JPH07309934A - Elastic copolyester - Google Patents
Elastic copolyesterInfo
- Publication number
- JPH07309934A JPH07309934A JP12836694A JP12836694A JPH07309934A JP H07309934 A JPH07309934 A JP H07309934A JP 12836694 A JP12836694 A JP 12836694A JP 12836694 A JP12836694 A JP 12836694A JP H07309934 A JPH07309934 A JP H07309934A
- Authority
- JP
- Japan
- Prior art keywords
- elastic
- copolyester
- polyester
- soft segment
- hard segment
- 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.)
- Pending
Links
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 26
- 229920000728 polyester Polymers 0.000 claims abstract description 21
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 44
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 18
- 238000005886 esterification reaction Methods 0.000 description 15
- 239000007795 chemical reaction product Substances 0.000 description 12
- 238000011084 recovery Methods 0.000 description 8
- -1 polyethylene terephthalate Polymers 0.000 description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 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
- 238000005809 transesterification reaction Methods 0.000 description 4
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- XGIAHMUOCFHQTI-UHFFFAOYSA-N Cl.Cl.Cl.Cl.CC Chemical compound Cl.Cl.Cl.Cl.CC XGIAHMUOCFHQTI-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
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- LNGAGQAGYITKCW-UHFFFAOYSA-N dimethyl cyclohexane-1,4-dicarboxylate Chemical compound COC(=O)C1CCC(C(=O)OC)CC1 LNGAGQAGYITKCW-UHFFFAOYSA-N 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing 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
- 230000032050 esterification Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、衣料用繊維や成形品用
として用いられる優れた弾性回復性を有し、かつ耐熱
性、耐光性に優れた弾性コポリエステルに関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an elastic copolyester having excellent elastic recoverability, heat resistance and light resistance, which is used for clothing fibers and molded articles.
【０００２】[0002]
【従来の技術】従来、衣料用繊維や成形品用として用い
られる弾性樹脂として、広くポリウレタン弾性体が用い
られているが、耐熱性、耐薬品性、耐光性が劣るという
欠点があり、近年、ポリエチレンテレフタレートやポリ
ブチレンテレフタレートのような高結晶性のポリエステ
ルをハードセグメントとし、ポリ−ε−カプロラクトン
のような脂肪族ポリエステルをソフトセグメントとした
ポリエステル系弾性体が開発されている（特開平６− 7
3611号等) 。しかしながら、上記のようなポリエステル
系弾性体は、ポリウレタンと異なり、ハードセグメント
の結晶によって分子鎖をつなぎ止めているため、永久歪
が大きかったり、弾性性能が劣るという欠点がある。ま
た、脂環族ジカルボン酸成分と脂肪族ジオール成分とか
らなるポリエステルは、優れた弾性性能を示すが、ガラ
ス転移点が低いため、重合反応器から払い出してペレッ
ト化する際にカッティングが難しいといった製造上の問
題があり、実用化は困難であった。2. Description of the Related Art Conventionally, polyurethane elastic bodies have been widely used as elastic resins used for clothing fibers and molded articles, but they have the drawback of poor heat resistance, chemical resistance, and light resistance. A polyester-based elastic body has been developed in which a highly crystalline polyester such as polyethylene terephthalate or polybutylene terephthalate is used as a hard segment and an aliphatic polyester such as poly-ε-caprolactone is used as a soft segment (Japanese Patent Laid-Open No. 6-7.
No. 3611). However, unlike the polyurethane, the polyester-based elastic body as described above has drawbacks in that it has a large permanent strain and inferior elastic performance because the molecular chains are held together by the crystals of the hard segment. Further, a polyester composed of an alicyclic dicarboxylic acid component and an aliphatic diol component shows excellent elastic performance, but since the glass transition point is low, it is difficult to cut when it is discharged from the polymerization reactor and pelletized. Due to the above problems, practical application was difficult.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、耐熱性及び
耐光性が良好で、優れた弾性性能を有し、容易に製造す
ることのできる弾性コポリエステルを提供しようとする
ものである。DISCLOSURE OF THE INVENTION The present invention is intended to provide an elastic copolyester which has good heat resistance and light resistance, excellent elastic performance, and can be easily produced.
【０００４】[0004]
【課題を解決するための手段】本発明は、上記の課題を
解決するもので、その要旨は、ソフトセグメントがシク
ロヘキサンジカルボン酸成分と脂肪族ジオール成分とか
らなるポリエステル、ハードセグメントが融点 200〜27
0 ℃の結晶性ポリエステルからなり、ソフトセグメント
とハードセグメントの重量比が30／70〜80／20であり、
極限粘度が 0.5以上である弾性コポリエステルにある。Means for Solving the Problems The present invention is to solve the above-mentioned problems, and the gist thereof is that a soft segment is a polyester composed of a cyclohexanedicarboxylic acid component and an aliphatic diol component, and a hard segment is a melting point of 200 to 27.
Made of crystalline polyester at 0 ° C., the weight ratio of the soft segment and the hard segment is 30/70 to 80/20,
An elastic copolyester with an intrinsic viscosity of 0.5 or higher.
【０００５】以下、本発明について詳細に説明する。本
発明のコポリエステルにおけるソフトセグメントは、シ
クロヘキサンジカルボン酸成分と脂肪族ジオール成分と
からなるポリエステルで構成される。The present invention will be described in detail below. The soft segment in the copolyester of the present invention is composed of a polyester composed of a cyclohexanedicarboxylic acid component and an aliphatic diol component.
【０００６】シクロヘキサンジカルボン酸としては、具
体的には、1,４−シクロヘキサンジカルボン酸が好まし
く用いられるが、1,２−シクロヘキサンジカルボン酸を
用いることもできる。（これらは、ジメチルエステル等
のエステル形成性誘導体の形で用いてもよい。）As the cyclohexanedicarboxylic acid, specifically, 1,4-cyclohexanedicarboxylic acid is preferably used, but 1,2-cyclohexanedicarboxylic acid can also be used. (These may be used in the form of ester-forming derivatives such as dimethyl ester.)
【０００７】脂肪族ジオールとしては、エチレングリコ
ール、1,３−プロパンジオール、1,４−ブタンジオー
ル、1,５−ペンタンジオール、1,６−ヘキサンジオール
等が挙げられる。Examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and the like.
【０００８】次に、ハードセグメントは、融点が 200〜
270 ℃の結晶性ポリエステルで構成される。ハードセグ
メントを構成するポリエステルは、結晶性の良好なもの
であって、かつ、上記の融点を有するものであることが
必要である。この融点が低すぎると、成形（紡糸）時の
操業性が悪いとともに、成形物（繊維）を実用に供する
ことが困難である。一方、この融点が高すぎると重合反
応温度を高くすることが必要になり、ソフトセグメント
を構成するポリエステルが反応中に熱分解するために好
ましくない。Next, the hard segment has a melting point of 200 to
Composed of 270 ° C crystalline polyester. The polyester constituting the hard segment needs to have good crystallinity and have the above melting point. If the melting point is too low, the operability during molding (spinning) is poor and it is difficult to put the molded product (fiber) into practical use. On the other hand, if the melting point is too high, it is necessary to raise the polymerization reaction temperature, which is not preferable because the polyester constituting the soft segment is thermally decomposed during the reaction.
【０００９】ハードセグメントを構成するポリエステル
としては、ポリアルキレンテレフタレート、具体的に
は、ポリエチレンテレフタレート(PET) 及び／又はポリ
ブチレンテレフタレート(PBT) が好ましく用いられる。As the polyester constituting the hard segment, polyalkylene terephthalate, specifically, polyethylene terephthalate (PET) and / or polybutylene terephthalate (PBT) is preferably used.
【００１０】ソフトセグメントとハードセグメントとの
割合は、優れた弾性回復性と物性を保つためには、重量
比で30／70〜80／20の範囲にすることが必要である。ソ
フトセグメントの量が30重量％未満では弾性回復性が悪
くて、実用的でなく、一方、80重量％を超えるとガラス
転移点が低く、重合反応器から払い出してペレット化す
る際にカッティングが難しいという問題があり、好まし
くない。The ratio of the soft segment to the hard segment must be in the range of 30/70 to 80/20 in weight ratio in order to maintain excellent elastic recovery and physical properties. If the amount of the soft segment is less than 30% by weight, the elastic recovery is poor and not practical, while if it exceeds 80% by weight, the glass transition point is low, and it is difficult to cut when it is discharged from the polymerization reactor and pelletized. Is not preferable.
【００１１】本発明の弾性コポリエステルを得るには、
ソフトセグメントを構成するポリエステルのオリゴマー
とハードセグメントを構成するポリエステルのオリゴマ
ーとを混合して重縮合してブロックコポリエステルを形
成させればよい。To obtain the elastic copolyester of the present invention,
The polyester oligomer forming the soft segment and the polyester oligomer forming the hard segment may be mixed and polycondensed to form a block copolyester.
【００１２】次に、弾性コポリエステルの製造法の具体
例を示す。まず、エステル化反応缶に1,４−シクロヘキ
サンジカルボン酸とエチレングリコールとをモル比１／
1.3 〜１／３で仕込み、常圧下、 160〜240 ℃の温度で
1.5〜４時間エステル化反応を行い、ソフトセグメント
用オリゴマーを得る。あるいは、エステル交換反応缶に
1,４−シクロヘキサンジカルボン酸ジメチルとエチレン
グリコールとをモル比１／1.3 〜１／３で仕込み、エス
テル交換触媒を添加した後、常圧下、 160〜240 ℃まで
２〜４時間かけて徐々に昇温し、同時に生成するメタノ
ールを連続的に系外に留出させながらエステル交換反応
を行い、ソフトセグメント用オリゴマーを得る。一方、
テレフタル酸又はテレフタル酸ジメチルとエチレングリ
コール又は1,４−ブタンジオールとから常法によってエ
ステル化又はエステル交換反応によって、ハードセグメ
ント用オリゴマーを得る。次いで、ソフトセグメント用
オリゴマーとハードセグメント用オリゴマーとを所定の
割合で、重合反応缶に仕込み、重縮合触媒の存在下、 2
50〜280 ℃の温度で１〜５時間、0.01〜５トルの減圧下
で、所定の極限粘度のコポリエステルが得られるまで重
縮合反応を行う。Next, a specific example of the method for producing the elastic copolyester will be shown. First, 1,4-cyclohexanedicarboxylic acid and ethylene glycol were added to an esterification reaction vessel in a molar ratio of 1 /
Charged at 1.3 to 1/3, at atmospheric pressure at a temperature of 160 to 240 ℃
An esterification reaction is carried out for 1.5 to 4 hours to obtain an oligomer for soft segment. Or in the transesterification reactor
Dimethyl 1,4-cyclohexanedicarboxylate and ethylene glycol were charged at a molar ratio of 1 / 1.3 to 1/3, an ester exchange catalyst was added, and the mixture was gradually heated to 160 to 240 ° C over 2 to 4 hours under normal pressure. While warming, the transesterification reaction is carried out while continuously distilling out simultaneously produced methanol to the outside of the system to obtain an oligomer for a soft segment. on the other hand,
The oligomer for hard segment is obtained from terephthalic acid or dimethyl terephthalate and ethylene glycol or 1,4-butanediol by esterification or transesterification reaction by a conventional method. Then, the oligomer for the soft segment and the oligomer for the hard segment were charged into a polymerization reaction vessel at a predetermined ratio, and in the presence of a polycondensation catalyst, 2
The polycondensation reaction is carried out at a temperature of 50 to 280 ° C for 1 to 5 hours under a reduced pressure of 0.01 to 5 torr until a copolyester having a predetermined intrinsic viscosity is obtained.
【００１３】弾性コポリエステルが、優れた機械的特性
（強度、弾性回復性等）を保持するには、極限粘度 0.5
以上とする必要があり、好ましくは、極限粘度が 0.5〜
2.0、最適には 0.6〜1.3 である。In order to maintain excellent mechanical properties (strength, elastic recovery, etc.), the elastic copolyester has an intrinsic viscosity of 0.5.
It is necessary to be above, preferably, the intrinsic viscosity is 0.5 ~
2.0, optimally 0.6-1.3.
【００１４】本発明の弾性コポリエステルには、必要に
応じて、紫外線吸収剤や酸化防止剤等の各種安定剤、顔
料等を含有させることができる。If desired, the elastic copolyester of the present invention may contain various stabilizers such as ultraviolet absorbers and antioxidants, pigments and the like.
【００１５】本発明の弾性コポリエステルは、常温にお
ける機械的特性、耐熱性、耐光性に優れているのみなら
ず、弾性回復性が極めて優れている。The elastic copolyester of the present invention is excellent not only in mechanical properties, heat resistance and light resistance at room temperature, but also in elastic recovery.
【００１６】[0016]
【作用】本発明の弾性コポリエステルは、ソフトセグメ
ントのポリエステルのシクロヘキサン環の柔軟性と、ハ
ードセグメントのポリエステルの優れた結晶性及び高融
点により優れた弾性性能を示すと同時に、ペレット化時
のカッティング性も良好である。また、エーテル結合を
有しないため、優れた耐光性を示す。The elastic copolyester of the present invention exhibits excellent elastic performance due to the flexibility of the cyclohexane ring of the soft segment polyester and the excellent crystallinity and high melting point of the hard segment polyester, and at the same time, cutting at the time of pelletization. The property is also good. Further, since it has no ether bond, it exhibits excellent light resistance.
【００１７】[0017]
【実施例】次に、実施例によって本発明を具体的に説明
する。なお、ポリエステルの特性値は、次のようにして
測定した。 極限粘度〔η〕 フェノールと四塩化エタンとの等重量混合物を溶媒とし
て、温度20℃で測定した。 弾性回復率 オリエンティック社製テンシロン UTM-4-100型を用い、
試料長20mm、引張速度20mm／分で一定速度で 200％伸長
した後、同速度で元の長さまで戻し、再び、伸長した
時、応力が現れた時の長さを求め、次式によって弾性回
復率を求めた。 弾性回復率（％）＝〔（Ｅ0−Ｅ1）／Ｅ0〕×100 Ｅ0：最初に伸ばした長さ Ｅ1：再度、伸ばした時、応力が現れたときの長さ 耐光性 JIS L-0841-74 に準じて、染色耐光堅牢度の測定した。EXAMPLES Next, the present invention will be specifically described with reference to examples. The characteristic values of polyester were measured as follows. Intrinsic viscosity [η] It was measured at a temperature of 20 ° C using an equal weight mixture of phenol and ethane tetrachloride as a solvent. Elastic recovery rate Orientic Tensilon UTM-4-100 type was used.
Sample length 20 mm, tensile speed 20 mm / min, 200% elongation at a constant speed, then return to the original length at the same speed, and when elongation again, find the length at which stress appears, and recover the elasticity by the following formula I asked for the rate. Elastic recovery rate (%) = [(E 0 −E 1 ) / E 0 ] × 100 E 0 : First stretched length E 1 : Length at which stress appears when stretched again Light resistance JIS Dyeing light fastness was measured according to L-0841-74.
【００１８】実施例１ 反応器に、1,４−シクロヘキサンジカルボン酸（1,4-CH
DA）43.1kg及びエチレングリコール（EG) 31.1kgを仕込
み、酸成分１モルに対して酢酸亜鉛２×10-4モルを触媒
として加え、常圧下、200 ℃で生成した水を連続的に反
応系外へ留出させながら 2.5時間エステル化反応を行っ
た。得られたエステル化反応物40kgを重合反応缶に移送
し、テレフタル酸(TPA) ととEGとから得られたエステル
化反応物を10kg仕込み、酸成分１モルに対して三酸化ア
ンチモン２×10-4モルを触媒として加え、 280℃で 2.5
時間、 0.2トルの減圧下で重縮合反応を行い、ペレット
化して弾性コポリエステルを得た。得られた弾性コポリ
エステルは、〔η〕0.88であった。この弾性コポリエス
テルを減圧乾燥後、通常の溶融紡糸機を用い、吐出孔数
10の紡糸口金により紡糸温度 260℃、紡糸速度 600ｍ／
分、吐出量30ｇ／分で溶融紡糸し、平均450d／10ｆ未延
伸糸を得た。この未延伸糸を延伸速度 200ｍ／分、延伸
倍率 1.8で延伸した後、 120℃の熱板に接触させながら
50％の熱収縮処理を行った。得られた糸条は、強度 1.3
ｇ／ｄ、伸度 360％、弾性回復率83％であった。Example 1 A reactor was charged with 1,4-cyclohexanedicarboxylic acid (1,4-CH
43.1 kg of DA) and 31.1 kg of ethylene glycol (EG) were charged, and 2 × 10 −4 mol of zinc acetate was added as a catalyst to 1 mol of the acid component, and water produced at 200 ° C. under normal pressure was continuously reacted. The esterification reaction was performed for 2.5 hours while distilling out. 40 kg of the obtained esterification reaction product was transferred to a polymerization reaction vessel, 10 kg of the esterification reaction product obtained from terephthalic acid (TPA) and EG was charged, and 2 × 10 parts of antimony trioxide was added to 1 mol of the acid component. Add -4 mol as a catalyst and add 2.5 at 280 ° C.
The polycondensation reaction was performed under a reduced pressure of 0.2 torr for a period of time and pelletized to obtain an elastic copolyester. The obtained elastic copolyester was [η] 0.88. After drying this elastic copolyester under reduced pressure, use a normal melt spinning machine and
Spinning temperature 260 ℃, spinning speed 600m / with 10 spinnerets
Melt-spun at a discharge rate of 30 g / min to obtain an average unstretched yarn of 450 d / 10 f. This undrawn yarn was drawn at a draw speed of 200 m / min and a draw ratio of 1.8, and then while contacting a hot plate at 120 ° C.
A heat shrinkage treatment of 50% was performed. The yarn obtained has a strength of 1.3.
It was g / d, the elongation was 360%, and the elastic recovery rate was 83%.
【００１９】実施例２〜４ 1,4-CHDAとEGとからのエステル化反応物と TPAとEGとか
らのエステル化反応物の割合（ソフトセグメント／ハー
ドセグメント比）を表１のように変更した以外は、実施
例１と同様に実施した。Examples 2 to 4 The ratio (soft segment / hard segment ratio) of the esterification reaction product from 1,4-CHDA and EG and the esterification reaction product from TPA and EG was changed as shown in Table 1. The same procedure as in Example 1 was carried out except that the above was carried out.
【００２０】実施例５〜７ EGに代えて表１に示す脂肪族ジオールを使用した以外
は、実施例１と同様に実施した。Examples 5 to 7 The procedure of Example 1 was repeated, except that the aliphatic diols shown in Table 1 were used instead of EG.
【００２１】実施例８ 1,4-CHDAに代えて1,２−シクロヘキサンジカルボン酸
（1,2-CHDA）を使用した以外は、実施例１と同様に実施
した。Example 8 The procedure of Example 1 was repeated, except that 1,2-cyclohexanedicarboxylic acid (1,2-CHDA) was used instead of 1,4-CHDA.
【００２２】実施例９ TPAとEGとからのエステル化反応物に代えて TPAと1,４
−ブタンジオール（1,4-BD）とからのエステル化反応物
を使用した以外は、実施例１と同様に実施した。Example 9 TPA and 1,4 instead of the esterification reaction product from TPA and EG
Example 1 was repeated except that the esterification reaction product from butanediol (1,4-BD) was used.
【００２３】実施例10〜11 1,4-CHDAとEGとからのエステル化反応物と TPAと1,4-BD
とからのエステル化反応物の割合を表１のように変更し
た以外は、実施例６と同様に実施した。Examples 10 to 11 Esterification reaction product from 1,4-CHDA and EG, TPA and 1,4-BD
Example 6 was carried out in the same manner as in Example 6 except that the ratio of the esterification reaction products from and was changed as shown in Table 1.
【００２４】比較例１ 重縮合反応の時間を短縮した以外は、実施例１と同様に
してコポリエステルを得た。得られたコポリエステル
は、〔η〕0.42であり、樹脂の強度が低く実用に供し得
なかった。Comparative Example 1 A copolyester was obtained in the same manner as in Example 1 except that the polycondensation reaction time was shortened. The obtained copolyester was [η] 0.42, and the resin strength was too low to be put to practical use.
【００２５】比較例２〜３ 1,4-CHDAとEGとからのエステル化反応物と TPAとEGとか
らのエステル化反応物の割合を表１のように変更した以
外は、実施例１と同様に実施した。比較例２で得られた
コポリエステルは、ガラス転移点が低く、カッティング
ができないため実用に供し得なかった。また、比較例３
で得られたコポリエステルは、弾性回復性が劣ってい
た。Comparative Examples 2 to 3 Example 1 except that the ratio of the esterification reaction product from 1,4-CHDA and EG and the esterification reaction product from TPA and EG was changed as shown in Table 1. It carried out similarly. The copolyester obtained in Comparative Example 2 could not be put to practical use because it had a low glass transition point and could not be cut. In addition, Comparative Example 3
The copolyester obtained in 1. had inferior elastic recovery.
【００２６】比較例４ TPAとEGとからのエステル化反応物に代えてテレフタル
酸ジメチルと1,４−シクロヘキサンジメタノールとから
のエステル交換反応物を使用し、重縮合反応の温度を 2
90℃にした以外は、実施例１と同様にしてコポリエステ
ルを得た。得られたコポリエステルは、重縮合反応時の
温度が高いためにソフトセグメント成分が反応中に熱分
解し、共重合できなかった。Comparative Example 4 The transesterification reaction product of dimethyl terephthalate and 1,4-cyclohexanedimethanol was used in place of the esterification reaction product of TPA and EG, and the temperature of the polycondensation reaction was 2
A copolyester was obtained in the same manner as in Example 1 except that the temperature was changed to 90 ° C. The obtained copolyester could not be copolymerized because the soft segment component was thermally decomposed during the reaction because the temperature during the polycondensation reaction was high.
【００２７】上記の実施例及び比較例で得られたコポリ
エステルの特性値等をまとめて表１に示す。Table 1 collectively shows characteristic values and the like of the copolyesters obtained in the above Examples and Comparative Examples.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【発明の効果】本発明によれば、耐熱性及び耐光性が良
好で、優れた弾性性能を有する弾性ポリエステルを容易
に製造することができる。According to the present invention, an elastic polyester having good heat resistance and light resistance and excellent elastic performance can be easily produced.
Claims (1)
ルボン酸成分と脂肪族ジオール成分とからなるポリエス
テル、ハードセグメントが融点 200〜270 ℃の結晶性ポ
リエステルからなり、ソフトセグメントとハードセグメ
ントの重量比が30／70〜80／20であり、極限粘度が 0.5
以上である弾性コポリエステル。1. A soft segment is a polyester composed of a cyclohexanedicarboxylic acid component and an aliphatic diol component, a hard segment is a crystalline polyester having a melting point of 200 to 270 ° C., and a weight ratio of the soft segment to the hard segment is 30/70 to. 80/20 with an intrinsic viscosity of 0.5
The above is an elastic copolyester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12836694A JPH07309934A (en) | 1994-05-17 | 1994-05-17 | Elastic copolyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12836694A JPH07309934A (en) | 1994-05-17 | 1994-05-17 | Elastic copolyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07309934A true JPH07309934A (en) | 1995-11-28 |
Family
ID=14983051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12836694A Pending JPH07309934A (en) | 1994-05-17 | 1994-05-17 | Elastic copolyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07309934A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5730782B2 (en) * | 2009-12-04 | 2015-06-10 | 株式会社クラレ | Normal pressure dyeable polyester fiber and method for producing the same |
| WO2020045156A1 (en) * | 2018-08-28 | 2020-03-05 | 東レ株式会社 | Polyester composition |
| JP2020055949A (en) * | 2018-10-02 | 2020-04-09 | 東レ株式会社 | Method for producing polyester composition |
-
1994
- 1994-05-17 JP JP12836694A patent/JPH07309934A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5730782B2 (en) * | 2009-12-04 | 2015-06-10 | 株式会社クラレ | Normal pressure dyeable polyester fiber and method for producing the same |
| WO2020045156A1 (en) * | 2018-08-28 | 2020-03-05 | 東レ株式会社 | Polyester composition |
| JP2020055949A (en) * | 2018-10-02 | 2020-04-09 | 東レ株式会社 | Method for producing polyester composition |
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