JP5740464B2 - Foamable composition and method for producing foamed molded article - Google Patents
Foamable composition and method for producing foamed molded article Download PDFInfo
- Publication number
- JP5740464B2 JP5740464B2 JP2013272092A JP2013272092A JP5740464B2 JP 5740464 B2 JP5740464 B2 JP 5740464B2 JP 2013272092 A JP2013272092 A JP 2013272092A JP 2013272092 A JP2013272092 A JP 2013272092A JP 5740464 B2 JP5740464 B2 JP 5740464B2
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- Prior art keywords
- epoxy group
- monomer
- particularly limited
- weight
- molding
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 60
- 238000004519 manufacturing process Methods 0.000 title description 17
- 239000002245 particle Substances 0.000 claims description 94
- 239000000178 monomer Substances 0.000 claims description 72
- 239000003795 chemical substances by application Substances 0.000 claims description 53
- 125000003700 epoxy group Chemical group 0.000 claims description 44
- -1 amine compound Chemical class 0.000 claims description 36
- 238000000465 moulding Methods 0.000 claims description 27
- 238000005187 foaming Methods 0.000 claims description 26
- 238000010097 foam moulding Methods 0.000 claims description 18
- 230000008961 swelling Effects 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 239000011159 matrix material Substances 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 13
- 150000002825 nitriles Chemical class 0.000 claims description 12
- 239000011342 resin composition Substances 0.000 claims description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- 239000003381 stabilizer Substances 0.000 description 20
- 239000002612 dispersion medium Substances 0.000 description 19
- 239000006185 dispersion Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 239000006260 foam Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- 239000007859 condensation product Substances 0.000 description 10
- 239000004088 foaming agent Substances 0.000 description 9
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- 150000001768 cations Chemical class 0.000 description 8
- 239000008119 colloidal silica Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
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- 238000004381 surface treatment Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 5
- 125000004386 diacrylate group Chemical group 0.000 description 5
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- 239000007788 liquid Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002984 plastic foam Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 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
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 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
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
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- 230000008901 benefit Effects 0.000 description 2
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- 239000012933 diacyl peroxide Substances 0.000 description 2
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- 239000003995 emulsifying agent Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
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- 238000002347 injection Methods 0.000 description 2
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- 229910052744 lithium Inorganic materials 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
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- 150000003512 tertiary amines Chemical class 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
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- TUGAMVVIFZLKTI-UHFFFAOYSA-N (3-methoxy-3-methylbutoxy)peroxycarbonyl (3-methoxy-3-methylbutyl)peroxy carbonate Chemical compound COC(C)(C)CCOOOC(=O)OC(=O)OOOCCC(C)(C)OC TUGAMVVIFZLKTI-UHFFFAOYSA-N 0.000 description 1
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- BPUIXAJWGWYVJH-UHFFFAOYSA-M 1,3-dibenzyl-2-methylimidazol-1-ium;chloride Chemical compound [Cl-].C1=C[N+](CC=2C=CC=CC=2)=C(C)N1CC1=CC=CC=C1 BPUIXAJWGWYVJH-UHFFFAOYSA-M 0.000 description 1
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- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical group CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
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- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
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- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 1
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- KYCGURZGBKFEQB-UHFFFAOYSA-N n',n'-dibutylpropane-1,3-diamine Chemical compound CCCCN(CCCC)CCCN KYCGURZGBKFEQB-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- ITZPOSYADVYECJ-UHFFFAOYSA-N n'-cyclohexylpropane-1,3-diamine Chemical compound NCCCNC1CCCCC1 ITZPOSYADVYECJ-UHFFFAOYSA-N 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
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- 229920002647 polyamide Polymers 0.000 description 1
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- WDIWAJVQNKHNGJ-UHFFFAOYSA-N trimethyl(propan-2-yl)silane Chemical compound CC(C)[Si](C)(C)C WDIWAJVQNKHNGJ-UHFFFAOYSA-N 0.000 description 1
- WNWMJFBAIXMNOF-UHFFFAOYSA-N trimethyl(propyl)silane Chemical compound CCC[Si](C)(C)C WNWMJFBAIXMNOF-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polymerisation Methods In General (AREA)
Description
本発明は、高温で加熱しても粒子の破裂及び収縮が生じにくく、高発泡倍率での発泡成形に用いることができる発泡性組成物に関する。また、本発明は、上記発泡性組成物を用いた発泡成形体の製造方法に関する。 The present invention relates to a foamable composition that is less susceptible to particle rupture and shrinkage even when heated at high temperatures and can be used for foam molding at a high foaming ratio. Moreover, this invention relates to the manufacturing method of the foaming molding using the said foamable composition.
プラスチック発泡体は、発泡体の素材と形成された気泡の状態に応じて遮熱性、断熱性、遮音性、吸音性、防振性、軽量化等を発現させることができることから、様々な用途で用いられている。プラスチック発泡体を製造する方法としては、例えば、熱可塑性樹脂等のマトリックス樹脂と発泡剤とを含有する樹脂組成物、マスターバッチ等を射出成形、押出成形等の成形方法を用いて成形し、成形時の加熱により発泡剤を発泡させる方法が挙げられる。 Plastic foam can exhibit heat insulation, heat insulation, sound insulation, sound absorption, vibration insulation, weight reduction, etc. depending on the foam material and the state of the formed bubbles, so it can be used in various applications. It is used. As a method for producing a plastic foam, for example, a resin composition containing a matrix resin such as a thermoplastic resin and a foaming agent, a masterbatch, and the like are molded using a molding method such as injection molding or extrusion molding, and then molded. The method of making a foaming agent foam by the heating of time is mentioned.
プラスチック発泡体を製造する際には、例えば、化学発泡剤、熱膨張性の発泡粒子等が発泡剤として用いられる。
例えば、特許文献1には、少なくともエチレン−α−オレフィン共重合体と発泡剤とを、混練、成形して得られた発泡性ペレットが記載されており、発泡剤としてアゾ化合物、ヒドラジン誘導体、重炭酸塩等が挙げられている。特許文献1には、同文献に記載の発泡性ペレットを用いると、樹脂の種類を問わず高発泡倍率で射出発泡成形することができ、多様な硬度で均一な気泡の射出発泡成形体が得られることが記載されている。
When manufacturing a plastic foam, for example, a chemical foaming agent, thermally expandable foamed particles, and the like are used as the foaming agent.
For example, Patent Document 1 describes foamable pellets obtained by kneading and molding at least an ethylene-α-olefin copolymer and a foaming agent. As the foaming agent, an azo compound, a hydrazine derivative, Carbonates and the like are mentioned. In Patent Document 1, when foamable pellets described in the same document are used, it is possible to perform injection foam molding at a high expansion ratio regardless of the type of resin, and to obtain an injection foam molded body with uniform hardness and various bubbles. It is described that
しかしながら、このような化学発泡剤を用いると、気泡の壁はマトリックス樹脂により形成されることとなり、壁の薄い部分が破裂して連続気泡が生じたり、壁の厚みにばらつきが生じたりすることがあるため、均一な独立気泡を有する発泡体を得ることは難しい。また、化学発泡剤が加熱分解して分解ガスが生じると、同時に発泡残渣が生じ、得られる発泡体の性能に影響を与えることがある。 However, when such a chemical foaming agent is used, the walls of the bubbles are formed by the matrix resin, and the thin portion of the wall may rupture, resulting in open cells or variations in the wall thickness. For this reason, it is difficult to obtain a foam having uniform closed cells. Further, when the chemical foaming agent is thermally decomposed to generate decomposition gas, a foaming residue is generated at the same time, which may affect the performance of the resulting foam.
一方、発泡剤として用いられる熱膨張性の発泡粒子としては、例えば、熱可塑性シェルポリマーの中に、シェルポリマーの軟化点以下の温度でガス状になる揮発性膨張剤を内包して得られる粒子が挙げられる。例えば、特許文献2には、熱膨張性マイクロバルーンを含有するマスターバッチを用いることにより、均一で微細な粒径のセルを有し、物性の均一性や機械的特性に優れた熱可塑性エラストマー発泡体が得られることが記載されている。 On the other hand, as the thermally expandable foam particles used as a foaming agent, for example, particles obtained by encapsulating a volatile swelling agent that becomes gaseous at a temperature below the softening point of the shell polymer in a thermoplastic shell polymer. Is mentioned. For example, in Patent Document 2, by using a masterbatch containing a thermally expandable microballoon, a thermoplastic elastomer foam having uniform and fine particle diameter cells and excellent physical property uniformity and mechanical properties is disclosed. It is described that a body is obtained.
しかしながら、この方法によって得られる発泡粒子は、80〜130℃程度の比較的低温では揮発性膨張剤がガス状になることによって熱膨張できるものの、高温又は長時間加熱すると、膨張した発泡粒子からガスが抜けることによって発泡倍率が低下してしまう。また、発泡粒子の耐熱性又は強度が不充分であると、いわゆる「へたり」と呼ばれる現象が生じ、高温時に潰れてしまうことがある。そのため、このような発泡粒子を用いると、高温での成形工程を必要とする場合には高発泡倍率で成形を行うことは難しく、適用できる用途が限定されてしまうことが問題である。 However, the expanded particles obtained by this method can be thermally expanded at a relatively low temperature of about 80 to 130 ° C. due to the volatile expansion agent becoming a gas. The foaming ratio decreases due to the loss of the foam. Further, if the heat resistance or strength of the expanded particles is insufficient, a phenomenon called “sag” occurs, and the foamed particles may be crushed at a high temperature. Therefore, when such foamed particles are used, it is difficult to perform molding at a high expansion ratio when a molding process at a high temperature is required, and there is a problem that applicable applications are limited.
本発明は、高温で加熱しても粒子の破裂及び収縮が生じにくく、高発泡倍率での発泡成形に用いることができる発泡性組成物を提供することを目的とする。また、本発明は、上記発泡性組成物を用いた発泡成形体の製造方法を提供することを目的とする。 An object of the present invention is to provide a foamable composition that is less likely to be ruptured and shrunk even when heated at a high temperature and can be used for foam molding at a high foaming ratio. Moreover, an object of this invention is to provide the manufacturing method of the foaming molding using the said foamable composition.
本発明は、発泡粒子と、エポキシ基と反応可能な硬化剤とを含有する発泡性組成物であって、前記発泡粒子は、共重合体からなるシェルに、コア剤として揮発性膨張剤を内包しており、前記共重合体は、ニトリル系モノマーと、少なくとも1つの重合性不飽和結合を有するエポキシ基含有モノマーとを含有するモノマー混合物を共重合することにより得られ、前記ニトリル系モノマー100重量部に対して前記少なくとも1つの重合性不飽和結合を有するエポキシ基含有モノマーを1〜30重量部含有する発泡性組成物である。
以下に本発明を詳述する。
The present invention relates to a foamable composition comprising foamed particles and a curing agent capable of reacting with an epoxy group, wherein the foamed particles contain a volatile swelling agent as a core agent in a shell made of a copolymer. and it is, the copolymer has a nitrile monomer, is obtained by copolymerizing a monomer mixture containing an epoxy group-containing monomer having at least one polymerizable unsaturated bond, the nitrile monomer 100 wt It is a foamable composition containing 1 to 30 parts by weight of an epoxy group-containing monomer having at least one polymerizable unsaturated bond with respect to parts .
The present invention is described in detail below.
本発明者らは、共重合体からなるシェルに、コア剤として揮発性膨張剤を内包する発泡粒子を含有する発泡性組成物において、シェルを構成する共重合体を特定のモノマー混合物から得るとともに、エポキシ基と反応可能な硬化剤を添加することにより、高温で加熱しても粒子の破裂及び収縮を生じにくく、高発泡倍率での発泡成形に用いることができる発泡性組成物が得られることを見出し、本発明を完成させるに至った。 In the foamable composition containing foamed particles containing a volatile swelling agent as a core agent in a shell made of a copolymer, the present inventors obtain a copolymer constituting the shell from a specific monomer mixture. By adding a curing agent capable of reacting with an epoxy group, it is possible to obtain a foamable composition that can be used for foam molding at a high foaming ratio without causing particle rupture and shrinkage even when heated at a high temperature. As a result, the present invention has been completed.
本発明に係る発泡粒子は、共重合体からなるシェルに、コア剤として揮発性膨張剤を内包している。
このような構造を有することにより、本発明に係る発泡粒子をマトリックス樹脂に配合して成形すると、成形時の加熱により上記コア剤がガス状になるとともに上記シェルが軟化して膨張し、即ち、本発明に係る発泡粒子が発泡し、発泡成形体を製造することができる。
The foamed particles according to the present invention include a volatile swelling agent as a core agent in a shell made of a copolymer.
Due to having such a structure, when the foamed particles according to the present invention are blended and molded into a matrix resin, the core agent becomes gaseous by heating during molding and the shell softens and expands, that is, The foamed particles according to the present invention can be foamed to produce a foamed molded article.
上記シェルを構成する共重合体は、モノマー混合物を共重合することによって得られる。
上記モノマー混合物は、ニトリル系モノマーを含有する。
上記ニトリル系モノマーは特に限定されず、例えば、アクリロニトリル、メタクリロニトリル、α−クロロアクリロニトリル、α−エトキシアクリロニトリル、フマルニトリル、又は、これらの混合物等が挙げられる。これらのなかでは、アクリロニトリル及びメタクリロニトリルが特に好ましい。これらは単独で用いられてもよく、2種以上が併用されてもよい。
The copolymer constituting the shell is obtained by copolymerizing a monomer mixture.
The monomer mixture contains a nitrile monomer.
The nitrile monomer is not particularly limited, and examples thereof include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, fumaronitrile, or a mixture thereof. Of these, acrylonitrile and methacrylonitrile are particularly preferred. These may be used independently and 2 or more types may be used together.
上記モノマー混合物は、少なくとも1つの重合性不飽和結合を有するエポキシ基含有モノマーを含有する。
上記少なくとも1つの重合性不飽和結合を有するエポキシ基含有モノマーは、少なくとも1つの重合性不飽和結合とエポキシ基とを分子内に有していれば特に限定されないが、重合性不飽和結合を1つ又は2つ有するエポキシ基含有モノマーが好ましい。
The monomer mixture contains an epoxy group-containing monomer having at least one polymerizable unsaturated bond.
The epoxy group-containing monomer having at least one polymerizable unsaturated bond is not particularly limited as long as it has at least one polymerizable unsaturated bond and an epoxy group in the molecule. One or two epoxy group-containing monomers are preferred.
上記重合性不飽和結合を1つ有するエポキシ基含有モノマーは特に限定されず、グリシジルメタクリレート、グリシジルアクリレート、フェノール型エポキシアクリレート等が挙げられる。これらのなかでは、グリシジルメタクリレートが好ましい。これらは単独で用いられてもよく、2種以上が併用されてもよい。 The epoxy group-containing monomer having one polymerizable unsaturated bond is not particularly limited, and examples thereof include glycidyl methacrylate, glycidyl acrylate, and phenol type epoxy acrylate. Of these, glycidyl methacrylate is preferred. These may be used independently and 2 or more types may be used together.
上記重合性不飽和結合を2つ有するエポキシ基含有モノマーは特に限定されず、アリルアルコール型エポキシジアクリレート、1,6−へキサンジオール型エポキシジアクリレート、ビスフェノール型エポキシジアクリレート、フタル酸型エポキシジアクリレート、ポリプロピレングリコール型エポキシジアクリレート(n=1、3、11)、ポリエチレングリコール型エポキシジメタクリレート(n=1、2、9)等が挙げられる。これらのなかでは、ポリプロピレングリコール型エポキシジアクリレート(n=1、3、11)が好ましい。これらは単独で用いられてもよく、2種以上が併用されてもよい。 The epoxy group-containing monomer having two polymerizable unsaturated bonds is not particularly limited, and is allyl alcohol type epoxy diacrylate, 1,6-hexanediol type epoxy diacrylate, bisphenol type epoxy diacrylate, phthalic acid type epoxy diester. Examples include acrylate, polypropylene glycol type epoxy diacrylate (n = 1, 3, 11), polyethylene glycol type epoxy dimethacrylate (n = 1, 2, 9), and the like. Among these, polypropylene glycol type epoxy diacrylate (n = 1, 3, 11) is preferable. These may be used independently and 2 or more types may be used together.
上記モノマー混合物中の上記少なくとも1つの重合性不飽和結合を有するエポキシ基含有モノマーの含有量は特に限定されないが、上記ニトリル系モノマー100重量部に対する好ましい下限が0.5重量部、好ましい上限が30重量部である。上記少なくとも1つの重合性不飽和結合を有するエポキシ基含有モノマーの含有量が0.5重量部未満であると、得られる発泡粒子をマトリックス樹脂に配合して成形する際、成形時に高温で加熱すると、粒子の破裂及び収縮が生じやすくなることがある。上記少なくとも1つの重合性不飽和結合を有するエポキシ基含有モノマーの含有量が30重量部を超えると、得られる発泡粒子は、シェルのガスバリア性が低下し、発泡性能が低下することがある。上記少なくとも1つの重合性不飽和結合を有するエポキシ基含有モノマーの含有量は、上記ニトリル系モノマー100重量部に対するより好ましい下限が1重量部、より好ましい上限が20重量部である。 The content of the epoxy group-containing monomer having at least one polymerizable unsaturated bond in the monomer mixture is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the nitrile monomer is 0.5 parts by weight, and a preferable upper limit is 30. Parts by weight. When the content of the epoxy group-containing monomer having at least one polymerizable unsaturated bond is less than 0.5 parts by weight, when the foamed particles obtained are molded into a matrix resin and molded, when heated at a high temperature during molding Particle rupture and shrinkage may occur easily. When the content of the epoxy group-containing monomer having at least one polymerizable unsaturated bond exceeds 30 parts by weight, the resulting foamed particles may have a deteriorated gas barrier property of the shell and a foaming performance. As for the content of the epoxy group-containing monomer having at least one polymerizable unsaturated bond, a more preferable lower limit with respect to 100 parts by weight of the nitrile monomer is 1 part by weight, and a more preferable upper limit is 20 parts by weight.
上記モノマー混合物は、上記ニトリル系モノマー、及び、上記少なくとも1つの重合性不飽和結合を有するエポキシ基含有モノマーと共重合することのできる他のモノマー(以下、単に他のモノマーともいう)を含有してもよい。
上記他のモノマーは特に限定されず、得られる発泡粒子に必要とされる特性に応じて適宜選択することができるが、例えば、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、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、1,4−ブタンジオールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、1,9−ノナンジオールジ(メタ)アクリレート、分子量が200〜600のポリエチレングリコールのジ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、トリメチロールプロパンジ(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、エチレンオキサイド変性トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリアリルホルマールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ジメチロール−トリシクロデカンジ(メタ)アクリレート等が挙げられる。また、上記他のモノマーとして、例えば、アクリル酸、メタクリル酸、エタクリル酸、クロトン酸、ケイ皮酸等の不飽和モノカルボン酸や、マレイン酸、イタコン酸、フマル酸、シトラコン酸等の不飽和ジカルボン酸や、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、ジシクロペンテニルアクリレート等のアクリル酸エステル類や、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、イソボルニルメタクリレート等のメタクリル酸エステル類や、塩化ビニル、塩化ビニリデン、酢酸ビニル、スチレン等のビニルモノマー等も挙げられる。
これらは単独で用いられてもよく、2種以上が併用されてもよい。これらのなかでは、アクリル酸、メタクリル酸、マレイン酸又は無水マレイン酸、イタコン酸が特に好ましい。
The monomer mixture contains the nitrile monomer and another monomer that can be copolymerized with the epoxy group-containing monomer having at least one polymerizable unsaturated bond (hereinafter also simply referred to as another monomer). May be.
The other monomers are not particularly limited and can be appropriately selected according to the characteristics required for the obtained expanded particles. For example, divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , Triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di ( (Meth) acrylate, di (meth) acrylate of polyethylene glycol having a molecular weight of 200 to 600, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modification Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triallyl formal tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dimethylol-tricyclodecandi ( And (meth) acrylate. Examples of the other monomers include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, and cinnamic acid, and unsaturated dicarboxylic acids such as maleic acid, itaconic acid, fumaric acid, and citraconic acid. Acrylic acid esters such as acid, methyl acrylate, ethyl acrylate, butyl acrylate, and dicyclopentenyl acrylate; and methacrylate esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and isobornyl methacrylate; And vinyl monomers such as vinyl chloride, vinylidene chloride, vinyl acetate, and styrene.
These may be used independently and 2 or more types may be used together. Among these, acrylic acid, methacrylic acid, maleic acid or maleic anhydride, and itaconic acid are particularly preferable.
上記モノマー混合物が上記他のモノマーを含有する場合、上記モノマー混合物中の上記他のモノマーの含有量は特に限定されないが、上記ニトリル系モノマー100重量部に対する好ましい上限が40重量部である。上記他のモノマーの含有量が40重量部を超えると、上記ニトリル系モノマー又は上記少なくとも1つの重合性不飽和結合を有するエポキシ基含有モノマーの含有量が低下して、得られる発泡粒子を用いると高発泡倍率で発泡成形を行うことができないことがある。 When the monomer mixture contains the other monomer, the content of the other monomer in the monomer mixture is not particularly limited, but a preferable upper limit with respect to 100 parts by weight of the nitrile monomer is 40 parts by weight. When the content of the other monomer exceeds 40 parts by weight, the content of the nitrile monomer or the epoxy group-containing monomer having at least one polymerizable unsaturated bond is decreased, and the obtained expanded particles are used. In some cases, foam molding cannot be performed at a high expansion ratio.
上記モノマー混合物は、金属カチオン塩を含有してもよい。
上記金属カチオンを含有することにより、例えば、メタクリル酸等の上記モノマー混合物中のカルボキシル基含有モノマーのカルボキシル基と、上記金属カチオンとがイオン架橋を形成し、得られる発泡粒子は、シェルの架橋効率が上がり、耐熱性が向上する。そのため、このような発泡粒子をマトリックス樹脂に配合して成形する際、成形時に高温で加熱しても粒子の破裂及び収縮が生じにくく、該粒子を用いて高発泡倍率で発泡成形を行うことができる。また、上記イオン架橋を形成することにより、得られる発泡粒子は、高温でもシェルの弾性率が低下しにくい。そのため、このような発泡粒子をマトリックス樹脂に配合して成形すると、強い剪断力が加えられる混練成形、カレンダー成形、押出成形、射出成形等の成形方法を用いる場合でも粒子の破裂及び収縮が生じにくく、該粒子を用いて高発泡倍率で発泡成形を行うことができる。
The monomer mixture may contain a metal cation salt.
By containing the metal cation, for example, the carboxyl group of the carboxyl group-containing monomer in the monomer mixture such as methacrylic acid and the metal cation form an ionic crosslink, and the resulting expanded particles have a cross-linking efficiency of the shell. And heat resistance is improved. Therefore, when such foamed particles are blended with a matrix resin and molded, even if heated at a high temperature during molding, the particles are unlikely to burst and shrink, and foam molding can be performed at a high foaming ratio using the particles. it can. Moreover, the foamed particles obtained by forming the ionic crosslinks are less likely to have a lower elastic modulus of the shell even at high temperatures. Therefore, when such foamed particles are blended with a matrix resin and molded, even when using a molding method such as kneading molding, calender molding, extrusion molding, injection molding, or the like in which a strong shear force is applied, the particles are unlikely to burst and shrink. Using the particles, foam molding can be performed at a high expansion ratio.
上記金属カチオン塩を形成する金属カチオンは、例えば、メタクリル酸等の上記モノマー混合物中のカルボキシル基含有モノマーのカルボキシル基とイオン架橋を形成することのできる金属カチオンであれば特に限定されず、例えば、Na、K、Li、Zn、Mg、Ca、Ba、Sr、Mn、Al、Ti、Ru、Fe、Ni、Cu、Cs、Sn、Cr、Pb等のイオンが挙げられる。これらのなかでは、2〜3価の金属カチオンであるCa、Zn、Alのイオンが好ましく、Znのイオンが特に好ましい。
また、上記金属カチオン塩は、上記金属カチオンの水酸化物であることが好ましい。これらの金属カチオン塩は、単独で用いられてもよく、2種以上が併用されてもよい。
The metal cation forming the metal cation salt is not particularly limited as long as it is a metal cation capable of forming an ionic bridge with the carboxyl group of the carboxyl group-containing monomer in the monomer mixture such as methacrylic acid, for example, Examples of the ions include Na, K, Li, Zn, Mg, Ca, Ba, Sr, Mn, Al, Ti, Ru, Fe, Ni, Cu, Cs, Sn, Cr, and Pb. Among these, ions of Ca, Zn, and Al, which are divalent to trivalent metal cations, are preferable, and Zn ions are particularly preferable.
The metal cation salt is preferably a hydroxide of the metal cation. These metal cation salts may be used independently and 2 or more types may be used together.
上記金属カチオン塩を2種以上併用する場合、例えば、アルカリ金属又はアルカリ土類金属のイオンからなる塩と、上記アルカリ金属又はアルカリ土類金属以外の金属カチオンからなる塩とを組み合わせて用いることが好ましい。上記アルカリ金属又はアルカリ土類金属のイオンは、カルボキシル基等の官能基を活性化することができ、該カルボキシル基等の官能基と、上記アルカリ金属又はアルカリ土類金属以外の金属カチオンとのイオン架橋形成を促進させることができる。
上記アルカリ金属又はアルカリ土類金属は特に限定されず、例えば、Na、K、Li、Ca、Ba、Sr等が挙げられる。これらのなかでは、塩基性の強いNa、K等が好ましい。
When two or more of the above metal cation salts are used in combination, for example, a salt composed of an alkali metal or alkaline earth metal ion and a salt composed of a metal cation other than the alkali metal or alkaline earth metal may be used in combination. preferable. The alkali metal or alkaline earth metal ion can activate a functional group such as a carboxyl group, and an ion between the functional group such as the carboxyl group and a metal cation other than the alkali metal or alkaline earth metal. Cross-linking can be promoted.
The alkali metal or alkaline earth metal is not particularly limited, and examples thereof include Na, K, Li, Ca, Ba, and Sr. Of these, strong basic Na and K are preferred.
上記モノマー混合物が上記金属カチオン塩を含有する場合、上記モノマー混合物中の上記金属カチオン塩の含有量は特に限定されないが、上記ニトリル系モノマー100重量部に対する好ましい下限が0.1重量部、好ましい上限が10重量部である。上記金属カチオン塩の含有量が0.1重量部未満であると、得られる発泡粒子の耐熱性を向上させる効果が充分に得られないことがある。上記金属カチオン塩の含有量が10重量部を超えると、得られる発泡粒子をマトリックス樹脂に配合して成形すると、得られる発泡成形体は発泡倍率が著しく低下することがある。 When the monomer mixture contains the metal cation salt, the content of the metal cation salt in the monomer mixture is not particularly limited, but a preferred lower limit to 100 parts by weight of the nitrile monomer is 0.1 part by weight, and a preferred upper limit. Is 10 parts by weight. When the content of the metal cation salt is less than 0.1 parts by weight, the effect of improving the heat resistance of the obtained expanded particles may not be sufficiently obtained. When the content of the metal cation salt exceeds 10 parts by weight, the foamed product may have a significantly reduced foaming ratio when the foamed particles obtained are blended with a matrix resin and molded.
上記モノマー組成物は、重合開始剤を含有することが好ましい。
上記重合開始剤は特に限定されないが、例えば、過酸化ジアルキル、過酸化ジアシル、パーオキシエステル、パーオキシジカーボネート、アゾ化合物等が挙げられる。
上記過酸化ジアルキルは特に限定されず、例えば、メチルエチルパーオキサイド、ジ−t−ブチルパーオキサイド、ジクミルパーオキサイド、イソブチルパーオキサイド等が挙げられる。
The monomer composition preferably contains a polymerization initiator.
The polymerization initiator is not particularly limited, and examples thereof include dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, and azo compound.
The dialkyl peroxide is not particularly limited, and examples thereof include methyl ethyl peroxide, di-t-butyl peroxide, dicumyl peroxide, isobutyl peroxide and the like.
上記過酸化ジアシルは特に限定されず、例えば、ベンゾイルパーオキサイド、2,4−ジクロロベンゾイルパーオキサイド、3,5,5−トリメチルヘキサノイルパーオキサイド等が挙げられる。
上記パーオキシエステルは特に限定されず、例えば、t−ブチルパーオキシピバレート、t−ヘキシルパーオキシピバレート、t−ブチルパーオキシネオデカノエート、t−ヘキシルパーオキシネオデカノエート、1−シクロヘキシル−1−メチルエチルパーオキシネオデカノエート、1,1,3,3−テトラメチルブチルパーオキシネオデカノエート、クミルパーオキシネオデカノエート、(α,α−ビス−ネオデカノイルパーオキシ)ジイソプロピルベンゼン等が挙げられる。
上記パーオキシジカーボネートは特に限定されず、例えば、ビス(4−t−ブチルシクロヘキシル)パーオキシジカーボネート、ジ−n−プロピル−パーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、ジ(2−エチルエチルパーオキシ)ジカーボネート、ジメトキシブチルパーオキシジカーボネート、ジ(3−メチル−3−メトキシブチルパーオキシ)ジカーボネート等が挙げられる。
上記アゾ化合物は特に限定されず、例えば、2、2’−アゾビスイソブチロニトリル、2,2’−アゾビス(4−メトキシ−2,4−ジメチルバレロニトリル)、2,2’−アゾビス(2,4−ジメチルバレロニトリル)、1,1’−アゾビス(1−シクロヘキサンカルボニトリル)等が挙げられる。
The diacyl peroxide is not particularly limited, and examples thereof include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and the like.
The peroxy ester is not particularly limited, and examples thereof include t-butyl peroxypivalate, t-hexyl peroxypivalate, t-butyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, 1- Cyclohexyl-1-methylethylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, cumylperoxyneodecanoate, (α, α-bis-neodecanoylper And oxy) diisopropylbenzene.
The peroxydicarbonate is not particularly limited. For example, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-n-propyl-peroxydicarbonate, diisopropyl peroxydicarbonate, di (2-ethylethyl) Peroxy) dicarbonate, dimethoxybutyl peroxydicarbonate, di (3-methyl-3-methoxybutylperoxy) dicarbonate, and the like.
The azo compound is not particularly limited. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis ( 2,4-dimethylvaleronitrile), 1,1′-azobis (1-cyclohexanecarbonitrile) and the like.
上記モノマー混合物は、更に、必要に応じて、安定剤、紫外線吸収剤、酸化防止剤、帯電防止剤、難燃剤、シランカップリング剤、色剤等を含有していてもよい。 The monomer mixture may further contain a stabilizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a flame retardant, a silane coupling agent, a colorant and the like, if necessary.
上述のようなモノマー混合物を共重合することにより、本発明に係る発泡粒子のシェルを構成する共重合体を得ることができる。
上記共重合体の重量平均分子量は特に限定されないが、好ましい下限は10万、好ましい上限は200万である。上記重量平均分子量が10万未満であると、得られる発泡粒子は、シェルの強度が低下し、該粒子を用いると高発泡倍率で発泡成形を行うことができないことがある。上記重量平均分子量が200万を超えると、得られる発泡粒子は、シェルの強度が高くなりすぎ、発泡性能が低下することがある。
By copolymerizing the monomer mixture as described above, a copolymer constituting the shell of the expanded particles according to the present invention can be obtained.
The weight average molecular weight of the copolymer is not particularly limited, but a preferable lower limit is 100,000 and a preferable upper limit is 2 million. When the weight average molecular weight is less than 100,000, the foamed particles obtained have a reduced shell strength, and if the particles are used, foam molding may not be performed at a high expansion ratio. When the weight average molecular weight exceeds 2,000,000, the foamed particles obtained have a shell strength that is too high, and foaming performance may deteriorate.
本発明に係る発泡粒子は、上記シェルの表面がエポキシ基と反応可能な硬化剤で表面処理がなされていてもよい。
従来、発泡成形体の製造に用いられる発泡粒子を成形時に高温で加熱すると、膨張した粒子からガスが抜けることによって発泡倍率が低下したり、いわゆる「へたり」と呼ばれる現象が生じて潰れたりすることがあり、高発泡倍率で発泡成形を行うことは難しかった。
The foamed particles according to the present invention may be subjected to a surface treatment with a curing agent whose surface of the shell can react with an epoxy group.
Conventionally, when foamed particles used in the production of foamed molded products are heated at a high temperature during molding, the expansion ratio is reduced due to the escape of gas from the expanded particles, or a phenomenon called so-called “sagging” occurs and the material is crushed. In some cases, it was difficult to perform foam molding at a high expansion ratio.
これに対し、本発明に係る発泡粒子は、上記シェルの表面が上記エポキシ基と反応可能な硬化剤で表面処理がなされていることにより、マトリックス樹脂に配合して成形すると成形時の加熱により発泡し、同時に、上記シェルの表面に存在するエポキシ基と、上記シェルの表面に存在する上記エポキシ基と反応可能な硬化剤とが反応し、上記シェルの表面が硬化して発泡状態が固定される。これにより、本発明に係る発泡粒子は、成形時に高温で加熱しても粒子の破裂及び収縮が生じにくく、本発明に係る発泡粒子を用いて高発泡倍率で発泡成形を行うことができる。
なお、上記シェルを構成するモノマーとして上記少なくとも1つの重合性不飽和結合を有するエポキシ基含有モノマーを用いることにより、上記シェルの表面にエポキシ基を存在させることができる。
On the other hand, the foamed particles according to the present invention are foamed by heating at the time of molding when the shell surface is treated with a curing agent capable of reacting with the epoxy group and molded into a matrix resin. At the same time, the epoxy group present on the surface of the shell and the curing agent capable of reacting with the epoxy group present on the surface of the shell react to cure the surface of the shell and fix the foamed state. . Thereby, even if the foamed particle which concerns on this invention is heated at high temperature at the time of shaping | molding, it is hard to produce a particle burst and shrinkage | contraction, and it can foam-mold at a high foaming ratio using the foamed particle which concerns on this invention.
In addition, an epoxy group can exist on the surface of the shell by using the epoxy group-containing monomer having at least one polymerizable unsaturated bond as a monomer constituting the shell.
上記エポキシ基と反応可能な硬化剤で表面処理する方法は特に限定されず、一般的な加熱攪拌方式で処理することができる。 The method for surface treatment with the curing agent capable of reacting with the epoxy group is not particularly limited, and the treatment can be performed by a general heating and stirring method.
上記シェルの表面を上記エポキシ基と反応可能な硬化剤で表面処理する際、上記エポキシ基と反応可能な硬化剤の添加量は特に限定されないが、上記少なくとも1つの重合性不飽和結合を有するエポキシ基含有モノマーのエポキシ当量に対する理論硬化剤量に対して、好ましい下限が0.5倍量、好ましい上限が5倍量である。上記エポキシ基と反応可能な硬化剤の添加量が0.5倍量未満であると、得られる発泡粒子をマトリックス樹脂に配合して成形する際、成形時に高温で加熱すると、粒子の破裂及び収縮が生じやすくなることがある。上記エポキシ基と反応可能な硬化剤の添加量が5倍量を超えると、表面処理の段階で上記シェルの表面に存在するエポキシ基と、上記エポキシ基と反応可能な硬化剤との反応が進みすぎて、発泡粒子を発泡させる前に表面処理の段階で硬化してしまうことがある。 When the surface of the shell is surface-treated with a curing agent capable of reacting with the epoxy group, the amount of the curing agent capable of reacting with the epoxy group is not particularly limited, but the epoxy having at least one polymerizable unsaturated bond is not limited. The preferred lower limit is 0.5 times the amount and the preferred upper limit is 5 times the theoretical hardener amount relative to the epoxy equivalent of the group-containing monomer. When the amount of the curing agent capable of reacting with the epoxy group is less than 0.5 times, when foamed particles obtained are molded into a matrix resin and heated at a high temperature during molding, the particles burst and shrink. May occur easily. When the addition amount of the curing agent capable of reacting with the epoxy group exceeds 5 times, the reaction between the epoxy group present on the surface of the shell at the surface treatment stage and the curing agent capable of reacting with the epoxy group proceeds. Thus, the foamed particles may be cured at the surface treatment stage before foaming.
本発明に係る発泡粒子は、コア剤として揮発性膨張剤を内包する。
本明細書中、揮発性膨張剤とは、本発明に係る発泡粒子のシェルを構成する共重合体の軟化点以下の温度でガス状になる物質をいう。
上記揮発性膨張剤は特に限定されないが、低沸点有機溶剤が好ましく、具体的には、例えば、エタン、エチレン、プロパン、プロペン、n−ブタン、イソブタン、ブテン、イソブテン、n−ペンタン、イソペンタン、ネオペンタン、n−へキサン、ヘプタン、石油エーテル等の低分子量炭化水素、CCl3F、CCl2F2、CClF3、CClF2−CClF2等のクロロフルオロカーボン、テトラメチルシラン、トリメチルエチルシラン、トリメチルイソプロピルシラン、トリメチル−n−プロピルシラン等のテトラアルキルシラン等が挙げられる。これらのなかでは、イソブタン、n−ブタン、n−ペンタン、イソペンタン、n−へキサン、石油エーテル、又は、これらの混合物を用いることにより、発泡倍率が高く、速やかに発泡を開始する粒子とすることができる。これらの揮発性膨張剤は単独で用いられてもよく、2種以上が併用されてもよい。
また、上記揮発性膨張剤として、加熱により熱分解してガス状になる熱分解型化合物を用いてもよい。
The expanded particles according to the present invention include a volatile swelling agent as a core agent.
In the present specification, the volatile swelling agent refers to a substance that becomes gaseous at a temperature below the softening point of the copolymer constituting the shell of the expanded particles according to the present invention.
Although the volatile swelling agent is not particularly limited, a low boiling point organic solvent is preferable, and specifically, for example, ethane, ethylene, propane, propene, n-butane, isobutane, butene, isobutene, n-pentane, isopentane, neopentane. , hexane n-, heptane, low molecular weight hydrocarbons such as petroleum ether, CCl 3 F, CCl 2 F 2, CClF 3, CClF 2 -CClF 2 such chlorofluorocarbons, tetramethylsilane, trimethylethyl silane, trimethyl isopropyl silane And tetraalkylsilanes such as trimethyl-n-propylsilane. Among these, by using isobutane, n-butane, n-pentane, isopentane, n-hexane, petroleum ether, or a mixture thereof, the foaming ratio is high and the particles start to foam quickly. Can do. These volatile swelling agents may be used alone or in combination of two or more.
Further, as the volatile expansion agent, a thermally decomposable compound that is thermally decomposed by heating and becomes gaseous may be used.
本発明に係る発泡粒子中の上記揮発性膨張剤の含有量は特に限定されないが、好ましい下限は10重量%、好ましい上限は25重量%である。上記揮発性膨張剤の含有量が10重量%未満であると、得られる発泡粒子は、シェルが厚くなりすぎ、発泡性能が低下することがある。上記揮発性膨張剤の含有量が25重量%を超えると、得られる発泡粒子は、シェルの強度が低下し、該粒子を用いると高発泡倍率で発泡成形を行うことができないことがある。 Although content of the said volatile expansion | swelling agent in the expanded particle which concerns on this invention is not specifically limited, A preferable minimum is 10 weight% and a preferable upper limit is 25 weight%. When the content of the volatile swelling agent is less than 10% by weight, the foamed particles obtained may have a too thick shell and the foaming performance may deteriorate. When the content of the volatile expansion agent exceeds 25% by weight, the foamed particles obtained have a reduced shell strength, and when these particles are used, foam molding may not be performed at a high expansion ratio.
本発明に係る発泡粒子の最大発泡温度(Tmax)は特に限定されないが、好ましい下限が200℃である。上記最大発泡温度が200℃未満であると、発泡粒子は耐熱性が低くなり、成形時に高温で加熱すると、粒子の破裂及び収縮が生じやすくなることがある。また、上記最大発泡温度が200℃未満であると、発泡粒子を用いてマスターバッチペレットを製造する場合には、ペレット製造時の剪断力により発泡が生じてしまい、未発泡のマスターバッチペレットを安定して製造することができないことがある。上記発泡粒子の最大発泡温度は、より好ましい下限が210℃である。
なお、本明細書中、上記最大発泡温度は、発泡粒子を常温から加熱しながらその径を測定したときに、該粒子が最大変位量となったときの温度を意味する。
The maximum foaming temperature (Tmax) of the foamed particles according to the present invention is not particularly limited, but a preferred lower limit is 200 ° C. When the maximum foaming temperature is less than 200 ° C., the foamed particles have low heat resistance, and when heated at a high temperature during molding, the particles may easily burst and shrink. In addition, when the maximum foaming temperature is less than 200 ° C., when producing master batch pellets using foamed particles, foaming occurs due to the shearing force at the time of pellet production, which stabilizes the unfoamed master batch pellets. Cannot be manufactured. The more preferable lower limit of the maximum foaming temperature of the foamed particles is 210 ° C.
In the present specification, the maximum foaming temperature means a temperature when the diameter of the foamed particles is measured while the foamed particles are heated from room temperature and the maximum displacement is obtained.
本発明に係る発泡粒子の体積平均粒子径は特に限定されないが、好ましい下限が10μm、好ましい上限が50μmである。上記体積平均粒子径が10μm未満であると、発泡粒子をマトリックス樹脂に配合して成形すると、得られる発泡成形体の気泡が小さすぎ、軽量化が不充分となることがある。上記体積平均粒子径が50μmを超えると、発泡粒子をマトリックス樹脂に配合して成形すると、得られる発泡成形体の気泡が大きくなりすぎ、強度等の面で問題となることがある。上記体積平均粒子径は、より好ましい下限が15μm、より好ましい上限が40μmである。 The volume average particle diameter of the expanded particles according to the present invention is not particularly limited, but a preferable lower limit is 10 μm and a preferable upper limit is 50 μm. When the volume average particle diameter is less than 10 μm, when foamed particles are blended into a matrix resin and molded, the foamed molded body obtained has too small bubbles, which may result in insufficient weight reduction. If the volume average particle diameter exceeds 50 μm, when foamed particles are blended with a matrix resin and molded, the foamed foam obtained is too large, which may cause problems in terms of strength and the like. The volume average particle diameter has a more preferable lower limit of 15 μm and a more preferable upper limit of 40 μm.
本発明に係る発泡粒子を製造する方法は特に限定されず、例えば、水性分散媒体を調製する工程と、該水性分散媒体中に、上記モノマー混合物と上記揮発性膨張剤とを含有する油性混合液を分散させる工程と、上記モノマー混合物を共重合させる工程とを行うことにより、共重合体からなるシェルに、コア剤として揮発性膨張剤を内包する粒子を得た後、必要に応じて該粒子のシェルの表面を上述のようにしてエポキシ基と反応可能な硬化剤で表面処理する工程を行う方法等が挙げられる。 The method for producing the expanded particles according to the present invention is not particularly limited. For example, the step of preparing an aqueous dispersion medium, and an oily liquid mixture containing the monomer mixture and the volatile swelling agent in the aqueous dispersion medium. And a step of copolymerizing the monomer mixture to obtain particles containing a volatile swelling agent as a core agent in a shell made of a copolymer, and then, if necessary, the particles The method of performing the process of surface-treating with the hardening | curing agent which can react with the epoxy group as mentioned above etc. is mentioned.
上記水性分散媒体を調製する工程では、例えば、重合反応容器に、水、分散安定剤、及び、必要に応じて補助安定剤を加えることにより、分散安定剤を含有する水性分散媒体を調製する。また、上記水性分散媒体には、必要に応じて、亜硝酸アルカリ金属塩、塩化第一スズ、塩化第二スズ、重クロム酸カリウム等を添加してもよい。 In the step of preparing the aqueous dispersion medium, for example, an aqueous dispersion medium containing the dispersion stabilizer is prepared by adding water, a dispersion stabilizer, and, if necessary, an auxiliary stabilizer to the polymerization reaction vessel. Moreover, you may add alkali metal nitrite, stannous chloride, stannic chloride, potassium dichromate, etc. to the said aqueous dispersion medium as needed.
上記分散安定剤は特に限定されず、例えば、シリカ、リン酸カルシウム、水酸化マグネシウム、水酸化アルミニウム、水酸化第二鉄、硫酸バリウム、硫酸カルシウム、硫酸ナトリウム、シュウ酸カルシウム、炭酸カルシウム、炭酸カルシウム、炭酸バリウム、炭酸マグネシウム等が挙げられる。 The dispersion stabilizer is not particularly limited. For example, silica, calcium phosphate, magnesium hydroxide, aluminum hydroxide, ferric hydroxide, barium sulfate, calcium sulfate, sodium sulfate, calcium oxalate, calcium carbonate, calcium carbonate, carbonate Examples include barium and magnesium carbonate.
上記補助安定剤は特に限定されず、例えば、ジエタノールアミンと脂肪族ジカルボン酸との縮合生成物、尿素とホルムアルデヒドとの縮合生成物、水溶性窒素含有化合物、ポリエチレンオキサイド、テトラメチルアンモニウムヒドロキシド、ゼラチン、メチルセルロース、ポリビニルアルコール、ジオクチルスルホサクシネート、ソルビタンエステル、各種乳化剤等が挙げられる。
上記水溶性窒素含有化合物は特に限定されず、例えば、ポリビニルピロリドン、ポリエチレンイミン、ポリオキシエチレンアルキルアミン、ポリジメチルアミノエチルメタクリレートやポリジメチルアミノエチルアクリレートに代表されるポリジアルキルアミノアルキル(メタ)アクリレート、ポリジメチルアミノプロピルアクリルアミドやポリジメチルアミノプロピルメタクリルアミドに代表されるポリジアルキルアミノアルキル(メタ)アクリルアミド、ポリアクリルアミド、ポリカチオン性アクリルアミド、ポリアミンサルフォン、ポリアリルアミン等が挙げられる。これらのなかでは、ポリビニルピロリドンが好ましい。
The auxiliary stabilizer is not particularly limited, and examples thereof include a condensation product of diethanolamine and an aliphatic dicarboxylic acid, a condensation product of urea and formaldehyde, a water-soluble nitrogen-containing compound, polyethylene oxide, tetramethylammonium hydroxide, gelatin, Examples include methyl cellulose, polyvinyl alcohol, dioctyl sulfosuccinate, sorbitan ester, and various emulsifiers.
The water-soluble nitrogen-containing compound is not particularly limited, for example, polyvinyl pyrrolidone, polyethyleneimine, polyoxyethylene alkylamine, polydialkylaminoalkyl (meth) acrylate represented by polydimethylaminoethyl methacrylate and polydimethylaminoethyl acrylate, Examples thereof include polydialkylaminoalkyl (meth) acrylamide, polyacrylamide, polycationic acrylamide, polyamine sulfone, polyallylamine and the like typified by polydimethylaminopropyl acrylamide and polydimethylaminopropyl methacrylamide. Of these, polyvinylpyrrolidone is preferred.
上記分散安定剤と上記補助安定剤との組み合わせは特に限定されず、例えば、コロイダルシリカと縮合生成物との組み合わせ、コロイダルシリカと水溶性窒素含有化合物との組み合わせ、水酸化マグネシウム又はリン酸カルシウムと乳化剤との組み合わせ等が挙げられる。これらのなかでは、コロイダルシリカと縮合生成物との組み合わせが好ましく、該縮合生成物としては、ジエタノールアミンと脂肪族ジカルボン酸との縮合生成物が好ましく、ジエタノールアミンとアジピン酸との縮合生成物、ジエタノールアミンとイタコン酸との縮合生成物が特に好ましい。 The combination of the dispersion stabilizer and the auxiliary stabilizer is not particularly limited. For example, a combination of colloidal silica and a condensation product, a combination of colloidal silica and a water-soluble nitrogen-containing compound, magnesium hydroxide or calcium phosphate and an emulsifier. And the like. Among these, a combination of colloidal silica and a condensation product is preferable, and the condensation product is preferably a condensation product of diethanolamine and an aliphatic dicarboxylic acid, a condensation product of diethanolamine and adipic acid, diethanolamine and A condensation product with itaconic acid is particularly preferred.
上記分散安定剤としてコロイダルシリカを用いる場合、コロイダルシリカの添加量は特に限定されず、目的とする発泡粒子の粒子径により適宜決定することができるが、全モノマー成分100重量部に対する好ましい下限が1重量部、好ましい上限が20重量部、更に好ましい下限が2重量部、更に好ましい上限が10重量部である。
また、上記補助安定剤として上記縮合生成物又は上記水溶性窒素含有化合物を用いる場合、上記縮合生成物又は水溶性窒素含有化合物の添加量は特に限定されず、目的とする発泡粒子の粒子径により適宜決定することができるが、全モノマー成分100重量部に対する好ましい下限が0.05重量部、好ましい上限が2重量部である。
When colloidal silica is used as the dispersion stabilizer, the amount of colloidal silica added is not particularly limited and can be appropriately determined depending on the particle diameter of the desired foamed particles, but the preferred lower limit for 100 parts by weight of the total monomer component is 1 Part by weight, a preferred upper limit is 20 parts by weight, a more preferred lower limit is 2 parts by weight, and a more preferred upper limit is 10 parts by weight.
In addition, when the condensation product or the water-soluble nitrogen-containing compound is used as the auxiliary stabilizer, the addition amount of the condensation product or the water-soluble nitrogen-containing compound is not particularly limited, and depends on the particle diameter of the target expanded particles. Although it can be suitably determined, the preferable lower limit with respect to 100 parts by weight of all monomer components is 0.05 part by weight, and the preferable upper limit is 2 parts by weight.
上記水性分散媒体には、上記分散安定剤及び上記補助安定剤に加えて、更に、塩化ナトリウム、硫酸ナトリウム等の無機塩を添加してもよい。このような無機塩を添加することで、より均一な粒子形状を有する発泡粒子を得ることができる。
上記無機塩の添加量は特に限定されないが、全モノマー成分100重量部に対する好ましい上限は100重量部である。
In addition to the dispersion stabilizer and the auxiliary stabilizer, an inorganic salt such as sodium chloride or sodium sulfate may be further added to the aqueous dispersion medium. By adding such an inorganic salt, expanded particles having a more uniform particle shape can be obtained.
The amount of the inorganic salt added is not particularly limited, but the preferable upper limit with respect to 100 parts by weight of all monomer components is 100 parts by weight.
上記水性分散媒体は、上記分散安定剤及び上記補助安定剤を脱イオン水に配合して調製され、上記脱イオン水のpHは、使用する分散安定剤及び補助安定剤の種類によって適宜決定することができる。例えば、上記分散安定剤としてコロイダルシリカ等のシリカを用いる場合には、必要に応じて塩酸等の酸を加えて系のpHを3〜4に調整し、後述する工程において酸性条件下で重合が行われる。また、上記分散安定剤として水酸化マグネシウム又はリン酸カルシウムを用いる場合には、系をアルカリ性に調整し、後述する工程においてアルカリ性条件下で重合が行われる。 The aqueous dispersion medium is prepared by blending the dispersion stabilizer and the auxiliary stabilizer with deionized water, and the pH of the deionized water is appropriately determined according to the type of the dispersion stabilizer and auxiliary stabilizer used. Can do. For example, when silica such as colloidal silica is used as the dispersion stabilizer, an acid such as hydrochloric acid is added as necessary to adjust the pH of the system to 3 to 4, and polymerization can be performed under acidic conditions in the steps described later. Done. When magnesium hydroxide or calcium phosphate is used as the dispersion stabilizer, the system is adjusted to be alkaline, and polymerization is performed under alkaline conditions in the steps described later.
本発明に係る発泡粒子を製造する方法では、次いで、上記水性分散媒体中に、上記モノマー混合物と上記揮発性膨張剤とを含有する油性混合液を分散させる工程を行う。
上記水性分散媒体中に、上記モノマー混合物と上記揮発性膨張剤とを含有する油性混合液を分散させる工程では、上記モノマー混合物と上記揮発性膨張剤とを別々に上記水性分散媒体に添加して、該水性分散媒体中で油性混合液を調製してもよいが、通常は、予め両者を混合して油性混合液としてから、上記水性分散媒体に添加する。この際、油性混合液と水性分散媒体とを予め別々の容器で調製しておき、別の容器で攪拌しながら混合することにより油性混合液を水性分散媒体に分散させた後、重合反応容器に添加しても良い。
なお、上記モノマー混合物中のモノマーを重合するために重合開始剤が用いられるが、上記重合開始剤は、予め油性混合液に添加してもよく、水性分散媒体と油性混合液とを重合反応容器内で攪拌混合した後に添加してもよい。
In the method for producing expanded particles according to the present invention, a step of dispersing an oily mixed solution containing the monomer mixture and the volatile swelling agent in the aqueous dispersion medium is then performed.
In the step of dispersing the oily mixture containing the monomer mixture and the volatile swelling agent in the aqueous dispersion medium, the monomer mixture and the volatile swelling agent are separately added to the aqueous dispersion medium. The oily mixed solution may be prepared in the aqueous dispersion medium, but usually, both are mixed in advance to obtain an oily mixed solution, and then added to the aqueous dispersion medium. At this time, the oil-based mixed liquid and the aqueous dispersion medium are prepared in separate containers in advance, and the oil-based mixed liquid is dispersed in the aqueous dispersion medium by mixing with stirring in another container, and then the polymerization reaction container. It may be added.
A polymerization initiator is used to polymerize the monomers in the monomer mixture. However, the polymerization initiator may be added to the oily mixture in advance, and the aqueous dispersion medium and the oily mixture are combined in a polymerization reaction vessel. It may be added after stirring and mixing.
上記油性混合液を水性分散媒体中に所定の粒子径で乳化分散させる方法は特に限定されず、例えば、ホモミキサー(例えば、特殊機化工業社製)等により攪拌する方法、ラインミキサー、エレメント式静止型分散器等の静止型分散装置を通過させる方法等が挙げられる。
なお、上記静止型分散装置には上記水性分散媒体と上記油性混合液とを別々に供給してもよく、予め混合、攪拌した分散液を供給してもよい。
The method of emulsifying and dispersing the oily mixture in an aqueous dispersion medium with a predetermined particle size is not particularly limited. For example, a method of stirring with a homomixer (for example, manufactured by Tokushu Kika Kogyo Co., Ltd.) or the like, a line mixer, an element type Examples thereof include a method of passing through a static dispersion device such as a static dispersion device.
The aqueous dispersion medium and the oily mixed liquid may be separately supplied to the static dispersion apparatus, or a dispersion liquid that has been mixed and stirred in advance may be supplied.
本発明に係る発泡粒子を製造する方法では、次いで、上記モノマー混合物を共重合させる工程を行う。上記共重合する方法は特に限定されず、例えば、加熱することにより上記モノマー混合物を共重合させる方法が挙げられる。
このようにして得られた共重合体からなるシェルに、コア剤として揮発性膨張剤を内包する粒子は、続いて該粒子のシェルの表面をエポキシ基と反応可能な硬化剤で表面処理する工程を行う前に、脱水する工程、乾燥する工程等を経てもよい。
In the method for producing expanded particles according to the present invention, a step of copolymerizing the monomer mixture is then performed. The method for copolymerization is not particularly limited, and examples thereof include a method for copolymerizing the monomer mixture by heating.
The particles encapsulating the volatile swelling agent as the core agent in the thus obtained copolymer shell are then subjected to a surface treatment with a curing agent capable of reacting with epoxy groups on the surface of the shell of the particles. You may pass through the process of dehydration, the process of drying, etc. before performing.
本発明に係る発泡粒子を製造する方法では、次いで、必要に応じて上記発泡粒子のシェルの表面をエポキシ基と反応可能な硬化剤で表面処理する工程を行う。
上記エポキシ基と反応可能な硬化剤で表面処理する方法は特に限定されず、例えば、上述したように、一般的な加熱攪拌方式で処理することができる。
In the method for producing expanded particles according to the present invention, the surface of the shell of the expanded particles is then subjected to a surface treatment with a curing agent capable of reacting with an epoxy group, if necessary.
The method of surface-treating with the curing agent capable of reacting with the epoxy group is not particularly limited, and for example, as described above, the surface can be treated by a general heating and stirring method.
本発明の発泡性組成物は、エポキシ基と反応可能な硬化剤を含有する。
上記エポキシ基と反応可能な硬化剤は特に限定されず、例えば、アミン化合物、酸無水物、ノボラック系硬化剤等が挙げられる。
上記アミン化合物は特に限定されず、例えば、脂肪族アミン、脂環族アミン、芳香族アミン、及び、これらの変性物等が挙げられる。
上記脂肪族アミンは特に限定されず、例えば、エチレンジアミン及びその付加物、ジエチレントリアミン、ジプロピレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ジメチルアミノプロピルアミン、ジエチルアミノプロピルアミン、ジブチルアミノプロピルアミン、ヘキサメチレンジアミン及びその変性物、N−アミノエチルピペラジン、ビス−アミノプロピルピペラジン、トリメチルヘキサメチレンジアミン、ビス−ヘキサメチレントリアミン、ジシアンジアミド、ジアセトアクリルアミド、各種変性脂肪族ポリアミン、ポリオキシプロピレンジアミン等が挙げられる。
The foamable composition of the present invention contains a curing agent capable of reacting with an epoxy group.
The curing agent capable of reacting with the epoxy group is not particularly limited, and examples thereof include amine compounds, acid anhydrides, novolak curing agents, and the like.
The amine compound is not particularly limited, and examples thereof include aliphatic amines, alicyclic amines, aromatic amines, and modified products thereof.
The aliphatic amine is not particularly limited, and examples thereof include ethylenediamine and its adduct, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, hexamethylenediamine. And modified products thereof, N-aminoethylpiperazine, bis-aminopropylpiperazine, trimethylhexamethylenediamine, bis-hexamethylenetriamine, dicyandiamide, diacetacrylamide, various modified aliphatic polyamines, polyoxypropylenediamine, and the like.
上記脂環族アミンは特に限定されず、例えば、3,3’−ジメチル−4,4’−ジアミノジシクロヘキシルメタン、3−アミノ−1−シクロヘキシルアミノプロパン、4,4’−ジアミノジシクロヘキシルメタン、イソホロンジアミン、1,3−ビス(アミノメチル)シクロヘキサン、N−ジメチルシクロヘキシルアミン等が挙げられる。 The alicyclic amine is not particularly limited. For example, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 3-amino-1-cyclohexylaminopropane, 4,4′-diaminodicyclohexylmethane, isophoronediamine. 1,3-bis (aminomethyl) cyclohexane, N-dimethylcyclohexylamine and the like.
上記芳香族アミンは特に限定されず、例えば、4,4’−ジアミノジフェニルメタン(メチレンジアニリン)、4,4’−ジアミノジフェニルエーテル、ジアミノジフェニルスルホン、m−フェニレンジアミン、2,4’−トルイレンジアミン、m−トルイレンジアミン、o−トルイレンジアミン、メタキシリレンジアミン、キシリレンジアミン等が挙げられる。 The aromatic amine is not particularly limited. For example, 4,4′-diaminodiphenylmethane (methylenedianiline), 4,4′-diaminodiphenyl ether, diaminodiphenylsulfone, m-phenylenediamine, 2,4′-toluylenediamine , M-toluylenediamine, o-toluylenediamine, metaxylylenediamine, xylylenediamine and the like.
また、上記アミン化合物として、3級アミン類、イミダゾール類、ヒドラジド類、アミドアミン、ケチミン、アミノポリアミド樹脂等のポリアミドアミン、エポキシ樹脂のアミノ付加物等のアミノ基含有プレポリマー、その他特殊アミン変性物等を用いてもよい。
上記3級アミン類は特に限定されず、例えば、ジメチルアミノメチルフェノール、2,4,6−トリ(ジメチルアミノメチル)フェノール、トリ(ジメチルアミノメチル)フェノールのトリ−2エチルヘキサン塩、及び、これらの錯化合物等が挙げられる。
In addition, as the amine compound, tertiary amines, imidazoles, hydrazides, amidoamines, ketimines, polyamide amines such as amino polyamide resins, amino group-containing prepolymers such as amino adducts of epoxy resins, and other special amine modified products May be used.
The tertiary amines are not particularly limited. For example, dimethylaminomethylphenol, 2,4,6-tri (dimethylaminomethyl) phenol, tri-2ethylhexane salt of tri (dimethylaminomethyl) phenol, and these And the like.
上記イミダゾール類は特に限定されず、例えば、2−メチルイミダゾール、2−エチル−4−メチルイミダゾール、2−ウンデシルイミダゾール、2−ヘプタデシルイミダゾール、2−フェニルイミダゾール、2−フェニル−4−メチルイミダゾール、1−ベンジル−2−メチルイミダゾール、2−エチルイミダゾール、2−イソプロピルイミダゾール、1−シアノエチル−2−メチルイミダゾール、1−シアノエチル−2ウンデシルイミダゾール、1−シアノエチル−2−イソプロピルイミダゾール、1−シアノエチル−2−フェニルイミダゾール、1−シアノエチル−2−メチルイミダゾールトリメリテート、1−シアノエチル−2−ウンデシルイミダゾールトリメリテート、1−シアノエチル−2−フェニルイミダゾールトリメリテート、2,4−ジアミノ−6−[2’−メチルイミダゾリル−(1)’]−エチル−s−トリアジン、2,4−ジアミノ−6−[2’−ウンデシルイミダゾリル−(1)’]−エチル−s−トリアジン、2,4−ジアミノ−6−[2’−エチル−4’−メチルイミダゾリル−(1)’]−エチル−s−トリアジン、1−ドデシル−2−メチル−3−ベンジルイミダゾリウムクロリド、1,3−ジベンジル−2−メチルイミダゾリウムクロリド、2−フェニル−4−メチル−5−ヒドロキシメチルイミダゾール、2−フェニル−4,5−ジヒドロキシメチルイミダゾール、1−シアノエチル−2−フェニル−4,5−ジ(シアノエトキシメチル)イミダゾール、2−メチルイミダゾールとトリアジンとの複合物、2−フェニルイミダゾールとトリアジンとの複合物等が挙げられる。 The imidazoles are not particularly limited. For example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole. 1-benzyl-2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2undecylimidazole, 1-cyanoethyl-2-isopropylimidazole, 1-cyanoethyl 2-phenylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate 2,4-diamino-6- [2'-methylimidazolyl- (1) ']-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1)']- Ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1) ′]-ethyl-s-triazine, 1-dodecyl-2-methyl-3-benzylimidazo Rium chloride, 1,3-dibenzyl-2-methylimidazolium chloride, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-cyanoethyl-2-phenyl- 4,5-di (cyanoethoxymethyl) imidazole, composite of 2-methylimidazole and triazine, 2-phenylimidazole and triazine Composite products of the gin and the like.
上記ヒドラジド類は特に限定されず、例えば、イソフタル酸ジヒドラジド、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド等が挙げられる。 The hydrazides are not particularly limited, and examples thereof include isophthalic acid dihydrazide, adipic acid dihydrazide, and sebacic acid dihydrazide.
上記酸無水物は特に限定されず、例えば、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロフタル酸、メチルナジック酸無水物、水素化メチルナジック酸無水物、トリアルキルテトラヒドロ無水フタル酸、メチルシクロヘキセンテトラカルボン酸二無水物、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸二無水物、エチレングリコールビスアンヒドロトリメリテート、グリセリンビス(アンヒドロトリメリテート)モノアセテート、ドデセニル無水コハク酸、脂肪族二塩基酸ポリ無水物、クロレンド酸無水物等が挙げられる。 The acid anhydride is not particularly limited. For example, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic acid, methylnadic acid anhydride, hydrogenated methylnadic acid anhydride, trialkyl Tetrahydrophthalic anhydride, methylcyclohexenetetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, ethylene glycol bisanhydrotrimellitate, glycerin bis (anhydro) Trimellitate) monoacetate, dodecenyl succinic anhydride, aliphatic dibasic acid polyanhydride, chlorendic anhydride and the like.
上記ノボラック系硬化剤は特に限定されず、例えば、フェノールノボラック、キシリレンノボラック、ビスAノボラック、トリフェニルメタンノボラック、ビフェニルノボラック、ジシクロペンタジエンフェノールノボラック、テルペンフェノールノボラック等が挙げられる。 The novolak curing agent is not particularly limited, and examples thereof include phenol novolak, xylylene novolak, bis A novolak, triphenylmethane novolak, biphenyl novolak, dicyclopentadienephenol novolak, and terpene phenol novolak.
本発明の発泡性組成物の用途は特に限定されず、例えば、マトリックス樹脂に配合して射出成形、押出成形等の成形方法を用いて成形することにより、遮熱性、断熱性、遮音性、吸音性、防振性、軽量化等を備えた発泡成形体を製造するために用いることができる。本発明の発泡性組成物は、高温で加熱しても粒子の破裂及び収縮が生じにくいことから、製造時に高温での成形工程等を必要とする場合であっても、本発明の発泡性組成物を用いて、高発泡倍率で発泡成形を行うことができる。 The use of the foamable composition of the present invention is not particularly limited, and for example, by blending with a matrix resin and molding using a molding method such as injection molding or extrusion molding, heat insulation, heat insulation, sound insulation, sound absorption It can be used to produce a foamed molded article having properties, vibration proofing, weight reduction and the like. Since the foamable composition of the present invention is less likely to cause particle rupture and shrinkage even when heated at high temperatures, the foamable composition of the present invention can be used even when a high temperature molding step is required during production. Using the product, foam molding can be performed at a high expansion ratio.
本発明の発泡性組成物と、マトリックス樹脂とを含有する発泡成形用樹脂組成物を作製する工程と、前記発泡成形用樹脂組成物を成形する工程とを有する発泡成形体の製造方法もまた、本発明の1つである。 A method for producing a foamed molded article comprising a step of producing a foamable resin composition containing the foamable composition of the present invention and a matrix resin, and a step of molding the foamable resin composition, It is one of the present inventions.
上記マトリックス樹脂は特に限定されず、例えば、ポリ塩化ビニル、ポリスチレン、ポリプロピレン、ポリプロピレンオキシド、ポリエチレン等の一般的な熱可塑性樹脂や、ポリブチレンテレフタレート、ナイロン、ポリカーボネート、ポリエチレンテレフタレート等のエンジニアリングプラスチックや、エチレン系、塩化ビニル系、オレフィン系、ウレタン系、エステル系等の熱可塑性エラストマー等が挙げられる。これらは単独で用いられてもよく、2種以上が併用されてもよい。 The matrix resin is not particularly limited, and examples thereof include general thermoplastic resins such as polyvinyl chloride, polystyrene, polypropylene, polypropylene oxide, and polyethylene, engineering plastics such as polybutylene terephthalate, nylon, polycarbonate, and polyethylene terephthalate, and ethylene. And thermoplastic elastomers such as vinyl chloride, vinyl chloride, olefin, urethane, and ester. These may be used independently and 2 or more types may be used together.
上記発泡成形用樹脂組成物を成形する方法は特に限定されず、例えば、混練成形、カレンダー成形、押出成形、射出成形等が挙げられる。射出成形の場合、工法は特に限定されず、金型に上記発泡成形用樹脂組成物を一部入れて発泡させるショートショット法や、金型に上記発泡成形用樹脂組成物をフル充填した後に金型を発泡させたいところまで開くコアバック法等が挙げられる。 The method for molding the foam molding resin composition is not particularly limited, and examples thereof include kneading molding, calendar molding, extrusion molding, and injection molding. In the case of injection molding, the construction method is not particularly limited, and a short shot method in which a part of the foam molding resin composition is put in a mold and foamed, or after the mold is fully filled with the foam molding resin composition. The core back method etc. which open to the place which wants to make a mold foam are mentioned.
本発明の発泡成形体の製造方法を用いて得られた発泡成形体の用途は特に限定されず、例えば、ドアトリム、インストルメントパネル(インパネ)等の自動車内装材や、バンパー等の自動車外装材や、木粉プラスチック等の建材用途や、靴底や、人工コルク等が挙げられる。 The use of the foam molded article obtained by using the method for producing a foam molded article of the present invention is not particularly limited. For example, automobile interior materials such as door trims and instrument panels (instrument panels), automobile exterior materials such as bumpers, Application of building materials such as wood powder plastic, shoe soles, artificial cork and the like.
本発明によれば、高温で加熱しても粒子の破裂及び収縮が生じにくく、高発泡倍率での発泡成形に用いることができる発泡性組成物を提供することができる。また、本発明によれば、上記発泡性組成物を用いた発泡成形体の製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, even if it heats at high temperature, the bursting and shrinkage | contraction of particle | grains are hard to produce, and the foamable composition which can be used for foam molding by a high foaming ratio can be provided. Moreover, according to this invention, the manufacturing method of the foaming molding using the said foamable composition can be provided.
以下に実施例を挙げて本発明の態様を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
(実施例1、比較例1)
重合反応容器に、水8Lと、分散安定剤としてコロイダルシリカ(旭電化社製)10重量部と、補助安定剤としてポリビニルピロリドン(BASF社製)0.3重量部と、1N塩酸0.7重量部とを投入し、水性分散媒体を調製した。次いで、表1に示した配合で油性混合液を調製し、この油性混合液を水性分散媒体に添加して、分散液を調製した。
得られた分散液をホモジナイザーで攪拌混合した後、窒素置換した加圧重合器(20L)内へ仕込み、加圧(0.2MPa)しながら、60℃で20時間反応させた。
(Example 1, Comparative Example 1)
In a polymerization reaction vessel, 8 L of water, 10 parts by weight of colloidal silica (manufactured by Asahi Denka) as dispersion stabilizer, 0.3 part by weight of polyvinylpyrrolidone (manufactured by BASF) as auxiliary stabilizer, 0.7 weight of 1N hydrochloric acid The aqueous dispersion medium was prepared. Next, an oily mixture was prepared with the formulation shown in Table 1, and this oily mixture was added to the aqueous dispersion medium to prepare a dispersion.
The obtained dispersion was stirred and mixed with a homogenizer, then charged into a pressure polymerizer (20 L) purged with nitrogen, and reacted at 60 ° C. for 20 hours while being pressurized (0.2 MPa).
得られた反応生成物について、 用いた油性混合液中の少なくとも1つの重合性不飽和結合を有するエポキシ基含有モノマーのエポキシ当量に対する理論硬化剤量に対して、エポキシ基と反応可能な硬化剤としてイソホロンジアミン1倍量を用いて、温度50℃で12時間反応させることにより、エポキシ基と反応可能な硬化剤で表面処理を行った。得られた反応生成物について、ろ過と水洗を繰り返した後、乾燥することにより、エポキシ基と反応可能な硬化剤で表面処理された発泡粒子を得た。 About the obtained reaction product, as a curing agent capable of reacting with an epoxy group with respect to the theoretical curing agent amount with respect to the epoxy equivalent of an epoxy group-containing monomer having at least one polymerizable unsaturated bond in the oily mixture used. Surface treatment was performed with a curing agent capable of reacting with an epoxy group by reacting at a temperature of 50 ° C. for 12 hours using a 1-fold amount of isophoronediamine. The obtained reaction product was repeatedly filtered and washed with water, and then dried to obtain expanded particles surface-treated with a curing agent capable of reacting with an epoxy group.
(評価)
実施例及び比較例で得られた発泡粒子について、以下の評価を行った。結果を表1に示した。
(Evaluation)
The following evaluation was performed about the expanded particle obtained by the Example and the comparative example. The results are shown in Table 1.
(1)発泡倍率評価
発泡粒子を約0.1g秤量し、10mLのメスシリンダーに入れた。このメスシリンダーを160℃、180℃、200℃又は220℃に加熱したオーブンに5分間投入し、膨張した粒子のメスシリンダー内での容積を測定した。
膨張した粒子のメスシリンダー内での容積が2mL未満であった場合を「×」と、2mL以上5mL未満であった場合を「△」と、5mL以上8mL未満であった場合を「○」と、8mL以上であった場合を「◎」として評価した。
(1) Evaluation of expansion ratio About 0.1 g of expanded particles was weighed and placed in a 10 mL measuring cylinder. This graduated cylinder was put into an oven heated to 160 ° C, 180 ° C, 200 ° C or 220 ° C for 5 minutes, and the volume of the expanded particles in the graduated cylinder was measured.
When the volume of the expanded particles in the graduated cylinder is less than 2 mL, “X”, when the volume is 2 mL or more and less than 5 mL, “△”, and when the volume is 5 mL or more and less than 8 mL, “◯” The case of 8 mL or more was evaluated as “と し て”.
(2)耐熱性評価
上記(1)の測定を行った後のサンプルを、220℃に加熱したオーブンに更に10分間投入し、膨張した粒子のメスシリンダー内での容積を測定した。
上記(1)の測定を行った直後の膨張した粒子のメスシリンダー内での容積をL、更に220℃で10分間処理した後の膨張した粒子のメスシリンダー内での容積をHとしたとき、H/Lが0.4未満であった場合を「×」と、0.4以上0.6未満であった場合を「△」と、0.6以上0.8未満であった場合を「○」と、0.8以上であった場合を「◎」として評価した。
(2) Evaluation of heat resistance The sample after the measurement of (1) was put into an oven heated to 220 ° C. for 10 minutes, and the volume of the expanded particles in the graduated cylinder was measured.
When the volume in the graduated cylinder of the expanded particles immediately after the measurement of (1) is performed is L, and the volume in the graduated cylinder of the expanded particles after treatment at 220 ° C. for 10 minutes is H, The case where H / L is less than 0.4 is “x”, the case where it is 0.4 or more and less than 0.6 is “Δ”, and the case where it is 0.6 or more and less than 0.8 is “ The case where it was 0.8 or more was evaluated as “と し て”.
本発明によれば、高温で加熱しても粒子の破裂及び収縮が生じにくく、高発泡倍率での発泡成形に用いることができる発泡性組成物を提供することができる。また、本発明によれば、上記発泡性組成物を用いた発泡成形体の製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, even if it heats at high temperature, the bursting and shrinkage | contraction of particle | grains are hard to produce, and the foamable composition which can be used for foam molding by a high foaming ratio can be provided. Moreover, according to this invention, the manufacturing method of the foaming molding using the said foamable composition can be provided.
Claims (4)
前記発泡粒子は、共重合体からなるシェルに、コア剤として揮発性膨張剤を内包しており、
前記共重合体は、ニトリル系モノマーと、少なくとも1つの重合性不飽和結合を有するエポキシ基含有モノマーとを含有するモノマー混合物を共重合することにより得られ、
前記ニトリル系モノマー100重量部に対して前記少なくとも1つの重合性不飽和結合を有するエポキシ基含有モノマーを1〜30重量部含有する
ことを特徴とする発泡性組成物。 A foamable composition comprising foamed particles and a curing agent capable of reacting with an epoxy group,
The foamed particles contain a volatile swelling agent as a core agent in a shell made of a copolymer,
The copolymer is obtained by copolymerizing a monomer mixture containing a nitrile monomer and an epoxy group-containing monomer having at least one polymerizable unsaturated bond ,
A foamable composition comprising 1 to 30 parts by weight of an epoxy group-containing monomer having at least one polymerizable unsaturated bond based on 100 parts by weight of the nitrile monomer .
前記発泡成形用樹脂組成物を成形する工程とを有する
ことを特徴とする発泡成形体の製造方法。 Producing a foam molding resin composition comprising the foamable composition according to claim 1, 2 or 3, and a matrix resin;
And a step of molding the foam molding resin composition.
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