JP3354164B2 - Aliphatic polyester composition - Google Patents
Aliphatic polyester compositionInfo
- Publication number
- JP3354164B2 JP3354164B2 JP23022991A JP23022991A JP3354164B2 JP 3354164 B2 JP3354164 B2 JP 3354164B2 JP 23022991 A JP23022991 A JP 23022991A JP 23022991 A JP23022991 A JP 23022991A JP 3354164 B2 JP3354164 B2 JP 3354164B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- saturated polyester
- acid
- melting point
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、実用上十分な強度をも
たせることができ、且つ融点が高いフィルム等に利用可
能な脂肪族ポリエステル組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aliphatic polyester composition which has sufficient strength for practical use and which can be used for films having a high melting point.
【０００２】[0002]
【従来の技術】脂肪族飽和ポリエステルは融点が低く、
たとえ分子量が10,000以上の高分子領域にあった場合で
も、飽和芳香族構造を含むポリエステル、例えばポリエ
チレンテレフタレートのように実用上十分な機械的物性
を示さないため、今迄実用性がないものとされていた。
実際、フィルムを形成させても、製造されたフィルム
は、引裂き強度や引張強度が弱く、実用に耐えるもので
はなかった。これらの中でも、1,4−ブタンジオールを
グリコール成分とする脂肪族ポリエステルは、比較的強
度があり、アジピン酸、セバシン酸、ドデカン酸といっ
た脂肪族ジカルボン酸とエステル化すれば、十分な強度
はもたないものの、フィルム形成可能なポリエステルを
製造できることが見出された。とくに、二塩基酸として
コハク酸を用いて製造した脂肪族ポリエステルの場合に
は、融点が１１０〜１１５℃と高くなり、脂肪族ポリエ
ステルのほとんどが７０℃以下の融点しか示さないのに
比較して特異的である。2. Description of the Related Art Aliphatic saturated polyesters have a low melting point,
Even if the molecular weight is in the high molecular range of 10,000 or more, it does not show practically sufficient mechanical physical properties like a polyester containing a saturated aromatic structure, for example, polyethylene terephthalate. I was
In fact, even when a film was formed, the produced film had low tear strength and tensile strength and was not practical. Among these, aliphatic polyesters containing 1,4-butanediol as a glycol component have relatively high strength, and if they are esterified with an aliphatic dicarboxylic acid such as adipic acid, sebacic acid or dodecanoic acid, sufficient strength can be obtained. Nevertheless, it has been found that film-forming polyesters can be produced. In particular, in the case of an aliphatic polyester produced using succinic acid as a dibasic acid, the melting point is as high as 110 to 115 ° C, compared to the fact that most of the aliphatic polyesters show only a melting point of 70 ° C or less. Specific.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、1,4−
ブタンジオールとコハク酸とを用いて製造した脂肪族ポ
リエステルは、結晶性であり、通常のエステル化および
脱グリコール反応を行って数平均分子量を10,000〜15,0
00としても、ややもろい傾向が認められる。このもろさ
は、他のジカルボン酸、例えばアジピン酸、セバシン
酸、ドデカン酸等を併用することにより改良できるが、
カルボキシル基間のメチレン結合の数が増加するに従っ
て、フレキシビイリィティは増す傾向があるが、融点は
下降してしまう。本発明は、上記のような従来の課題を
解決し、実用上十分な強度を有し且つ融点も７０℃以上
と高い脂肪族ポリエステル組成物を提供することを目的
とするものである。[Problems to be solved by the invention] However, 1,4-
Aliphatic polyesters produced using butanediol and succinic acid are crystalline and undergo normal esterification and deglycolization reactions to give a number average molecular weight of 10,000 to 15,0
Even with a value of 00, a rather fragile tendency is observed. This fragility can be improved by using other dicarboxylic acids such as adipic acid, sebacic acid and dodecanoic acid in combination,
As the number of methylene bonds between the carboxyl groups increases, the flexibility increases, but the melting point decreases. An object of the present invention is to solve the above-mentioned conventional problems and to provide an aliphatic polyester composition having a practically sufficient strength and a melting point as high as 70 ° C. or higher.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、鋭意検討
の結果、上記のような従来の課題を解決することができ
た。 すなわち本発明は、（１） 1,4−ブタンジオールとコ
ハク酸とから合成された分子量10,000以上の飽和ポリエ
ステル５０〜９９重量部と、 （２） 1,4−ブタンジオールとアジピン酸とから合成
された分子量10,000以上の飽和ポリエステル５０〜１重
量部と、を熔融ブレンドしたことを特徴とする、脂肪族
ポリエステル組成物を提供するものである。As a result of intensive studies, the present inventors have been able to solve the above-mentioned conventional problems. That is, the present invention relates to (1) 50 to 99 parts by weight of a saturated polyester having a molecular weight of 10,000 or more synthesized from 1,4-butanediol and succinic acid, and (2) synthesized from 1,4-butanediol and adipic acid. And 50 to 1 part by weight of the obtained saturated polyester having a molecular weight of 10,000 or more.
【０００５】以下に、本発明をさらに詳細に説明する。
本発明は、1,4−ブタンジオールとコハク酸とから製造
された飽和ポリエステル（以下、コハク酸系飽和ポリエ
ステルという）および1,4−ブタンジオールとアジピン
酸とから製造された飽和ポリエステル（以下、アジピン
酸系飽和ポリエステルという）をブレンドすることによ
り、両者の飽和ポリエステルのそれぞれの欠点を補い合
うことができることを見出し、完成したものである。す
なわち、コハク酸系飽和ポリエステルは結晶性が良く、
融点も１１０〜１１５℃と高いが、やや固く、もろい傾
向を示す。これに反して、アジピン酸系飽和ポリエステ
ルは、融点が約６０℃と低いうえ、フィルムとしたとき
も軟らかすぎる傾向にある。この両者を、適切な割合で
混合することにより、コハク酸系飽和ポリエステルが有
する高い融点を維持しながら、しかもフレキシビイリィ
ティのある実用上十分な強度をもつ脂肪族ポリエステル
フィルムが形成可能となる。Hereinafter, the present invention will be described in more detail.
The present invention relates to a saturated polyester produced from 1,4-butanediol and succinic acid (hereinafter, referred to as a succinic acid-based saturated polyester) and a saturated polyester produced from 1,4-butanediol and adipic acid (hereinafter, referred to as “saturated polyester”). It has been found that blending of adipic acid-based saturated polyester) can make up for the disadvantages of both saturated polyesters. That is, succinic acid-based saturated polyester has good crystallinity,
Although the melting point is as high as 110 to 115 ° C, it tends to be slightly hard and brittle. On the contrary, the adipic acid-based saturated polyester has a low melting point of about 60 ° C. and tends to be too soft when formed into a film. By mixing the two at an appropriate ratio, it is possible to form an aliphatic polyester film having sufficient practicality and sufficient flexibility while maintaining the high melting point of the succinic acid-based saturated polyester. .
【０００６】コハク酸系飽和ポリエステルおよびアジピ
ン酸系飽和ポリエステルのそれぞれの製造は、公知技術
で行うことができる。コハク酸系飽和ポリエステルとア
ジピン酸系飽和ポリエステルの混合割合は、組成物の融
点が７０℃以上になるように両者を混合した１００重量
部に対し、コハク酸系飽和ポリエステルを５０〜９９重
量部、好ましくは６０重量部〜９０重量部である。５０
重量部未満では、融点が上昇しない。また、９９重量部
を超えると、混合の意味を失い好ましくない。混合は、
上記各成分の熔融状態で行われる。混合時に、両飽和ポ
リエステル成分のエステル交換が行われるような状態
は、製造される混合ポリマーの性質が一定しないので、
避けるのがよい。均一に混合した後、得られた脂肪族ポ
リエステル組成物を、極力短時間で冷却し、固化させる
のが好適である。上記のように製造した本発明の脂肪族
ポリエステル組成物は、実用上十分な強度およびフレキ
シビリティを有し、さらに融点も７０℃以上と高いので
各種用途に合わせて、各種の成形方法を利用できる。例
えば本発明の組成物を用いてフィルムを形成する場合
は、公知のフィルム形成方法を利用でき、とくに制限さ
れない。また、成形時に、その用途に応じて各種の成形
助剤を添加することができる。The production of each of the saturated succinic polyester and the saturated adipic polyester can be carried out by known techniques. The mixing ratio of the succinic acid-saturated polyester and the adipic acid-saturated polyester is 50 to 99 parts by weight of the succinic acid-based saturated polyester with respect to 100 parts by weight of the mixture so that the melting point of the composition becomes 70 ° C. or higher. Preferably it is 60 parts by weight to 90 parts by weight. 50
If the amount is less than parts by weight, the melting point does not increase. If it exceeds 99 parts by weight, the meaning of mixing is lost, which is not preferable. Mixing is
It is performed in a molten state of each of the above components. At the time of mixing, a state in which transesterification of both saturated polyester components is performed, since the properties of the mixed polymer to be produced are not constant,
Good to avoid. After uniformly mixing, it is preferable that the obtained aliphatic polyester composition is cooled and solidified as quickly as possible. The aliphatic polyester composition of the present invention produced as described above has practically sufficient strength and flexibility, and further has a high melting point of 70 ° C. or higher, so that various molding methods can be used according to various uses. . For example, when a film is formed using the composition of the present invention, a known film forming method can be used, and there is no particular limitation. At the time of molding, various molding auxiliaries can be added according to the use.
【０００７】[0007]
【実施例】以下、本発明を実施例によって説明する。飽和ポリエステル製造例 （コハク酸系飽和ポリエステル（Ａ）の製造）撹拌機、
分溜コンデンサー、温度計、ガス導入管を備えた１l容
セパラブルフラスコに、1,4−ブタンジオール２５０
ｇ、コハク酸２９５ｇを仕込み、窒素気流中１９０〜２
００℃でエステル化して酸価を７.４とした後、テトラ
イソプロピルチタネート０.６ｇを加え、最終的には０.
４Torrの減圧下、２００〜２１０℃で７時間脱グリコー
ル反応を行った。その結果、分子量14,600（Shodex GP
CSYSTEM-11、昭和電工社製を用いたＧＰＣ分析の結果）
のコハク酸系飽和ポリエステルが得られた。室温まで冷
却したコハク酸系飽和ポリエステル（Ａ）は、白色で、
ワックス状となって固化した。融点は１１２℃であっ
た。 （アジピン酸系飽和ポリエステル（Ｂ）の製造）上記の
ポリエステル（Ａ）の製造例と同様の設備を備えた１l
容セパラブルフラスコに、1,4−ブタンジオール２５０
ｇおよびアジピン酸３６５ｇを仕込み、窒素気流中１９
０〜２００℃でエステル化し、酸価を９.１とした後、
テトライソプロピルチタネート０.６ｇ加え、最終的に
は０.５Torrの減圧下、２００〜２１０℃で７時間脱グ
リコール反応を行った。その結果、分子量13,900のアジ
ピン酸系飽和ポリエステルが得られた。室温まで冷却し
たアジピン酸系飽和ポリエステル（Ｂ）は、やや黄色を
帯び、ワックス状となって固化した。融点は、約５８℃
であった。The present invention will be described below with reference to examples. Saturated polyester production example ( production of succinic acid-based saturated polyester (A)) stirrer,
In a 1 l separable flask equipped with a distillation condenser, a thermometer and a gas introduction tube, 1,4-butanediol 250
g, and 295 g of succinic acid in a nitrogen stream of 190 to 2 g.
After esterification at 00 ° C. to an acid value of 7.4, 0.6 g of tetraisopropyl titanate was added, and finally 0.1 g of isoisopropyl titanate was added.
The glycol removal reaction was performed at 200 to 210 ° C. for 7 hours under a reduced pressure of 4 Torr. As a result, molecular weight 14,600 (Shodex GP
GPC analysis results using CSYSTEM-11, Showa Denko)
Was obtained. The succinic acid-based saturated polyester (A) cooled to room temperature is white,
It became waxy and solidified. The melting point was 112 ° C. (Production of adipic acid-based saturated polyester (B)) 1 l equipped with the same equipment as the above-mentioned production example of polyester (A)
1,4-butanediol 250
g and adipic acid 365 g in a nitrogen stream.
After esterification at 0 to 200 ° C. and acid value of 9.1,
0.6 g of tetraisopropyl titanate was added, and finally a glycol removal reaction was performed at 200 to 210 ° C. for 7 hours under a reduced pressure of 0.5 Torr. As a result, an adipic acid-based saturated polyester having a molecular weight of 13,900 was obtained. The adipic acid-based saturated polyester (B) cooled to room temperature took on a slightly yellow color and became a wax and solidified. Melting point is about 58 ° C
Met.
【０００８】実施例１〜３および比較例１〜２ 表１に示した配合において、脂肪族ポリエステル組成物
を調製し、それぞれの融点を測定した。さらにこの組成
物からフィルムを形成し、延伸温度６０℃で、約３倍に
一軸延伸してフィルム形成性を試験した。その結果を表
１に示す。 Examples 1 to 3 and Comparative Examples 1 to 2 Aliphatic polyester compositions were prepared in the formulations shown in Table 1 and the melting points of the compositions were measured. Further, a film was formed from this composition and uniaxially stretched about three times at a stretching temperature of 60 ° C. to test the film forming property. Table 1 shows the results.
【０００９】[0009]
【表１】 [Table 1]
【００１０】[0010]
【発明の効果】本発明の脂肪族ポリエステル組成物は、
例えば実用上十分な強度をもつフィルムを形成すること
ができ、融点が従来のものよりも高いため、各種用途に
好適に用いることができる。The aliphatic polyester composition of the present invention comprises:
For example, a film having practically sufficient strength can be formed, and has a higher melting point than conventional ones, so that it can be suitably used for various applications.
Claims (1)
酸とから合成された分子量10,000以上の飽和ポリエステ
ル５０〜９９重量部と、 （２） 1,4−ブタンジオールとアジピン酸とから合成
された分子量10,000以上の飽和ポリエステル５０〜１重
量部と、を熔融ブレンドしたことを特徴とする、脂肪族
ポリエステル組成物。(1) 50 to 99 parts by weight of a saturated polyester having a molecular weight of 10,000 or more synthesized from 1,4-butanediol and succinic acid; and (2) synthesized from 1,4-butanediol and adipic acid. An aliphatic polyester composition obtained by melt-blending 50 to 1 part by weight of a saturated polyester having a molecular weight of 10,000 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23022991A JP3354164B2 (en) | 1991-09-10 | 1991-09-10 | Aliphatic polyester composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23022991A JP3354164B2 (en) | 1991-09-10 | 1991-09-10 | Aliphatic polyester composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0570673A JPH0570673A (en) | 1993-03-23 |
| JP3354164B2 true JP3354164B2 (en) | 2002-12-09 |
Family
ID=16904568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23022991A Expired - Lifetime JP3354164B2 (en) | 1991-09-10 | 1991-09-10 | Aliphatic polyester composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3354164B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0569143B1 (en) * | 1992-05-08 | 1998-03-18 | Showa Highpolymer Co., Ltd. | Polyester tying tape-like materials |
-
1991
- 1991-09-10 JP JP23022991A patent/JP3354164B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0570673A (en) | 1993-03-23 |
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