JPH0580508B2 - - Google Patents
Info
- Publication number
- JPH0580508B2 JPH0580508B2 JP28099185A JP28099185A JPH0580508B2 JP H0580508 B2 JPH0580508 B2 JP H0580508B2 JP 28099185 A JP28099185 A JP 28099185A JP 28099185 A JP28099185 A JP 28099185A JP H0580508 B2 JPH0580508 B2 JP H0580508B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- ethylene
- component
- present
- acid
- 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.)
- Expired - Lifetime
Links
- 229920000728 polyester Polymers 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 7
- 229920001038 ethylene copolymer Polymers 0.000 claims description 6
- 150000002118 epoxides Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- -1 polyethylene terephthalate Polymers 0.000 description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 17
- 239000005977 Ethylene Substances 0.000 description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 13
- 229920002554 vinyl polymer Polymers 0.000 description 13
- 239000000178 monomer Substances 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 8
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 7
- 229920005604 random copolymer Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- WLQXEFXDBYHMRG-UPHRSURJSA-N (z)-4-(oxiran-2-ylmethoxy)-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OCC1CO1 WLQXEFXDBYHMRG-UPHRSURJSA-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
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- NMSZFQAFWHFSPE-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxycarbonyl)but-3-enoic acid Chemical compound OC(=O)CC(=C)C(=O)OCC1CO1 NMSZFQAFWHFSPE-UHFFFAOYSA-N 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
- 229920000049 Carbon (fiber) Polymers 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical group CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Description
(利用分野)
本発明は耐衝撃性が著しく改良されたポリエス
テル組成物に関するものである。
(先行技術)
ポリエチレンテレフタレートやポリブチレンテ
レフタレートに代表される芳香族ポリエステルは
その優れた特性から電気および電子機器部品、自
動車部品などの広い分野で使用されている。しか
しながら、芳香族ポリエステルは耐衝撃性、特に
ノツチ付衝撃強度が劣るため、従来から多くの改
善方法が提案されて来た。特開昭51−144452号、
特開昭52−32045号、特開昭53−117049号で示さ
れるα−オレフインおよびα,β−不飽和酸グリ
シジルエステルなどのモノマーからなる共重合体
をブレンドする方法は比較的優れている。しか
し、これらの方法で得られる成形品は常温付近で
は良好な耐衝撃性を示すが−30℃などの低温では
それほど改良されず、かえつて流動性を著しく悪
化させたり、ポリエステルの有するせつかくの高
い耐熱性、例えば熱変形温度を大巾に低下したり
する。
特開昭58−17151号はα−オレフインとα,β
−不飽和グリシリルエステルからなるグリシジル
基含有共重合体とエチレン、炭素数3以上のα−
オレフインおよび非共役ジエンからなるエチレン
系三元共重合体を芳香族ポリエステルに配合する
ことにより低温の耐衝撃性を改良した。しかしな
がらこの方法によつても依然として流動性や熱変
形温度の低下は解決されなかつた。
(発明の概要)
本発明者らは、かかる技術上の問題点、すなわ
ち、流動性や熱変形温度の低下をまねくことなく
ポリエステルの衝撃強度を低温領域も含め改善す
るべく鋭意検討した結果、ポリエステルに対して
特定の変性エチレン系共重合体と変性エチレン・
プロピレンランダム共重体を配合することにより
本目的を達成しうる本発明を見出した。
すなわち、本発明は、次の(A)成分と(B)成分を配
合、混練した耐衝撃性ポリエステル組成物を提供
するものである。
(A)成分:ポリエステル 100重量部
(B)成分:次の成分からなる樹脂成分
5〜50重量部
(B−1) ビニルアルコキシシラン化合物を
グラフトしたエポキシドを含むエチレン系
共重合体、10〜60重量%
(B−2) ビニルアルコキシシラン化合物を
グラフトしたエチレンプロピレンランダム
共重合体、90〜40重量%
(発明の具体的説明)
本発明の(A)成分であるポリエステルとは、ジカ
ルボン酸の少なくとも40モル%がテレフタル酸で
あるジカルボン酸成分およびジオール成分を主成
分とする縮合反応により得られるポリエステルで
あり、上記テレフタル酸以外のジカルボン酸成分
としてはアゼライン酸、セバシン酸、アジピン
酸、ドデカンジカルボン酸、イソフタル酸、オル
トフタル酸、ナフタレンジカルボン酸、ジフエニ
ル−4,4'−ジカルボン酸、ジフエニルエタン−
4,4'−ジカルボン酸などの芳香族ジカルボン酸
またはシクロヘキサンジカルボン酸などの脂環式
ジカルボン酸の単独ないしは混合物があげられ
る。上記ジオールとしては、C2〜20の脂肪族グ
リコール、すなわち、エチレングリコール、プロ
ピレングリコール、1,4−ブタンジオール、ネ
オペンチルグリコール、1,5−ペンタンジオー
ル、1,6−ヘキサンジオール、デカメメチレン
グリコール、シクロヘキサンジメタノール、シク
ロヘキサンジオールなど、あるいは分子量400〜
6000の長鎖グリコール、すなわち、ポリエチレン
グリコール、ポリ−1,3−プロピレングリコー
ル、ポリテトラメチレングリコールなどおよびそ
れらの混合物があげられる。
具体的なポリエステルの例としては、ポリエチ
レンテレフタレート、ポリプロピレンテレフタレ
ート、ポリブチレンテレフタレート、ポリヘキサ
メチレンテレフタレート、ポリシクロヘキサンジ
メチレンテレフタレートなどがあげられる。これ
らの中でも、特に好しいのは、ポリエチレンテレ
フタレートとポリブチレンテレフタレートであ
る。これらポリエステルは、フエノールとテトラ
クロルエタンの1:1の重量比混合溶媒中、30℃
で測定した固有粘度が0.3以上、1.5以下、好まし
く0.4以上、1.2以下である。0.3以下では本発明の
効果は十分でなく、また1.5以上では本発明の組
成物の流動性が著しく悪く、成形できない。
本発明の(B)成分を構成する(B−1)成分であ
るビニルアルコキシシランをグラフトしたエポキ
シドを含有するエチレン系共重合とは、エチレン
と不飽和エポキシド及び必要に応じて他のビニル
モノマーを共重合して得られたエチレン共重合体
にビニルアルコキシシランをグラフトしたもので
ある。
幹ポリマー中に存在するエチレン単量体の含量
は20〜95モル%、好ましくは、30〜90モル%が望
ましい。20モル%以下では共重合体は固くて脆く
なり、また、95モル%以上ではポリエステルとの
親和性が弱くなりすぎ、耐衝撃性の向上が乏し
い。
不飽和エポキシド単量体は炭素数6〜11のもの
が用いられ、その幹ポリマー中の含量は、1〜20
モル%、好ましくは、5〜15モル%が望ましい。
1モル%以下では耐衝撃性の向上は少なく、20モ
ル%以上では、本発明の組成物がゲル化しやす
い。
その代表的単量体は、グリシジル(メタ)アク
リレート、ビニルグリシジルエーテル、グリシジ
ルイタコネートマレイン酸グリシジルエステルな
どである。
上記単量体以外には該幹ポリマーは、酢酸ビニ
ル、スチレン、(メタ)アクリル酸エステルなど
のビニル単量体が0〜20モル%含まれる。これら
単量体は交互またはランダムに共重合する。
幹ポリマーにグラフトされるビニルアルコキシ
シラン単量体の炭素数5〜10であり、その代表的
なものは、ビニルトリメトキシシラン、ビニルト
リエトキシシラン、ビニルトリn−ブトキシシラ
ン、γ−メタクリロキシプロピルトリメトキシシ
ランである。グラフト率は0.1〜5重量%、好ま
しくは、0.5〜3重量%が望ましい。0.1重量%以
下では本発明の効果が乏しく、5重量%以上では
グラフト化共重合体がゲル化しやすい。
具体的には、エチレン/(メタ)アクリル酸グ
リシジル−g−ビニルトリメトキシシラン、エチ
レル/酢酸ビニル/(メタ)アクリル酸グリシジ
ル−g−ビニルトリメトキシシラン、エチレン/
(メタ)アクリル酸メチル/(メタ)アクリル酸
グリシジル−g−ビニルトリメトキシシラン、エ
チレン/(メタ)アクリル酸ベンジレート/(メ
タ)アクリル酸グリシジル−g−ビニルトリメト
キシシラン、エチレン/酢酸ビニル/ビニルグリ
シリルエーテル−g−ビニルトリn−ブトキシシ
ラン、エチレン/酢酸ビニル/グリシジルイタコ
ネート−g−ビニルトリメトキシシラン、エチレ
ン/マレイン酸イソプロピルグリシジル−g−ビ
ニルトリメトキシシラン共重合体などである。
該グラフト化共重合体は、高圧ラジカル重合法
で重合された幹ポリマーをビニルアルコキシシラ
ン単量体と溶液状態または溶融状態で反応させ得
られる。この時、ラジカル発生剤を使用するとグ
ラフト化の効率が高められる。ラジカル発生剤と
しては、ベンゾイルパーオキサイド、ジクミルパ
ーオキサイドなどの有機過酸化物が用ちいられ
る。ラジカル発生剤の添加量は0〜2重量%、好
ましくは0〜1重量%である。
次に(B−2)成分であるビニルアルコキシシ
ランをグラフトしたエチレン・プロピレンランダ
ム共重合体は、プロピレン含量15〜50重量%、好
ましくは、20〜30重量%からなるランダム共重合
体に、溶液状態または溶融状態で上記ビニルアル
コキシシラン単量体をグラフト反応したものが適
する。ビニルアルコキシシランのグラフト率は
0.1〜5重量%、好ましくは、0.5〜3重量%が望
ましい。0.1重量%以下では本発明の効果が弱く、
5重量%以上では該ビニルアルコキシシラングラ
フトエチレン・プロピレン共重合体がゲル化しや
すい。
(B−1)成分と(B−2)成分は、各々、10
〜60重量%、90〜40重量%の範囲でドライブレン
ド後溶融混練され(B)成分としてポリエステルに配
合される。この場合、(B−1)成分、(B−2)
成分のアルコキシシラノール基の一部を水架橋さ
せると一層本発明の効果が発揮される。水架橋の
方法は、(B−1)成分、(B−2)成分または(B)
成分を空気中または水中に放置することにより簡
単に達成される。この場合、一般によく知られて
いるアルコキシシラノール基の水架橋用触媒であ
る、錫、亜鉛、鉄、コバルトなどの金属のカルボ
ン酸化合物、有機塩基、無機酸および有機酸、例
えば、ジブチル錫ラウリレート、ジブチル錫ジア
セテート、酢酸第1錫、ナフテン酸鉛、ステアリ
ン酸などを(B−1)成分、(B−2)成分に配
合すると水架橋が効率的に実行される。
本発明における、ポリエステル100重量部に対
して配合される(B)成分の量は、5〜50重量部、好
ましくは、10〜40重量部である。5重量部以下で
は耐衝撃性の向上は認められず、50重量%以上で
は、耐衝撃性の向上効果は飽和し、かえつて、剛
性などの力学的性質の低下が著しい。また、該組
成物中に分散する(B)成分は平均粒径1〜20μ、好
ましくは、2μ〜10μの範囲で分散することが望ま
しい。1μ以下では該組成物の流動性が著しく低
下する、また、20μ以上では耐衝撃性の向上は認
められない。
ここでいう平均粒径とは重量平均粒径であつ
て、走査型電子顕微鏡によつて測定される。
本発明の発現する理由は定かでないが、アルコ
キシシラノール基同志の反応、アルコキシシラノ
ール基とポリエステル、エポキシ基とポリエステ
ルの反応にもとずく、ポリエステル、エチレン系
共重合体、エチレン・プロピレンランダム共重合
体の多相構造が形成されるためと推定される。
本発明の組成物に対して、本発明の目的を損わ
ない範囲で、繊維状および粒状の強化・充填材核
剤・結晶化促進剤、酸化防止剤、熱安定剤、紫外
線吸収剤、可塑剤、離形剤、着色剤・顔料、難燃
剤などを配合することが出来る。特に、ガラス繊
維、炭素繊維を配合したものは、剛性、熱変形温
度が著しく向上し、有用な材料となる。
また、本発明の組成物には、他の熱可塑性樹
脂、例えば、ポリアミド、ポリカーボネート、ス
チレン系樹脂、ポリフエニレンエーテル、ポリフ
エニレンサルフアイド、ポリオキシメチレン、ポ
リエチレン、ポリプロピレン、エチレン・プロピ
レンエラストマーなどを1種または2種以上を、
本発明の目的を損じない範囲で配合することが出
来る。
本発明の組成物は、通常の溶融混練手法、例え
ば、押出機、ニーダー、バンバリーミキサーなど
で容易に製造することが出来る。
以下に実施例をあげ、本発明を更に詳しく説明
する。
変性(ポリエチレン/エチレン・プロピレンラン
ダム共重合体)の製造法−1。
エチレン・酢酸ビニル・グリシジルメタアクリ
レート三元共重合体(89重量%・5重量%・9重
量%)2.5Kgとエチレン・プロピレンランダム共
重合体(エチレン、73重量%、プロピレン、27重
量%)2.5Kg、ビニルトリメトキシシラン、25Kg
をドライブレンド後、200℃で、30mmφ二軸押出
機にて溶融混練し、変性(ポリエチレン/エチレ
ン・プロピレンランダム共重合体)のペレツトを
得た。得られたペレツトの一部を常温の水中に一
昼夜浸漬し水架橋させた。水架橋度は、キシレン
沸点抽出で約5%であつた。
実施例1〜7、比較例1〜7
ポリエチレンテレフタレート(クラレ社製、フ
エノールとテトラクロルエタンの1:1重量比混
合溶媒、30℃、固有粘度0.68)100重量部に対し
て変性(ポリエチレン/エチレン・プロピレンラ
ンダム共重合体)およびその水架橋物を表に示す
割合でドライブレンド後、30mmφ二軸押出機に
て、260℃、スクリユー回転数、200rpmにて溶融
混練した。得られた組成物のペレツトを、130℃、
5時間、熱風乾燥機にて乾燥後、5オンス射出成
形機にて、260℃、金型温度、90℃にてテストピ
ースを成形、評価した。比較例として、エチレ
ン・酢酸ビニル・グリシジルメタアクリレート三
元共重合体(89重量%・5重量%・9重量%)の
みの場合およびエチレン・プロピレン・非共役ジ
エン共重合を併用した場合をあげた。本発明によ
る組成物は、流動性の低下、熱変形温度の低下が
極めて少なく、耐衝撃性が著
(Field of Application) The present invention relates to polyester compositions with significantly improved impact resistance. (Prior Art) Aromatic polyesters represented by polyethylene terephthalate and polybutylene terephthalate are used in a wide range of fields such as electrical and electronic equipment parts and automobile parts due to their excellent properties. However, aromatic polyesters have poor impact resistance, particularly notched impact strength, and many improvements have been proposed heretofore. JP-A-51-144452,
The method of blending a copolymer consisting of monomers such as α-olefin and α,β-unsaturated acid glycidyl ester as shown in JP-A-52-32045 and JP-A-53-117049 is relatively superior. However, although the molded products obtained by these methods exhibit good impact resistance at around room temperature, the impact resistance is not significantly improved at low temperatures such as -30℃, and on the contrary, the fluidity deteriorates significantly and the impact resistance of polyester High heat resistance, for example, significantly lower heat distortion temperature. JP-A-58-17151 discloses α-olefin and α,β
- Glycidyl group-containing copolymer consisting of unsaturated glycilyl ester, ethylene, α- having 3 or more carbon atoms
Low-temperature impact resistance was improved by blending an ethylene-based terpolymer consisting of an olefin and a nonconjugated diene into an aromatic polyester. However, even with this method, the problems of fluidity and heat distortion temperature still remain unsolved. (Summary of the Invention) The present inventors have conducted intensive studies to solve the above technical problem, that is, to improve the impact strength of polyester, including in the low temperature range, without causing a decrease in fluidity or heat distortion temperature. Certain modified ethylene copolymers and modified ethylene copolymers
We have discovered the present invention, which can achieve this object by blending a propylene random copolymer. That is, the present invention provides an impact-resistant polyester composition in which the following components (A) and (B) are blended and kneaded. (A) Component: 100 parts by weight of polyester (B) Component: 5 to 50 parts by weight of a resin component consisting of the following components (B-1) Ethylene copolymer containing epoxide grafted with a vinyl alkoxysilane compound, 10 to 60 parts by weight Weight % (B-2) Ethylene propylene random copolymer grafted with vinyl alkoxysilane compound, 90 to 40 weight % (Detailed description of the invention) It is a polyester obtained by a condensation reaction mainly composed of a dicarboxylic acid component of which 40 mol% is terephthalic acid and a diol component, and the dicarboxylic acid components other than terephthalic acid include azelaic acid, sebacic acid, adipic acid, and dodecanedicarboxylic acid. , isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenylethane-
Examples include aromatic dicarboxylic acids such as 4,4'-dicarboxylic acid and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, alone or in mixtures. The above-mentioned diols include C2-20 aliphatic glycols, such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, and decamethylene glycol. , cyclohexanedimethanol, cyclohexanediol, etc., or molecular weight 400~
6000 long chain glycols, namely polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. and mixtures thereof. Specific examples of polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, and the like. Among these, particularly preferred are polyethylene terephthalate and polybutylene terephthalate. These polyesters were prepared at 30°C in a mixed solvent of phenol and tetrachloroethane at a weight ratio of 1:1.
The intrinsic viscosity measured is 0.3 or more and 1.5 or less, preferably 0.4 or more and 1.2 or less. If it is less than 0.3, the effect of the present invention is not sufficient, and if it is more than 1.5, the fluidity of the composition of the present invention is extremely poor and it cannot be molded. Ethylene-based copolymerization containing epoxide grafted with vinyl alkoxysilane, component (B-1) constituting component (B) of the present invention, refers to ethylene copolymerization containing epoxide grafted with vinyl alkoxysilane, which is component (B-1) that constitutes component (B) of the present invention. Vinyl alkoxysilane is grafted onto an ethylene copolymer obtained by copolymerization. The content of ethylene monomer present in the backbone polymer is preferably 20 to 95 mol%, preferably 30 to 90 mol%. If it is less than 20 mol%, the copolymer becomes hard and brittle, and if it is more than 95 mol%, its affinity with polyester becomes too weak, resulting in poor impact resistance. The unsaturated epoxide monomer used has 6 to 11 carbon atoms, and its content in the backbone polymer is 1 to 20.
A mole %, preferably 5 to 15 mole % is desirable.
If it is less than 1 mol %, there is little improvement in impact resistance, and if it is more than 20 mol %, the composition of the present invention tends to gel. Typical monomers include glycidyl (meth)acrylate, vinyl glycidyl ether, glycidyl itaconate and maleic acid glycidyl ester. In addition to the above monomers, the backbone polymer contains 0 to 20 mol% of vinyl monomers such as vinyl acetate, styrene, and (meth)acrylic acid ester. These monomers are copolymerized alternately or randomly. The vinyl alkoxysilane monomer grafted onto the backbone polymer has 5 to 10 carbon atoms, and typical examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-butoxysilane, and γ-methacryloxypropyltritrisilane. It is methoxysilane. The grafting rate is preferably 0.1 to 5% by weight, preferably 0.5 to 3% by weight. If it is less than 0.1% by weight, the effect of the present invention is poor, and if it is more than 5% by weight, the grafted copolymer tends to gel. Specifically, ethylene/glycidyl(meth)acrylate-g-vinyltrimethoxysilane, ethylene/vinyl acetate/glycidyl(meth)acrylate-g-vinyltrimethoxysilane, ethylene/vinyl acetate/glycidyl(meth)acrylate-g-vinyltrimethoxysilane,
Methyl (meth)acrylate/glycidyl (meth)acrylate-g-vinyltrimethoxysilane, ethylene/benzylate (meth)acrylate/glycidyl (meth)acrylate-g-vinyltrimethoxysilane, ethylene/vinyl acetate/vinyl These include glycilylether-g-vinyltri-n-butoxysilane, ethylene/vinyl acetate/glycidyl itaconate-g-vinyltrimethoxysilane, and ethylene/isopropylglycidyl maleate-g-vinyltrimethoxysilane copolymer. The grafted copolymer can be obtained by reacting a backbone polymer polymerized by high-pressure radical polymerization with a vinyl alkoxysilane monomer in a solution or melt state. At this time, the efficiency of grafting can be increased by using a radical generator. As the radical generator, organic peroxides such as benzoyl peroxide and dicumyl peroxide are used. The amount of the radical generator added is 0 to 2% by weight, preferably 0 to 1% by weight. Next, the ethylene/propylene random copolymer grafted with vinyl alkoxysilane, which is component (B-2), is added to a random copolymer having a propylene content of 15 to 50% by weight, preferably 20 to 30% by weight, in a solution. Suitable materials are those obtained by grafting the above-mentioned vinyl alkoxysilane monomers in a state or a molten state. The grafting rate of vinyl alkoxysilane is
0.1 to 5% by weight, preferably 0.5 to 3% by weight. If it is less than 0.1% by weight, the effect of the present invention is weak;
If it is 5% by weight or more, the vinyl alkoxysilane grafted ethylene/propylene copolymer tends to gel. (B-1) component and (B-2) component are each 10
~60% by weight and 90~40% by weight after dry blending, melt kneading, and blending into polyester as component (B). In this case, (B-1) component, (B-2)
The effects of the present invention are further exhibited when a portion of the alkoxysilanol groups of the components are water-crosslinked. The water crosslinking method includes component (B-1), component (B-2), or component (B).
This is easily accomplished by leaving the ingredients in air or water. In this case, carboxylic acid compounds of metals such as tin, zinc, iron, cobalt, organic bases, inorganic acids and organic acids, such as dibutyltin laurylate, which are generally well-known catalysts for water crosslinking of alkoxysilanol groups, When dibutyltin diacetate, stannous acetate, lead naphthenate, stearic acid, and the like are added to components (B-1) and (B-2), water crosslinking is efficiently carried out. In the present invention, the amount of component (B) added to 100 parts by weight of polyester is 5 to 50 parts by weight, preferably 10 to 40 parts by weight. If the amount is less than 5 parts by weight, no improvement in impact resistance is observed, and if it is more than 50 parts by weight, the effect of improving impact resistance is saturated, and on the contrary, mechanical properties such as rigidity are significantly reduced. Further, it is desirable that the component (B) dispersed in the composition has an average particle size of 1 to 20 microns, preferably 2 microns to 10 microns. If it is less than 1μ, the fluidity of the composition will be significantly reduced, and if it is more than 20μ, no improvement in impact resistance will be observed. The average particle size here refers to a weight average particle size, and is measured using a scanning electron microscope. Although the reason for the manifestation of the present invention is not clear, polyesters, ethylene copolymers, and ethylene-propylene random copolymers are produced based on reactions between alkoxysilanol groups, alkoxysilanol groups and polyesters, and epoxy groups and polyesters. This is presumed to be due to the formation of a multiphase structure. The composition of the present invention may contain fibrous and granular reinforcing agents, filler nucleating agents, crystallization accelerators, antioxidants, heat stabilizers, ultraviolet absorbers, plasticizers, etc., to the extent that the purpose of the present invention is not impaired. Agents, mold release agents, colorants/pigments, flame retardants, etc. can be added. In particular, materials containing glass fibers and carbon fibers have significantly improved rigidity and heat distortion temperature, making them useful materials. The composition of the present invention may also contain other thermoplastic resins, such as polyamide, polycarbonate, styrene resin, polyphenylene ether, polyphenylene sulfide, polyoxymethylene, polyethylene, polypropylene, ethylene propylene elastomer, etc. One or more types of
They can be blended within a range that does not impair the purpose of the present invention. The composition of the present invention can be easily produced using a conventional melt-kneading method such as an extruder, kneader, or Banbury mixer. The present invention will be explained in more detail with reference to Examples below. Manufacturing method of modified (polyethylene/ethylene/propylene random copolymer)-1. Ethylene/vinyl acetate/glycidyl methacrylate terpolymer (89%, 5%, 9% by weight) 2.5 kg and ethylene/propylene random copolymer (ethylene, 73% by weight, propylene, 27% by weight) 2.5 kg Kg, vinyltrimethoxysilane, 25Kg
After dry blending, the mixture was melt-kneaded at 200°C in a 30mmφ twin-screw extruder to obtain modified (polyethylene/ethylene/propylene random copolymer) pellets. A portion of the obtained pellets was immersed in water at room temperature for a day and night to cause water crosslinking. The degree of water crosslinking was approximately 5% in xylene boiling point extraction. Examples 1 to 7, Comparative Examples 1 to 7 Modified (polyethylene/ethylene・Propylene random copolymer) and its water-crosslinked product were dry-blended in the proportions shown in the table, and then melt-kneaded in a 30 mmφ twin-screw extruder at 260° C. and a screw rotation speed of 200 rpm. The pellets of the obtained composition were heated at 130°C.
After drying in a hot air dryer for 5 hours, a test piece was molded and evaluated in a 5-ounce injection molding machine at 260°C and a mold temperature of 90°C. As comparative examples, cases where only ethylene/vinyl acetate/glycidyl methacrylate terpolymer (89% by weight, 5% by weight, 9% by weight) were used and cases where ethylene/propylene/non-conjugated diene copolymer were used together were given. . The composition according to the present invention shows very little decrease in fluidity and heat distortion temperature, and has remarkable impact resistance.
【表】【table】
【表】 しく改良されていることが解る。 *PET:ポリエチレンテレフタレート (クラレ社製 固有粘度0.68) GF :ガラス繊維 (旭フアイバーグラス社製 CS03JA416) エチレン・プロピレン・非共役ジエン共重合体: (日本合成ゴム社製 EP57P) エチレン・酢ビ・グリンジルメタアクリレート 三元共重合体: (住友化学社製 ボンドフアースト2B) 測定法 アイゾツト強度 ASTM−D256 流動性 ASTM−D1238 熱変形温度 ASTM−D648 曲げ弾性率 ASTM−D790。【table】 It can be seen that it has been significantly improved. *PET: Polyethylene terephthalate (manufactured by Kuraray, intrinsic viscosity 0.68) GF: Glass fiber (Manufactured by Asahi Fiber Glass Co., Ltd. CS03JA416) Ethylene/propylene/non-conjugated diene copolymer: (EP57P manufactured by Japan Synthetic Rubber Co., Ltd.) Ethylene/vinyl acetate/grindyl methacrylate Terpolymer: (Sumitomo Chemical Bond First 2B) Measurement method Izot strength ASTM-D256 Fluidity ASTM-D1238 Heat distortion temperature ASTM-D648 Flexural modulus ASTM-D790.
Claims (1)
撃性ポリエステル組成物。 (A)成分:ポリエステル、100重量部 (B)成分:次の成分からなる樹脂成分5〜50重量部 (B−1)ニルアルコキシシラン化合物をグラ
フトした、エポキシドを含むエチレン系共
重合体、10〜60重量% (B−2)、ビニルアルコキシシラン化合物を
グラフトした、エチレン・プロピレンラン
ダム共重合体、90〜40重量%。[Scope of Claims] 1. An impact-resistant polyester composition prepared by blending and kneading the following components (A) and (B). (A) Component: Polyester, 100 parts by weight (B) Component: 5 to 50 parts by weight of a resin component consisting of the following components (B-1) Ethylene copolymer containing epoxide grafted with a nyl alkoxysilane compound, 10 -60% by weight (B-2), ethylene-propylene random copolymer grafted with a vinylalkoxysilane compound, 90-40% by weight.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28099185A JPS62141056A (en) | 1985-12-16 | 1985-12-16 | Impact-resistant polyester composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28099185A JPS62141056A (en) | 1985-12-16 | 1985-12-16 | Impact-resistant polyester composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62141056A JPS62141056A (en) | 1987-06-24 |
JPH0580508B2 true JPH0580508B2 (en) | 1993-11-09 |
Family
ID=17632734
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP28099185A Granted JPS62141056A (en) | 1985-12-16 | 1985-12-16 | Impact-resistant polyester composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62141056A (en) |
-
1985
- 1985-12-16 JP JP28099185A patent/JPS62141056A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS62141056A (en) | 1987-06-24 |
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