JPS6345708B2 - - Google Patents
Info
- Publication number
- JPS6345708B2 JPS6345708B2 JP5676681A JP5676681A JPS6345708B2 JP S6345708 B2 JPS6345708 B2 JP S6345708B2 JP 5676681 A JP5676681 A JP 5676681A JP 5676681 A JP5676681 A JP 5676681A JP S6345708 B2 JPS6345708 B2 JP S6345708B2
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- resin
- acid
- resin composition
- propanediol
- 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
Links
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- -1 poly2-methyl-1,3-propylene terephthalate Polymers 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 11
- 229920001225 polyester resin Polymers 0.000 claims description 9
- 239000004645 polyester resin Substances 0.000 claims description 9
- 229920000874 polytetramethylene terephthalate Polymers 0.000 claims 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 22
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003112 inhibitor Substances 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
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-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
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- OWFJMIVZYSDULZ-PXOLEDIWSA-N (4s,4ar,5s,5ar,6s,12ar)-4-(dimethylamino)-1,5,6,10,11,12a-hexahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O OWFJMIVZYSDULZ-PXOLEDIWSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- RCZPHVPIOWNERS-UHFFFAOYSA-N CCCO[Ti] Chemical compound CCCO[Ti] RCZPHVPIOWNERS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-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
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229920001887 crystalline plastic Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- GAJQCIFYLSXSEZ-UHFFFAOYSA-L tridecyl phosphate Chemical compound CCCCCCCCCCCCCOP([O-])([O-])=O GAJQCIFYLSXSEZ-UHFFFAOYSA-L 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は改質されたポリエステル樹脂組成物に
関する。
さらに詳しくは可撓性に優れ、且つ成形収縮の
少ない改良されたポリテトラメチレンテレフタレ
ート(以後PBTと記す)樹脂から実質的になる
ポリエステル樹脂組成物に関する。
PBT樹脂は結晶性の高い熱可塑性ポリエステ
ル樹脂であり、各種充填材,添加剤との親和性が
よい。それ故、ガラス繊維,マイカ,タルク,難
燃剤などが添加された強化PBT樹脂は、優れた
使用特性を発揮することから、電機・電子部品、
あるいは自動車部品などの工業的用途に広く用い
られている。すなわち、PBT樹脂は、高い機械
的強度,優れた耐久性,耐候性,耐薬品性,耐熱
性,寸法安定性および電気特性などを有する。ま
た、ポリエチレンテレフタレート樹脂に比べ結晶
化度が高く、しかも結晶化速度も速く、従つて冷
却固化速度も速く、その上流動性にも優れている
ために成型性が良い。かくの如きPBT樹脂は電
気・機械特性と加工特性がバランスした優れたエ
ンジニアリングプラスチエツクスである。
しかるに一方PBT樹脂は以下の如き欠点を有
する。すなわち
(1) 非晶性および難結晶性プラスチツクスに比較
して、当然のことながら寸法精度に劣り、特に
金型温度分布の影響を受けやすい。また成形収
縮率の肉厚依存性が大きく、冷却速度のバラツ
キと相まつて変形やヒケを生じやすい。この好
ましくない性質は、ガラス繊維などで強化され
た強化PBT樹脂において、繊維の配向性によ
る収縮異方性を助長し、成形物は変形を生じや
すくなり、いわゆるそりが発生する。
(2) 特に強化されていないPBT樹脂は、可撓性
に劣り、ノツチ感度が大きい、などの欠点を有
する。
これまで、これらの欠点を改善するためにテレ
フタル酸の一部を脂肪族ジカルボン酸に置き換え
ることによつて、あるいは他の樹脂をブレンドす
ることによつて結晶性を低下させ、成型時の収縮
による変形を小さくする方法とか、ガラス繊維よ
りは異方性の少ないガラスビーズ,タルク,マイ
カなどの充填剤を用いる方法などが知られている
が、まだユーザーの要求に充分適合するものが得
られていない。
本発明者らは上述の如き欠点が著しく改善され
た実質的にPBT樹脂からなるポリエステル樹脂
組成物について鋭意研究した結果、該ポリエステ
ル樹脂組成物にテレフタル酸と2―メチル―1,
3―プロパンジオールから構成されるポリ2―メ
チル―1,3―プロピレンテレフタレート成分を
適量含有させることによつて、実用に充分耐え得
る機械的・電気的強度を保持し、しかも収縮率が
大巾に小さくなり、且つ可撓性が著しく向上する
ことを見出し、本発明に到つたものである。
すなわち、本発明は、テレフタル酸とテトラメ
チレングリコールとから構成されるポリテトラメ
チレンテレフタレート樹脂に、テレフタル酸と2
―メチル―1,3―プロパンジオールから構成さ
れるポリ2―メチル―1,3―プロピレンテレフ
タレート成分を0.1〜25重量%含有せしめてなる
改質されたポリエステル樹脂組成物である。
本発明による改質されたポリエステル樹脂組成
物は以下の如き任意の方法により得ることが出来
る。
(1)実質的にPBT樹脂からなる樹脂組成物、(2)
実質的にテレフタル酸と2―メチル―1,3―プ
ロパンジオールを重合してなるポリエステル重合
体からなる樹脂組成物、(3)実質的にテレフタル酸
とテトラメチレングリコールおよび2―メチル―
1,3―プロパンジオールとを重合してなるポリ
エステル共重合体からなる樹脂組成物から、(3)の
単独としてあるいは(1)に(2)および/または(3)をブ
レンドすることによつて得られる。
ブレンド方法には溶剤に溶解して混合する化学
的方法、あるいはロール,バンバリーミキサー,
押出機,成形機などによつて混練する機械的方法
など、いずれも通常用いられている方法および装
置を使用することが出来る。
上述の重合体および共重合体ポリエステル(1),
(2),(3)の製造には従来からのポリエステル製造方
法をそのまま適用することが出来る。すなわち、
ジカルボン酸化合物とジオール化合物とを直接重
縮合反応させる直接法、あるいはジカルボン酸化
合物の低級アルキルエステル化合物とジオール化
合物とを反応させエステル交換反応によつて重縮
合反応させるエステル交換反応法のいずれによつ
ても製造され得る。
本発明のポリエステル樹脂組成物はテレフタル
酸と2―メチル―1,3―プロパンジオールおよ
びテトラメチレングリコールを出発原料として製
造されるが、その他共重合樹脂成分としてアジピ
ン酸,アゼライン酸,セバチン酸などの多価脂肪
族カルボン酸,イソフタル酸,トリメリツト酸,
ピロメリツト酸,2,6―ナフタリンジカルボン
酸などの多価芳香族カルボン酸,エチレングリコ
ール,プロピレングリコール,ネオペンチルグリ
コール,1,6―ヘキサンジオール,1,4―シ
クロヘキサンジオール,シクロヘキサンジメタノ
ール,トリメチロールプロパン,ペンタエリスリ
トールなどの多価アルコールを目的に応じて適当
量用いることが出来る。
本発明において使用される2―メチル―1,3
―プロパンジオールは、1個のメチル基を側鎖に
有し、化学構造上非対称をなすジオールであり、
これを成分とするポリエステル重合体の構造を不
規則化し、従つて非晶化するのに極めて有効な化
合物である。しかも2個の水酸基はいずれも第一
級であるために反応性に富み、テレフタル酸など
のカルボキシル基を有する化合物と容易に反応し
てエステル結合を形成する。
一例として、テレフタル酸とテトラメチレング
リコールおよび2―メチル―1,3―プロパンジ
オールとから得られる共重合体の製造方法につい
て示すと、ジメチルテレフタレート1モルと過剰
モル数すなわちその合計が1.1〜2.0倍モルのテト
ラメチレングリコールおよび2―メチル―1,3
―プロパンジオールの混合ジオールを通常のエス
テル化触媒を用い、窒素気流中下、常圧,約150
〜240℃の温度でエステル化交換反応を行ない、
メタノールを溜出させ、必要に応じて触媒、着色
防止剤などの添加剤を添加した後、5mmHg以下
の減圧下で約200〜280℃で重縮合させる。上記触
媒としては広範囲のものを用いうるが、テトラメ
トキシチタン,テトラエトキシチタン,テトラn
―プロポキシチタン,テトライソ―プロポキシチ
タン,テトラブトキシチタン等の如きチタン化合
物、ジ―n―ブチル―錫―ジラウレート,ジ―n
―ブチル―錫―オキサイド,ジブチル―錫―ジア
セテート等の如き錫化合物、マグネシウム,カル
シウム,亜鉛などの酢酸塩と酸化アンチモンまた
は上記チタン化合物との組合せなどを挙げること
が出来る。これらの触媒は生成した全共重合体に
対し、0.002〜0.8重量%の範囲で用いることが好
ましい。また着色防止剤としては亜リン酸,トリ
メチルフオスフエート,トリデシルフオスフエー
ト,トリフエニルフオスフエートなどの含燐化合
物が有効で、生成した全共重合体に対し、0.001
〜0.3重量%の範囲で用いることが好ましい。
本発明によつて得られる改質されたポリエステ
ル樹脂組成物中に含まれるテレフタル酸と2―メ
チル―1,3―プロパンジオールとから構成され
るポリ2―メチル―1,3―プロピレンテレフタ
レート成分は、テレフタル酸とテトラメチレング
リコールから構成されるポリテトラメチレンテレ
フタレート成分との合計量に対し0.1〜25重量%、
好ましくは1〜20重量%であり、0.1重量%より
少ないときは成形収縮および可撓性などの改善が
ほとんど期待出来ず、25重量%より多いときは樹
脂組成物の融点および結晶化度が低下し過ぎ、熱
的・機械的強度が実用に耐えない程に低下するの
で好ましくない。
以下、本発明を実施例により詳述するが、これ
により本発明が限定されるものでない。
尚、例中における「部」は重量部を意味する。
また表1,2中の測定値は以下の如き測定法によ
つて得られたものである。
(1) ポリ2―メチル―1,3―プロピレンテレフ
タレート成分の含量
表1に示される含量は、得られた樹脂のNMR
(核磁気共鳴)スペクトルを分析して求めた重量
%である。表2に示される含量は、各樹脂の混合
比から計算された重量%である。
(2) 固有粘度
オルトクロルフエノール中、25℃で測定した値
である。
(3) 融点
Perkin Elmer DSC―1B型示差走査熱量計に
よつて測定した。
(4) 相対結晶化度
上記示差走査熱量計によつて得られた樹脂の融
解に基づくピーク面積を測定し、PBT(表1の樹
脂1)のピーク面積を100%とした場合の値であ
る。
(5) 収縮率
一定量の樹脂をその融点より10℃高い温度で、
長さ150mm,幅25mm,厚み7mmの金型に加圧成形
し、温度23℃,相対湿度50%に状態調節された室
に48時間放置した後、成形された板の長さの変化
を百分率で示した。
(6) 曲げ弾性率
ASTM―D790に準じ、東洋ボールドウイン社
製テンシロンUTM―−500型万能試験機で測
定した。
合成例 1〜4
表1に示される仕込量で合成例1から合成例4
で示される4種類のポリエステル樹脂を以下の重
合方法で得た。
ジメチルテレフタレート194.0部,テトラメチ
レングリコールおよび2―メチル―1,3―プロ
パンジオールの各々単独または混合物135部をチ
タンテトラブトキシド触媒0.20部と共にダブルヘ
リカルリボン型撹拌翼を備えた反応容器に仕込
み、常圧,窒素気流中下180℃で1時間、ついで
230℃で2.5時間加熱し、生成するメタノールを理
論量の94%溜出せしめた。ついで反応混合物にト
リメチルオスフエート0.02部を添加した後、250
℃に昇温し、40分かけて系内の圧力を0.2mmHg
の減圧とし、その条件下で3.5時間重合を行なわ
しめた。
The present invention relates to modified polyester resin compositions. More specifically, the present invention relates to a polyester resin composition consisting essentially of an improved polytetramethylene terephthalate (hereinafter referred to as PBT) resin that has excellent flexibility and low mold shrinkage. PBT resin is a highly crystalline thermoplastic polyester resin and has good compatibility with various fillers and additives. Therefore, reinforced PBT resin to which glass fiber, mica, talc, flame retardants, etc. are added exhibits excellent usage characteristics and is used in electrical and electronic parts.
It is also widely used in industrial applications such as automobile parts. That is, PBT resin has high mechanical strength, excellent durability, weather resistance, chemical resistance, heat resistance, dimensional stability, electrical properties, etc. In addition, it has a higher degree of crystallinity than polyethylene terephthalate resin, has a faster crystallization rate, and therefore has a faster cooling solidification rate, and has excellent flowability, so it has good moldability. PBT resins like these are excellent engineering plastics with a good balance of electrical/mechanical properties and processability. However, PBT resin has the following drawbacks. That is, (1) compared to amorphous and difficult-to-crystalline plastics, they naturally have inferior dimensional accuracy and are particularly susceptible to mold temperature distribution. In addition, the molding shrinkage rate is highly dependent on the wall thickness, and together with the variation in cooling rate, deformation and sink marks are likely to occur. This undesirable property promotes shrinkage anisotropy due to fiber orientation in reinforced PBT resins reinforced with glass fibers, etc., making the molded product more likely to deform, causing so-called warpage. (2) PBT resin that is not particularly reinforced has drawbacks such as poor flexibility and high notch sensitivity. Until now, in order to improve these drawbacks, we have reduced crystallinity by replacing part of terephthalic acid with aliphatic dicarboxylic acid or by blending with other resins. There are known methods to reduce deformation and to use fillers such as glass beads, talc, and mica, which have less anisotropy than glass fibers, but none have yet been found that fully meet the needs of users. do not have. The present inventors conducted intensive research on a polyester resin composition consisting essentially of PBT resin, which has significantly improved the above-mentioned drawbacks, and found that terephthalic acid and 2-methyl-1,
By containing an appropriate amount of poly 2-methyl-1,3-propylene terephthalate composed of 3-propanediol, it maintains sufficient mechanical and electrical strength for practical use, and has a large shrinkage rate. The present invention was developed based on the discovery that the size of the material can be reduced and the flexibility can be significantly improved. That is, the present invention provides polytetramethylene terephthalate resin composed of terephthalic acid and tetramethylene glycol, and terephthalic acid and tetramethylene glycol.
This is a modified polyester resin composition containing 0.1 to 25% by weight of a poly2-methyl-1,3-propylene terephthalate component composed of -methyl-1,3-propanediol. The modified polyester resin composition according to the present invention can be obtained by any of the following methods. (1) A resin composition consisting essentially of PBT resin, (2)
(3) a resin composition consisting of a polyester polymer obtained by polymerizing substantially terephthalic acid and 2-methyl-1,3-propanediol; (3) a resin composition consisting essentially of terephthalic acid, tetramethylene glycol, and 2-methyl-
From a resin composition consisting of a polyester copolymer obtained by polymerizing with 1,3-propanediol, (3) can be used alone or by blending (2) and/or (3) with (1). can get. Blending methods include chemical methods of dissolving and mixing in a solvent, or using rolls, Banbury mixers,
Any of the commonly used methods and equipment can be used, such as a mechanical method of kneading using an extruder, a molding machine, or the like. Polymer and copolymer polyesters (1) as described above,
For the production of (2) and (3), conventional polyester production methods can be applied as is. That is,
Either a direct method in which a dicarboxylic acid compound and a diol compound are subjected to a direct polycondensation reaction, or a transesterification method in which a lower alkyl ester compound of a dicarboxylic acid compound and a diol compound are reacted and a polycondensation reaction is carried out by transesterification. It can also be manufactured. The polyester resin composition of the present invention is produced using terephthalic acid, 2-methyl-1,3-propanediol, and tetramethylene glycol as starting materials, but other copolymer resin components include adipic acid, azelaic acid, sebacic acid, etc. Polyvalent aliphatic carboxylic acid, isophthalic acid, trimellitic acid,
Polyvalent aromatic carboxylic acids such as pyromellitic acid, 2,6-naphthalene dicarboxylic acid, ethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, trimethylolpropane , polyhydric alcohol such as pentaerythritol can be used in an appropriate amount depending on the purpose. 2-methyl-1,3 used in the present invention
-Propanediol is a diol that has one methyl group in its side chain and has an asymmetric chemical structure.
It is an extremely effective compound for disordering the structure of polyester polymers containing this compound, thereby making them amorphous. Moreover, since both of the two hydroxyl groups are primary, they are highly reactive and easily react with compounds having a carboxyl group, such as terephthalic acid, to form an ester bond. As an example, a method for producing a copolymer obtained from terephthalic acid, tetramethylene glycol, and 2-methyl-1,3-propanediol is shown in which 1 mole of dimethyl terephthalate and the excess number of moles, that is, the total number of moles, are 1.1 to 2.0 times as large. moles of tetramethylene glycol and 2-methyl-1,3
- Mixed diol of propanediol using a normal esterification catalyst under nitrogen stream, normal pressure, about 150
The transesterification reaction is carried out at a temperature of ~240°C,
After distilling methanol and adding additives such as a catalyst and a color inhibitor as necessary, polycondensation is carried out at about 200 to 280°C under reduced pressure of 5 mmHg or less. A wide range of catalysts can be used as the above catalyst, including tetramethoxytitanium, tetraethoxytitanium, tetran
- Titanium compounds such as propoxytitanium, tetraiso-propoxytitanium, tetrabutoxytitanium, etc., di-n-butyl-tin-dilaurate, di-n
Examples include tin compounds such as -butyl-tin-oxide and dibutyl-tin-diacetate, combinations of acetates of magnesium, calcium, zinc, etc., and antimony oxide or the above-mentioned titanium compounds. These catalysts are preferably used in an amount of 0.002 to 0.8% by weight based on the total copolymer produced. In addition, phosphorus-containing compounds such as phosphorous acid, trimethyl phosphate, tridecyl phosphate, and triphenyl phosphate are effective as coloring inhibitors;
It is preferable to use it in a range of 0.3% by weight. The poly2-methyl-1,3-propylene terephthalate component composed of terephthalic acid and 2-methyl-1,3-propanediol contained in the modified polyester resin composition obtained by the present invention is , 0.1 to 25% by weight based on the total amount of the polytetramethylene terephthalate component composed of terephthalic acid and tetramethylene glycol,
Preferably it is 1 to 20% by weight; if it is less than 0.1% by weight, little improvement in molding shrinkage and flexibility can be expected, and if it is more than 25% by weight, the melting point and crystallinity of the resin composition will decrease. If the temperature is too high, the thermal and mechanical strength will decrease to such an extent that it cannot withstand practical use, which is not preferable. EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto. In addition, "parts" in the examples mean parts by weight.
The measured values in Tables 1 and 2 were obtained by the following measuring method. (1) Content of poly2-methyl-1,3-propylene terephthalate component The content shown in Table 1 is based on the NMR of the obtained resin.
It is the weight percent determined by analyzing the (nuclear magnetic resonance) spectrum. The contents shown in Table 2 are weight % calculated from the mixing ratio of each resin. (2) Intrinsic viscosity Value measured at 25°C in orthochlorophenol. (3) Melting point Measured using a Perkin Elmer DSC-1B differential scanning calorimeter. (4) Relative crystallinity This is the value obtained by measuring the peak area based on the melting of the resin obtained using the above differential scanning calorimeter, and taking the peak area of PBT (resin 1 in Table 1) as 100%. . (5) Shrinkage rate A certain amount of resin is heated to a temperature 10℃ higher than its melting point.
After pressure forming into a mold with a length of 150 mm, width of 25 mm, and thickness of 7 mm, and leaving it in a room conditioned at a temperature of 23°C and a relative humidity of 50% for 48 hours, the change in length of the formed plate was calculated as a percentage. It was shown in (6) Flexural modulus Measured according to ASTM-D790 using a Tensilon UTM-500 universal testing machine manufactured by Toyo Baldwin. Synthesis Examples 1 to 4 Synthesis Examples 1 to 4 using the amounts shown in Table 1
Four types of polyester resins shown in were obtained by the following polymerization method. 194.0 parts of dimethyl terephthalate, 135 parts of each of tetramethylene glycol and 2-methyl-1,3-propanediol alone or as a mixture were charged together with 0.20 parts of titanium tetrabutoxide catalyst into a reaction vessel equipped with a double helical ribbon stirring blade, and the mixture was heated to normal pressure. , 1 hour at 180℃ in a nitrogen stream, then
The mixture was heated at 230°C for 2.5 hours, and 94% of the theoretical amount of methanol produced was distilled off. Then, after adding 0.02 part of trimethyl osphate to the reaction mixture, 250
The temperature was raised to ℃, and the pressure in the system was reduced to 0.2 mmHg over 40 minutes.
The pressure was reduced to , and polymerization was carried out for 3.5 hours under these conditions.
【表】【table】
【表】
* 軟化温度、柳本商事(株)製ミクロ融点測定装置に
より測定
実施例1〜3および比較例1〜2
合成例1〜4までの4種類の樹脂を、表2に示
されるが如く、単独またはブラベンダーで良く混
練し、得られた樹脂について収縮率と曲げ弾性率
を測定した。[Table] * Softening temperature measured using a micro-melting point measuring device manufactured by Yanagimoto Shoji Co., Ltd. , alone or well kneaded with a Brabender, and the shrinkage rate and flexural modulus of the resulting resin were measured.
Claims (1)
し0.1〜25重量%のポリ2―メチル―1,3―プ
ロピレンテレフタレートを含有せしめてなる改質
されたポリエステル樹脂組成物。1. A modified polyester resin composition containing 0.1 to 25% by weight of poly2-methyl-1,3-propylene terephthalate based on polytetramethylene terephthalate resin.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5676681A JPS57170953A (en) | 1981-04-15 | 1981-04-15 | Modified polyester resin composition |
US06/360,493 US4381379A (en) | 1981-03-25 | 1982-03-22 | Polyester containing 2-methyl-1,3-propylene terephthalate units |
DE19823210845 DE3210845A1 (en) | 1981-03-25 | 1982-03-24 | 2-METHYL-1,3-PROPYLENE TEREPHTHALATE UNITS CONTAINING POLYESTER |
GB8208719A GB2095267B (en) | 1981-03-25 | 1982-03-25 | Polyester containing 2-methyl-1,3-propylene terephthalate units |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5676681A JPS57170953A (en) | 1981-04-15 | 1981-04-15 | Modified polyester resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57170953A JPS57170953A (en) | 1982-10-21 |
JPS6345708B2 true JPS6345708B2 (en) | 1988-09-12 |
Family
ID=13036609
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5676681A Granted JPS57170953A (en) | 1981-03-25 | 1981-04-15 | Modified polyester resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS57170953A (en) |
-
1981
- 1981-04-15 JP JP5676681A patent/JPS57170953A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS57170953A (en) | 1982-10-21 |
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