JPS6150093B2 - - Google Patents
Info
- Publication number
- JPS6150093B2 JPS6150093B2 JP53112380A JP11238078A JPS6150093B2 JP S6150093 B2 JPS6150093 B2 JP S6150093B2 JP 53112380 A JP53112380 A JP 53112380A JP 11238078 A JP11238078 A JP 11238078A JP S6150093 B2 JPS6150093 B2 JP S6150093B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- germanium
- added
- compounds
- present
- 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 44
- -1 tertiary amine compound Chemical class 0.000 claims description 43
- 150000002291 germanium compounds Chemical class 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 18
- 229920000728 polyester Polymers 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000006068 polycondensation reaction Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005886 esterification reaction Methods 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000002087 whitening effect Effects 0.000 description 5
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 4
- 238000000071 blow moulding Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910017464 nitrogen compound Inorganic materials 0.000 description 4
- 150000002830 nitrogen compounds Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- 229940119177 germanium dioxide Drugs 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XSMIOONHPKRREI-UHFFFAOYSA-N undecane-1,11-diol Chemical compound OCCCCCCCCCCCO XSMIOONHPKRREI-UHFFFAOYSA-N 0.000 description 2
- 238000007666 vacuum forming Methods 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N 1,5-Pentadiol Natural products OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- SLGGJMDAZSEJNG-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;terephthalic acid Chemical group OCCOCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 SLGGJMDAZSEJNG-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-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 compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- IHLDFUILQQSDCQ-UHFFFAOYSA-L C(C)(=O)[O-].[Ge+2].C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].[Ge+2].C(C)(=O)[O-] IHLDFUILQQSDCQ-UHFFFAOYSA-L 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- MRLQSGZHMHONNG-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Ge+3] Chemical compound P(=O)([O-])([O-])[O-].[Ge+3] MRLQSGZHMHONNG-UHFFFAOYSA-K 0.000 description 1
- DZKUVVFEQHCDSK-UHFFFAOYSA-N P([O-])([O-])[O-].[Ge+3] Chemical compound P([O-])([O-])[O-].[Ge+3] DZKUVVFEQHCDSK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- QFBYBEDCELVEAJ-UHFFFAOYSA-L [Ge+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 Chemical compound [Ge+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 QFBYBEDCELVEAJ-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GGHTWSNOKADVAG-UHFFFAOYSA-N butan-1-olate germanium(4+) Chemical compound [Ge+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] GGHTWSNOKADVAG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- CTCOPPBXAFHGRB-UHFFFAOYSA-N ethanolate;germanium(4+) Chemical compound [Ge+4].CC[O-].CC[O-].CC[O-].CC[O-] CTCOPPBXAFHGRB-UHFFFAOYSA-N 0.000 description 1
- CIENLGXGFYBTAO-UHFFFAOYSA-N ethene;germanium Chemical group [Ge].C=C CIENLGXGFYBTAO-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- IBENSVMKFVWLLF-UHFFFAOYSA-N germanium(4+) methanolate Chemical compound [Ge+4].[O-]C.[O-]C.[O-]C.[O-]C IBENSVMKFVWLLF-UHFFFAOYSA-N 0.000 description 1
- GGQZVHANTCDJCX-UHFFFAOYSA-N germanium;tetrahydrate Chemical compound O.O.O.O.[Ge] GGQZVHANTCDJCX-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002604 lanthanum compounds Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000008961 swelling Effects 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
- 150000003512 tertiary amines Chemical class 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、厚肉成形品においてもガラス様の優
れた透明性を有し、かつ加工特性、落下衝撃強度
の向上したポリエステルの製造方法に関するもの
である。
一般に線状飽和ポリエステル、特にポリエチレ
ンテレフタレートはその優れた機械的特性および
化学的特性のため、広く衣料用、産業用の繊維の
ほか、磁気テープ用、写真用、コンデンサー用な
どのフイルムとして使用されている。しかし、こ
のような有用な特性を有するポリエチレンテレフ
タレートも、射出成形、押出成形、中空成形、真
空成形用には従来活用されていなかつた。
これまで、ポリエチレンテレフタレートが繊
維、フイルム以外への用途展開が制限された理由
は、各種の要因があるが、他の樹脂に対してコ
スト高であつたこと、ガラスライクの無色透明
な成形品が得られなかつたこと、３mm以上の厚
肉品において、不透明化すること、不透明性を
軽減させるために、冷却条件を特殊化する必要が
あること、成形加工範囲が狭く、加工特性が劣
ること、未延伸品あるいは低延伸品の耐衝撃性
が劣ることなどの問題があつた。
一般に、ポリエチレン、ポリプロピレンからな
る成形品は不透明であり、内容物の透視を要求す
る用途には自ずと制限を受けている。またポリス
チレン、ポリメチルメタクリレートからなる成形
品は極めて透明性が優れているが、割れ易く、通
常の溶剤に膨潤、溶解する欠点がある。さらに、
ポリ塩化ビニルからなる成形品は透明性に優れて
いるが、使用する可塑剤や残存モノマーが人体衛
生上悪影響を及ぼす問題がある。また、ポリカー
ボネートは透明性耐衝撃性に優れているが、コス
ト高のため、用途に制限を受ける。
本発明者等は、ポリエチレンテレフタレートを
主体とする樹脂から、上述の技術的欠点を一挙に
解決可能な無色透明で加工特性、耐衝撃性の優れ
た成形品を得ることを目的として検討した結果、
本発明をなすに至つたものである。
すなわち、本発明は主たる成分としてテレフタ
ル酸とエチレングリコールのエステル化により得
られた生成物を重縮合せしめてポリエステルを製
造する際に、
() ポリエステルを構成する全酸成分に対し、
0.005〜0.2モル％のゲルマニウム化合物およ
び、280℃以下で揮散し得る第３級アミン化合
物または、第４級アミン化合物をゲルマニウム
化合物に対し、0.2〜2.0モル倍および
() 一般式HO−（CH2）o−OH（ｎ＝５〜12）で
示される化合物0.05〜15重量％（対生成ポリ
マ）を重縮合反応前の任意の時期に添加し、重
縮合反応せしめることを特徴とする透明性良好
なポリエステルの製造法である。
本発明の第１の特徴は、主としてテレフタル酸
とエチレングリコールとから直接エステル化させ
る方法を採用することにより、添加する触媒を最
小限にし、結晶核剤または、異物の発生剤になり
やすい物質を極力排除することにある。従来か
ら、ポリエチレンテレフタレートの製造法として
は、テレフタル酸のジエステル化合物とエチレン
グリコールとからエステル交換反応による方法が
多用されているが、エステル交換反応触媒として
金属化合物を添加することを必須としている。そ
のため、触媒適量の金属化合物の添加において
も、ポリマ中に触媒残渣として、金属化合物が残
存し、屈折率差により透明性を損なうこと、さら
に肉厚品において、不透明化をより促進するこ
と、異物が多量に発生する問題があつた。それ故
に本発明の特徴は、直接エステル化法を採用し、
金属化合物の添加を避けることにある。
本発明の第２の大きな特徴は、ゲルマニウム化
合物を重縮合触媒として使用することにある。ポ
リエチレンテレフタレートは、重合触媒の添加な
しに、固有粘度0.45以上に上昇させることは困難
であり、従来アンチモン化合物、ゲルマニウム化
合物、チタン化合物、ランタン化合物などを添加
させ、重合度を上昇させることはよく知られてい
る。しかし、アンチモン化合物は触媒量を多く必
要とし、ポリマが黒ずみ、肉厚品が不透明化しや
すい。また、チタン化合物は、黄色に着色しやす
い欠点がある。本発明の目的である無色透明品を
得るためゲルマニウム化合物を選択することが特
徴である。
さらに、第３の大きな特徴は、280℃以下で揮
発し得る第３級アミン化合物または、第４級アミ
ン化合物および
一般式HO−（CH2）o−OH、（ｎ＝５〜12）
で示される化合物を併用することにある。
従来直接エステル化法においてゲルマニウム化
合物を使用する方法は知られているが、次の欠点
があり、本発明の目標を達成することができなか
つた。
ゲルマニウム化合物は、水あるいはエチレン
グリコールに対する溶解性が劣り、ゲルマニウ
ム化合物が析出して異物になり、透明性を損な
う。
３mm以上の肉厚品では、不透明化する。
成形加工条件が狭く、加工特性が劣る。
本発明においては、第３級アミン化合物または
第４級アミン化合物および
一般式HO−（CH2）o−OH、（ｎ＝５〜12）
で示される化合物を併用することにより、上記問
題点を一挙に解決するものである。
従来、ゲルマニウム化合物の水あるいは、エチ
レングリコールに対する溶解性を著しく改良させ
ること、およびエステル化反応速度を促進するた
めに、各種の方法、各種の添加剤の添加が知られ
ている。しかし例えば、NaOH、KOH、Ca
（OH）2のようなアルカリ金属、アルカリ土類金属
化合物の添加では、ポリマ中に金属化合物が残渣
として残り、透明性、特に厚肉品の透明性を著し
く低下させる。本発明においては、ゲルマニウム
化合物の水あるいは、エチレングリコールに対す
る溶解性を著しく改良させるが重縮合完了時には
ポリマ中から飛散して残渣として残らないアミン
化合物を使用する。つまり、残渣がポリマ中に存
在しないことにより、異物による透明性の低下は
起こらないし、結晶化促進による厚肉品の不透明
化も軽減されるものである。
このために、本発明では、280℃以下で揮散し
得る第３級アミン化合物または、第４級アミン化
合物を使用することを特徴とする。
しかし、ゲルマニウム化合物と第３級アミン化
合物または、第４級アミン化合物の添加のみで
は、２〜３mm肉薄品でも不透明化する問題がある
と同時に、成形条件が狭い問題があつた。本発明
においては、これらの問題を一挙に解決するた
め、さらに一般式HO−（CH2）o−OH（ｎ＝５〜
12）で示される化合物を併用することにより特
に、厚肉成形品の透明性と耐衝撃性、加工特性を
同時に向上させるものである。また、第３級アミ
ン化合物と第４級アミン化合物はもちろん併用し
ても構わない。
本発明のポリエステル成形体を構成するポリエ
ステルはそのくりかえし単位がエチレンテレフタ
レート単位のものがあるが、副生によるジエチレ
ングリコールテレフタレート単位が含まれていて
もよい。
本発明方法において、重合触媒として使用する
ゲルマニウム化合物は、二酸化ゲルマニウム、水
酸化ゲルマニウム、ゲルマニウムテトラメトキシ
ド、ゲルマニウムテトラエトキシド、ゲルマニウ
ムテトラブトキシド、ゲルマニウムエチレングリ
コキシドなどのゲルマニウムアルコキシド化合
物、ゲルマニウムフエノレート、ゲルマニウムβ
−ナフトレートなどのゲルマニウムフエノキシド
化合物、リン酸ゲルマニウム、亜リン酸ゲルマニ
ウム、次亜リン酸ゲルマニウムなどのリン含有ゲ
ルマニウム化合物および酢酸ゲルマニウムなどが
好ましく使用される。使用するゲルマニウム化合
物の添加量がポリエステルを構成する全酸成分に
対して少なすぎる場合には重合度が上昇しない。
多すぎる場合には、ポリマの着色が大きくなるの
で、ゲルマニウム化合物の添加量は全酸成分に対
して、0.005〜0.2モル％であり、好ましくは、
0.01〜0.1モル％である。
本発明方法において、280℃以下で揮散し得る
第３級アミン化合物または、第４級アミン化合物
とは、トリメチルアミン、トリエチルアミン、ト
リプロピルアミン、トリブチルアミンなどの第３
級アミン化合物、水酸化テトラメチルアンモニウ
ム、水酸化テトラエチルアンモニウム、水酸化テ
トラプロピルアンモニウム、水酸化テトラブチル
アンモニウム、水酸化トリメチルベンジルアンモ
ニウムなどの第４級アンモニウム塩が好ましく使
用される。第３級アミンあるいは、第４級アミン
化合物においても分子量が大きくなると280℃以
下で揮散しなくなり、好ましくない。通常の場合
280℃以下の沸点を示すものが好ましく使用され
る。アミン化合物の添加量が少なすぎると、ゲル
マニウム化合物の溶解性が低下し、多すぎる場合
には、ポリマ中にアミン化合物が残存し、ポリマ
色調を悪化させる。使用するアミン化合物の添加
量は、ゲルマニウム化合物に対して0.2〜2.0モル
倍であり、好ましくは0.3〜1.0モル倍である。
本発明で使用する一般式
HO−（CH2）o−OH（但しｎ＝５〜12）
で表わされる化合物は例えば、１・５−ペンタジ
オール、１・６−ヘキサンジオール、１・７−ヘ
プタンジオール、１・８−オクタンジオール、
１・９−ノナンジオール、１・10−デカンジオー
ル、１・11−ウンデカンジオール、１・12−ドデ
カンジオールである。これらの化合物は、１種で
も２種以上混合して使用してもよい。
添加量が少なすぎると、本発明の特徴である厚
肉品の透明性、耐衝撃性、加工特性の向上効果が
期待できない。また、添加量が多すぎると、カツ
テイング時、乾燥時の融着が起こりやすいので、
添加量は生成ポリマに対し、0.05〜15重量％であ
り、好ましくは、0.1〜10重量％である。本発明
においては、これらグリコール化合物が共重合鎖
として、ポリマ中に含有される。
本発明において、酸成分及びグリコール成分か
らポリエステルを製造するには、従来公知の製造
方法のうちエチレングリコールとテレフタル酸を
直接縮合させて実質的にビス−（β−ヒドロキシ
エチル）−テレフタレートもしくは、その低重合
体を形成せしめ、これを減圧下250℃以上の温度
で重縮合させる方法である。直接重合法のうち、
ビス−（β−ヒドロキシエチル）−テレフタレート
もしくは、その低重合体を媒体として、これにテ
レフタル酸および、エチレングリコールを添加し
ていく方法が通常使用されるが、テレフタル酸と
エチレングリコールのスラリーを一度に、あるい
は連続に、あるいは遂次に添加させる方法がさら
に好ましく使用される。
本発明で用いられるゲルマニウム化合物触媒あ
るいは、アミン化合物、あるいはHO−（CH2）o−
OH（但しｎ＝５〜12）化合物の添加時期は通常
重縮合反応初期以前なら何時添加してもよい。た
だし、ゲルマニウム化合物は、アミン化合物で溶
解させる必要がある。また、エステル化反応を促
進させるために、エステル化反応開始前から、ゲ
ルマニウム化合物、アミン化合物を添加してもよ
い。
HO−（CH2）o−OH化合物はエチレングリコー
ルと混合添加してもよく、重合開始初期に添加し
てもよく、またゲルマニウム化合物、アミン化合
物と混合添加してもよい。
本発明方法でポリエステルを製造するに際し、
公知の安定剤、例えばリン酸、亜リン酸又はこれ
らの誘導体を併用して使用することができる。本
発明において、ゲルマニウム化合物とアミン化合
物のみを使用する場合には、厚肉品の成形におい
て、結晶化による白化が起こり、透明な成形品が
得られないが、HO−（CH2）o−OHを併用添加す
ることにより、透明な成形品が得られると共にさ
らに、耐衝撃性、成形加工性が向上する。
本発明の製造方法により得られるポリエステル
樹脂から、射出成形による透明な射出成形体、特
に、３mm厚み以上の肉厚射出成形体、あるいは押
出成形による透明な押出シート、特に、３mm厚み
以上の押出シート、あるいはパイプ成形による透
明な管状成形体、特に３mm厚み以上の管状成形体
が得られる特徴がある。さらに得られた射出成形
体、管状成形体は一軸あるいは二軸吹込み成形時
の成形加工性が優れ、透明で偏肉の少ない瓶状成
形体が得られる。また、得られた押出シートは、
真空成形、圧縮成形時加工性が優れ、透明で偏肉
の少ないトレイ状成形体が得られる。
また押出シートを一軸あるいは二軸に延伸加工
して、従来にない透明で厚肉のシートが得られ超
透明写真用フイルムなどに有用である。
本発明の効果をとりまとめると次のとおりであ
る。
ガラスライクの無色透明な成形品が得られ
る。
３mm以上の厚肉品においても透明な成形品が
得られるようになる。
金型温度を０〜40℃においても、透明な成形
品が得られる。
成形加工範囲が広くなり、加工特性が優れ
る。
成形品の耐衝撃性が向上する。
添加されるゲルマニウム化合物は、アミン化
合物で完全溶解させるので、異物はほとんど存
在しないのである。
以下に実施例を挙げて本発明を具体的に説明す
る。
なお、実施例中の各特性の測定法は次のとおり
である。
（ポリマの固有粘度）
Ｏ−クロルフエノールを溶媒として、25℃で測
定した値である。
（異物の観察）
ポリマを0.8mmにプレス成形後、3.0倍に同時二
軸延伸し、異物レベルを肉眼判定した。
（耐衝撃性）
瓶状成形物に水を充満し、2.3ｍの高さから落
下テストを行ない、破壊に至る落下回数を求め
た。
なお、実施例中の部は重量部を示す。
実施例 １〜10
テレフタル酸100部とエチレングリコール45部
とからなるスラリーを245℃に加熱したビス−（β
−ヒドロキシエチル）テレフタレート低縮合体
135部に２時間30分かけて連続添加した。さら
に、２時間加熱撹拌し留出水を除去し、エステル
化反応率98.0％のビス（β−ヒドロキシエチル）
テレフタレート低縮合物を得た。
一方、表１の実施例１〜10に示すように、酸成
分に対し、0.04モル％あるいは、0.06モル％のゲ
ルマニウム化合物および、酸成分に対して0.025
モル％、0.03モル％あるいは、0.04モル％の窒素
化合物を秤量し、ゲルマニウム化合物を窒素化合
物に溶解させた。さらに、表１の実施例に示すグ
リコール化合物を所定量秤量し、ゲルマニウム化
合物および窒素化合物と混合溶液とした。上記エ
ステル化反応終了したビス−（β−ヒドロキシエ
チル）−テレフタレート低縮合物に該混合溶液お
よび、リン酸トリメチルを0.03部を添加し、真空
下、280℃で３時間40分〜４時間かけて重縮合を
行ない、表１に示す固有粘度のポリマを得た。
次いで、該ポリマを170℃の真空乾燥機で３時
間乾燥し、3.5オンスの射出成形機（東芝機械KK
製IS−50型）により、成形温度290℃、射出圧力
40〜60Kg/cm金型温度25℃で、厚さ２mm、３mm、
４mmの射出成形板を作製した。実施例１〜10のい
ずれも白化はみられず無色透明な成形板が得られ
た。
同じ射出成形機で、外径24mm、長さ100mm壁厚
３mmの有底パリソンを成形した。
この有底パリソンを115℃のオーブン中で３分
間予備加熱を行ないキヤビテイの吹込金型へ移し
た。ついで、軸方向へブローピンを移動させて、
機械的に約2.5倍延伸した後、加圧空気を導入し
て、円周方向への延伸吹込成形を行ない、内容積
500c.c.で、胴部の壁厚0.3mmのビール瓶状成形品を
得た。
実施例１〜10のいずれも、射出成形性は良好で
あり、成形パリソンの白化は認められず、それに
続く縦延伸成形性、吹込み成形性も良好であり、
光沢透明性の優れた成形容器が得られた。また、
成形品には全く異物は認められなかつた。この瓶
状成形物に水を充満し、密栓後、2.3ｍの高さか
らコンクリート上に落下させたが、数回以上の落
下回数に耐えることができた。
比較実施例 １〜８
実施例１〜10と同様にして、エステル化反応完
了後に表１の比較実施例１〜８に示す化合物を添
加し、重縮合を行ないポリマを得た。
比較実施例１、２では、ゲルマニウム化合物を
添加しないか、添加しても量が少ない場合には、
４時間後にも重合度が上昇しなかつた。
比較実施例２、３では、二酸化ゲルマニウムを
溶解せず、粉末のまま添加した場合には、ポリマ
中に多量の異物が残存した。グリコール化合物を
添加しない比較実施例４では異物は無くなるが、
２mm厚の射出成形板も白化し、透明性に劣る欠点
がある。
比較実施例５、６において、窒素化合物を添加
しないか、添加しても少なすぎると、成形品に異
物が多発した。
比較実施例７において、グリコール化合物の量
が少ないと、肉厚成形品が白化し、透明性が劣
る。
比較実施例８に示すSb2O3触媒使用の場合に
は、厚物成形品で白化しやすく、黒味を帯び、色
調が悪い。
次に実施例１〜10と同様に壁厚３mmの有底パリ
ソンを成形し、延伸吹込成形をしたところ比較実
施例１、２は、重合度が低く、成形できなかつ
た。
比較実施例３、４、７、８は、成形品が得られ
るが、かすみがかかつたように、白化していた。
比較実施例３、５、６は異物が多数認められ
た。また落下衝撃性は比較実施例３〜８のいずれ
も劣る結果であつた。
The present invention relates to a method for producing polyester that has excellent glass-like transparency even in thick-walled molded products, and has improved processing characteristics and drop impact strength. Linear saturated polyester in general, and polyethylene terephthalate in particular, has excellent mechanical and chemical properties and is widely used as textiles for clothing and industrial use, as well as films for magnetic tape, photography, capacitors, etc. There is. However, polyethylene terephthalate, which has such useful properties, has not been utilized for injection molding, extrusion molding, blow molding, and vacuum forming. Up until now, polyethylene terephthalate has been limited in its use in applications other than fibers and films due to various factors, including its high cost compared to other resins and the lack of glass-like colorless and transparent molded products. For thick-walled products of 3 mm or more, it becomes opaque, it is necessary to use special cooling conditions to reduce opacity, the molding process range is narrow, and the processing characteristics are poor. There were problems such as poor impact resistance of unstretched products or low-stretched products. Generally, molded products made of polyethylene and polypropylene are opaque, which naturally limits their use in applications that require seeing through the contents. Although molded products made of polystyrene and polymethyl methacrylate have excellent transparency, they have the drawback of being easily broken and of swelling and dissolving in common solvents. moreover,
Molded products made of polyvinyl chloride have excellent transparency, but the plasticizers and residual monomers used have a negative impact on human health. Furthermore, although polycarbonate has excellent transparency and impact resistance, its use is limited due to its high cost. The present inventors conducted studies with the aim of obtaining a colorless and transparent molded product with excellent processability and impact resistance, which can solve the above-mentioned technical drawbacks all at once, from a resin mainly composed of polyethylene terephthalate.
This has led to the present invention. That is, in the present invention, when producing a polyester by polycondensing a product obtained by esterifying terephthalic acid and ethylene glycol as main components, () with respect to all acid components constituting the polyester,
0.005 to 0.2 mol % of a germanium compound and a tertiary amine compound or a quaternary amine compound that can be volatilized at 280°C or less to the germanium compound, and 0.2 to 2.0 mol % of the germanium compound and () general formula HO-(CH 2 ) Good transparency characterized by adding 0.05 to 15% by weight (based on the polymer produced) of a compound represented by o -OH (n = 5 to 12) at any time before the polycondensation reaction to cause the polycondensation reaction. This is a method for producing polyester. The first feature of the present invention is that by employing a method of directly esterifying terephthalic acid and ethylene glycol, the amount of catalyst to be added is minimized, and substances that tend to become crystal nucleating agents or foreign matter generators are eliminated. The goal is to eliminate it as much as possible. Conventionally, as a method for producing polyethylene terephthalate, a method using a transesterification reaction between a diester compound of terephthalic acid and ethylene glycol has been frequently used, but it is essential to add a metal compound as a transesterification reaction catalyst. Therefore, even when an appropriate amount of catalyst metal compound is added, the metal compound remains as catalyst residue in the polymer, impairing transparency due to the difference in refractive index, further promoting opacity in thick-walled products, and causing foreign matter. There was a problem where a large amount of Therefore, the feature of the present invention is that a direct esterification method is adopted,
The aim is to avoid the addition of metal compounds. The second major feature of the present invention is the use of germanium compounds as polycondensation catalysts. It is difficult to increase the intrinsic viscosity of polyethylene terephthalate to 0.45 or higher without adding a polymerization catalyst, and it is well known that antimony compounds, germanium compounds, titanium compounds, lanthanum compounds, etc. can be added to increase the degree of polymerization. It is being However, antimony compounds require a large amount of catalyst, which tends to darken the polymer and make thick-walled products opaque. Furthermore, titanium compounds have the disadvantage of being easily colored yellow. A feature of the present invention is that a germanium compound is selected in order to obtain a colorless and transparent product, which is the object of the present invention. Furthermore, the third major feature is a tertiary amine compound or a quaternary amine compound that can volatilize at temperatures below 280°C and a compound represented by the general formula HO-( CH2 ) o -OH, (n=5 to 12). The key is to use compounds that can be used in combination. Conventionally, a method of using germanium compounds in a direct esterification method is known, but it has the following drawbacks and cannot achieve the goal of the present invention. Germanium compounds have poor solubility in water or ethylene glycol, and germanium compounds precipitate and become foreign matter, impairing transparency. Products with a wall thickness of 3 mm or more will become opaque. The molding conditions are narrow and the processing characteristics are poor. In the present invention, the above problems can be solved by using together a tertiary amine compound or a quaternary amine compound and a compound represented by the general formula HO-( CH2 ) o -OH, (n=5 to 12). This is a one-shot solution. Hitherto, various methods and addition of various additives have been known to significantly improve the solubility of germanium compounds in water or ethylene glycol and to accelerate the esterification reaction rate. But for example, NaOH, KOH, Ca
When an alkali metal or alkaline earth metal compound such as (OH) 2 is added, the metal compound remains as a residue in the polymer, significantly reducing transparency, especially in thick-walled products. In the present invention, an amine compound is used that significantly improves the solubility of the germanium compound in water or ethylene glycol, but does not scatter from the polymer and remain as a residue upon completion of polycondensation. In other words, since no residue is present in the polymer, there is no reduction in transparency due to foreign matter, and the opacity of thick-walled products due to promotion of crystallization is also reduced. For this purpose, the present invention is characterized by using a tertiary amine compound or a quaternary amine compound that can volatilize at 280°C or lower. However, if only a germanium compound and a tertiary amine compound or a quaternary amine compound were added, there was a problem that even products with a thickness of 2 to 3 mm became opaque, and at the same time, the molding conditions were narrow. In the present invention, in order to solve these problems all at once, the general formula HO-(CH 2 ) o -OH (n=5 to
By using the compound shown in 12) in combination, the transparency, impact resistance, and processability of thick-walled molded products can be improved at the same time. Furthermore, it is of course possible to use a tertiary amine compound and a quaternary amine compound in combination. The polyester constituting the polyester molded article of the present invention may have a repeating unit of ethylene terephthalate, but it may also contain diethylene glycol terephthalate units as a by-product. In the method of the present invention, germanium compounds used as polymerization catalysts include germanium alkoxide compounds such as germanium dioxide, germanium hydroxide, germanium tetramethoxide, germanium tetraethoxide, germanium tetrabutoxide, germanium ethylene glycoxide, germanium phenolate, germanium β
- Germanium phenoxide compounds such as naphthlate, phosphorus-containing germanium compounds such as germanium phosphate, germanium phosphite, germanium hypophosphite, and germanium acetate are preferably used. If the amount of the germanium compound used is too small relative to the total acid components constituting the polyester, the degree of polymerization will not increase.
If the amount is too large, the coloring of the polymer will increase, so the amount of germanium compound added is 0.005 to 0.2 mol% based on the total acid components, and preferably,
It is 0.01-0.1 mol%. In the method of the present invention, tertiary amine compounds or quaternary amine compounds that can be volatilized at 280°C or lower refer to tertiary amine compounds such as trimethylamine, triethylamine, tripropylamine, and tributylamine.
Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide are preferably used. If the molecular weight of a tertiary amine or quaternary amine compound becomes too large, it will not volatilize at temperatures below 280°C, which is not preferable. Normal case
Those exhibiting a boiling point of 280°C or lower are preferably used. If the amount of the amine compound added is too small, the solubility of the germanium compound will decrease, and if it is too large, the amine compound will remain in the polymer, worsening the color tone of the polymer. The amount of the amine compound used is 0.2 to 2.0 times the amount of the germanium compound, preferably 0.3 to 1.0 times the amount of the germanium compound. Examples of the compound represented by the general formula HO-( CH2 ) o -OH (where n=5 to 12) used in the present invention include 1,5-pentadiol, 1,6-hexanediol, and 1,7-heptane. Diol, 1,8-octanediol,
These are 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol. These compounds may be used alone or in combination of two or more. If the amount added is too small, the effects of improving the transparency, impact resistance, and processing characteristics of thick-walled products, which are the characteristics of the present invention, cannot be expected. Also, if the amount added is too large, fusion may easily occur during cutting and drying.
The amount added is 0.05 to 15% by weight, preferably 0.1 to 10% by weight, based on the produced polymer. In the present invention, these glycol compounds are contained in the polymer as copolymer chains. In the present invention, in order to produce polyester from an acid component and a glycol component, ethylene glycol and terephthalic acid are directly condensed to obtain substantially bis-(β-hydroxyethyl)-terephthalate or its This is a method in which a low polymer is formed and then polycondensed under reduced pressure at a temperature of 250°C or higher. Among the direct polymerization methods,
Usually, a method is used in which terephthalic acid and ethylene glycol are added to bis-(β-hydroxyethyl)-terephthalate or its low polymer as a medium, but once a slurry of terephthalic acid and ethylene glycol is More preferably, a method is used in which it is added continuously, or sequentially. The germanium compound catalyst, amine compound, or HO−(CH 2 ) o − used in the present invention
The OH (n=5 to 12) compound may be added at any time before the initial stage of the polycondensation reaction. However, the germanium compound needs to be dissolved with an amine compound. Further, in order to promote the esterification reaction, a germanium compound or an amine compound may be added before the esterification reaction starts. The HO-( CH2 ) o -OH compound may be added as a mixture with ethylene glycol, may be added at the initial stage of polymerization initiation, or may be added as a mixture with a germanium compound or an amine compound. When producing polyester using the method of the present invention,
Known stabilizers such as phosphoric acid, phosphorous acid or derivatives thereof can be used in combination. In the present invention, when only a germanium compound and an amine compound are used, whitening occurs due to crystallization when molding a thick-walled product, and a transparent molded product cannot be obtained . By adding in combination, a transparent molded article can be obtained, and the impact resistance and molding processability are further improved. A transparent injection molded article, especially a thick injection molded article with a thickness of 3 mm or more, or a transparent extruded sheet, especially an extruded sheet with a thickness of 3 mm or more, made by extrusion molding from the polyester resin obtained by the production method of the present invention. Alternatively, a transparent tubular molded product, particularly a tubular molded product with a thickness of 3 mm or more, can be obtained by pipe forming. Furthermore, the obtained injection molded product and tubular molded product have excellent molding processability during uniaxial or biaxial blow molding, and a transparent bottle-shaped molded product with less uneven thickness can be obtained. In addition, the obtained extruded sheet is
It has excellent workability during vacuum forming and compression molding, and produces transparent tray-shaped molded products with less uneven thickness. Furthermore, by uniaxially or biaxially stretching the extruded sheet, a transparent and thick sheet that has never been seen before can be obtained, which is useful for ultra-transparent photographic films. The effects of the present invention are summarized as follows. A glass-like colorless and transparent molded product can be obtained. Transparent molded products can now be obtained even for thick-walled products of 3 mm or more. Transparent molded products can be obtained even at mold temperatures of 0 to 40°C. The molding process range is wide and the processing characteristics are excellent. Improves the impact resistance of molded products. Since the germanium compound added is completely dissolved in the amine compound, there are almost no foreign substances present. The present invention will be specifically described below with reference to Examples. In addition, the measurement method of each characteristic in an Example is as follows. (Intrinsic viscosity of polymer) This is a value measured at 25°C using O-chlorophenol as a solvent. (Observation of foreign matter) After press-molding the polymer to 0.8 mm, it was simultaneously biaxially stretched to 3.0 times, and the level of foreign matter was determined with the naked eye. (Impact resistance) A bottle-shaped molded product was filled with water and subjected to a drop test from a height of 2.3 m to determine the number of drops that would cause it to break. Note that parts in the examples indicate parts by weight. Examples 1 to 10 A slurry consisting of 100 parts of terephthalic acid and 45 parts of ethylene glycol was heated to 245°C.
-Hydroxyethyl)terephthalate low condensate
The mixture was continuously added to 135 parts over 2 hours and 30 minutes. Furthermore, by heating and stirring for 2 hours to remove distilled water, bis(β-hydroxyethyl) with an esterification reaction rate of 98.0% was produced.
A terephthalate low condensate was obtained. On the other hand, as shown in Examples 1 to 10 in Table 1, 0.04 mol% or 0.06 mol% of the germanium compound was added to the acid component, and 0.025 mol% to the acid component.
Mol%, 0.03 mol%, or 0.04 mol% of the nitrogen compound was weighed out, and the germanium compound was dissolved in the nitrogen compound. Furthermore, a predetermined amount of the glycol compound shown in the Examples in Table 1 was weighed out, and a mixed solution was prepared with the germanium compound and the nitrogen compound. The mixed solution and 0.03 part of trimethyl phosphate were added to the bis-(β-hydroxyethyl)-terephthalate low condensate after the esterification reaction was completed, and the mixture was heated at 280°C under vacuum for 3 hours and 40 minutes to 4 hours. Polycondensation was carried out to obtain a polymer having the inherent viscosity shown in Table 1. The polymer was then dried in a vacuum dryer at 170°C for 3 hours, and a 3.5 oz injection molding machine (Toshiba Machine KK
IS-50 type), molding temperature 290℃, injection pressure
40～60Kg/cm mold temperature 25℃, thickness 2mm, 3mm,
A 4 mm injection molded plate was produced. No whitening was observed in any of Examples 1 to 10, and colorless and transparent molded plates were obtained. A bottomed parison with an outer diameter of 24 mm, a length of 100 mm, and a wall thickness of 3 mm was molded using the same injection molding machine. This bottomed parison was preheated in an oven at 115° C. for 3 minutes and then transferred to a cavity blowing mold. Next, move the blow pin in the axial direction,
After mechanically stretching approximately 2.5 times, pressurized air is introduced and stretch blow molding is performed in the circumferential direction to reduce the internal volume.
A beer bottle-shaped molded product of 500 c.c. and a body wall thickness of 0.3 mm was obtained. In all of Examples 1 to 10, the injection moldability was good, no whitening of the molded parison was observed, and the subsequent longitudinal stretch moldability and blow moldability were also good.
A molded container with excellent gloss and transparency was obtained. Also,
No foreign matter was observed in the molded product. This bottle-shaped molded product was filled with water, sealed, and dropped onto concrete from a height of 2.3 meters, but it was able to withstand multiple drops. Comparative Examples 1 to 8 In the same manner as Examples 1 to 10, the compounds shown in Comparative Examples 1 to 8 in Table 1 were added after the esterification reaction was completed, and polycondensation was performed to obtain polymers. In Comparative Examples 1 and 2, if no germanium compound was added or if the amount was small even if it was added,
The degree of polymerization did not increase even after 4 hours. In Comparative Examples 2 and 3, when germanium dioxide was added as a powder without being dissolved, a large amount of foreign matter remained in the polymer. In Comparative Example 4 in which no glycol compound was added, there were no foreign substances, but
Injection molded plates with a thickness of 2 mm also have the disadvantage of whitening and poor transparency. In Comparative Examples 5 and 6, when no nitrogen compound was added, or when too little was added, foreign matter frequently appeared in the molded product. In Comparative Example 7, when the amount of the glycol compound is small, the thick molded product turns white and has poor transparency. In the case of using the Sb 2 O 3 catalyst shown in Comparative Example 8, thick molded products tend to whiten, have a blackish tinge, and have poor color tone. Next, a bottomed parison with a wall thickness of 3 mm was molded in the same manner as in Examples 1 to 10, and stretch blow molding was performed. Comparative Examples 1 and 2 had a low degree of polymerization and could not be molded. In Comparative Examples 3, 4, 7, and 8, molded products were obtained, but they were white, as if they were hazy. In Comparative Examples 3, 5, and 6, many foreign substances were observed. Furthermore, all of Comparative Examples 3 to 8 had poor drop impact resistance.
【表】
実施例 11
240℃に加熱したビス−（β−ヒドロキシエチ
ル）テレフタレート低縮合物100部に0.025モル％
の水酸化テトラエチルアンモニウムに溶解した
0.04モル％の二酸化ゲルマニウム溶液および、
１・５−ヘキサジオール６部を添加し５分間撹拌
混合した。さらにテレフタル酸86.5部および、エ
チレングリコール42部を添加し、４時間30分かけ
て、初期圧1.5気圧で、留出水を除去しエステル
化反応率96.2％とした。
これにリン酸ジメチルを0.025部添加し真空下
285℃で４時間10分重合し、固有粘度0.70のポリ
マを得た。射出成形テストしたところ、白化は認
められなかつた。
次に実施例１〜10と同様に延伸ブロー成形を行
ない、0.3mmの壁厚の無色透明な成形品を得た。
成形品には、異物は観察されなく、落下衝撃テ
ストで７回の落下回数に耐えた。[Table] Example 11 0.025 mol% in 100 parts of bis-(β-hydroxyethyl) terephthalate low condensate heated to 240°C
dissolved in tetraethylammonium hydroxide of
0.04 mol% germanium dioxide solution and
6 parts of 1,5-hexadiol was added and mixed with stirring for 5 minutes. Further, 86.5 parts of terephthalic acid and 42 parts of ethylene glycol were added, and distilled water was removed at an initial pressure of 1.5 atm over 4 hours and 30 minutes, resulting in an esterification reaction rate of 96.2%. Add 0.025 part of dimethyl phosphate to this and under vacuum
Polymerization was carried out at 285°C for 4 hours and 10 minutes to obtain a polymer with an intrinsic viscosity of 0.70. No whitening was observed during injection molding tests. Next, stretch blow molding was performed in the same manner as in Examples 1 to 10 to obtain a colorless and transparent molded product with a wall thickness of 0.3 mm. No foreign matter was observed in the molded product, and it withstood 7 drops in the drop impact test.
Claims (1)
リコールのエステル化により得られた生成物を重
縮合せしめて、ポリエステルを製造する際に () ポリエステルを構成する全酸成分に対し、
0.005〜0.2モル％のゲルマニウム化合物およ
び、280℃以下で揮散し得る第３級アミン化合
物または、第４級アミン化合物をゲルマニウム
化合物に対し、0.2〜2.0モル倍および () 一般式HO−（CH2）o−OH（ｎ＝５〜12）で
示される化合物0.05〜15重量％（対生成ポリ
マ）を重縮合反応前の任意の時期に添加し、重
縮合反応せしめることを特徴とする透明性良好
なポリエステルの製造法。[Claims] 1. When polyester is produced by polycondensing a product obtained by esterifying terephthalic acid and ethylene glycol as main components, () for all acid components constituting the polyester,
0.005 to 0.2 mol % of a germanium compound and a tertiary amine compound or a quaternary amine compound that can be volatilized at 280°C or less to the germanium compound, and 0.2 to 2.0 mol % of the germanium compound and () general formula HO-(CH 2 ) Good transparency characterized by adding 0.05 to 15% by weight (based on the polymer produced) of a compound represented by o -OH (n = 5 to 12) at any time before the polycondensation reaction to cause the polycondensation reaction. Polyester manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11238078A JPS5540704A (en) | 1978-09-14 | 1978-09-14 | Preparation of polyester having improved transparency |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11238078A JPS5540704A (en) | 1978-09-14 | 1978-09-14 | Preparation of polyester having improved transparency |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5540704A JPS5540704A (en) | 1980-03-22 |
| JPS6150093B2 true JPS6150093B2 (en) | 1986-11-01 |
Family
ID=14585220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11238078A Granted JPS5540704A (en) | 1978-09-14 | 1978-09-14 | Preparation of polyester having improved transparency |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5540704A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020194721A1 (en) | 2019-03-28 | 2020-10-01 | 信行 射場 | Angle adjustment stage device for dental technique |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5880251A (en) * | 1997-06-18 | 1999-03-09 | Cook Composites & Polymers Co. | Polyester synthesis using catalysts having low decomposition temperatures |
-
1978
- 1978-09-14 JP JP11238078A patent/JPS5540704A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020194721A1 (en) | 2019-03-28 | 2020-10-01 | 信行 射場 | Angle adjustment stage device for dental technique |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5540704A (en) | 1980-03-22 |
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