JP5497978B2 - Thermally expandable microcapsules and foamed molded articles - Google Patents
Thermally expandable microcapsules and foamed molded articles Download PDFInfo
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- JP5497978B2 JP5497978B2 JP2006320415A JP2006320415A JP5497978B2 JP 5497978 B2 JP5497978 B2 JP 5497978B2 JP 2006320415 A JP2006320415 A JP 2006320415A JP 2006320415 A JP2006320415 A JP 2006320415A JP 5497978 B2 JP5497978 B2 JP 5497978B2
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- JP
- Japan
- Prior art keywords
- thermally expandable
- expandable microcapsule
- weight
- agent
- temperature
- Prior art date
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- 239000003094 microcapsule Substances 0.000 title claims description 96
- 239000000178 monomer Substances 0.000 claims description 54
- 150000001768 cations Chemical class 0.000 claims description 39
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 238000005187 foaming Methods 0.000 claims description 35
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 22
- 238000006073 displacement reaction Methods 0.000 claims description 20
- 229920001577 copolymer Polymers 0.000 claims description 19
- 150000002825 nitriles Chemical class 0.000 claims description 19
- 238000009835 boiling Methods 0.000 claims description 17
- 238000001746 injection moulding Methods 0.000 claims description 16
- 150000002148 esters Chemical group 0.000 claims description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920005992 thermoplastic resin Polymers 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 6
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 claims 1
- 238000000465 moulding Methods 0.000 description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 21
- 239000006185 dispersion Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- 239000003381 stabilizer Substances 0.000 description 19
- 238000004898 kneading Methods 0.000 description 15
- -1 ethylene oxide modified trimethylolpropane Chemical class 0.000 description 14
- 239000002612 dispersion medium Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 230000008961 swelling Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000003431 cross linking reagent Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 10
- 239000008188 pellet Substances 0.000 description 10
- 239000007859 condensation product Substances 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 239000006260 foam Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 239000004594 Masterbatch (MB) Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 239000012736 aqueous medium Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-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
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000004888 barrier function Effects 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
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000011777 magnesium Substances 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
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000002994 raw material 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
- 229940113165 trimethylolpropane Drugs 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000004743 Polypropylene 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 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
- 230000002378 acidificating effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 2
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 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 2
- 239000011259 mixed solution Substances 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 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
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- 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
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- ZQHJVIHCDHJVII-OWOJBTEDSA-N (e)-2-chlorobut-2-enedioic acid Chemical compound OC(=O)\C=C(\Cl)C(O)=O ZQHJVIHCDHJVII-OWOJBTEDSA-N 0.000 description 1
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- TZJQCUDHKUWEFU-UHFFFAOYSA-N 2,2-dimethylpentanenitrile Chemical compound CCCC(C)(C)C#N TZJQCUDHKUWEFU-UHFFFAOYSA-N 0.000 description 1
- CRJIYMRJTJWVLU-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yl 3-(5,5-dimethylhexyl)dioxirane-3-carboxylate Chemical compound CC(C)(C)CCCCC1(C(=O)OC(C)(C)CC(C)(C)C)OO1 CRJIYMRJTJWVLU-UHFFFAOYSA-N 0.000 description 1
- PJABOTZVAHGVAF-UHFFFAOYSA-N 2-(2-cyclohexylpropan-2-yl)-7,7-dimethyloctaneperoxoic acid Chemical compound CC(C)(C)CCCCC(C(=O)OO)C(C)(C)C1CCCCC1 PJABOTZVAHGVAF-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
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- RVBFWXYFXKDVKG-UHFFFAOYSA-N 2-ethoxyprop-2-enenitrile Chemical compound CCOC(=C)C#N RVBFWXYFXKDVKG-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
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- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
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- UKAJDOBPPOAZSS-UHFFFAOYSA-N ethyl(trimethyl)silane Chemical compound CC[Si](C)(C)C UKAJDOBPPOAZSS-UHFFFAOYSA-N 0.000 description 1
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- 235000019322 gelatine Nutrition 0.000 description 1
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- 235000011187 glycerol Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
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- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
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- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
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- DYGOPFFOGFHOIB-UHFFFAOYSA-N methylperoxyethane Chemical compound CCOOC DYGOPFFOGFHOIB-UHFFFAOYSA-N 0.000 description 1
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- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- WGOROJDSDNILMB-UHFFFAOYSA-N octatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O WGOROJDSDNILMB-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 239000003973 paint Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
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- 239000004800 polyvinyl chloride Substances 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 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
- 239000011342 resin composition Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 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
- 239000000243 solution Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 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
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer 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
- 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
- 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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Description
本発明は、優れた耐熱性と発泡倍率を有し、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、射出成形等にも好適に使用可能であり、特に射出成形に用いられた場合に高い外観品質が得られる熱膨張性マイクロカプセル及び該熱膨張性マイクロカプセルを用いた発泡成形体に関する。 The present invention can be suitably used for kneading molding, calender molding, extrusion molding, injection molding, etc., which have excellent heat resistance and expansion ratio and a strong shear force is applied, particularly when used for injection molding The present invention relates to a thermally expandable microcapsule that can provide a high appearance quality and a foam-molded article using the thermally expandable microcapsule.
熱膨張性マイクロカプセルは、意匠性付与剤や軽量化剤として幅広い用途に使用されており、発泡インク、壁紙をはじめとした軽量化を目的とした塗料等にも利用されている。
このような熱膨張性マイクロカプセルとしては、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が内包されているものが広く知られており、例えば、特許文献１には、低沸点の脂肪族炭化水素等の揮発性膨張剤をモノマーと混合した油性混合液を、油溶性重合触媒とともに分散剤を含有する水系分散媒体中に攪拌しながら添加し懸濁重合を行うことにより、揮発性膨張剤を内包する熱膨張性マイクロカプセルを製造する方法が開示されている。
Thermally expandable microcapsules are used in a wide range of applications as a design-imparting agent and a lightening agent, and are also used in paints for the purpose of weight reduction such as foamed ink and wallpaper.
As such a heat-expandable microcapsule, one in which a volatile expansion agent that becomes gaseous at a temperature below the softening point of the shell polymer is included in a thermoplastic shell polymer is widely known. In Patent Document 1, an oily mixed liquid obtained by mixing a volatile expansion agent such as a low-boiling point aliphatic hydrocarbon with a monomer is added to an aqueous dispersion medium containing a dispersant together with an oil-soluble polymerization catalyst while stirring. A method for producing thermally expandable microcapsules encapsulating a volatile swelling agent by performing suspension polymerization is disclosed.
しかしながら、この方法によって得られた熱膨張性マイクロカプセルは、８０〜１３０℃程度の比較的低温で熱膨張させることができるものの、高温又は長時間加熱すると、膨張したマイクロカプセルが破裂又は収縮してしまい発泡倍率が低下するため、耐熱性に優れた熱膨張性マイクロカプセルを得ることができないという欠点を有していた。 However, although the thermally expandable microcapsule obtained by this method can be thermally expanded at a relatively low temperature of about 80 to 130 ° C., the expanded microcapsule is ruptured or contracted when heated at a high temperature or for a long time. In other words, since the expansion ratio is reduced, there is a drawback that it is not possible to obtain thermally expandable microcapsules having excellent heat resistance.
一方、特許文献２には、ニトリル系モノマー８０〜９７重量％、非ニトリル系モノマー２０〜３重量％及び三官能性架橋剤０．１〜１重量％を含有する重合成分から得られるポリマーをシェルとして用い、揮発性膨張剤を内包させた熱膨張性マイクロカプセルを製造する方法が開示されている。
また、特許文献３には、ニトリル系モノマー８０重量％以上、非ニトリル系モノマー２０重量％以下及び架橋剤０．１〜１重量％を含有する重合成分から得られるポリマーを用い、揮発性膨張剤を内包させた熱膨張性マイクロカプセルにおいて、非ニトリル系モノマーがメタクリル酸エステル類又はアクリル酸エステル類である熱膨張性マイクロカプセルが開示されている。
On the other hand, in Patent Document 2, a polymer obtained from a polymerization component containing 80 to 97% by weight of a nitrile monomer, 20 to 3% by weight of a non-nitrile monomer and 0.1 to 1% by weight of a trifunctional crosslinking agent is shelled. And a method for producing a thermally expandable microcapsule encapsulating a volatile expansion agent is disclosed.
Patent Document 3 uses a polymer obtained from a polymerization component containing 80% by weight or more of a nitrile monomer, 20% by weight or less of a non-nitrile monomer and 0.1 to 1% by weight of a crosslinking agent, and uses a volatile swelling agent. In the thermally expandable microcapsules encapsulating, a thermally expandable microcapsule in which the non-nitrile monomer is a methacrylic acid ester or an acrylic acid ester is disclosed.
これらの方法によって得られる熱膨張性マイクロカプセルは、従来のマイクロカプセルに比べ耐熱性に優れ、１４０℃以下では発泡しないとされているが、実際には１３０〜１４０℃で１分程度加熱を続けると一部のマイクロカプセルが熱膨張してしまうものであり、最大発泡温度が１８０℃以上の優れた耐熱性を有する熱膨張性マイクロカプセルを得ることは困難であった。 The heat-expandable microcapsules obtained by these methods have excellent heat resistance compared to conventional microcapsules and do not foam at 140 ° C. or lower, but actually continue heating at 130 to 140 ° C. for about 1 minute. Some of the microcapsules are thermally expanded, and it has been difficult to obtain thermally expandable microcapsules having excellent heat resistance with a maximum foaming temperature of 180 ° C. or higher.
更に、特許文献４には、最大発泡温度が１８０℃以上、好ましくは１９０℃以上である熱膨張性マイクロカプセルを得ることを目的として、８５重量％以上のニトリル基をもつエチレン性不飽和モノマーの単独重合体又は共重合体からなるシェルポリマーと５０重量％以上のイソオクタンを有する発泡剤からなる熱膨張性マイクロカプセルが開示されている。
このような熱膨張性マイクロカプセルでは、最大発泡温度が非常に高い値となっているものの、その後の膨張した状態を維持することができず、高温領域における長時間の使用は困難であった。
Furthermore, Patent Document 4 discloses an ethylenically unsaturated monomer having 85% by weight or more of a nitrile group for the purpose of obtaining a thermally expandable microcapsule having a maximum foaming temperature of 180 ° C. or higher, preferably 190 ° C. or higher. There is disclosed a thermally expandable microcapsule comprising a foaming agent having a shell polymer comprising a homopolymer or a copolymer and 50% by weight or more of isooctane.
In such a heat-expandable microcapsule, although the maximum foaming temperature is a very high value, the subsequent expanded state cannot be maintained, and it has been difficult to use for a long time in a high temperature region.
更に、特許文献５、特許文献６には、耐熱性をより向上させた熱膨張性マイクロカプセルが開示されている。しかしながら、これらの熱膨張性マイクロカプセルを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、射出成形等の成形加工、特に射出成形に使用した場合、種々の課題があった。
具体的には、一般的な射出プロセスにおいては、シリンダー内でマトリックス樹脂と熱膨張性マイクロカプセルとを溶融混練する工程を行った後、金型に樹脂溶融物を充填し、金型を開いて（コアバック）発泡させる工程を行うが、シリンダー内で溶融混練する工程では、熱膨張性マイクロカプセルの耐熱性や強度の問題から、いわゆる「へたり」と呼ばれる現象が生じたり、潰れてしまうがことがあった。また、コアバック後に熱膨張性マイクロカプセルを発泡させる工程においては、熱膨張性マイクロカプセルが充分に発泡せず、未発泡のままとなるため、得られる成形体は、外観や、軽量性等の機能性の面で劣るものとなっていた。これに対して、コアバック後に発泡倍率を発現させる手段としては、蒸気圧の高い炭化水素を揮発性膨張剤に使用する方法や、熱膨張性マイクロカプセルの粒径を大きくする方法等が考えられるが、これらの方法を用いた場合、所望の倍率が得られ、発泡性能には優れるものの、成形品表面でも発泡が起こり、表面がざらつくという問題があった。
従って、優れた耐熱性を有し、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、射出成形等に使用する場合であっても、へたり等が生じにくく、得られた成形品は、優れた外観品質と発泡倍率を有する熱膨張性マイクロカプセルが必要とされていた。
Furthermore, Patent Document 5 and Patent Document 6 disclose thermally expandable microcapsules with further improved heat resistance. However, when these heat-expandable microcapsules are used in molding processes such as kneading molding, calender molding, extrusion molding, injection molding, and the like to which a strong shear force is applied, there are various problems.
Specifically, in a general injection process, after performing a step of melting and kneading the matrix resin and the thermally expandable microcapsule in a cylinder, the mold is filled with a resin melt, and the mold is opened. (Core back) A foaming step is performed, but in the step of melt-kneading in a cylinder, a phenomenon called so-called “sag” occurs or is crushed due to heat resistance and strength problems of the thermally expandable microcapsules. There was a thing. Further, in the step of foaming the thermally expandable microcapsules after the core back, the thermally expandable microcapsules are not sufficiently foamed and remain unfoamed. It was inferior in terms of functionality. On the other hand, as a means for expressing the expansion ratio after the core back, a method of using a hydrocarbon having a high vapor pressure as a volatile expansion agent, a method of increasing the particle size of the thermally expandable microcapsule, or the like can be considered. However, when these methods are used, a desired magnification can be obtained and the foaming performance is excellent, but there is a problem that foaming occurs on the surface of the molded product and the surface becomes rough.
Therefore, even when used for kneading molding, calender molding, extrusion molding, injection molding, etc., which has excellent heat resistance and a strong shear force, it is difficult for sag to occur, and the obtained molded product is There has been a need for thermally expandable microcapsules having excellent appearance quality and expansion ratio.
本発明は、優れた耐熱性を有し、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、特に射出成形等に使用する場合であっても、へたり等が生じにくく、得られる成形品は、優れた外観品質と発泡倍率を有する熱膨張性マイクロカプセルを用いた発泡成形体を提供することを目的とする。 The present invention has excellent heat resistance and is capable of forming a kneading molding, a calendar molding, an extrusion molding, particularly an injection molding, etc., to which a strong shearing force is applied, and it is difficult to cause sag etc. An object of the present invention is to provide a foam molded article using thermally expandable microcapsules having excellent appearance quality and expansion ratio.
本発明は、重合体からなるシェルに、コア剤として揮発性膨張剤が内包された熱膨張性マイクロカプセルであって、最大変位量（Ｄｍａｘ）が１０００μｍ以上、最大発泡温度（Ｔｍａｘ）が２１０℃以上、かつ、発泡開始温度（Ｔｓ）が１９０℃以上であり、前記シェルは、ニトリル系モノマーに由来するセグメントと、カルボキシル基を有し、エステル残基を除いた炭素数が３〜８のラジカル重合性不飽和カルボン酸モノマーに由来するセグメントとを有する共重合体、並びに、アルカリ金属イオン及びＺｎイオンからなる金属カチオン０．１〜１０重量％を含有し、前記コア剤は、沸点が６０℃以上の炭化水素を含む２種以上の揮発性膨張剤からなり、沸点が最も低い揮発性膨張剤と、沸点が最も高い揮発性膨張剤との沸点の差が６０℃以上であることを特徴とする熱膨張性マイクロカプセルである。前記最大変位量は、熱膨張性マイクロカプセル２５μｇを直径７ｍｍ、深さ１ｍｍの容器に入れ、上から０．１Ｎの力を加えた状態で、５℃／ｍｉｎの昇温速度で８０℃から２２０℃まで加熱した場合の測定端子の垂直方向における変位の最大値を示す。
以下に本発明を詳述する。
The present invention is a thermally expandable microcapsule in which a volatile expansion agent is included as a core agent in a polymer shell, and the maximum displacement (Dmax) is 1000 μm or more and the maximum foaming temperature (Tmax) is 210 ° C. The foaming start temperature (Ts) is 190 ° C. or higher, and the shell has a segment derived from a nitrile monomer, a carboxyl group, and a radical having 3 to 8 carbon atoms excluding an ester residue. A copolymer having a segment derived from a polymerizable unsaturated carboxylic acid monomer, and 0.1 to 10% by weight of a metal cation composed of an alkali metal ion and a Zn ion, and the core agent has a boiling point of 60 ° C. consists of two or more volatile expansion agent containing at least hydrocarbons, a difference of the boiling point of the lowest volatility expanding agent having a boiling point, the boiling point is the highest volatility expansion agent 60 A thermally expandable microcapsule, characterized in that at least. The maximum amount of displacement is as follows: 25 μg of thermally expandable microcapsules are placed in a container having a diameter of 7 mm and a depth of 1 mm, and a force of 0.1 N is applied from above, and a temperature increase rate of 5 ° C./min is 80 to 220 ° C. The maximum value of the displacement in the vertical direction of the measurement terminal when heated to ° C. is shown.
The present invention is described in detail below.
本発明者らは鋭意検討した結果、熱膨張性マイクロカプセルの最大変位量（Ｄｍａｘ）を１０００μｍ以上とし、Ｔｍａｘを２１０℃以上、かつ、Ｔｓを１９０℃以上とすることにより、熱膨張性マイクロカプセルをシリンダー内に投入した際の熱膨張性マイクロカプセルのへたりを防止することができ、かつ、金型に充填した後に、出来るだけ速くコアバックさせることにより、金型内で充分に発泡させ、かつ、優れた外観品質の成形品が得られることを見出し、本発明を完成させるに至った。 As a result of intensive studies, the present inventors have determined that the maximum displacement (Dmax) of the thermally expandable microcapsule is 1000 μm or more, Tmax is 210 ° C. or more, and Ts is 190 ° C. or more. Can be prevented from sag of the thermally expandable microcapsule when it is put into the cylinder, and after filling the mold, it is sufficiently foamed in the mold by making the core back as fast as possible, And it discovered that the molded article of the outstanding external appearance quality was obtained, and came to complete this invention.
本発明の熱膨張性マイクロカプセルは、最大変位量（Ｄｍａｘ）の下限が１０００μｍである。１０００μｍ未満であると、熱膨張性マイクロカプセルを含有する樹脂溶融物が金型に充填した後に金型内で充分に発泡しない。好ましい下限は１２００μｍである。また、好ましい上限は２０００μｍである。
なお、本明細書において、最大変位量は、熱膨張性マイクロカプセル２５μｇを直径７ｍｍ、深さ１ｍｍの容器に入れ、上から０．１Ｎの力を加えた状態で、５℃／ｍｉｎの昇温速度で８０℃から２２０℃まで加熱した場合の測定端子の垂直方向における変位の最大値のことである。
In the thermally expandable microcapsule of the present invention, the lower limit of the maximum displacement (Dmax) is 1000 μm. When the thickness is less than 1000 μm, the resin melt containing the thermally expandable microcapsules does not sufficiently foam in the mold after filling the mold. A preferred lower limit is 1200 μm. Moreover, a preferable upper limit is 2000 micrometers.
In this specification, the maximum amount of displacement is a temperature increase of 5 ° C./min in a state where 25 μg of thermally expandable microcapsules are placed in a container having a diameter of 7 mm and a depth of 1 mm and a force of 0.1 N is applied from the top. It is the maximum value of the displacement in the vertical direction of the measurement terminal when heated from 80 ° C. to 220 ° C. at a speed.
本発明の熱膨張性マイクロカプセルは、最大発泡温度（Ｔｍａｘ）の下限が２１０℃である。Ｔｍａｘを２１０℃以上とすることで、熱膨張性マイクロカプセルをシリンダー内に投入した際の熱膨張性マイクロカプセルのへたりを低減することが可能となる。
２１０℃未満であると、シリンダー内で熱膨張性マイクロカプセルのへたりが生じてしまうことから、発泡倍率の低下が生じる。好ましい下限は２３０℃である。
また、好ましい上限は２５０℃である。
なお、本明細書において、最大発泡温度は、熱膨張性マイクロカプセルを常温から加熱しながらその径を測定したときに、熱膨張性マイクロカプセルの径が最大となったとき（最大変位量）における温度を意味する。
In the thermally expandable microcapsule of the present invention, the lower limit of the maximum foaming temperature (Tmax) is 210 ° C. By setting Tmax to 210 ° C. or higher, it is possible to reduce the sag of the thermally expandable microcapsule when the thermally expandable microcapsule is put into the cylinder.
When the temperature is lower than 210 ° C., the expansion of the thermally expandable microcapsule occurs in the cylinder, and the expansion ratio is reduced. A preferred lower limit is 230 ° C.
Moreover, a preferable upper limit is 250 degreeC.
In the present specification, the maximum foaming temperature is when the diameter of the thermally expandable microcapsule becomes maximum when the diameter is measured while heating the thermally expandable microcapsule from room temperature (maximum displacement). It means temperature.
本発明の熱膨張性マイクロカプセルは、発泡開始温度（Ｔｓ）の下限が１９０℃である。Ｔｓを１９０℃以上とすることで、熱膨張性マイクロカプセルを含む樹脂溶融物が金型に充填した後に金型内で充分に発泡した場合でも成形品表面で発泡がおこらず、外観品質の優れた成形品が得ることが可能となる。１９０℃未満であると、成形品表面で発泡現象がみられる。好ましい下限は２００℃である。また、好ましい上限は２３０℃である。 In the thermally expandable microcapsule of the present invention, the lower limit of the foaming start temperature (Ts) is 190 ° C. By setting Ts to 190 ° C. or higher, foaming does not occur on the surface of the molded product even when the resin melt containing the thermally expandable microcapsule is sufficiently foamed after filling the mold, and the appearance quality is excellent. A molded product can be obtained. When it is lower than 190 ° C., a foaming phenomenon is observed on the surface of the molded product. A preferred lower limit is 200 ° C. Moreover, a preferable upper limit is 230 degreeC.
本発明の熱膨張性マイクロカプセルは、ニトリル系モノマーを６０重量％以上、非ニトリル系モノマーを４０重量％以下、金属カチオンを０．１〜１０重量％及び架橋剤を含有するビニル系モノマー組成物を重合させてなるシェルに、コア剤としてシェルの軟化点以下の温度でガス状になる揮発性膨張剤が内包されたものであることが好ましい。
このようなビニル系モノマー組成物及び揮発性膨張剤を用いることで、上述した範囲のＤｍａｘ、Ｔｍａｘ及びＴｓを有する熱膨張性マイクロカプセルを実現することができる。
The thermally expandable microcapsule of the present invention is a vinyl monomer composition containing a nitrile monomer of 60 wt% or more, a non-nitrile monomer of 40 wt% or less, a metal cation of 0.1 to 10 wt%, and a crosslinking agent. It is preferable that a shell obtained by polymerizing a volatile expansion agent that becomes gaseous at a temperature equal to or lower than the softening point of the shell is included as a core agent.
By using such a vinyl monomer composition and a volatile swelling agent, a thermally expandable microcapsule having Dmax, Tmax and Ts in the above-described range can be realized.
上記ニトリル系モノマーとしては、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−クロルアクリロニトリル、α−エトキシアクリロニトリル、フマロニトリル又はこれらの任意の混合物等が挙げられ、アクリロニトリル又はメタクリロニトリルが好適に用いられる。 The nitrile monomer is not particularly limited, and examples thereof include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, fumaronitrile, and any mixture thereof, and acrylonitrile or methacrylonitrile is preferable. Used.
本発明では、上記シェルの原料であるビニル系モノマー組成物中における上記ニトリル系モノマーの含有量の好ましい下限は６０重量％である。６０重量％未満であると、シェルのガスバリア性が低くなるため発泡倍率が低下ことがある。
より好ましい下限は７０重量％、好ましい上限は８０重量％である。
In the present invention, the preferable lower limit of the content of the nitrile monomer in the vinyl monomer composition that is the raw material of the shell is 60% by weight. If it is less than 60% by weight, the gas barrier property of the shell is lowered, so that the expansion ratio may be lowered.
A more preferred lower limit is 70% by weight, and a preferred upper limit is 80% by weight.
上記非ニトリル系モノマーとしては、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；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からなる群から選択される。これらのなかでメタクリル酸メチル、メタクリル酸エチル、アクリル酸メチルが特に好ましい。 Examples of the non-nitrile monomers include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and dicyclopentenyl acrylate; methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and isobornyl methacrylate. Selected from the group consisting of esters. Of these, methyl methacrylate, ethyl methacrylate, and methyl acrylate are particularly preferred.
上記ビニル系モノマー組成物中における非ニトリル系モノマーの含有量の好ましい上限は４０重量％である。４０重量％を超えると、上記と同様にシェルのガスバリア性が低くなるため発泡倍率が低下することがある。
より好ましい上限は３０重量％、好ましい下限は２０重量％である。
The upper limit with preferable content of the non-nitrile-type monomer in the said vinyl-type monomer composition is 40 weight%. If it exceeds 40% by weight, the gas barrier property of the shell is lowered as described above, and the expansion ratio may be lowered.
A more preferred upper limit is 30% by weight, and a preferred lower limit is 20% by weight.
上記ビニル系モノマー組成物は、金属カチオンを含有することが好ましい。上記金属カチオンを含有するビニル系モノマー組成物を重合させることにより、上記金属カチオンが非ニトリル系モノマーと反応し、得られる共重合体がイオン架橋していると考えられることから、耐熱性が向上し、高温領域において長時間破裂、収縮の起こらない熱膨張性マイクロカプセルとすることが可能となる。また、高温領域においてもシェルの弾性率が低下しにくいことから、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、射出成形等の成形加工を行う場合であっても、熱膨張性マイクロカプセルの破裂、収縮が起こることがない。 The vinyl monomer composition preferably contains a metal cation. By polymerizing the vinyl monomer composition containing the metal cation, the metal cation reacts with the non-nitrile monomer, and the resulting copolymer is considered to be ionically crosslinked, improving heat resistance. In addition, it is possible to obtain a thermally expandable microcapsule that does not rupture or shrink for a long time in a high temperature region. In addition, since the elastic modulus of the shell is difficult to decrease even in a high temperature region, even when molding processing such as kneading molding, calender molding, extrusion molding, injection molding, etc. to which a strong shear force is applied, the thermal expansion micro Capsule rupture and shrinkage do not occur.
上記金属カチオンとしては、非ニトリル系モノマーと反応し、イオン架橋させ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、特にＺｎのイオンが好適である。これらの金属カチオンは、単独で用いても良く、２種以上を併用してもよい。
なお、上記金属カチオンを２種以上用いる場合の組み合わせとしては特に限定されないが、アルカリ金属のイオンと上記アルカリ金属以外の金属カチオンとを組み合わせて用いることが好ましい。上記アルカリ金属のイオンを有することにより、ビニル系モノマー等の官能基が活性化され、上記アルカリ金属以外の金属カチオンと上記カルボキシル基との反応を促進させることができる。上記アルカリ金属としては、例えば、Ｎａ、Ｋ、Ｌｉ等が挙げられる。
The metal cation is not particularly limited as long as it is a metal cation that reacts with a non-nitrile monomer and ionically crosslinks. For example, Na, K, Li, Zn, Mg, Ca, Ba, Sr, Mn, Al, Examples include ions such as 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. These metal cations may be used alone or in combination of two or more.
In addition, although it does not specifically limit as a combination when using the said metal cation 2 or more types, It is preferable to use combining the ion of an alkali metal, and metal cations other than the said alkali metal. By having the alkali metal ion, a functional group such as a vinyl monomer is activated, and the reaction between the metal cation other than the alkali metal and the carboxyl group can be promoted. Examples of the alkali metal include Na, K, and Li.
上記ビニル系モノマー組成物中における上記金属カチオンの含有量の好ましい下限は０．１重量％、好ましい上限は１０重量％である。０．１重量％未満であると、充分に共重合体をイオン架橋できないことがあり、耐熱性を向上させる効果が得られず、逆に、１０重量％を超えると、発泡特性が著しく悪くなることがある。 The minimum with preferable content of the said metal cation in the said vinyl-type monomer composition is 0.1 weight%, and a preferable upper limit is 10 weight%. If the amount is less than 0.1% by weight, the copolymer may not be sufficiently ionically crosslinked, and the effect of improving the heat resistance may not be obtained. Conversely, if the amount exceeds 10% by weight, the foaming properties are significantly deteriorated. Sometimes.
上記シェルは、架橋剤を含有することが好ましい。上記架橋剤を含有することにより、シェルの強度を強化することができ、熱膨張時にセル壁が破泡し難くなる。
上記架橋剤としては特に限定はされず、一般的にはラジカル重合性二重結合を２以上有するモノマーが好適に用いられる。具体例には例えば、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。これらのなかでは、２００℃を超える高温領域でも熱膨張したマイクロカプセルが収縮しにくく、膨張した状態を維持しやすいので、ポリエチレングリコールのジ（メタ）アクリレート等の２官能性架橋剤が好しく、トリメチロールプロパンのトリ（メタ）アクリレート等の３官能性架橋剤がより好ましい。
The shell preferably contains a cross-linking agent. By containing the said crosslinking agent, the intensity | strength of a shell can be strengthened and it becomes difficult to foam a cell wall at the time of thermal expansion.
The crosslinking agent is not particularly limited, and generally, a monomer having two or more radical polymerizable double bonds is preferably used. Specific examples include, 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, tri Methylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate Triallyl formal tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dimethylol - tricyclodecane (meth) acrylate. Among these, since the thermally expanded microcapsules are difficult to contract even in a high temperature region exceeding 200 ° C., and easily maintain the expanded state, bifunctional crosslinking agents such as di (meth) acrylate of polyethylene glycol are preferred. A trifunctional cross-linking agent such as tri (meth) acrylate of trimethylolpropane is more preferable.
上記シェルにおける上記架橋剤の含有量の好ましい下限は０．１重量％、好ましい上限は３重量％である。より好ましい下限は０．１重量％、より好ましい上限は１重量％である。 The minimum with preferable content of the said crosslinking agent in the said shell is 0.1 weight%, and a preferable upper limit is 3 weight%. A more preferred lower limit is 0.1% by weight, and a more preferred upper limit is 1% by weight.
また、本発明の熱膨張性マイクロカプセルのシェルは、ニトリル系モノマーに由来するセグメントと、カルボキシル基を有し、エステル残基を除いた炭素数が３〜８のラジカル重合性不飽和カルボン酸モノマーに由来するセグメントとを有する共重合体、及び、２〜３価の金属カチオン０．１〜１０重量％を含有するものであることが好ましい。 The shell of the thermally expandable microcapsule of the present invention is a radically polymerizable unsaturated carboxylic acid monomer having a segment derived from a nitrile monomer and a carboxyl group and having 3 to 8 carbon atoms excluding an ester residue. It is preferable to contain a copolymer having a segment derived from the above and 0.1 to 10% by weight of a divalent or trivalent metal cation.
上記カルボキシル基を有し、エステル残基を除いた炭素数が３〜８のラジカル重合性不飽和カルボン酸モノマーとしては、例えば、イオン架橋させるための遊離カルボキシル基を分子当たり１個以上持つものを用いることができ、具体的には例えば、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、マレイン酸、イタコン酸、フマル酸、シトラコン酸、クロロマレイン酸等の不飽和ジカルボン酸やその無水物又はマレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノブチル、フマル酸モノメチル、フマル酸モノエチル、イタコン酸モノメチル、イタコン酸モノエチル、イタコン酸モノブチル等の不飽和ジカルボン酸のモノエステルやその誘導体挙げられ、これらは単独で用いてもよく、２種以上を併用してもよい。これらのなかでは、特にアクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸が好ましい。 Examples of the radical polymerizable unsaturated carboxylic acid monomer having a carboxyl group and having 3 to 8 carbon atoms excluding an ester residue include those having at least one free carboxyl group per molecule for ionic crosslinking. Specifically, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, cinnamic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid, chloromaleic acid, etc. Unsaturated dicarboxylic acids and anhydrides thereof or monoesters of unsaturated dicarboxylic acids such as monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monoethyl fumarate, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate And their derivatives, which may be used alone It may be used in combination of two or more. Of these, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, and itaconic acid are particularly preferable.
上記シェルを構成する共重合体における、前記カルボキシル基を有し、エステル残基を除いた炭素数３〜８のラジカル重合性不飽和カルボン酸モノマーに由来するセグメントの含有量の好ましい下限は１０重量％、好ましい上限は５０重量％である。１０重量％未満であると、最大発泡温度が１８０℃以下となることがあり、５０重量％を超えると、最大発泡温度は向上するものの、発泡倍率が低下するため好ましくない。 In the copolymer constituting the shell, the preferred lower limit of the content of the segment derived from the radically polymerizable unsaturated carboxylic acid monomer having 3 to 8 carbon atoms excluding the ester residue and having the carboxyl group is 10 wt. %, And a preferred upper limit is 50% by weight. If it is less than 10% by weight, the maximum foaming temperature may be 180 ° C. or less. If it exceeds 50% by weight, the maximum foaming temperature is improved, but the foaming ratio is lowered, which is not preferable.
上記共重合体は、必要に応じて、上記ニトリル系モノマーに由来するセグメント及び上記カルボキシル基を有し、エステル残基を除いた炭素数が３〜８のラジカル重合性不飽和カルボン酸モノマーに由来するセグメント以外のセグメントを有していてもよい。このようなセグメントとしては、特に限定されず、例えば、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、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、酢酸ビニル、スチレン等のビニルモノマー等に由来するセグメント等が挙げられる。これらのモノマーは、熱膨張性マイクロカプセルに必要な特性に応じて適宜選択されて使用され得るが、なかでも、メタクリル酸メチル、メタクリル酸エチル、アクリル酸メチル等が好適に用いられる。
ただし、このようなセグメントの含有量は１０重量％未満であることが好ましい。１０重量％以上であると、シェルのガスバリア性が低下してしまうことがある。
If necessary, the copolymer has a segment derived from the nitrile monomer and the carboxyl group, and is derived from a radically polymerizable unsaturated carboxylic acid monomer having 3 to 8 carbon atoms excluding an ester residue. You may have segments other than the segment to do. Such segments are not particularly limited. For example, acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and dicyclopentenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, Examples include segments derived from methacrylic esters such as bornyl methacrylate, vinyl monomers such as vinyl acetate and styrene, and the like. These monomers can be appropriately selected and used depending on the properties required for the thermally expandable microcapsules, and among them, methyl methacrylate, ethyl methacrylate, methyl acrylate and the like are preferably used.
However, the content of such a segment is preferably less than 10% by weight. If it is 10% by weight or more, the gas barrier property of the shell may be lowered.
上記共重合体の重量平均分子量の好ましい下限は１０万、好ましい上限は２００万である。１０万未満であると、シェルの強度が低下することがあり、２００万を超えると、シェルの強度が高くなりすぎ、発泡倍率が低下することがある。 The minimum with a preferable weight average molecular weight of the said copolymer is 100,000, and a preferable upper limit is 2 million. If it is less than 100,000, the strength of the shell may be reduced, and if it exceeds 2 million, the strength of the shell becomes too high, and the expansion ratio may be reduced.
本発明の熱膨張性マイクロカプセルにおいて、上記シェルの架橋度の好ましい下限は７５重量％である。７５重量％未満であると、最大発泡温度が低くなることがある。
上記架橋度は、架橋剤による共有結合性架橋と、上記共重合体の有する遊離カルボキシル基と上記金属カチオンとによってイオン架橋された架橋の双方を含む。
なお、本発明の熱膨張性マイクロカプセルでは、上記共重合体の有する遊離カルボキシル基の一部又は全部がイオン化して、カルボキシルアニオンとなり、上記金属カチオンをカウンターカチオンとしてイオン結合を形成することから、上記金属カチオンの含有量によって架橋度を容易に調節することができる。
また、上記イオン架橋は、例えば、赤外吸収スペクトル測定を行った場合に、１５００〜１６００ｃｍ−１付近にＣＯＯ−の非対称伸縮運動による吸収が存在することにより確認することができる。
In the thermally expandable microcapsule of the present invention, a preferable lower limit of the degree of crosslinking of the shell is 75% by weight. If it is less than 75% by weight, the maximum foaming temperature may be lowered.
The degree of cross-linking includes both covalent cross-linking by a cross-linking agent and cross-linking that is ionically cross-linked by the free carboxyl group of the copolymer and the metal cation.
In the thermally expandable microcapsule of the present invention, part or all of the free carboxyl group of the copolymer is ionized to form a carboxyl anion, and an ionic bond is formed using the metal cation as a counter cation. The degree of crosslinking can be easily adjusted by the content of the metal cation.
Moreover, the said ion bridge | crosslinking can be confirmed by the absorption by the asymmetrical expansion / contraction motion of COO- around 1500-1600 cm < -1 >, for example, when an infrared absorption spectrum measurement is performed.
本発明の熱膨張性マイクロカプセルにおいて、上記シェルの中和度の好ましい下限は５％である。５％未満であると、最大発泡温度が低くなることがある。
なお、上記中和度は、上記共重合体の有する遊離カルボキシル基のうち、上記金属カチオンが結合したカルボキシル基の割合を表す。
In the thermally expandable microcapsule of the present invention, the preferable lower limit of the degree of neutralization of the shell is 5%. If it is less than 5%, the maximum foaming temperature may be lowered.
In addition, the said neutralization degree represents the ratio of the carboxyl group which the said metal cation couple | bonded among the free carboxyl groups which the said copolymer has.
本発明の熱膨張性マイクロカプセルとして、ニトリル系モノマーに由来するセグメントと、カルボキシル基を有するエステル残基を除いた炭素数３〜８のラジカル重合性不飽和カルボン酸モノマーに由来するセグメントとを有する共重合体を含有するシェルを有するものを用いる場合、上記金属カチオンとしては、２〜３価のものを用いることが好ましい。
上記金属カチオンは、シェルを構成する共重合体のカルボキシル基と反応して共重合体がイオン架橋していると考えられることから、耐熱性が向上し、高温領域において長時間破裂、収縮の起こらない熱膨張性マイクロカプセルとすることが可能となる。また、高温領域においてもシェルの弾性率が低下しにくいことから、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、射出成形等の成形加工を行う場合であっても、熱膨張性マイクロカプセルの破裂、収縮が起こることがない。
The thermally expandable microcapsule of the present invention has a segment derived from a nitrile monomer and a segment derived from a radically polymerizable unsaturated carboxylic acid monomer having 3 to 8 carbon atoms excluding an ester residue having a carboxyl group. When using what has a shell containing a copolymer, as said metal cation, it is preferable to use a thing of 2-3 values.
Since the metal cation reacts with the carboxyl group of the copolymer constituting the shell and the copolymer is considered to be ionically cross-linked, the heat resistance is improved, and long-term rupture and shrinkage occur in a high temperature region. No heat-expandable microcapsules. In addition, since the elastic modulus of the shell is difficult to decrease even in a high temperature region, even when molding processing such as kneading molding, calender molding, extrusion molding, injection molding, etc. to which a strong shear force is applied, the thermal expansion micro Capsule rupture and shrinkage do not occur.
上記シェルにおける上記金属カチオンの含有量の下限は０．１重量％、上限は１０重量％である。０．１重量％未満であると、充分に共重合体をイオン架橋できず、耐熱性を向上させる効果が得られず、逆に、１０重量％を超えると、発泡特性が著しく悪くなる。 The lower limit of the content of the metal cation in the shell is 0.1% by weight, and the upper limit is 10% by weight. If the amount is less than 0.1% by weight, the copolymer cannot be sufficiently ionically crosslinked, and the effect of improving the heat resistance cannot be obtained. Conversely, if the amount exceeds 10% by weight, the foaming properties are remarkably deteriorated.
また、上記共重合体の有するカルボキシル基と金属カチオンとを適度にイオン架橋させるためには、所望の架橋度に応じて、上記共重合体の有する遊離カルボキシル基あたりの金属カチオンの量を調整する必要があるが、金属カチオンの量の好ましい下限は、上記共重合体のカルボン酸量に対して０．０１倍モル、好ましい上限は０．５倍モルである。０．０１倍モル未満であると、架橋度が上がらず耐熱性に効果が得られにくい。０．５倍モルを超えで配合してもそれ以上の効果が得られない。より好ましい下限は０．０５倍モルである。 Further, in order to appropriately ion-crosslink the carboxyl group and metal cation of the copolymer, the amount of metal cation per free carboxyl group of the copolymer is adjusted according to the desired degree of crosslinking. Although it is necessary, the preferable lower limit of the amount of the metal cation is 0.01 times mol and the preferable upper limit is 0.5 times mol with respect to the amount of carboxylic acid of the copolymer. If it is less than 0.01 times mol, the degree of cross-linking does not increase and it is difficult to obtain an effect on heat resistance. Even if it is blended in excess of 0.5 times mol, no further effect can be obtained. A more preferred lower limit is 0.05 times mol.
上記シェルは、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 shell 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 as necessary.
本発明の熱膨張性マイクロカプセルは、上記シェルにコア剤として揮発性膨張剤が内包されている。
上記揮発性膨張剤は、シェルを構成するポリマーの軟化点以下の温度でガス状になる物質が好ましく、低沸点有機溶剤が好適である。
上記揮発性膨張剤としては、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。これらは、それぞれ単独で用いてもよく、２種以上を併用してもよい。
In the thermally expandable microcapsule of the present invention, a volatile expansion agent is included as a core agent in the shell.
The volatile swelling agent is preferably a substance that becomes gaseous at a temperature below the softening point of the polymer constituting the shell, and a low-boiling organic solvent is preferred.
Examples of the volatile swelling agent include low molecular weight carbonization such as ethane, ethylene, propane, propene, n-butane, isobutane, butene, isobutene, n-pentane, isopentane, neopentane, n-hexane, heptane, and petroleum ether. Hydrogen; chlorofluorocarbons such as CCl 3 F, CCl 2 F 2 , CClF 3 , CClF 2 —CClF 2 ; tetraalkylsilanes such as tetramethylsilane, trimethylethylsilane, trimethylisopropylsilane, trimethyl-n-propylsilane, etc. It is done. These may be used alone or in combination of two or more.
本発明の熱膨張性マイクロカプセルでは、上述した揮発性膨張剤のなかでも、沸点が６０℃以上の炭化水素を用いることが好ましい。このような炭化水素を用いることにより、成形時の高温、高剪断条件下においても、熱膨張性マイクロカプセルが容易に破壊されず、耐熱性に優れた熱膨張性マイクロカプセルとすることができる。 In the heat-expandable microcapsule of the present invention, it is preferable to use a hydrocarbon having a boiling point of 60 ° C. or higher among the above-described volatile expansion agents. By using such a hydrocarbon, the thermally expandable microcapsule is not easily broken even under high temperature and high shear conditions during molding, and a thermally expandable microcapsule having excellent heat resistance can be obtained.
上記沸点が６０℃以上の炭化水素としては、例えば、ｎ−へキサン、ヘプタン、イソオクタン等が挙げられる。なお、６０℃以上の沸点を有する炭化水素は、それぞれ単独で用いてもよく、沸点が６０℃未満の炭化水素と組み合わせて用いてもよい。
また、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ることとしてもよい。
Examples of the hydrocarbon having a boiling point of 60 ° C. or higher include n-hexane, heptane, isooctane and the like. In addition, each hydrocarbon having a boiling point of 60 ° C. or higher may be used alone or in combination with a hydrocarbon having a boiling point of less than 60 ° C.
Moreover, it is good also as using the thermal decomposition type compound which thermally decomposes by heating and becomes a gaseous state as a volatile expansion | swelling agent.
また、揮発性膨張剤として、２種以上のものを用いる場合は、沸点が最も低い揮発性膨張剤と、沸点が最も高い揮発性膨張剤との沸点の差が６０℃以上であるものを用いることが好ましい。これにより、シリンダー内での熱膨張性マイクロカプセルのへたり防止と、金型内での発泡性とを両立させることが可能となる。これらの組み合わせとしては、例えば、ｎ−ペンタンとイソオクタンとの組み合わせ等が挙げられる。 Moreover, when using 2 or more types as a volatile expansion | swelling agent, the difference in boiling point of a volatile expansion | swelling agent with the lowest boiling point and a volatile swelling agent with the highest boiling point uses 60 degreeC or more. It is preferable. As a result, it is possible to achieve both the prevention of the sag of the thermally expandable microcapsules in the cylinder and the foamability in the mold. Examples of these combinations include a combination of n-pentane and isooctane.
本発明の熱膨張性マイクロカプセルの平均粒子径の好ましい下限は５μｍ、好ましい上限は１００μｍである。５μｍ未満であると、得られる成形体の気泡が小さすぎるため、成形体の軽量化が不充分となることがあり、１００μｍを超えると、得られる成形体の気泡が大きくなりすぎるため、強度等の面で問題となることがある。より好ましい下限は１０μｍ、より好ましい上限は４０μｍである。 The preferable lower limit of the average particle size of the heat-expandable microcapsules of the present invention is 5 μm, and the preferable upper limit is 100 μm. If the thickness is less than 5 μm, the resulting molded body has too small bubbles, which may result in insufficient weight reduction of the molded body. If the thickness exceeds 100 μm, the resulting molded body has excessively large bubbles, resulting in strength and the like. May cause problems. A more preferred lower limit is 10 μm, and a more preferred upper limit is 40 μm.
本発明の熱膨張性マイクロカプセルを製造する方法としては特に限定されないが、例えば、水性媒体を調製する工程、ニトリル系モノマー、カルボキシル基を有し、エステル残基を除いた炭素数が３〜８のラジカル重合性不飽和カルボン酸モノマー及び揮発性膨張剤を含有する油性混合液を水性媒体中に分散させる工程、金属カチオンを生じる化合物を添加して、上記カルボキシル基と金属カチオンとを反応させる工程、並びに、分散液を加熱することによりモノマーを重合させる工程を行うことにより製造することができる。 The method for producing the thermally expandable microcapsule of the present invention is not particularly limited. For example, the step of preparing an aqueous medium, a nitrile monomer, a carboxyl group, and having 3 to 8 carbon atoms excluding the ester residue. A step of dispersing an oily mixture containing a radical polymerizable unsaturated carboxylic acid monomer and a volatile swelling agent in an aqueous medium, a step of adding a compound that generates a metal cation, and reacting the carboxyl group with the metal cation Moreover, it can manufacture by performing the process which superposes | polymerizes a monomer by heating a dispersion liquid.
本発明の熱膨張性マイクロカプセルを製造する場合、最初に水性媒体を調製する工程を行う。具体例には例えば、重合反応容器に、水と分散安定剤、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、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。 When producing the heat-expandable microcapsules of the present invention, a step of preparing an aqueous medium is first performed. In a specific example, for example, an aqueous dispersion medium containing a dispersion stabilizer is prepared by adding water, a dispersion stabilizer and, if necessary, an auxiliary stabilizer to a polymerization reaction vessel. Moreover, you may add alkali metal nitrite, stannous chloride, stannic chloride, potassium dichromate, etc. as needed.
上記分散安定剤としては、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。 Examples of the dispersion stabilizer include silica, calcium phosphate, magnesium hydroxide, aluminum hydroxide, ferric hydroxide, barium sulfate, calcium sulfate, sodium sulfate, calcium oxalate, calcium carbonate, calcium carbonate, barium carbonate, and carbonate. Examples thereof include magnesium.
上記分散安定剤の添加量は特に限定されず、分散安定剤の種類、マイクロカプセルの粒子径等により適宜決定されるが、モノマー１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が２０重量部である。 The addition amount of the dispersion stabilizer is not particularly limited, and is appropriately determined depending on the type of dispersion stabilizer, the particle size of the microcapsules, and the like, but a preferred lower limit is preferably 0.1 parts by weight with respect to 100 parts by weight of the monomer. The upper limit is 20 parts by weight.
上記補助安定剤としては、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、ポリビニルピロリドン、ポリエチレンオキサイド、ポリエチレンイミン、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。 Examples of the auxiliary stabilizer include a condensation product of diethanolamine and aliphatic dicarboxylic acid, a condensation product of urea and formaldehyde, polyvinylpyrrolidone, polyethylene oxide, polyethyleneimine, tetramethylammonium hydroxide, gelatin, methylcellulose, polyvinyl Examples include alcohol, dioctyl sulfosuccinate, sorbitan ester, various emulsifiers, and the like.
また、上記分散安定剤と補助安定剤との組み合わせとしては特に限定されず、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。これらの中では、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い。
更に、上記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、特にジエタノールアミンとアジピン酸との縮合物やジエタノールアミンとイタコン酸との縮合生成物が好ましい。
Further, 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, A combination with an emulsifier may be mentioned. In these, the combination of colloidal silica and a condensation product is preferable.
Further, the condensation product is preferably a condensation product of diethanolamine and an aliphatic dicarboxylic acid, particularly a condensation product of diethanolamine and adipic acid or a condensation product of diethanolamine and itaconic acid.
上記水溶性窒素含有化合物としては、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適に用いられる。 Examples of the water-soluble nitrogen-containing compound include polyvinyl pyrrolidone, polyethyleneimine, polyoxyethylene alkylamine, polydialkylaminoalkyl (meth) acrylate represented by polydimethylaminoethyl methacrylate and polydimethylaminoethyl acrylate, and polydimethylamino. Examples thereof include polydialkylaminoalkyl (meth) acrylamides represented by propylacrylamide and polydimethylaminopropylmethacrylamide, polyacrylamide, polycationic acrylamide, polyamine sulfone, and polyallylamine. Of these, polyvinylpyrrolidone is preferably used.
上記コロイダルシリカの添加量は、熱膨張性マイクロカプセルの粒子径により適宜決定されるが、ビニル系モノマー１００重量部に対して、好ましい下限が１重量部、好ましい上限が２０重量部である。更に好ましい下限は２重量部、更に好ましい上限は１０重量部である。また、上記縮合生成物又は水溶性窒素含有化合物の量についても熱膨張性マイクロカプセルの粒子径により適宜決定されるが、モノマー１００重量部に対して、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。 The amount of colloidal silica added is appropriately determined depending on the particle size of the thermally expandable microcapsule, but the preferred lower limit is 1 part by weight and the preferred upper limit is 20 parts by weight with respect to 100 parts by weight of the vinyl monomer. A more preferred lower limit is 2 parts by weight, and a more preferred upper limit is 10 parts by weight. Further, the amount of the condensation product or the water-soluble nitrogen-containing compound is also appropriately determined depending on the particle size of the thermally expandable microcapsule, but a preferable lower limit is 0.05 parts by weight and a preferable upper limit with respect to 100 parts by weight of the monomer. Is 2 parts by weight.
上記分散安定剤及び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。無機塩を添加することで、より均一な粒子形状を有する熱膨張性マイクロカプセルが得ることができる。上記無機塩の添加量は、通常、モノマー１００重量部に対して０〜１００重量部が好ましい。 In addition to the dispersion stabilizer and auxiliary stabilizer, inorganic salts such as sodium chloride and sodium sulfate may be added. By adding an inorganic salt, a thermally expandable microcapsule having a more uniform particle shape can be obtained. Usually, the amount of the inorganic salt added is preferably 0 to 100 parts by weight with respect to 100 parts by weight of the monomer.
上記分散安定剤を含有する水性分散媒体は、分散安定剤や補助安定剤を脱イオン水に配合して調製され、この際の水相のｐＨは、使用する分散安定剤や補助安定剤の種類によって適宜決められる。例えば、分散安定剤としてコロイダルシリカ等のシリカを使用する場合は、酸性媒体で重合がおこなわれ、水性媒体を酸性にするには、必要に応じて塩酸等の酸を加えて系のｐＨが３〜４に調製される。一方、水酸化マグネシウム又はリン酸カルシウムを使用する場合は、アルカリ性媒体の中で重合させる。 The aqueous dispersion medium containing the above dispersion stabilizer is prepared by blending a dispersion stabilizer or auxiliary stabilizer with deionized water, and the pH of the aqueous phase at this time depends on the type of dispersion stabilizer or auxiliary stabilizer used. As appropriate. For example, when silica such as colloidal silica is used as a dispersion stabilizer, polymerization is performed in an acidic medium. To make the aqueous medium acidic, an acid such as hydrochloric acid is added as necessary to adjust the pH of the system to 3 To ˜4. On the other hand, when using magnesium hydroxide or calcium phosphate, it is polymerized in an alkaline medium.
次いで、熱膨張性マイクロカプセルを製造する方法では、ニトリル系モノマー、カルボキシル基を有し、エステル残基を除いた炭素数が３〜８のラジカル重合性不飽和カルボン酸モノマー及び揮発性膨張剤を含有する油性混合液を水性媒体中に分散させる工程を行う。この工程では、モノマー及び揮発性膨張剤を別々に水性分散媒体に添加して、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、予め両者を混合し油性混合液としてから、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、上記モノマーを重合するために、重合開始剤が使用されるが、上記重合開始剤は、予め上記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。
Next, in a method for producing a thermally expandable microcapsule, a nitrile monomer, a carboxyl group, a radically polymerizable unsaturated carboxylic acid monomer having 3 to 8 carbon atoms excluding an ester residue, and a volatile swelling agent are used. A step of dispersing the oily mixture contained therein in an aqueous medium is performed. In this step, the monomer and the volatile swelling agent may be separately added to the aqueous dispersion medium to prepare an oily mixture in the aqueous dispersion medium. 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.
In order to polymerize the monomer, a polymerization initiator is used. However, the polymerization initiator may be added in advance to the oily mixed solution, and the aqueous dispersion medium and the oily mixed solution are added to the polymerization reaction vessel. It may be added after stirring and mixing.
上記重合開始剤としては特に限定されず、例えば、上記モノマーに可溶な過酸化ジアルキル、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、アゾ化合物等が好適に用いられる。具体例には、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等の過酸化ジアルキル；イソブチルパーオキサイド、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の過酸化ジアシル；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のパーオキシエステル；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−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）ジカーボネート等のパーオキシジカーボネート；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）等のアゾ化合物等が挙げられる。 The polymerization initiator is not particularly limited, and for example, dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, azo compound and the like that are soluble in the monomer are preferably used. Specific examples include, for example, dialkyl peroxides such as methyl ethyl peroxide, di-t-butyl peroxide, dicumyl peroxide; isobutyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 3, 5 , 5-trimethylhexanoyl peroxide and other diacyl peroxides; t-butyl peroxypivalate, t-hexyl peroxypivalate, t-butyl peroxyneodecanoate, t-hexylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, cumylperoxyneodecanoate, (α, α-bis-neodecane Noyl peroxy) peroxye such as diisopropylbenzene Steal; bis (4-t-butylcyclohexyl) peroxydicarbonate, di-n-propyl-oxydicarbonate, diisopropylperoxydicarbonate, di (2-ethylethylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate Peroxydicarbonates such as di (3-methyl-3-methoxybutylperoxy) dicarbonate; 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4- And azo compounds such as dimethylvaleronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis (1-cyclohexanecarbonitrile), and the like.
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としては、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や、ラインミキサーや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水系分散媒体と重合性混合物を別々に供給してもよいし、予め混合、攪拌した分散液を供給してもよい。
As a method of emulsifying and dispersing the oily mixed liquid in an aqueous dispersion medium with a predetermined particle size, a method of stirring with a homomixer (for example, manufactured by Tokushu Kika Kogyo Co., Ltd.) or the like, a line mixer or an element type static disperser For example, a method of passing through a static dispersion device such as the above.
The above-mentioned static dispersion device may be supplied with the aqueous dispersion medium and the polymerizable mixture separately, or may be supplied with a dispersion that has been mixed and stirred in advance.
次いで、熱膨張性マイクロカプセルを製造する方法では、上記金属カチオンを生じる化合物（以下、金属カチオン供給体ともいう）を添加して、上記カルボキシル基と金属カチオンとを反応させる工程を行う。この工程を行うことにより、上記金属カチオンとカルボキシル基とが反応してイオン架橋することから、耐熱性が向上し、高温領域において長時間破裂、収縮の起こらない熱膨張性マイクロカプセルを製造することが可能となる。また、上記シェルの弾性率が向上することから、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、射出成形等の成形加工を行う場合であっても、熱膨張性マイクロカプセルの破裂、収縮が起こることがない。 Next, in a method for producing a thermally expandable microcapsule, a step of adding a compound that generates the metal cation (hereinafter also referred to as a metal cation supplier) and reacting the carboxyl group with the metal cation is performed. By carrying out this step, the metal cation reacts with the carboxyl group and ion-crosslinks, so that heat resistance is improved and a thermally expandable microcapsule that does not rupture or shrink for a long time in a high temperature region is produced. Is possible. In addition, since the elastic modulus of the shell is improved, even when molding such as kneading molding, calender molding, extrusion molding, injection molding or the like in which a strong shear force is applied, rupture of the thermally expandable microcapsule, There is no contraction.
上記金属カチオン供給体は、上記モノマーを重合させる前の分散液中に添加してもよく、上記モノマーを重合した後に添加してもよい。また、上記金属カチオン供給体は、それ自体を直接添加してもよく、水溶液等の溶液の形態で添加してもよい。 The metal cation supplier may be added to the dispersion before the monomer is polymerized, or may be added after the monomer is polymerized. Further, the metal cation supplier may be added directly or in the form of a solution such as an aqueous solution.
上記金属カチオン供給体としては、特に限定されず、例えば、上述した金属カチオンの酸化物、水酸化物、リン酸塩、炭酸塩、硝酸塩、硫酸塩、塩化物、亜硝酸塩、亜硫酸塩やオクチル酸、ステアリン酸等の各有機酸の塩等が挙げられる。これらのなかでは、水酸化物、塩化物、カルボン酸塩が好ましい。具体的には、Ｚｎ（ＯＨ）２、ＺｎＯ、Ｍｇ（ＯＨ）２等が好ましく、高温領域における弾性率の低下が少ないことから、Ｚｎ（ＯＨ）２がより好ましい。 The metal cation supplier is not particularly limited. For example, the metal cation oxide, hydroxide, phosphate, carbonate, nitrate, sulfate, chloride, nitrite, sulfite, and octylic acid described above. And salts of organic acids such as stearic acid. Of these, hydroxides, chlorides and carboxylates are preferred. Specifically, Zn (OH) 2 , ZnO, Mg (OH) 2 and the like are preferable, and Zn (OH) 2 is more preferable because there is little decrease in elastic modulus in a high temperature region.
また、上記金属カチオン供給体を添加する場合は、予めアルカリ金属の水酸化物を添加した後、上記アルカリ金属の水酸化物以外の金属カチオン供給体を添加することが好ましい。上記アルカリ金属の水酸化物を予め添加することにより、カルボキシル基等の官能基が活性化され、上記金属カチオンとの反応を促進させることができる。
また、Ｚｎ（ＯＨ）２は水溶性が低く、添加によって所望のイオン架橋を得ることができないことがあるが、このような方法を用いることで、例えば、ＮａＯＨを添加した後、水溶液の高いＺｎＣｌ２を添加することにより、Ｚｎ（ＯＨ）２を添加した場合と同様の効果を得ることができる。
When the metal cation supplier is added, it is preferable to add an alkali metal hydroxide in advance and then add a metal cation supplier other than the alkali metal hydroxide. By adding the alkali metal hydroxide in advance, a functional group such as a carboxyl group is activated, and the reaction with the metal cation can be promoted.
In addition, Zn (OH) 2 has low water solubility, and it may not be possible to obtain a desired ionic crosslink by addition. However, by using such a method, for example, after adding NaOH, ZnCl in the aqueous solution is high. By adding 2 , the same effect as the case of adding Zn (OH) 2 can be obtained.
上記アルカリ金属の水酸化物としては特に限定されないが、Ｎａ、Ｋ、Ｌｉの水酸化物が好ましく、なかでも塩基性の強いＮａ、Ｋの水酸化物を用いることが好ましい。 The alkali metal hydroxide is not particularly limited, but is preferably a hydroxide of Na, K, or Li, and more preferably a strongly basic Na or K hydroxide.
本発明の熱膨張性マイクロカプセルは、上述した工程を経て得られた分散液を加熱することによりモノマーを重合させる工程を行うことにより、製造することができる。このような方法により製造された熱膨張性マイクロカプセルは、最大発泡温度が高く、耐熱性に優れ、高温領域や成形加工時においても破裂、収縮することがない。 The thermally expandable microcapsule of the present invention can be produced by performing a step of polymerizing a monomer by heating the dispersion obtained through the above-described steps. The thermally expandable microcapsules produced by such a method have a high maximum foaming temperature, excellent heat resistance, and do not rupture or shrink even in a high temperature region or during molding.
本発明の熱膨張性マイクロカプセルに、熱可塑性樹脂等のマトリックス樹脂を加えた樹脂組成物又はマスターバッチペレットを、射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、上記熱膨張性マイクロカプセルを発泡させることにより、発泡成形体を製造することができる。このような発泡成形体もまた本発明の１つである。
このような方法で得られる本発明の発泡成形体は、高外観品質が得られ、独立気泡が均一に形成されており、軽量性、断熱性、耐衝撃性、剛性等に優れるものとなり、住宅用建材、自動車用部材、靴底等の用途に好適に用いることができる。
A resin composition or a master batch pellet obtained by adding a matrix resin such as a thermoplastic resin to the thermally expandable microcapsule of the present invention is molded using a molding method such as injection molding, and the above thermal expansion is performed by heating during molding. Foamed molded articles can be produced by foaming the conductive microcapsules. Such a foam-molded article is also one aspect of the present invention.
The foamed molded article of the present invention obtained by such a method has high appearance quality, has closed cells uniformly formed, has excellent lightness, heat insulation, impact resistance, rigidity, etc. It can be suitably used for applications such as building materials for automobiles, automobile members, and shoe soles.
上記熱可塑性樹脂としては、本発明の目的を阻害しない限り、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；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が挙げられる。また、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を使用してもよく、これらの樹脂を併用して使用してもよい。 The thermoplastic resin is not particularly limited as long as the object of the present invention is not impaired. For example, general thermoplastic resins such as polyvinyl chloride, polystyrene, polypropylene, polypropylene oxide, and polyethylene; polybutylene terephthalate, nylon, Engineering plastics such as polycarbonate and polyethylene terephthalate are listed. Further, thermoplastic elastomers such as ethylene, vinyl chloride, olefin, urethane, and ester may be used, or these resins may be used in combination.
上記熱可塑性樹脂１００重量部に熱膨張性マイクロカプセルの添加量は０．５〜２０重量部、好ましくは１〜１０重量部が適量である。また、重曹などの化学発泡剤と併用することも出来る。 The amount of thermally expandable microcapsules added to 100 parts by weight of the thermoplastic resin is 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight. It can also be used in combination with a chemical foaming agent such as baking soda.
上記マスターバッチペレットを製造する方法としては、特に限定されず、例えば、熱可塑性樹脂等のマトリックス樹脂、各種添加剤等の原材料を、同方向２軸押出機等を用いて予め混練する。次いで、所定温度まで加熱し、熱膨張マイクロカプセル等の発泡剤を添加した後、更に混練することにより得られる混練物を、ペレタイザーにて所望の大きさに切断することによりペレット形状にしてマスターバッチペレットとする方法等が挙げられる。また、熱可塑性樹脂等のマトリックス樹脂や熱膨張性マイクロカプセル等の原材料をバッチ式の混練機で混練した後、造粒機で造粒することによりペレット形状のマスターバッチペレットを製造してもよい。
上記混練機としては、熱膨張性マイクロカプセルを破壊することなく混練できるものであれば特に限定されず、例えば、加圧ニーダー、バンバリーミキサー等が挙げられる。
The method for producing the master batch pellet is not particularly limited. For example, a matrix resin such as a thermoplastic resin and raw materials such as various additives are kneaded in advance using a same-direction twin-screw extruder or the like. Next, after heating to a predetermined temperature and adding a foaming agent such as a thermal expansion microcapsule, the kneaded product obtained by further kneading is cut into a desired size with a pelletizer to form a master batch. The method etc. which are made into a pellet are mentioned. Alternatively, a master batch pellet in the form of a pellet may be manufactured by kneading a matrix resin such as a thermoplastic resin or a raw material such as a thermally expandable microcapsule with a batch kneader and then granulating with a granulator. .
The kneader is not particularly limited as long as it can knead without destroying the thermally expandable microcapsules, and examples thereof include a pressure kneader and a Banbury mixer.
本発明の発泡成形体の成形方法としては、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。 The molding method of the foamed molded product of the present invention is not particularly limited, and examples thereof include kneading molding, calendar molding, extrusion molding, injection molding, and the like.
本発明は、優れた耐熱性と発泡倍率を有し、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、射出成形等にも好適に使用可能であり、特に射出成形に用いられた場合に発泡成形体表面において高い外観品質が得られる熱膨張性マイクロカプセル、及び、該熱膨張性マイクロカプセルを用いた発泡成形体である。 The present invention can be suitably used for kneading molding, calender molding, extrusion molding, injection molding, etc., which have excellent heat resistance and expansion ratio and a strong shear force is applied, particularly when used for injection molding Furthermore, there are a thermally expandable microcapsule capable of obtaining a high appearance quality on the surface of the foamed molded product, and a foamed molded product using the thermally expandable microcapsule.
以下に実施例を掲げて本発明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るものではない。 Hereinafter, 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１〜２、参考例３、比較例１〜３）
（熱膨張性マイクロカプセルの作製）
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重量部及びポリビニルピロリドン（ＢＡＳＦ社製）０．３重量部を投入し、水性分散媒体を調製した。次いで、表１に示した配合量のモノマー、架橋剤、揮発性膨張剤及び重合開始剤からなる油性混合液を水溶性分散媒体に添加し、更に表１に示した配合量の金属カチオン供給体を添加することにより、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、窒素置換した加圧重合器（２０Ｌ）内へ仕込み、加圧（０．２ＭＰａ）し、６０℃で２０時間反応させることにより、反応生成物を調製した。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、乾燥して熱膨張性マイクロカプセル１〜６を得た。
(Examples 1-2, Reference Example 3 , Comparative Examples 1-3)
(Production of thermally expandable microcapsules)
8 L of water, 10 parts by weight of colloidal silica (manufactured by Asahi Denka Co., Ltd.) and 0.3 part by weight of polyvinylpyrrolidone (manufactured by BASF) were charged as a dispersion stabilizer in a polymerization reaction vessel to prepare an aqueous dispersion medium. Next, an oily mixed liquid composed of a monomer, a cross-linking agent, a volatile swelling agent and a polymerization initiator shown in Table 1 was added to the water-soluble dispersion medium, and a metal cation supplier having a compounding quantity shown in Table 1 was added. Was added to prepare a dispersion. The resulting dispersion is stirred and mixed with a homogenizer, charged into a nitrogen-substituted pressure polymerization vessel (20 L), pressurized (0.2 MPa), and reacted at 60 ° C. for 20 hours to prepare a reaction product. did. About the obtained reaction product, after repeating filtration and washing with water, it dried and obtained thermally expansible microcapsules 1-6.
（熱膨張性マイクロカプセルの評価）
実施例１〜２、参考例３及び比較例１〜３で得られた熱膨張性マイクロカプセル１〜６の性能（体積平均粒子径、発泡開始温度、最大発泡温度、最大変位量）について、性能を評価した。結果を表１に示した。
(Evaluation of thermally expandable microcapsules)
About the performance (volume average particle diameter, foaming start temperature, maximum foaming temperature, maximum displacement) of the thermally expandable microcapsules 1 to 6 obtained in Examples 1-2, Reference Example 3 and Comparative Examples 1-3 Evaluated. The results are shown in Table 1.
（１−１）体積平均粒子径
粒度分布径測定器（ＬＡ−９１０、ＨＯＲＩＢＡ社製）を用い、体積平均粒子径を測定した。
(1-1) Volume average particle diameter The volume average particle diameter was measured using a particle size distribution diameter measuring device (LA-910, manufactured by HORIBA).
（１−２）発泡開始温度、最大発泡温度、最大変位量、５０％変位時発泡温度
熱機械分析装置（ＴＭＡ）（ＴＭＡ２９４０、ＴＡ ｉｎｓｔｒｕｍｅｎｔｓ社製）を用い、発泡開始温度（Ｔｓ）、最大変位量（Ｄｍａｘ）及び最大発泡温度（Ｔｍａｘ）を測定した。具体的には、試料２５μｇを直径７ｍｍ、深さ１ｍｍのアルミ製容器に入れ、上から０．１Ｎの力を加えた状態で、５℃／ｍｉｎの昇温速度で８０℃から２２０℃まで加熱し、測定端子の垂直方向における変位を測定し、変位が上がり始める温度を発泡開始温度、その変位の最大値を最大変位量とし、最大変位量における温度を最大発泡温度とした。
(1-2) Foam start temperature, maximum foam temperature, maximum displacement, 50% displacement foam temperature Thermomechanical analyzer (TMA) (TMA2940, manufactured by TA instruments), foam start temperature (Ts), maximum displacement The amount (Dmax) and the maximum foaming temperature (Tmax) were measured. Specifically, 25 μg of a sample is put into an aluminum container having a diameter of 7 mm and a depth of 1 mm, and heated from 80 ° C. to 220 ° C. at a temperature rising rate of 5 ° C./min with a force of 0.1 N applied from above. Then, the displacement in the vertical direction of the measurement terminal was measured, and the temperature at which the displacement began to rise was defined as the foaming start temperature, the maximum value of the displacement as the maximum displacement, and the temperature at the maximum displacement as the maximum foaming temperature.
（実施例４〜６、参考例７、比較例４〜６）
（マスターバッチペレットの作製）
粉体状及びペレット状の低密度ポリエチレン１００重量部と、滑剤としてエチレンビスステアリン酸アマイド０．２重量部とをバンバリーミキサーで混練し、約１４０℃になったところで得られた熱膨張性マイクロカプセル５０重量部を添加し、更に３０秒間混練して押し出すと同時にペレット化し、マスターバッチペレットを得た。
(Examples 4 to 6, Reference Example 7 , Comparative Examples 4 to 6)
(Preparation of master batch pellet)
Thermally expandable microcapsules obtained by kneading 100 parts by weight of low-density polyethylene in powder form and pellets and 0.2 part by weight of ethylenebisstearic acid amide as a lubricant with a Banbury mixer and reaching about 140 ° C. 50 parts by weight was added, and the mixture was further kneaded for 30 seconds and extruded to be pelletized at the same time to obtain master batch pellets.
（成形体の作製）
得られたマスターバッチペレット５重量部と、ポリプロピレン樹脂１００重量部とを混合し、得られた混合ペレットをアキュムレーターを備えたスクリュー式の射出成形機のホッパーに供給して溶融混練し、射出成形を行い、板状の成形体を得た。なお、成形条件は、シリンダー温度：２００℃、射出速度：６０ｍｍ／ｓｅｃ、型開遅延時間：０秒、金型温度：４０℃とした。
(Production of molded body)
5 parts by weight of the obtained master batch pellets and 100 parts by weight of polypropylene resin are mixed, and the obtained mixed pellets are supplied to a hopper of a screw-type injection molding machine equipped with an accumulator, melt-kneaded, and injection molded. To obtain a plate-like molded body. The molding conditions were as follows: cylinder temperature: 200 ° C., injection speed: 60 mm / sec, mold opening delay time: 0 seconds, mold temperature: 40 ° C.
（成形体の評価）
実施例４〜６、参考例７及び比較例４〜６で得られた成形体について、性能（発泡倍率、外観、密度）を評価した。結果を表２に示した。
(Evaluation of molded body)
For the molded bodies obtained in Examples 4 to 6, Reference Example 7 and Comparative Examples 4 to 6, performance (foaming ratio, appearance, density) was evaluated. The results are shown in Table 2.
（２−１）発泡倍率
発泡後の成形体の板厚を発泡前の成形体の板厚で除した値を算出し、発泡倍率とした。
(2-1) Foaming ratio A value obtained by dividing the plate thickness of the molded body after foaming by the plate thickness of the molded body before foaming was calculated as the foaming ratio.
（２−２）外観
得られた成形体の表面状態を最大山高さとして表面粗さ形状測定機（サーフコム１３０Ａ／４８０Ａ、東京精密社製）にて測定した。
(2-2) Appearance The surface state of the obtained molded body was measured with a surface roughness shape measuring machine (Surfcom 130A / 480A, manufactured by Tokyo Seimitsu Co., Ltd.) with the maximum peak height.
（２−３）密度の測定
得られた成形体の密度をＪＩＳ Ｋ−７１１２ Ａ法（水中置換法）に準拠した方法により測定した。
(2-3) Measurement of density The density of the obtained molded body was measured by a method based on JIS K-7112 A method (submersion method in water).
表２に示すように、実施例４〜６、参考例７では発泡倍率が高く、また、成形品表面の外観品質も良好であった。一方、比較例４〜６では発泡倍率の高いものは、外観品質が悪く、外観品質の良いものは、発泡倍率が低く、双方を満足するものは出来なかった。 As shown in Table 2, in Examples 4 to 6 and Reference Example 7 , the expansion ratio was high, and the appearance quality on the surface of the molded product was also good. On the other hand, in Comparative Examples 4 to 6, those with a high expansion ratio had poor appearance quality, and those with good appearance quality had a low expansion ratio and could not satisfy both.
本発明は、優れた耐熱性と発泡倍率を有し、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、射出成形等にも好適に使用可能であり、特に射出成形に用いられた場合に発泡成形体表面において高い外観品質が得られる熱膨張性マイクロカプセル及び該熱膨張性マイクロカプセルを用いた発泡成形体に関する。 The present invention can be suitably used for kneading molding, calender molding, extrusion molding, injection molding, etc., which have excellent heat resistance and expansion ratio and a strong shear force is applied, particularly when used for injection molding In particular, the present invention relates to a thermally expandable microcapsule capable of obtaining high appearance quality on the surface of the foamed molded product, and a foamed molded product using the thermally expandable microcapsule.
Claims (4)
前記シェルは、ニトリル系モノマーに由来するセグメントと、カルボキシル基を有し、エステル残基を除いた炭素数が３〜８のラジカル重合性不飽和カルボン酸モノマーに由来するセグメントとを有する共重合体、並びに、アルカリ金属イオン及びＺｎイオンからなる金属カチオン０．１〜１０重量％を含有し、
前記コア剤は、沸点が６０℃以上の炭化水素を含む２種以上の揮発性膨張剤からなり、沸点が最も低い揮発性膨張剤と、沸点が最も高い揮発性膨張剤との沸点の差が６０℃以上であることを特徴とする熱膨張性マイクロカプセル。
前記最大変位量は、熱膨張性マイクロカプセル２５μｇを直径７ｍｍ、深さ１ｍｍの容器に入れ、上から０．１Ｎの力を加えた状態で、５℃／ｍｉｎの昇温速度で８０℃から２２０℃まで加熱した場合の測定端子の垂直方向における変位の最大値を示す。 A thermally expandable microcapsule in which a volatile expansion agent is encapsulated as a core agent in a polymer shell, the maximum displacement (Dmax) is 1000 μm or more, the maximum foaming temperature (Tmax) is 210 ° C. or more, and The foaming start temperature (Ts) is 190 ° C. or higher,
The shell is a copolymer having a segment derived from a nitrile monomer and a segment derived from a radically polymerizable unsaturated carboxylic acid monomer having a carboxyl group and having 3 to 8 carbon atoms excluding an ester residue. And 0.1 to 10% by weight of a metal cation composed of alkali metal ions and Zn ions,
The core agent is composed of two or more volatile expansion agents containing hydrocarbons having a boiling point of 60 ° C. or higher, and there is a difference in boiling point between the volatile expansion agent having the lowest boiling point and the volatile expansion agent having the highest boiling point. A thermally expandable microcapsule characterized by having a temperature of 60 ° C. or higher .
The maximum amount of displacement is as follows: 25 μg of thermally expandable microcapsules are placed in a container having a diameter of 7 mm and a depth of 1 mm, and a force of 0.1 N is applied from above, and a temperature increase rate of 5 ° C./min is 80 to 220 ° C. The maximum value of the displacement in the vertical direction of the measurement terminal when heated to ° C. is shown.
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