JPS63268750A - Foamable copolymer resin particle composition - Google Patents
Foamable copolymer resin particle compositionInfo
- Publication number
- JPS63268750A JPS63268750A JP10269287A JP10269287A JPS63268750A JP S63268750 A JPS63268750 A JP S63268750A JP 10269287 A JP10269287 A JP 10269287A JP 10269287 A JP10269287 A JP 10269287A JP S63268750 A JPS63268750 A JP S63268750A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- resin particles
- acid ester
- propylene glycol
- acrylonitrile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 63
- 229920006026 co-polymeric resin Polymers 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- -1 fatty acid ester Chemical class 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 18
- 239000000194 fatty acid Substances 0.000 claims abstract description 18
- 229930195729 fatty acid Natural products 0.000 claims abstract description 18
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 13
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims 1
- 239000005642 Oleic acid Substances 0.000 claims 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 abstract description 9
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract 2
- 235000011187 glycerol Nutrition 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 238000005187 foaming Methods 0.000 description 9
- 239000004088 foaming agent Substances 0.000 description 9
- 239000006260 foam Substances 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000001273 butane Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- ZVTDEEBSWIQAFJ-KHPPLWFESA-N 2-hydroxypropyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(C)O ZVTDEEBSWIQAFJ-KHPPLWFESA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000010097 foam moulding Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 description 2
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- IYBPIDAYDPNCTP-UHFFFAOYSA-N 1-methyl-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(C)C(=O)C=C1C1=CC=CC=C1 IYBPIDAYDPNCTP-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- JDDMPHKHKQRDPT-UHFFFAOYSA-N 3-naphthalen-1-ylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C3=CC=CC=C3C=CC=2)=C1 JDDMPHKHKQRDPT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 206010040844 Skin exfoliation Diseases 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- RHZIVIGKRFVETQ-UHFFFAOYSA-N butyl 2-methylpropaneperoxoate Chemical compound CCCCOOC(=O)C(C)C RHZIVIGKRFVETQ-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 229940042935 dichlorodifluoromethane Drugs 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- QWTDNUCVQCZILF-UHFFFAOYSA-N iso-pentane Natural products CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 235000001055 magnesium Nutrition 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- JZFHXRUVMKEOFG-UHFFFAOYSA-N tert-butyl dodecaneperoxoate Chemical compound CCCCCCCCCCCC(=O)OOC(C)(C)C JZFHXRUVMKEOFG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は発泡性共重合体樹脂粒子組成物に関する。さら
に詳しくは耐熱性ことに熱安定性にすぐれた発泡成形体
を得るための発泡性共重合体樹脂粒子組成物に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a composition of expandable copolymer resin particles. More specifically, the present invention relates to a foamable copolymer resin particle composition for obtaining a foamed molded article having excellent heat resistance and particularly heat stability.
近年、とみに発泡成形体に体する耐熱性の要求が高まっ
ており、エアーコンディショナーの風洞。In recent years, there has been an increasing demand for heat resistance in foam molded products, and wind tunnels for air conditioners.
自動車のヘッドライナー、ドアトリム、インスツルメン
トパネル等の構造部材、ソーラー関係の断熱材などに対
して、高温雰囲気下にあっても寸法の安定した発泡成形
体が求められている。本発明の発泡性共重合体樹脂粒子
組成物は主としてこのような分野において有用なもので
ある。Foam molded products that are dimensionally stable even in high-temperature environments are required for structural members such as automobile headliners, door trims, and instrument panels, and as insulation materials for solar panels. The expandable copolymer resin particle composition of the present invention is mainly useful in such fields.
（従来の技術）
ポリスチレン粒子に易揮発性発泡剤を含ませ発泡性ポリ
スチレン粒子とし、これを水蒸気で加熱して予備発泡粒
子とした後金型に充填し再加熱して型内で粒子間を融着
させたポリスチレン発泡成形体は広く知られている。し
かして、この発泡成形体は剛性が強く断熱性、保形性が
良い反面、脆弱で耐薬品性、耐油性にも劣る欠点があっ
た。(Prior art) Polystyrene particles are impregnated with an easily volatile blowing agent to form expandable polystyrene particles, which are then heated with steam to form pre-expanded particles, which are then filled into a mold and reheated to seal the particles between the particles within the mold. Fused polystyrene foam moldings are widely known. However, although this foamed molded product has strong rigidity and good heat insulation and shape retention properties, it has the disadvantage of being brittle and having poor chemical resistance and oil resistance.
このような欠点を改善するために、ポリスチレンの代わ
りに、アクリロニトリルとスチレン類との共重合体（特
開昭５９−２０４６２９号公報）やこれに更に改良単量
体成分を含ませた多元共重合体を用いる提案がなされて
いる。このようなスチレン−アクリロニトリル系共重合
体類を用いることにより、基材樹脂自体の耐薬品性等が
向上され、ひいてはこれを原料とする発泡成形体の耐薬
品性、耐油性等が改善されるとされている。In order to improve these drawbacks, in place of polystyrene, copolymers of acrylonitrile and styrenes (Japanese Unexamined Patent Publication No. 59-204629) and multi-component copolymers containing improved monomer components have been developed. Proposals have been made to use coalescence. By using such styrene-acrylonitrile copolymers, the chemical resistance, etc. of the base resin itself is improved, which in turn improves the chemical resistance, oil resistance, etc. of the foam molded product made from it. It is said that
（発明が解決しようとする問題点）
しかし、このようなスチレン−アクリロニトリル系共重
合体を基材樹脂とする発泡性樹脂粒子を用いて得られた
発泡成形体は、高温環境下（ことに１００℃以上）にお
いて熱変形を受は易く、ことに、軟化温度の高い基材樹
脂を用いた場合においても、成形体表面に凹凸が発生し
て著しく外観が損なわれるという問題があった。そして
かかる熱変形の発生は外観のみならず、他の材料と貼り
合わせて使用される場合の接着界面での剥離の危険性を
招く点でも問題となる。(Problems to be Solved by the Invention) However, foamed molded articles obtained using expandable resin particles having such a styrene-acrylonitrile copolymer as a base resin cannot be used in high-temperature environments (particularly 100% ℃ or higher), and even when a base resin with a high softening temperature is used, there is a problem in that unevenness occurs on the surface of the molded product, significantly impairing its appearance. The occurrence of such thermal deformation poses a problem not only in terms of appearance but also in the risk of peeling at the adhesive interface when used in combination with other materials.
かかる熱変形ことに凹凸の発生は、主として発泡成形体
中、ことに表面層に存在する残留発泡剤の再発泡により
生ずるものと考えられる。It is thought that such thermal deformation and the occurrence of irregularities are mainly caused by the re-foaming of the residual foaming agent present in the foamed molded article, particularly in the surface layer.
そこで本発明者は、表面の再発泡による熱変形ことに表
面の凹凸発生を防止するには、発泡成形中に残っている
発泡剤を減うせば良く、その手段として、予め発泡性樹
脂粒子の表面層付近に無敗の微細なひび割れ（以下「微
細クラック」と呼ぶ）を入れ、その予備発泡粒子、さら
に発泡成形体の表面積を飛躍的に増大させて発泡剤の逸
散を促進する点について検討を行った。Therefore, the inventor of the present invention discovered that in order to prevent thermal deformation and surface unevenness due to surface re-foaming, it is sufficient to reduce the remaining foaming agent during foam molding. We investigated the possibility of creating undefeated microscopic cracks (hereinafter referred to as "microcracks") near the surface layer to dramatically increase the surface area of the pre-expanded particles and the foamed product to promote the escape of the foaming agent. I did it.
従来、ポリスチレン発泡粒子においてこのような微細ク
ラックを形成させる方法としては、針を用いた機械的な
方法（特公昭５６−１９８０９号公報）やパラフィン油
、炭素数１２〜３０の高級脂肪酸のグリセライド等を被
覆して成形時に物理化学的に形成させる方法（特公昭６
１−１８９３４号公報）が知られている。Conventionally, methods for forming such fine cracks in expanded polystyrene particles include a mechanical method using a needle (Japanese Patent Publication No. 19809/1983), paraffin oil, glyceride of higher fatty acids having 12 to 30 carbon atoms, etc. A method of coating and physicochemically forming it during molding (Tokukō Sho 6)
1-18934) is known.
しかし、前者の方法は煩雑で特殊な装置を必要とする点
不利である。また、後者の方法をスチレン−アクリロニ
トリル系共重合体樹脂粒子に適用しても全く効果は現れ
ず、微細クラックを発生させることはできなかった。However, the former method has the disadvantage of requiring complicated and special equipment. Further, even when the latter method was applied to styrene-acrylonitrile copolymer resin particles, no effect was obtained at all, and microcracks could not be generated.
（問題点を解決するための手段）
本発明者らは、かかる状況に鑑み、鋭意研究を重ねた結
果、前記スチレン−アクリロニトリル系共重合体を基材
とする発泡性共重合体樹脂粒子に種々のグリセライドの
うち特定の化合物を被覆させることにより、成形時に微
細クラックが効率良く発生して発泡剤の残留が防止又は
抑制され、それにより得られた成形体の熱変形ことに表
面変形が著しく防止・抑制される事実を見出した。(Means for Solving the Problems) In view of the above situation, the present inventors have conducted extensive research and have found that various foamable copolymer resin particles based on the styrene-acrylonitrile copolymer have been developed. By coating with a specific compound of glyceride, fine cracks are efficiently generated during molding, preventing or suppressing the residual foaming agent, and thereby significantly preventing thermal deformation and surface deformation of the resulting molded product.・I found a fact that can be suppressed.
かくして本発明によれば、アクリロニトリル系単量体残
基１５〜４０重量％、スチレン系単量体残基４０〜８５
重量％及び他の重合性単量体残基０〜３０重量％より構
成される共重合体を基材樹脂とし、これに易揮発性発泡
剤を１〜１０重量％含有してなる発泡性共重合体樹脂粒
子の表面及び／又は表面付近に、常温で液状めプロピレ
ングリコールの高級脂肪酸エステルを存在させてなる発
泡性共重合体樹脂粒子組成物が提供される。Thus, according to the present invention, 15 to 40% by weight of acrylonitrile monomer residues and 40 to 85% of styrene monomer residues.
A foamable copolymer comprising a copolymer composed of 0 to 30 weight % of other polymerizable monomer residues as a base resin and containing 1 to 10 weight % of an easily volatile blowing agent to this copolymer. A foamable copolymer resin particle composition is provided in which a liquid higher fatty acid ester of propylene glycol is present at room temperature on the surface and/or near the surface of the polymer resin particles.
本発明に用いる共重合体樹脂を構成するアクリロニトリ
ル系単量体としては、アクリロニトリル。The acrylonitrile monomer constituting the copolymer resin used in the present invention is acrylonitrile.
メタクリロニトリル、α−クロロアクリロニトリル、フ
マロニトリル等が挙げられ、特にアクリロニトリルが好
ましい。Examples include methacrylonitrile, α-chloroacrylonitrile, and fumaronitrile, with acrylonitrile being particularly preferred.
また、スチレン系単量体としては、スチレン。In addition, as a styrene monomer, styrene is used.
α−メチルスチレン、ｔ−ブチルスチレン、ビニルトル
エン、ビニルキシレン、モノクロルスチレン、ジクロル
スチレン等が挙げられるが、特にスチレン及び／又はα
−メチルスチレンが好ましい。Examples include α-methylstyrene, t-butylstyrene, vinyltoluene, vinylxylene, monochlorostyrene, dichlorostyrene, and in particular styrene and/or α
- Methylstyrene is preferred.
一方、他の共重合可能な単量体としては、Ｎ−ラウリル
マレイミド、Ｎ−シクロへキシルマレイミド、Ｎ−フェ
ニルマレイミド、Ｎ−メチルフェニルマレイミド、Ｎ−
ナフチルマレイミド、ビスマレイミド等のマレイミド系
単量体、メチルアクリレート、エチルアクリレート、ブ
チルアクリレート等のアクリレート系単量体、メチルメ
タクリレート、エチルメタクリレート等のメタクリレー
ト系単量体、アクリル酸、メタクリル酸等のビニルカル
ボン酸系単量体等が挙げられる。On the other hand, other copolymerizable monomers include N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-
Maleimide monomers such as naphthylmaleimide and bismaleimide; acrylate monomers such as methyl acrylate, ethyl acrylate and butyl acrylate; methacrylate monomers such as methyl methacrylate and ethyl methacrylate; vinyl such as acrylic acid and methacrylic acid. Examples include carboxylic acid monomers.
これらの各単量体はそれぞれ２種以上用いられてもよい
。Two or more types of each of these monomers may be used.
各単量体の共重合比は、得られた共重合体中のアクリロ
ニトリル系単量体残基が１５〜４０重量％、スチレン系
単量体残基が４０〜８５重量％及び他の重合性単量体残
基が０〜３０重量％となるように調整するのが適してい
る。ここでアクリロニトリル系単量体残基が少なすぎる
と、脆弱さ、耐薬品性。The copolymerization ratio of each monomer is such that the resulting copolymer contains 15 to 40% by weight of acrylonitrile monomer residues, 40 to 85% by weight of styrene monomer residues, and 40 to 85% by weight of other polymerizable monomer residues. It is suitable to adjust the monomer residue content to 0 to 30% by weight. If there are too few acrylonitrile monomer residues here, the brittleness and chemical resistance will deteriorate.
耐油性等が不充分となり好ましくない。一方、スチレン
系単量体残基が少なすぎると発泡剤の保持性が低下して
高発泡倍率の成形体が得られず好ましくない。他の重合
性単量体残基は必要に応じて共重合体の物性を改良する
ために用いられ、せいぜい３０重量％で充分である。と
くに、この重合性単量体として前記したマレイミド系単
量体のうちＮ−フェニルマレイミド等のＮ−置換芳香族
マレイミドを用いた場合には、基材樹脂自体の軟化温度
を著しく上昇でき、本願発明の効果とも相俟って１２０
℃程度の高温環境下においても成形体に優れた寸法安定
性１表面安定性を付与することができる。この際のマレ
イミド系単量体残基の量としては０．５〜３０重量％が
適しており、特に５〜２０重量％が好ましい。Oil resistance etc. will be insufficient, which is not preferable. On the other hand, if the amount of styrene monomer residues is too small, the retention of the blowing agent decreases, making it impossible to obtain a molded article with a high expansion ratio, which is not preferable. Other polymerizable monomer residues are used to improve the physical properties of the copolymer, if necessary, and at most 30% by weight is sufficient. In particular, when an N-substituted aromatic maleimide such as N-phenylmaleimide is used as the polymerizable monomer, the softening temperature of the base resin itself can be significantly increased. Combined with the effects of invention, 120
Excellent dimensional stability and surface stability can be imparted to the molded article even in a high temperature environment of about 0.degree. The amount of the maleimide monomer residue in this case is suitably 0.5 to 30% by weight, particularly preferably 5 to 20% by weight.
本発明の基材となる樹脂粒子は、塊状−懸濁重合、溶液
重合、懸濁重合又は乳化重合等の方法で製造することが
できるが、特に球状の樹脂粒子が簡便に得られる事から
懸濁重合法が好ましい。The resin particles that serve as the base material of the present invention can be produced by a method such as bulk-suspension polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, but this is particularly problematic because spherical resin particles can be easily obtained. The turbidity polymerization method is preferred.
懸濁重合法に使用できる分散剤としては、例えば部分鹸
化ポリビニルアルコール、ポリアクリル酸塩、ポリビニ
ルピロリドン、カルボキシメチルセルロース、メチルセ
ルロース等の有機化合物の他、ピロリン酸カルシウム、
リン酸カルシウム、炭酸カルシウム、リン酸マグネシウ
ム、ビロリン酸マグネシウム、酸化マグネシウム等の水
に難溶性の微粉末からなる無機化合物を挙げることがで
きる。分散剤として無機化合物を用いる際には、ドデシ
ルベンゼンスルフオン酸ソーダ等の界面活性剤を併用す
ることが好ましい。Examples of dispersants that can be used in the suspension polymerization method include organic compounds such as partially saponified polyvinyl alcohol, polyacrylates, polyvinylpyrrolidone, carboxymethylcellulose, and methylcellulose, as well as calcium pyrophosphate,
Examples include inorganic compounds consisting of fine powder hardly soluble in water, such as calcium phosphate, calcium carbonate, magnesium phosphate, magnesium birophosphate, and magnesium oxide. When using an inorganic compound as a dispersant, it is preferable to use a surfactant such as sodium dodecylbenzenesulfonate.
また、上記重合法における重合開始剤は通常のポリスチ
レンの重合に使用されているもので良く、例えばベンゾ
イルパーオキサイド、ターシャリ−ブチルパーオキシベ
ンゾエート、ラウロイルパーオキサイド、ターシャリ−
ブチルパーオキシイソブチレート、ターシャリ−ブチル
パーオキシラウレート、ターシャリ−ブチルパーオキサ
イド等の有機過酸化物、アゾビスイソブチロニトリル、
アゾビスジメチルバレロニトリル等のアゾ化合物等が挙
げられる。In addition, the polymerization initiator in the above polymerization method may be one that is commonly used in the polymerization of polystyrene, such as benzoyl peroxide, tert-butyl peroxybenzoate, lauroyl peroxide, tert-butyl peroxide, etc.
Organic peroxides such as butyl peroxyisobutyrate, tert-butyl peroxylaurate, tert-butyl peroxide, azobisisobutyronitrile,
Examples include azo compounds such as azobisdimethylvaleronitrile.
重合処理は６０〜１４０℃の温度で２〜２０時間加熱す
ることにより行うのが適している。The polymerization treatment is suitably carried out by heating at a temperature of 60 to 140°C for 2 to 20 hours.
その他の重合条件については公知の条件を準用すること
ができる。As for other polymerization conditions, known conditions can be applied mutatis mutandis.
また、上記共重合体樹脂粒子への発泡剤の含有は、樹脂
粒子を懸濁液に懸濁させた状態でこれに易揮発性発泡剤
を添加するか、上記懸濁重合途中に懸濁液中に易揮発性
発泡剤を添加することによって行うことができる。The blowing agent may be added to the copolymer resin particles by adding an easily volatile blowing agent to the resin particles suspended in a suspension, or by adding a readily volatile blowing agent to the suspension during the suspension polymerization. This can be done by adding an easily volatile foaming agent therein.
易揮発性発泡剤どしては、プロパン、ｎ−ブタン、ｉ−
ブタン、ｎ−ペンタン、ｉ−ペンタン、ｎ−ヘキサン等
の脂肪族炭化水素、メチルクロライド、エチルクロライ
ド、ジクロロジフルオロメタン、トリクロロフルオロメ
タン等のハロゲン化炭化水素を挙げることができ、好ま
しくはｎ−ブタン、ｉ−ブタンである。これらの易揮発
性発泡剤は単独に又は２種以上混合して使用でき、樹脂
粒子に対して１〜１０重量％の割合で含有するようにし
て使用される。Easily volatile blowing agents include propane, n-butane, i-
Examples include aliphatic hydrocarbons such as butane, n-pentane, i-pentane, and n-hexane, and halogenated hydrocarbons such as methyl chloride, ethyl chloride, dichlorodifluoromethane, and trichlorofluoromethane, preferably n-butane. , i-butane. These easily volatile foaming agents can be used alone or in a mixture of two or more, and are used in an amount of 1 to 10% by weight based on the resin particles.
なお、このようにして得られる発泡性共重合体樹脂粒子
中には、他の成分、例えば、酸化防止剤、紫外線吸収剤
、着色剤等の種々の添加剤か任意に含まれていてもよい
。Note that the expandable copolymer resin particles thus obtained may optionally contain other components, such as various additives such as antioxidants, ultraviolet absorbers, and colorants. .
以上述べた発泡性共重合体樹脂粒子に常温で液状のプロ
ピレングリコールの高級脂肪酸エステルを被覆処理させ
ることにより本発明の発泡性共重合体樹脂粒子組成物が
得られる。ここで用いるプロピレングリコールの高級脂
肪酸エステルとしては、プロピレングリコールのＣ＋ａ
脂肪酸エステルが適しており、プロピレングリコールオ
レイン酸エステルが好ましく、プロピレングリコールモ
ノオレイン酸エステルがより好ましい。このようなプロ
ピレングリコール脂肪酸エステルの使用量は、発泡性共
重合体樹脂粒子に対して０．００１〜０．５重量％が好
ましい。ｏ、ｏｏｉ重量％未満では、微細クラックを発
生させる効果は少なく、Ｏ，Ｓ重量％を超過すると微細
クラックの発生効果は飽和になり経済性の点で不利であ
ると共に発泡性共重合体樹脂粒子が互いにベトッキ状態
となる。ので、予備発泡機の計量ホッパー等への搬送は
困難となり、実質上連続状懇での予備発泡操作はできな
くなるため好ましくない。The foamable copolymer resin particle composition of the present invention can be obtained by coating the foamable copolymer resin particles described above with a higher fatty acid ester of propylene glycol that is liquid at room temperature. The higher fatty acid ester of propylene glycol used here is C+a of propylene glycol.
Fatty acid esters are suitable, with propylene glycol oleate being preferred and propylene glycol monooleate being more preferred. The amount of propylene glycol fatty acid ester used is preferably 0.001 to 0.5% by weight based on the foamable copolymer resin particles. If it is less than O, ooi weight percent, the effect of generating fine cracks is small, and if it exceeds O, S weight percent, the effect of generating fine cracks becomes saturated, which is disadvantageous in terms of economic efficiency and expandable copolymer resin particles. become sticky with each other. Therefore, it becomes difficult to transport the foam to the weighing hopper of the pre-foaming machine, and it becomes impossible to perform the pre-foaming operation in a substantially continuous manner, which is not preferable.
なお、用いるプロピレングリコール脂肪酸エステルは、
他の脂肪酸エステルを含有する混合脂肪酸エステルの形
態で用いられていてもよい。ただし、少なくとも前記脂
肪酸エステルが上記壷金まれていることが必要である。The propylene glycol fatty acid ester used is
It may also be used in the form of a mixed fatty acid ester containing other fatty acid esters. However, it is necessary that at least the fatty acid ester is contained in the pot.
上記被覆処理する方法には特に制限はなく、例えば、連
続式もしくは回分式の混合機中で発泡性共重合体樹脂粒
子ど上記エステルを流動混合する方法、発泡性共重合体
樹脂粒子を耐圧容器中で懸濁重合状態で製造する際、そ
の工程で懸濁液中に上記エステルを分散させて付着させ
る方法などで行えばよい。これにより、プロピレングリ
コール高級脂肪酸エステルは樹脂粒子の表面及び／又は
表面付近（表面層内）に含有されることとなる。There are no particular restrictions on the method of coating, and examples include a method of fluidly mixing the foamable copolymer resin particles and the above ester in a continuous or batch mixer, a method of fluidly mixing the foamable copolymer resin particles and the above ester, and a method of mixing the foamable copolymer resin particles in a pressure-resistant container. When producing in a suspension polymerization state, the above-mentioned ester may be dispersed and attached to the suspension in the process. As a result, the propylene glycol higher fatty acid ester is contained on the surface and/or near the surface (in the surface layer) of the resin particles.
（作 用）
常温で液状のプロピレングリコール高級脂肪酸エステル
の存在で成形時に微細クラックが発生し、表面積が飛躍
的に増大した発泡成形体が得られる。(Function) The presence of propylene glycol higher fatty acid ester, which is liquid at room temperature, causes microcracks during molding, resulting in a foamed molded product with a dramatically increased surface area.
そのため発泡成形体は、成形中、成形後を通じて発泡剤
の逸散性が良好となり、結局発泡成形体中に残留する発
泡剤は非常に少ないものとなる。Therefore, the foamed molded product has good dissipation of the foaming agent during and after molding, and as a result, very little foaming agent remains in the foamed molded product.
また、上記プロピレングリコール高級脂肪酸エステルの
存在で予備発泡時に粒子同士が結合することもなく、し
かも発泡成形時の融着も悪化させることもない。Further, due to the presence of the propylene glycol higher fatty acid ester, particles do not bond to each other during pre-foaming, and fusion during foam molding does not deteriorate.
（実施例）
実施例１
発泡性共重合体樹脂粒子としては、ａ）アクリロニトリ
ル２０重量１％、スチレン８０重量％を単量体組成とし
て構成され、ｂ） １００ｍ１２中ｉｇのテトラヒドロ
フラン溶液で温度３０±０．２℃の条件下、オストワル
ド粘度計にて測定した比粘度ηｓｐが１．１２である共
重合体樹脂粒子（粒子径は０．７〜１．０ａｕａ）に発
泡剤として、ブタンを３．９重量％含有しているものを
用いた。(Example) Example 1 Expandable copolymer resin particles were a) composed of a monomer composition of 20% by weight of acrylonitrile and 80% by weight of styrene, and b) a solution of ig of tetrahydrofuran in 100m12 at a temperature of 30± Butane was added as a blowing agent to copolymer resin particles (particle size: 0.7 to 1.0 aua) having a specific viscosity ηsp of 1.12 as measured by an Ostwald viscometer at 0.2°C. The one containing 9% by weight was used.
そこで、プロピレングリコールモノオレイン酸エステル
を上記発泡性共重合体樹脂粒子に対して０．１０重量％
混合して、ポリエチレン袋に入れて充分に振り、発泡性
共重合体樹脂粒子の表面処理を行い本発明の試料（発泡
性共重合体樹脂粒子組成物）を作製した。Therefore, propylene glycol monooleate was added at 0.10% by weight based on the foamable copolymer resin particles.
The mixture was mixed, placed in a polyethylene bag, and shaken thoroughly, and the foamable copolymer resin particles were surface-treated to prepare a sample of the present invention (expandable copolymer resin particle composition).
次に、バッチ式発泡機によって、この試料７０Ｇｇを水
蒸気で加熱し、カサ倍率１０倍に予備発泡させ、粒子表
面における微細クラックの発生の有無をルーペで調べそ
の後、閉鎮型の金型（４００Ｘ ２００Ｘ１０ａｍ）に
充填し水蒸気で再び加熱することにより板状の発泡成形
体を得た。Next, 70 Gg of this sample was heated with steam using a batch foaming machine, pre-foamed to a bulk magnification of 10 times, and the presence or absence of microcracks on the particle surface was examined with a magnifying glass. A plate-shaped foam molded product was obtained by filling the mixture into a container (200×10 am) and heating it again with steam.
ここで得られた発泡成形体を６０℃の乾燥室内で４時間
乾燥した後、ガスクロマトグラフで残存する発泡網（ブ
タン）の量を調べた。After drying the foamed molded article obtained here for 4 hours in a drying chamber at 60° C., the amount of remaining foamed mesh (butane) was examined using a gas chromatograph.
また耐熱試験として８５℃の熱風循環式恒温槽内に２４
時間放置し、発泡成形体表面における、再発泡による凹
凸の状態を調べた。In addition, as a heat resistance test, we placed 24
The foamed molded product was left to stand for a period of time, and the state of unevenness on the surface of the foamed molded product due to re-foaming was examined.
測定結果を表１に示す。The measurement results are shown in Table 1.
実施例２
発泡性共重合体樹脂体粒子としては、ａ）アクリロニト
リル３０重量％、α−メチルスチレン７０重量％を単量
体組成として構成され、ｂ） １０Ｏｎ＋１２中１ｇの
テトラヒドロフラン溶液で温度３０℃±０．２℃の条件
下、オストワルド粘度計にて測定した比粘度ηｓｐがｏ
、ｇｔｔである共重合体樹脂粒子（粒子径は０．７〜１
０ｍｍ）に発泡剤としてブタン３．７重量％含有してい
るものを用い、耐熱試験の温度を１０５℃とした以外は
実施例１と同様にして評価を行った。Example 2 Expandable copolymer resin particles were a) composed of a monomer composition of 30% by weight of acrylonitrile and 70% by weight of α-methylstyrene, and b) a solution of 1g of tetrahydrofuran in 10On+12 at a temperature of 30°C±. The specific viscosity ηsp measured with an Ostwald viscometer under the condition of 0.2°C is o
, gtt copolymer resin particles (particle size is 0.7-1
Evaluation was carried out in the same manner as in Example 1, except that the foam containing 3.7% by weight of butane as a blowing agent was used and the temperature of the heat resistance test was 105°C.
測定結果を表１に示す。The measurement results are shown in Table 1.
実施例３
発泡性共重合体樹脂粒子としては、ａ）アクリロニトリ
ル２５重量％、α−メチルスチレン６５重量％、Ｎ−フ
ェニルマレイミド１０重量％を単量体組成として構成さ
れ、ｂ） ｔｏｏｌ中ｔｇのテトラヒドロフラン溶液で
温度３０℃±０．２℃の条件下、オストワルド粘度計に
て測定した比粘度ηｓｐが０．５６４であり、且つＣ）
常圧沸点１００℃以上の溶剤成分量が０，４７重量％で
あるＮ−置換マレイミド系共重合体樹脂粒子（粒子径は
０．７〜１．０ｍｍ）に発泡剤としてブタンを３．６重
量％含有しているものを用い、耐熱試験の温度を１１５
℃とした以外は実施例１と同様にして作業を行った。測
定結果を表１に示す。Example 3 The expandable copolymer resin particles had a monomer composition of a) 25% by weight of acrylonitrile, 65% by weight of α-methylstyrene, and 10% by weight of N-phenylmaleimide, and b) tg in the tool. The specific viscosity ηsp measured in a tetrahydrofuran solution at a temperature of 30°C ± 0.2°C using an Ostwald viscometer is 0.564, and C)
N-substituted maleimide copolymer resin particles (particle size: 0.7 to 1.0 mm) containing 0.47% by weight of a solvent component with a boiling point at normal pressure of 100°C or higher were mixed with 3.6 weight percent of butane as a blowing agent. %, and the temperature of the heat resistance test was set to 115%.
The work was carried out in the same manner as in Example 1 except that the temperature was changed to ℃. The measurement results are shown in Table 1.
実施例４．５
実施例３においてグリセリントリカプリル酸エステルの
量を各々０．０５重量％（実施例４ ） 、０．３０重
量％（実施例５）とした以外、同様にして本発明の発泡
性共重合体樹脂粒子組成物を作製した。Example 4.5 Foaming of the present invention was carried out in the same manner as in Example 3, except that the amount of glycerin tricaprylate was changed to 0.05% by weight (Example 4) and 0.30% by weight (Example 5), respectively. A copolymer resin particle composition was prepared.
測定結果をまとめて表１に示す。The measurement results are summarized in Table 1.
比較例！、２．３
実施例１，２．３においてそれぞれプロピレングリコー
ルモノオレイン酸エステルを使用しなかった以外、同様
の作業を行った。Comparative example! , 2.3 The same operations as in Examples 1 and 2.3 were performed except that propylene glycol monooleate was not used.
測定結果をまとめて表２に示す。The measurement results are summarized in Table 2.
比較例４〜９
実施例３において、プロピレングリコールモノオレイン
酸エステルのかわりに表２に示した添加化合物をそれぞ
れ０．１０重量％使用した。Comparative Examples 4 to 9 In Example 3, 0.10% by weight of each of the additive compounds shown in Table 2 was used in place of propylene glycol monooleate.
測定結果をまとめて表２に示した。The measurement results are summarized in Table 2.
比較例１０
１００１ＩＱ中１ｇのトルエン溶液の３０±０，２℃に
おける比粘度が１．２２で、且つその粒径が０６７〜１
．ｈ＋ｍのポリスチレン樹脂粒子に発泡剤としてブタン
を４．３重量％含有しているものを発泡性樹脂粒子とし
て用いた以外は実施例１と同様にして評価を行った。
ところが予備発泡において、カサ倍率６゜１倍までしか
発泡せず、また成形においても予備発泡粒子同志が接着
せず全く発泡成形体は得られなかった。Comparative Example 10 The specific viscosity at 30±0.2°C of 1 g of toluene solution in 1001IQ is 1.22, and the particle size is 067-1
．． Evaluation was conducted in the same manner as in Example 1, except that h+m polystyrene resin particles containing 4.3% by weight of butane as a foaming agent were used as foamable resin particles.
However, during pre-foaming, the foam was only expanded to a bulk ratio of 6.1 times, and during molding, the pre-foamed particles did not adhere to each other and no foamed molded product was obtained.
（以下余白）
（発明の効果）
本発明の発泡性共重合体樹脂粒子組成物を用いて成形し
た発泡成形体は、単なるスチレン−アクリロニトリル系
共重合体樹脂からなる発泡性樹脂粒子を用いて成型した
ものに比して、高温環境下における耐熱変形性ことに表
面安定性に優れ、ことに成形体としての熱許容温度を５
〜１０℃程度も向上させる二七ができる。(The following is a blank space) (Effects of the invention) A foam molded article molded using the expandable copolymer resin particle composition of the present invention is molded using expandable resin particles made of a simple styrene-acrylonitrile copolymer resin. It has excellent heat deformation resistance and surface stability in high-temperature environments, especially when the heat permissible temperature as a molded product is 5.
It is possible to improve the temperature by about 10°C.
従って、種々の耐熱性を要求される成形品を製造する原
料として極めて有用なものである。Therefore, it is extremely useful as a raw material for manufacturing molded products that require various heat resistances.
手続補正書
昭和６２年６月１０日
昭和６２年特許願第１０２６９２号
２、発明の名称
発泡性共重合体樹脂粒子組成物
３、補正をする者
事件との関係 特許出願人
住 所 奈良市南京終町１丁目２５番地名 称
＜２４４）積水化成品工業株式会社代表者 川 本
貢
４、代理人 〒５３０
住 所 大阪市北区西天満５丁目１−３クォーター・
ワンビルビ・８１・
５、補正命令の日付 自発
６、補正の対象
補正の内容
１、明細書第５頁第１５行の「グリセライド」をｒ油脂
類」と補正する。Procedural amendment June 10, 1988 Patent Application No. 102692 of 1988 2 Name of the invention Expandable copolymer resin particle composition 3 Relationship to the case of the person making the amendment Patent applicant address Nanjing, Nara City 1-25 Shuumachi Name
<244) Sekisui Plastics Co., Ltd. Representative Kawamoto
Mitsugu 4, Agent 530 Address 1-3 Quarter, Nishitenma 5-chome, Kita-ku, Osaka
Wanbilbi 81.5, Date of amendment order Voluntary action 6, Contents of amendment subject to amendment 1, ``Glyceride'' on page 5, line 15 of the specification is amended to read ``r oils and fats''.
２、同書中１６頁第２〜３行の「グリセリントリカプリ
ル酸エステル」を「ブＯピレングリコールモノオレイン
酸エステル」と補正する。2. In the same book, page 16, lines 2 and 3, "glycerin tricaprylate" is corrected to "buOpyrene glycol monooleate".
Claims (1)
スチレン系単量体残基４０〜８５重量％及び他の重合性
単量体残基０〜３０重量％より構成される共重合体を基
材樹脂とし、これに易揮発性発泡剤を１〜１０重量％含
有してなる発泡性共重合体樹脂粒子の表面及び／又は表
面付近に、常温で液状のプロピレングリコールの高級脂
肪酸エステルを存在させてなる発泡性共重合体樹脂粒子
組成物。 ２、プロピレングリコールの高級脂肪酸エステルがプロ
ピレングリコールのオレイン酸エステルである特許請求
の範囲第１項記載の樹脂粒子組成物。 ３、プロピレングリコールの高級脂肪酸エステルが、発
泡性樹脂粒子に対して０．００１〜０．５重量％用いら
れる特許請求の範囲第１項記載の樹脂粒子組成物。 ４、スチレン系単量体がスチレン及び／又はα−メチル
スチレンである特許請求の範囲第１項記載の樹脂粒子組
成物。 ５、アクリロニトリル系単量体が、アクリロニトリルで
ある特許請求の範囲第１項記載の樹脂粒子組成物。[Claims] 1. 15 to 40% by weight of acrylonitrile monomer residues;
A copolymer composed of 40 to 85% by weight of styrene monomer residues and 0 to 30% by weight of other polymerizable monomer residues is used as the base resin, and 1 to 10% of easily volatile blowing agent is added to this base resin. A foamable copolymer resin particle composition comprising a higher fatty acid ester of propylene glycol, which is liquid at room temperature, present on the surface and/or near the surface of the foamable copolymer resin particles containing 10% by weight. 2. The resin particle composition according to claim 1, wherein the higher fatty acid ester of propylene glycol is an oleic acid ester of propylene glycol. 3. The resin particle composition according to claim 1, wherein the higher fatty acid ester of propylene glycol is used in an amount of 0.001 to 0.5% by weight based on the foamable resin particles. 4. The resin particle composition according to claim 1, wherein the styrenic monomer is styrene and/or α-methylstyrene. 5. The resin particle composition according to claim 1, wherein the acrylonitrile monomer is acrylonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62102692A JPH0610274B2 (en) | 1987-04-24 | 1987-04-24 | Expandable copolymer resin particle composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62102692A JPH0610274B2 (en) | 1987-04-24 | 1987-04-24 | Expandable copolymer resin particle composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63268750A true JPS63268750A (en) | 1988-11-07 |
| JPH0610274B2 JPH0610274B2 (en) | 1994-02-09 |
Family
ID=14334303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62102692A Expired - Lifetime JPH0610274B2 (en) | 1987-04-24 | 1987-04-24 | Expandable copolymer resin particle composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0610274B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2565225A1 (en) | 2011-08-31 | 2013-03-06 | Basf Se | Coated expandable polymer particle |
| DE102012217659A1 (en) | 2012-09-27 | 2014-03-27 | Basf Se | Expandable polymer particle useful for producing foam molded part or block of foam which is useful in e.g. furniture, construction and stand construction automotive industry, comprises polymerized styrene and/or alpha-methyl styrene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5149261A (en) * | 1974-10-25 | 1976-04-28 | Sekisui Plastics | HATSUHOSEISUCHIRENJUGOTAIRYUSHISOSEIBUTSU |
| JPS5397060A (en) * | 1977-02-04 | 1978-08-24 | Hitachi Chem Co Ltd | Novel expandable styrene resin granule and its production |
| JPS5716037A (en) * | 1981-06-01 | 1982-01-27 | Hitachi Chem Co Ltd | Expandable styrene resin particle |
-
1987
- 1987-04-24 JP JP62102692A patent/JPH0610274B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5149261A (en) * | 1974-10-25 | 1976-04-28 | Sekisui Plastics | HATSUHOSEISUCHIRENJUGOTAIRYUSHISOSEIBUTSU |
| JPS5397060A (en) * | 1977-02-04 | 1978-08-24 | Hitachi Chem Co Ltd | Novel expandable styrene resin granule and its production |
| JPS5716037A (en) * | 1981-06-01 | 1982-01-27 | Hitachi Chem Co Ltd | Expandable styrene resin particle |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2565225A1 (en) | 2011-08-31 | 2013-03-06 | Basf Se | Coated expandable polymer particle |
| DE102012217659A1 (en) | 2012-09-27 | 2014-03-27 | Basf Se | Expandable polymer particle useful for producing foam molded part or block of foam which is useful in e.g. furniture, construction and stand construction automotive industry, comprises polymerized styrene and/or alpha-methyl styrene |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0610274B2 (en) | 1994-02-09 |
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