JPH0548256B2 - - Google Patents
Info
- Publication number
- JPH0548256B2 JPH0548256B2 JP59178513A JP17851384A JPH0548256B2 JP H0548256 B2 JPH0548256 B2 JP H0548256B2 JP 59178513 A JP59178513 A JP 59178513A JP 17851384 A JP17851384 A JP 17851384A JP H0548256 B2 JPH0548256 B2 JP H0548256B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- weight
- parts
- group
- polyethylene terephthalate
- 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
- -1 polyethylene terephthalate Polymers 0.000 claims description 30
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 19
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000011342 resin composition Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 229920000620 organic polymer Polymers 0.000 claims description 5
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000004711 α-olefin Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 239000000178 monomer Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000002202 Polyethylene glycol Substances 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 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 6
- 238000000034 method Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229940048053 acrylate Drugs 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 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
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical group C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920008651 Crystalline Polyethylene terephthalate Polymers 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 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
- 230000006866 deterioration Effects 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- 239000012778 molding material 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
- 229910052757 nitrogen Inorganic materials 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
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
(産業上の利用分野)
本発明は射出成形用途において有用な結晶化速
度の速い結晶性ポリエチレンテレフタレート樹脂
組成物に関する。
ポリエチレンテレフタレートはその優れた性質
を生かし繊維、フイルム、ボトル等の分野に広く
使用されているが、こと射出成形分野についてみ
ると本来極めて優れた成形材料となると可能性を
有しているにもかかわらず、それほど使用されて
いない。これはポリエチレンテレフタレートの低
温での結晶化速度が遅いため射出成形時に金型温
度を160℃以上に保持する必要があり、このよう
な高い金型温度では成形サイクルが著しく長くな
り生産上好ましくない事情による。成形サイクル
を短かくするため金型温度を100℃近くに設定す
ると結晶化がほとんど進行せず成形品の機械的性
質、寸法安定性、表面外観が極めて悪い。
(従来の技術)
このような欠点を改良すべく従来より種々の方
法が提案されている。
本発明者らは、先に一般式(―R1O)―oR2と−
COOMで表わされる基を含有する有機重合体を
ポリエチレンテレフタレートに配合することによ
り前述の欠点を大巾に改良する方法を提案した
(特願昭59−89549号)。しかしながら、この方法
において金型温度をより低温にすべく該有機重合
体の添加量を増加させると、ポリエチレンテレフ
タレート樹脂組成物の衝撃強度が低下するという
欠点を有している。
(発明が解決しようとする問題点)
そこで、本発明者らは該ポリエチレンテレフタ
レート樹脂組成物の衝撃強度を改良するべく更に
研究を進めた結果、この問題を解決した本発明の
樹脂組成物に到達した。
(問題点を解決するための手段)
すなわち本発明は、
(A) 成分;
ポリエチレンテレフタレート 100重量部
(B) 成分;
下記一般式(B−1)、(B−2)および(B
−3)で示される単位のランダム共重合体から
なる
有機重合体 1〜20重量部
〔式中、R1は炭素数2〜5のアルキレン基、
R2は炭素数1以上の脂肪族、脂環式、芳香族
またはそれらの組合せよりなる炭化水素基、
R3は水素またはメチル基、Xは水素またはア
ルキル基、nは1〜50の整数、Mはアルカリ金
属、p、q、rは各構成単位が重合体1分子当
りに含有される数値を表わし、pは5〜80、q
は1以上でかつq/p=10〜0.11となる数、r
はr/p+q+r=0〜0.5となる数である。〕
(C) 成分;
α−オレフインとα,β−不飽和カルボン酸
とからなり、上記カルボン酸の少なくとも一部
がアルカリ金属塩であるイオン性共重合体 1
〜20重量部
(D) 成分;
一般式R3O(―R5O)o――R4で表わされるポリア
ルキレングリコール化合物 0.5〜10重量部
(ただし、R3、R4はHまたは低級アルキル基、
R5は炭素数2〜5のアルキレン基、nは1〜
50の整数)
を混練してなるポリエチレンテレフタレート樹脂
組成物である。
次に本発明を詳細に説明する。本発明の(A)成分
として使用されるポリエチレンテレフタレートと
は、エチレンテレフタレートの繰返し単位を主体
とするポリエステルである。
一般にエチレングリコール、テレフタール酸を
用いて製造され、結晶性を損わない範囲で他の酸
成分、グリコール成分を共重合させても良い。酸
成分としてはイソフタル酸、ナフタレンジカルボ
ン酸、アジピン酸、セバシン酸およびシクロヘキ
サンジカルボン酸等のジカルボン酸、グリコール
成分としてはトリメチレングリコール、テトラメ
チレングリコール、ヘキサメチレングリコール、
ポリエチレングリコール、ポリプロピレングリコ
ール、ポリテトラメチレングリコール、ポリエチ
レングリコールとポリプロピレングリコールの共
重合体等を挙げる事が出来る。
一般に、酸成分およびグリコール成分の少なく
とも80モル%、好ましくは90モル%以上がそれぞ
れエチレングリコール、テレフタール酸であるも
のが用いられ、好ましくは少なくとも80モル%以
上、さらに好ましくは90モル%以上のエチレンテ
レフタレート繰返し単位を含むポリエチレンテレ
フタレートが用いられる。
この(A)成分のポリエチレンテレフタレートは、
フエノールとテトラクロルエタンの1:1重量比
混合溶媒中で30℃で測定した固有粘度が0.3以上、
好ましくは0.5以上のもので、溶融重縮合反応、
またはこれと固相重合反応の組合された方法で製
造される。
(B)成分は、一般式(―R1O)o――R2、−COOMで示
される基を併せ有する有機共重合体である。ここ
でR1は炭素数2〜5のアルキレン基、具体的に
はエチレン基、トリメチレン基、テトラメチレン
基、ペンタメチレン基である。R2としては、炭
素数1以上の脂肪族、脂環式、芳香族またはそれ
らの組合せよりなる炭化水素基で、具体的にはメ
チル基、エチル基、プロピル基、グリシリル基、
フエニル基等である。また、Mはアルカリ金属で
あり、具体的にはナトリウム、カリウム等であ
る。
nは1〜50の好ましくは2〜30の整数である。
(B)成分は、一般式(B−1)で示される基を有
する不飽和単量体と、一般式(B−2)で示され
る不飽和単量体、場合によつてはこれ等不飽和単
量体と共重合性を有する一般式(B−3)で示さ
れる不飽和単量体とを共重合することによつて得
ることができる。
かかる単量体を具体的に挙げれば、一般式(B
−1)としては、ポリエチレングリコールモノメ
チルエーテルメタクリレート、ポリプロピレング
リコールモノメチルエーテルメタクリレート、ポ
リエチレングリコールモノエチルエーテルアクリ
レート等の(ポリ)アルキレングリコールモノア
ルキルエーテル(メタ)アクリレート類やフエノ
キシポリアルキレングリコール(メタ)アクリレ
ートである。
一般式(B−2)としては、メタクリル酸ナト
リウム、メタクリル酸カリウム、アクリル酸ナト
リウム等である。また、これ等の単量体と共重性
を有する一般式(B−3)としては、例えばアク
リル酸、メタクリル酸、アクリル酸アルキルエス
テル類、メタクリル酸アルキルエステル類であ
る。
一般式(B−1)を有する不飽和単量体と一般
式(B−2)を有する不飽和単量体のモル割合
は、(B−2)/(B/1)=10〜0.11、好ましく
は5〜0.33、特に好ましくは3.3〜1である。
また、これ等不飽和単量体と共重合される(B
−3)不飽和単量体は、全単量体中のモル%で表
示して0〜50%、好ましくは1〜20%添加するこ
とが出来る。
かかる(B)成分の有機共重合体は重合性能に応
じ、無触媒熱重合、ラジカル重合、カチオン重
合、アニオン重合、配位重合等適宜選択する方法
で重合される。
(B)成分の重合体は、一般式(B−1)で示され
る(ポリ)アルキレングリコールのモノエーテル
誘導体鎖を5〜80含有し、一般式(B−2)で示
されるカルボン酸塩基を1以上、好ましくは5以
上、特に好ましくは10〜100含有したものが用い
られる。
(B)成分の配合量は、ポリエチレンテレフタレー
ト100重量部に対し1〜20重量部であり、1重量
部に満たざる場合は低温金型での成形性が悪い。
また20重量部を超えると機械的性質や耐熱性の低
下を招き好ましくない。
本発明組成物の(C)成分は、α−オレフインα,
β−不飽和カルボン酸の共重合体をアルカリ金属
化合物と反応させて得られるイオン共重合体であ
る。特公昭39−6810号公報に記載の方法で製造す
る事が出来る。ここでα−オレフインとしてはエ
チレン、プロピレン、ブテン−1が用いられる
が、中でもエチレンが重合性が高く分子量の高い
ポリマーを与える点から好ましい。また、α,β
−不飽和カルボン酸としてはアクリル酸、メタク
リル酸、イタコン酸、マレイン酸が用いられる。
共重合体中のα−オレフイン成分は50モル%以
上、特に80モル%以上が好ましく、また、カルボ
ン酸の10モル%以上がナトリウムまたはカリウム
で中和されているものがよい。
(C)成分の配合量はポリエチレンテレフタレート
100重量部に対して1〜20重量部であり、1重量
部に満たざる場合は本発明の効果はなく、また20
重量部を超えると組成物の剛性が低下し好ましく
ない。
このようなイオン性共重合体として特に好まし
いものは、イー・アイ・デユポン社より商品名
「サーリン」として市販されている一連のポリマ
ーを挙げることができる。
本発明組成物の(D)成分は、一般式R3O(―R5O
)o――R4で表わされるポリアルキレングリコール化
合物である。ここでR3、R4はHまたは炭素数1
〜5の低級アルキル基、R5は炭素数2〜5のア
ルキレン基を表わす。また、nは1〜50の整数で
ある。具体的にはポリエチレングリコール、ポリ
プロピレングリコール、ポリテトラメチレングリ
コールおよびこれらのモノまたはジアルキルエー
テル(例えばモノメチルまたはジメチルエール、
モノエチルまたはジエチルエーテル、モノプロピ
ルまたはジプロピルエーテル、モノブチルまたは
ジブチルエーテル等)を挙げる事が出来る。本発
明組成物においては、成形時のポリエチレンテレ
フタレートの加水分解劣化の少ない点でポリアル
キレングリコール化合物は両末端がアルキルエー
テル化されたものが好ましい。nは5以上である
ことが好ましい。5末満では成形物の表面に成分
(D)がブリードアウトしやすい。(D)成分の配合量は
ポリエチレンテレフタレート100重量部に対して
0.5〜10重量部である。0.5に満たざる場合は本発
明の効果なく、また10を超える場合は成形品の表
面に成分(D)がブリードアウトしやすく好ましくな
い。
(作用効果)
本発明の組成物は比較的低温でも結晶化が速
く、100℃以下の金型温度でも均一に結晶化する。
得られた成形品は優れた表面光沢を持ち、高温に
しても添加物のブリードアウトがなく、且つ衝撃
強度などの機械的強度も良好で優れた射出成形用
材料となる。
本発明の組成物が優れた上記特性を有する理由
は明確でないが、(B)成分が(D)成分と相溶性が良
く、(D)成分の高温ブリードアウトを抑えているこ
と、(C)成分が(B)成分のポリエチレンテレフタレー
トへの相溶性を助け、結果として衝撃強度の低下
を抑えている等の相乗的作用によるものと考えら
れる。
本発明組成物は、従来使用されている核剤、結
晶化促進剤を併用することにより一層の効果を期
待する事が出来る。これら核剤、結晶化促進剤と
しては、例えばタルク、クレー、マイカ、シリカ
等の無機化合物、ステアリン酸、モンタン酸等の
有機カルボン酸のナトリウム、カリウム塩、フエ
ナントレン等の多核環状化合物が挙げられる。
本発明組成物にはガラス繊維、炭素繊維、ワラ
ストナイト、ウイスカー等の強化剤を加える事が
出来る。特にガラス繊維を全組成物中に5〜60重
量%加える事は機械的性質を著しく向上させ好ま
しい。更に難燃剤、紫外線吸収剤、酸化防止剤、
着色剤、耐加水分解剤を配合してもよく。更にま
た、他の熱可塑性樹脂、例えばポリブチレンテレ
フタレート、ポリエチレン、ポリプロピレン、ポ
リカーボネート、ポリアミド、ポリスチレン等を
配合してもよい。
本発明のポリエチレンテレフタレート樹脂組成
物は通常の方法で製造される。例えば、(A)、(B)、
(C)、(D)成分、必要に応じて前記核剤、結晶化促進
剤、強化剤、難燃剤、着色剤、酸化防止剤等を適
当な混合機中でドライブレンドし、押出機、ニー
ダー、バンバリーミキサー等で溶融混練し製造さ
れる。
(実施例)
次に本発明の実施例、比較例を述べるが、本発
明は以下の例によりなんら制約されるものでな
い。
ポリエチレングリコールモノメチルエーテルメ
タクリレート、メタクリル酸、メタクリル酸ナト
リウム共重合体(イ)の製造
ポリエチレングリコールモノメチルエーテルメ
タクリレート(分子量496)250g、メタクリル酸
250g、アゾビスイソブチロニトリル10g、エタ
ノール5、をガラス製反応器に仕込み、窒素気
流中で撹拌しつつ80℃で3時間重合した後、苛性
ソーダ79g(80%中和理論量)を加え部分中和
後、エタノールを蒸発させ本発明の有機共重合体
(イ)を得た。
共重合体(イ)1分子中に含まれる各構成単位の数
値は次のとおりであつた。
(B−1)=p=9
(B−2)=q=40
(B−3)=r=10
p+q+r=59
ポリエチレングリコール、メタクリル酸、メタ
クリル酸ナトリウム共重合体(ロ)の製造
共重合体(イ)の製造においてアゾビスイソブチロ
ニトリルの使用量を100gとした他は共重合体(イ)
の製法に準じて共重合体(ロ)を得た。
共重合体(ロ)1分子中に含まれる各構成単位の数
値は次のとおりであつた。
(B−1)=p=2
(B−2)=q=2
(B−3)=r=1
p+q+r=5
実施例1〜7、比較例1〜20
ポリエチレンテレフタレート(クラレ社製、フ
エノール/テトラクロルエタン1対1重量混合溶
媒中、30℃の固有粘度0.68)の(A)成分と本発明に
よる配合成分(B)、(C)、(D)およびガラス繊維(旭フ
アイバーグラス社製CSO3 JA429)を第1表に示
す配合割合でドライブレンドした後、40mmφ、
L/D=28の単軸スクリユー押出機にて、280℃
で溶融混練した。得られたペレツトを130℃、10
時間熱風乾燥した後、日本製鋼社製射出成形機N
−100B型にて、樹脂温度280℃、射出圧力400
〜600Kg/cm2、金型温度90℃、冷却時間20秒、成
形サイクル40秒で成形した。
なお、結晶化促進効果は、各ペレツトを溶融後
氷水で急冷して作成した試料につき、パーキンエ
ルマー社製差動熱量計DSC型で60℃から290℃
まで、10℃/分の昇温速度で加熱した場合の発熱
ピーク温度(Tcc)と290℃より同一速度で降温
した場合の発熱ピーク温度(T290 c)により判断し
た。Tccが低い程、金型温度は低く出来、T290 Cが
高い程、成形サイクルは短かく出来る。アイゾツ
ト衝撃強度や曲げ剛性の測定は、各々ASTM D
−256、D−790に準拠した。
ブリードアウトの有無は、成形シートを180℃、
1日、ギヤーオーブン中に放置した後のシート表
面へのブリードアウト物の有無を目視した。ま
た、表面外観は成形シートが、目視にて均一で且
つ光沢があるかどうかにより判断した。
(発明の効果)
第1表に示した如く、(B)成分の有機重合体のみ
の配合では確かに結晶化は促進されるが衝撃強度
が著しく低下する(比較例12、13)。しかし、(C)、
(D)成分を適当な範囲に配合すると結晶化が促進さ
れると共に衝撃強度、剛性、ブリードアウト、表
面光沢の良好な組成物を得る事が出来る。
(Industrial Application Field) The present invention relates to a crystalline polyethylene terephthalate resin composition with a high crystallization rate useful in injection molding applications. Due to its excellent properties, polyethylene terephthalate is widely used in the fields of textiles, films, bottles, etc. However, in the field of injection molding, it has the potential to become an extremely excellent molding material. It's not used that much. This is because polyethylene terephthalate has a slow crystallization rate at low temperatures, so it is necessary to maintain the mold temperature at 160°C or higher during injection molding, and such high mold temperatures will significantly lengthen the molding cycle, which is unfavorable for production. by. If the mold temperature is set near 100°C to shorten the molding cycle, crystallization hardly progresses and the mechanical properties, dimensional stability, and surface appearance of the molded product are extremely poor. (Prior Art) Various methods have been proposed in the past to improve these drawbacks. The present inventors previously demonstrated that the general formula (-R 1 O) - o R 2 and -
A method was proposed to greatly improve the above-mentioned drawbacks by blending an organic polymer containing a group represented by COOM into polyethylene terephthalate (Japanese Patent Application No. 89549/1989). However, this method has the disadvantage that when the amount of the organic polymer added is increased in order to lower the mold temperature, the impact strength of the polyethylene terephthalate resin composition decreases. (Problem to be Solved by the Invention) Therefore, the present inventors conducted further research to improve the impact strength of the polyethylene terephthalate resin composition, and as a result, arrived at the resin composition of the present invention that solved this problem. did. (Means for Solving the Problems) That is, the present invention comprises (A) component; 100 parts by weight of polyethylene terephthalate (B) component;
-3) Consists of a random copolymer of units shown in Organic polymer 1 to 20 parts by weight [wherein R 1 is an alkylene group having 2 to 5 carbon atoms,
R 2 is an aliphatic, alicyclic, aromatic, or a combination thereof hydrocarbon group having 1 or more carbon atoms;
R 3 is hydrogen or a methyl group, X is hydrogen or an alkyl group, n is an integer from 1 to 50, M is an alkali metal, and p, q, and r represent the numerical values contained in each structural unit per molecule of the polymer. , p is 5 to 80, q
is a number greater than or equal to 1 and q/p=10 to 0.11, r
is a number such that r/p+q+r=0 to 0.5. ] (C) Component; Ionic copolymer consisting of α-olefin and α,β-unsaturated carboxylic acid, in which at least a portion of the carboxylic acid is an alkali metal salt 1
~20 parts by weight (D) Component; polyalkylene glycol compound represented by the general formula R 3 O (-R 5 O) o --R 4 0.5-10 parts by weight (R 3 and R 4 are H or lower alkyl basis,
R 5 is an alkylene group having 2 to 5 carbon atoms, and n is 1 to 5.
This is a polyethylene terephthalate resin composition obtained by kneading (an integer of 50). Next, the present invention will be explained in detail. The polyethylene terephthalate used as component (A) of the present invention is a polyester mainly composed of repeating units of ethylene terephthalate. Generally, it is produced using ethylene glycol and terephthalic acid, and other acid components and glycol components may be copolymerized within a range that does not impair crystallinity. Acid components include dicarboxylic acids such as isophthalic acid, naphthalene dicarboxylic acid, adipic acid, sebacic acid, and cyclohexanedicarboxylic acid; glycol components include trimethylene glycol, tetramethylene glycol, hexamethylene glycol,
Examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymers of polyethylene glycol and polypropylene glycol. Generally, at least 80 mol%, preferably 90 mol% or more of the acid component and glycol component are ethylene glycol and terephthalic acid, respectively, and preferably at least 80 mol% or more, more preferably 90 mol% or more of ethylene. Polyethylene terephthalate containing terephthalate repeat units is used. This (A) component polyethylene terephthalate is
Intrinsic viscosity measured at 30℃ in a 1:1 weight ratio mixed solvent of phenol and tetrachloroethane is 0.3 or more,
Preferably 0.5 or more, melt polycondensation reaction,
Alternatively, it can be produced by a method combining this and solid phase polymerization reaction. Component (B) is an organic copolymer having groups represented by the general formula (-R 1 O) o --R 2 and -COOM. Here, R 1 is an alkylene group having 2 to 5 carbon atoms, specifically an ethylene group, a trimethylene group, a tetramethylene group, or a pentamethylene group. R 2 is an aliphatic, alicyclic, aromatic, or a combination thereof hydrocarbon group having 1 or more carbon atoms, specifically a methyl group, ethyl group, propyl group, glycylyl group,
Such as phenyl group. Moreover, M is an alkali metal, specifically sodium, potassium, etc. n is an integer of 1 to 50, preferably 2 to 30. Component (B) is an unsaturated monomer having a group represented by general formula (B-1), an unsaturated monomer represented by general formula (B-2), and in some cases, these unsaturated monomers have a group represented by general formula (B-1). It can be obtained by copolymerizing a saturated monomer and an unsaturated monomer having copolymerizable general formula (B-3). Specific examples of such monomers include the general formula (B
-1) Examples include (poly)alkylene glycol monoalkyl ether (meth)acrylates such as polyethylene glycol monomethyl ether methacrylate, polypropylene glycol monomethyl ether methacrylate, polyethylene glycol monoethyl ether acrylate, and phenoxy polyalkylene glycol (meth)acrylate. It is. General formula (B-2) includes sodium methacrylate, potassium methacrylate, sodium acrylate, and the like. Further, examples of general formula (B-3) having copolymerizability with these monomers include acrylic acid, methacrylic acid, acrylic acid alkyl esters, and methacrylic acid alkyl esters. The molar ratio of the unsaturated monomer having the general formula (B-1) and the unsaturated monomer having the general formula (B-2) is (B-2)/(B/1)=10 to 0.11, Preferably it is 5-0.33, particularly preferably 3.3-1. It is also copolymerized with these unsaturated monomers (B
-3) The unsaturated monomer can be added in an amount of 0 to 50%, preferably 1 to 20%, expressed as mol% based on the total monomers. The organic copolymer of component (B) is polymerized by an appropriately selected method such as non-catalytic thermal polymerization, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization, etc., depending on the polymerization performance. The polymer of component (B) contains 5 to 80 monoether derivative chains of (poly)alkylene glycol represented by the general formula (B-1) and a carboxylic acid group represented by the general formula (B-2). Those containing 1 or more, preferably 5 or more, particularly preferably 10 to 100 are used. The blending amount of component (B) is 1 to 20 parts by weight per 100 parts by weight of polyethylene terephthalate, and if it is less than 1 part by weight, moldability in a low-temperature mold is poor.
Moreover, if it exceeds 20 parts by weight, mechanical properties and heat resistance will deteriorate, which is not preferable. Component (C) of the composition of the present invention is α-olefin α,
It is an ionic copolymer obtained by reacting a copolymer of β-unsaturated carboxylic acid with an alkali metal compound. It can be produced by the method described in Japanese Patent Publication No. 39-6810. Here, ethylene, propylene, and butene-1 are used as the α-olefin, and among them, ethylene is preferred because it has high polymerizability and provides a polymer with a high molecular weight. Also, α, β
- Acrylic acid, methacrylic acid, itaconic acid, and maleic acid are used as unsaturated carboxylic acids.
The α-olefin component in the copolymer is preferably 50 mol% or more, particularly 80 mol% or more, and preferably 10 mol% or more of the carboxylic acid is neutralized with sodium or potassium. The amount of component (C) is polyethylene terephthalate.
The amount is 1 to 20 parts by weight per 100 parts by weight, and if it is less than 1 part by weight, there is no effect of the present invention, and 20 parts by weight is less than 1 part by weight.
If the amount exceeds 1 part by weight, the rigidity of the composition decreases, which is not preferable. Particularly preferred as such ionic copolymers are a series of polymers commercially available from EI DuPont under the trade name "Surlyn". Component (D) of the composition of the present invention has the general formula R 3 O (-R 5 O
) o --- A polyalkylene glycol compound represented by R 4 . Here, R 3 and R 4 are H or carbon number 1
~5 lower alkyl group, R 5 represents an alkylene group having 2 to 5 carbon atoms. Moreover, n is an integer of 1 to 50. Specifically, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and their mono- or dialkyl ethers (e.g. monomethyl or dimethyl ale,
(monoethyl or diethyl ether, monopropyl or dipropyl ether, monobutyl or dibutyl ether, etc.). In the composition of the present invention, it is preferable that the polyalkylene glycol compound is alkyl etherified at both ends in view of less hydrolytic deterioration of polyethylene terephthalate during molding. It is preferable that n is 5 or more. At the end of 5th grade, components appear on the surface of the molded product.
(D) tends to bleed out. The amount of component (D) is based on 100 parts by weight of polyethylene terephthalate.
It is 0.5 to 10 parts by weight. If it is less than 0.5, the effect of the present invention is not achieved, and if it exceeds 10, component (D) tends to bleed out onto the surface of the molded product, which is not preferable. (Effects) The composition of the present invention crystallizes quickly even at relatively low temperatures, and uniformly crystallizes even at mold temperatures of 100° C. or lower.
The obtained molded product has excellent surface gloss, does not bleed out of additives even at high temperatures, and has good mechanical strength such as impact strength, making it an excellent material for injection molding. The reason why the composition of the present invention has the above-mentioned excellent properties is not clear, but the reason is that component (B) has good compatibility with component (D) and suppresses high-temperature bleed-out of component (D), and (C) This is thought to be due to a synergistic effect, such as the component helping the compatibility of component (B) with polyethylene terephthalate and, as a result, suppressing the drop in impact strength. The composition of the present invention can be expected to be more effective when used in combination with conventionally used nucleating agents and crystallization promoters. Examples of these nucleating agents and crystallization promoters include inorganic compounds such as talc, clay, mica, and silica, sodium and potassium salts of organic carboxylic acids such as stearic acid and montanic acid, and polynuclear cyclic compounds such as phenanthrene. Reinforcing agents such as glass fibers, carbon fibers, wollastonite, whiskers, etc. can be added to the compositions of the present invention. In particular, it is preferable to add glass fibers in an amount of 5 to 60% by weight to the total composition, as this significantly improves mechanical properties. Furthermore, flame retardants, ultraviolet absorbers, antioxidants,
A coloring agent and a hydrolysis-resistant agent may be added. Furthermore, other thermoplastic resins such as polybutylene terephthalate, polyethylene, polypropylene, polycarbonate, polyamide, polystyrene, etc. may be blended. The polyethylene terephthalate resin composition of the present invention is produced by a conventional method. For example, (A), (B),
Components (C) and (D), if necessary, the above-mentioned nucleating agent, crystallization promoter, reinforcing agent, flame retardant, coloring agent, antioxidant, etc. are dry blended in a suitable mixer, then transferred to an extruder or kneader. It is manufactured by melting and kneading in a Banbury mixer or the like. (Examples) Next, examples and comparative examples of the present invention will be described, but the present invention is not limited in any way by the following examples. Production of polyethylene glycol monomethyl ether methacrylate, methacrylic acid, sodium methacrylate copolymer (a) Polyethylene glycol monomethyl ether methacrylate (molecular weight 496) 250 g, methacrylic acid
250g of azobisisobutyronitrile, 10g of azobisisobutyronitrile, and 5% of ethanol were placed in a glass reactor, and after polymerization at 80°C for 3 hours while stirring in a nitrogen stream, 79g of caustic soda (theoretical amount of 80% neutralization) was added. After neutralization, ethanol is evaporated and the organic copolymer of the present invention
I got (a). The numerical values of each structural unit contained in one molecule of copolymer (a) were as follows. (B-1) = p = 9 (B-2) = q = 40 (B-3) = r = 10 p + q + r = 59 Production of polyethylene glycol, methacrylic acid, sodium methacrylate copolymer (b) Copolymer Copolymer (A) except that the amount of azobisisobutyronitrile used in the production of (A) was 100g.
A copolymer (b) was obtained according to the production method. The numerical values of each structural unit contained in one molecule of the copolymer (b) were as follows. (B-1) = p = 2 (B-2) = q = 2 (B-3) = r = 1 p + q + r = 5 Examples 1 to 7, Comparative Examples 1 to 20 Polyethylene terephthalate (manufactured by Kuraray Co., Ltd., phenol/ Component (A) (intrinsic viscosity 0.68 at 30°C) in a 1:1 weight mixed solvent of tetrachloroethane, blended components (B), (C), (D) according to the present invention, and glass fiber (CSO3 manufactured by Asahi Fiberglass Co., Ltd.) After dry blending JA429) in the proportions shown in Table 1,
280℃ using a single screw extruder with L/D=28
The mixture was melted and kneaded. The obtained pellets were heated at 130℃ for 10
After drying with hot air for an hour, the injection molding machine manufactured by Nippon Steel Corporation N
-100B type, resin temperature 280℃, injection pressure 400
Molding was carried out at ~600 Kg/cm 2 , mold temperature 90°C, cooling time 20 seconds, and molding cycle 40 seconds. The crystallization promotion effect was measured using a PerkinElmer differential calorimeter DSC model from 60℃ to 290℃ for samples prepared by melting each pellet and then rapidly cooling it with ice water.
The judgment was made based on the exothermic peak temperature (Tcc) when heating at a heating rate of 10°C/min and the exothermic peak temperature (T 290 c ) when lowering the temperature from 290°C at the same rate. The lower the Tcc, the lower the mold temperature, and the higher the T 290 C , the shorter the molding cycle. Izotsu impact strength and bending rigidity measurements are each performed using ASTM D
-256, compliant with D-790. To check for bleed-out, heat the molded sheet at 180°C.
After being left in a gear oven for one day, the presence or absence of bleed-out material on the sheet surface was visually observed. Moreover, the surface appearance was judged by whether the molded sheet was visually uniform and glossy. (Effects of the Invention) As shown in Table 1, when only the organic polymer of component (B) is blended, crystallization is certainly promoted, but the impact strength is significantly lowered (Comparative Examples 12 and 13). However, (C)
When component (D) is blended in an appropriate range, crystallization is promoted and a composition with good impact strength, rigidity, bleed-out, and surface gloss can be obtained.
【表】【table】
【表】
(D) DM:ポリエチレングリコールジメチルエー
テル(重量平均分子量〓1000)
[Table] (D) DM: Polyethylene glycol dimethyl ether (weight average molecular weight = 1000)
Claims (1)
−3)で示される単位のランダム共重合体から
なる 有機重合体 1〜20重量部 〔式中、R1は炭素数2〜5のアルキレン基、
R2は炭素数1以上の脂肪族、脂環式、芳香族
またはそれらの組合せよりなる炭化水素基、
R3は水素またはメチル基、Xは水素またはア
ルキル基、nは1〜50の整数、Mはアルカリ金
属、p、q、rは各構成単位が重合体1分子当
りに含有される数値を表わし、pは5〜80、q
は1以上でかつq/p=10〜0.11となる値、r
はr/p+q+r=0〜0.5となる値である。〕 (C) 成分; α−オレフインとα,β−不飽和カルボン酸
とからなり、上記カルボン酸の少くとも一部が
アルカリ金属塩であるイオン性共重合体
1〜20重量部 (D) 成分; 一般式R3O(―R5O)o――R4で表わされるポリア
ルキレングリコール化合物 0.5〜10重量部 (ただし、R3、R4はHまたは低級アルキル基、
R5は炭素数2〜5のアルキレン基、nは1〜
50の整数) を混練してなるポリエチレンテレフタレート樹脂
組成物。[Scope of Claims] 1 (A) Component; 100 parts by weight of polyethylene terephthalate (B) Component; General formulas (B-1), (B-2) and (B)
-3) Consists of a random copolymer of units shown in Organic polymer 1 to 20 parts by weight [wherein R 1 is an alkylene group having 2 to 5 carbon atoms,
R 2 is an aliphatic, alicyclic, aromatic, or a combination thereof hydrocarbon group having 1 or more carbon atoms;
R 3 is hydrogen or a methyl group, X is hydrogen or an alkyl group, n is an integer from 1 to 50, M is an alkali metal, and p, q, and r represent the numerical values contained in each structural unit per molecule of the polymer. , p is 5 to 80, q
is a value of 1 or more and q/p = 10 to 0.11, r
is a value such that r/p+q+r=0 to 0.5. ] Component (C): an ionic copolymer consisting of an α-olefin and an α,β-unsaturated carboxylic acid, at least a part of which is an alkali metal salt.
1 to 20 parts by weight (D) Component; polyalkylene glycol compound represented by the general formula R 3 O (-R 5 O) o --R 4 0.5 to 10 parts by weight (R 3 and R 4 are H or lower alkyl group,
R 5 is an alkylene group having 2 to 5 carbon atoms, and n is 1 to 5.
A polyethylene terephthalate resin composition made by kneading (an integer of 50).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17851384A JPS6157643A (en) | 1984-08-29 | 1984-08-29 | Polyethylene terephthalate resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17851384A JPS6157643A (en) | 1984-08-29 | 1984-08-29 | Polyethylene terephthalate resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6157643A JPS6157643A (en) | 1986-03-24 |
JPH0548256B2 true JPH0548256B2 (en) | 1993-07-21 |
Family
ID=16049784
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17851384A Granted JPS6157643A (en) | 1984-08-29 | 1984-08-29 | Polyethylene terephthalate resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6157643A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58198559A (en) * | 1982-05-15 | 1983-11-18 | Kanegafuchi Chem Ind Co Ltd | Flame-retardant modified polyester resin composition |
-
1984
- 1984-08-29 JP JP17851384A patent/JPS6157643A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58198559A (en) * | 1982-05-15 | 1983-11-18 | Kanegafuchi Chem Ind Co Ltd | Flame-retardant modified polyester resin composition |
Also Published As
Publication number | Publication date |
---|---|
JPS6157643A (en) | 1986-03-24 |
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