価（水まわり製品表面に対する水の転落角）−
得られた水まわり製品１表面に蒸留水３０μＬを付着させたときの転落角を測定し、結果を表３に示した。水の転落角は、協和界面科学製接触角測定装置によって測定し、３回の測定結果の平均値を記した。
<Evaluation>
-Evaluation of water rollability (water fall angle with respect to the surface of water products)-
The falling angle when 30 μL of distilled water was allowed to adhere to the surface of the obtained water product 1 was measured, and the results are shown in Table 3. The falling angle of water was measured by a contact angle measuring device manufactured by Kyowa Interface Science, and the average value of three measurement results was recorded.
〔実施例２〜実施例８、及び、比較例１〕
実施例１のＦＲＰ組成物１の調製において、メタクリルモノマー（１）のＦＲＰ組成物中の含有量を、表３の「含有量」欄に示す量としたほかは同様にして、実施例２〜実施例８のＦＲＰ組成物２〜８、及び、比較例１のＦＲＰ組成物１０１を調製した。また、ＦＲＰ組成物の調製にあたっては、ＦＲＰ組成物中のガラス繊維含有率が２５質量％となるように、シリコーン化合物の割合に応じて水分量を調整した。
[Examples 2 to 8 and Comparative Example 1]
In the preparation of the FRP composition 1 of Example 1, the content of the methacrylic monomer (1) in the FRP composition was the same as that of Example 2 except that the content shown in the “Content” column of Table 3 was used. FRP compositions 2 to 8 of Example 8 and FRP composition 101 of Comparative Example 1 were prepared. In preparing the FRP composition, the water content was adjusted according to the ratio of the silicone compound so that the glass fiber content in the FRP composition was 25% by mass.
次いで、実施例１の水まわり製品１の製造において、ＦＲＰ組成物１に替えて、実施例２〜実施例８のＦＲＰ組成物２〜８、または、比較例１のＦＲＰ組成物１０１を用いた他は同様にして、実施例２〜実施例８の水まわり製品２〜８、及び、比較例１の水まわり製品１０１を製造した。 Next, in the production of the plumbing product 1 of Example 1, instead of the FRP composition 1, the FRP compositions 2 to 8 of Examples 2 to 8 or the FRP composition 101 of Comparative Example 1 were used. In the same manner, the plumbing products 2 to 8 of Examples 2 to 8 and the plumbing product 101 of Comparative Example 1 were produced.
得られた実施例２〜実施例８の水まわり製品２〜８、及び、比較例１の水まわり製品１０１を、実施例１と同様の方法にて、水の転落角を測定し、測定結果を表３に示した。 The water drop products 2 to 8 of Example 2 to Example 8 and the water drop product 101 of Comparative Example 1 were measured for the falling angle of water in the same manner as in Example 1, and the measurement results were obtained. Are shown in Table 3.
〔実施例９〕
＜ＦＲＰ組成物の調製＞
表２に示す成分を混合し、ＦＲＰ組成物９を調製した。
具体的には、基体樹脂１００部に対し、特定シリコーン化合物（ＪＮＣ(株)社製、ＦＭ０７２５）を１．００部、およびアクリルモノマー（２）（共栄社化学製、ライトアクリレートＩＢ−ＸＡ、イソボルニルアクリレート）を表３に示す割合（０．５部）で配合した。これに、表２に示す成分のうち、基体樹脂、シリコーン化合物、アクリルモノマー（２）及びガラス繊維以外の他の成分を添加して混練したものを、ガラス繊維のチョップドストランドマットに含浸させて、実施例９のＦＲＰ組成物９（ガラス繊維強化プラスチック組成物）を得た。なお、表２中、ガラス繊維の量（％）は、ＦＲＰ組成物９（ガラス繊維強化プラスチック組成物）の全質量に対する割合を示す。
Example 9
<Preparation of FRP composition>
The components shown in Table 2 were mixed to prepare FRP composition 9.
Specifically, with respect to 100 parts of the base resin, 1.00 part of a specific silicone compound (manufactured by JNC Corporation, FM0725) and acrylic monomer (2) (manufactured by Kyoeisha Chemical Co., Ltd., Light Acrylate IB-XA, Isovol) Nyl acrylate) was blended in the proportions shown in Table 3 (0.5 parts). To this, a glass fiber chopped strand mat is impregnated with a base resin, a silicone compound, an acrylic monomer (2), and other components other than glass fiber among the components shown in Table 2, and kneaded. The FRP composition 9 (glass fiber reinforced plastic composition) of Example 9 was obtained. In Table 2, the amount (%) of the glass fiber indicates a ratio with respect to the total mass of the FRP composition 9 (glass fiber reinforced plastic composition).
実施例１〜９と比較例１については、表３より明らかなように、比較例は転落角が大きくなっているのに対し、実施例はいずれも転落角が小さくなっている。従って、より厳格な評価においては、実施例の水まわり製品の方が、防汚性に優れていることがわかった。 As is clear from Table 3 for Examples 1 to 9 and Comparative Example 1, the comparative example has a large falling angle, while the examples all have a small falling angle. Therefore, in the stricter evaluation, it was found that the water-based products of the examples were superior in antifouling property.
Claims (4)
前記基体樹脂１００質量部に対して、１質量部〜４質量部の、数平均分子量が５，０００〜２０，０００であり、片末端に反応性基を有するシリコーン化合物と、
（メタ）アクリルモノマーと、
（メタ）アクリルモノマー以外の架橋剤と、
を含有する繊維強化プラスチック組成物。 A base resin containing at least an unsaturated resin;
A silicone compound having a number average molecular weight of 5,000 to 20,000 and having a reactive group at one end, with respect to 100 parts by weight of the base resin,
(Meth) acrylic monomers,
Cross-linking agents other than (meth) acrylic monomers;
A fiber-reinforced plastic composition comprising:
前記基体樹脂１００質量部に対して、１質量部〜４質量部の、数平均分子量が５，０００〜２０，０００であり、片末端に反応性基を有するシリコーン化合物と、
（メタ）アクリルモノマーと、
（メタ）アクリルモノマー以外の架橋剤と、
補強材として、シート形状でない、長さ１５ｍｍ以上１００ｍｍ以下の長繊繊及び長さ３ｍｍ以上１５ｍｍ未満の短繊維の少なくとも一方と、
を含有する繊維強化プラスチック組成物。 A base resin containing at least an unsaturated resin;
A silicone compound having a number average molecular weight of 5,000 to 20,000 and having a reactive group at one end, with respect to 100 parts by weight of the base resin,
(Meth) acrylic monomers,
Cross-linking agents other than (meth) acrylic monomers;
As a reinforcing material, at least one of a long fiber having a length of 15 mm or more and 100 mm or less and a short fiber having a length of 3 mm or more and less than 15 mm, which is not a sheet shape,
A fiber-reinforced plastic composition comprising:
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