JPH10120890A - Polylactic resin composition for transparent molding - Google Patents
Polylactic resin composition for transparent moldingInfo
- Publication number
- JPH10120890A JPH10120890A JP29117396A JP29117396A JPH10120890A JP H10120890 A JPH10120890 A JP H10120890A JP 29117396 A JP29117396 A JP 29117396A JP 29117396 A JP29117396 A JP 29117396A JP H10120890 A JPH10120890 A JP H10120890A
- Authority
- JP
- Japan
- Prior art keywords
- caprolactone
- polylactic acid
- polylactate
- molding
- resin composition
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、生分解性、透明性
および靱性に優れた透明成形品用ポリ乳酸樹脂組成物に
関する。[0001] The present invention relates to a polylactic acid resin composition for transparent molded articles having excellent biodegradability, transparency and toughness.
【０００２】[0002]
【従来の技術】従来、汎用プラスチックは、安定性、耐
久性のあることが特徴であり、包装材、建築資材、自動
車、その他様々な分野に使用され、大量消費されてい
る。それらの使用後の廃棄処分方法としては、焼却処分
や、埋め立て処分が挙げられるが、ポリオレフィン樹脂
や塩化ビニール等の難分解性の樹脂は、焼却の際には高
発熱量による焼却炉の損傷や、有害性廃ガスの発生が問
題となり、一方、埋め立て処分の場合は、環境中にいつ
までも残留することによる環境汚染が問題になってい
る。2. Description of the Related Art Conventionally, general-purpose plastics are characterized by stability and durability, and are used in packaging materials, building materials, automobiles, and various other fields, and are consumed in large quantities. Disposal methods after their use include incineration and landfill disposal.However, hardly decomposable resins such as polyolefin resin and vinyl chloride can damage incinerators due to high calorific value during incineration. In addition, the generation of harmful waste gas becomes a problem, while the landfill disposal poses a problem of environmental pollution caused by remaining in the environment forever.
【０００３】そこで、天然素材系のバイオセルロースや
澱粉主体のプラスチック、低置換度セルロース系エステ
ル、微生物の合成するポリエステル、脂肪族のポリエス
テル樹脂等が生分解性のあるプラスチックとしてその用
途等が検討されている。[0003] In view of the above, the use of bio-cellulose or starch-based plastics of natural materials, low-substituted cellulose esters, polyesters synthesized by microorganisms, aliphatic polyester resins, etc. as biodegradable plastics has been studied. ing.
【０００４】ポリ乳酸は生体内で数ヶ月から１年で完全
に分解し、無害な水と炭酸ガスになり、また、土壌や水
中では数週間で分解を開始し１年で完全に分解するた
め、従来の汎用プラスチックに代わって、使い捨ての包
装材料や容器等における使用が検討されている。ポリ乳
酸はガラス転移点が高く高剛性であるが低靱性であり、
また、生分解性が低いことから、乳酸とでん粉の組成物
や乳酸と脂肪族ヒドロキシカルボン酸とのコポリマーが
検討されている（特開平５−３９３８１号公報）。Polylactic acid is completely decomposed in vivo within several months to one year to become harmless water and carbon dioxide, and starts decomposing in soil and water in a few weeks and is completely decomposed in one year. Instead of conventional general-purpose plastics, use in disposable packaging materials, containers, and the like has been studied. Polylactic acid has high glass transition point and high rigidity but low toughness,
Further, a composition of lactic acid and starch and a copolymer of lactic acid and an aliphatic hydroxycarboxylic acid have been studied because of their low biodegradability (Japanese Patent Laid-Open No. 5-39381).
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、透明
性、分解性および靱性に優れた生分解性樹脂組成物並び
にその成形物及び成形方法を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide a biodegradable resin composition having excellent transparency, decomposability and toughness, and a molded product and a molding method thereof.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、ポリ乳酸
にカプロラクトンモノマーを加えた組成物を成形するこ
とにより、透明性、分解性および靱性に優れた成形品を
得られることを見いだし本発明を完成するに至った。す
なわち、本発明は、ポリ乳酸８５〜７０重量％およびε
−カプロラクトン（Ｂ）１５〜３０重量％からなる透明
成形品用ポリ乳酸樹脂組成物並びにその組成物を成形し
て得られた透明性ポリ乳酸成形品および該組成物を押し
出し成形、射出成形、圧空成形、真空成形またはインフ
レーション成形する透明性ポリ乳酸成形品の製造方法に
関するものである。Means for Solving the Problems The present inventors have found that a molded article excellent in transparency, decomposability and toughness can be obtained by molding a composition obtained by adding a caprolactone monomer to polylactic acid. The invention has been completed. That is, the present invention relates to 85 to 70% by weight of polylactic acid and ε
-A polylactic acid resin composition for transparent molded articles comprising 15 to 30% by weight of caprolactone (B), a transparent polylactic acid molded article obtained by molding the composition, and extrusion-molding, injection molding, and pressurizing the composition. The present invention relates to a method for producing a transparent polylactic acid molded article to be molded, vacuum molded or inflation molded.
【０００７】[0007]
【発明の実施の形態】本発明で使用するポリ乳酸は、好
ましくは、数平均分子量Ｍｎが３０，０００〜３００，
０００のものであり、ラクタイドの開環重合によって得
られたものでも、乳酸の脱水重縮合によって得られたも
のでも、両者を重合させたものでもよい。また、ラクタ
イドおよび乳酸はｄ体、ｌ体、ｄｌ体等光学活性体又は
不活性体さらにはそれらの混合物が使用できる。DETAILED DESCRIPTION OF THE INVENTION The polylactic acid used in the present invention preferably has a number average molecular weight Mn of 30,000 to 300,
000, and may be obtained by ring-opening polymerization of lactide, may be obtained by dehydration polycondensation of lactic acid, or may be obtained by polymerizing both. In addition, lactide and lactic acid may be used in the form of an optically active substance such as d-form, l-form, dl-form or an inactive form, or a mixture thereof.
【０００８】上記で、数平均分子量はゲルパーミエーシ
ョンクロマトグラフィー（ＧＰＣ）により標準ポリスチ
レンを基準にして求めたものである。[0008] The number average molecular weight is determined by gel permeation chromatography (GPC) based on standard polystyrene.
【０００９】本発明で使用するε−カプロラクトン
（Ｂ）は、本発明の組成物中に１５〜３０重量％含まれ
る。ε−カプロラクトンの比率が１５重量％未満ではポ
リ乳酸の低生分解性や低靱性があまり改善されず、３０
重量％を超えると剛性が低下する。ε−カプロラクトン
（Ｂ）は、乳酸樹脂の分散に作用し、透明性、分解性お
よび靱性に優れた成形品が得られる。The ε-caprolactone (B) used in the present invention is contained in the composition of the present invention in an amount of 15 to 30% by weight. When the ratio of ε-caprolactone is less than 15% by weight, the low biodegradability and low toughness of polylactic acid are not so much improved,
When the content exceeds% by weight, the rigidity decreases. ε-Caprolactone (B) acts on the dispersion of the lactic acid resin, and a molded article having excellent transparency, degradability and toughness can be obtained.
【００１０】本発明の透明成形品用ポリ乳酸樹脂組成物
には、その他生分解性を有する可塑剤や従来の樹脂添加
剤、充填剤等を添加することが出来る。生分解性を有す
る可塑剤としては、ジオクチルアジペート、ジノニルセ
バケート、クエン酸トリブチル、アセチルクエン酸トリ
ブチル等の脂肪族エステルが挙げられる。充填剤として
は、たとえば、炭酸カルシウム、マイカ、珪酸カルシウ
ム、ホワイトカーボン、石綿、陶土（焼成）、ガラス繊
維等を添加することができる。The polylactic acid resin composition for a transparent molded article of the present invention may further contain a biodegradable plasticizer, a conventional resin additive, a filler, and the like. Examples of the biodegradable plasticizer include aliphatic esters such as dioctyl adipate, dinonyl sebacate, tributyl citrate and acetyl tributyl citrate. As the filler, for example, calcium carbonate, mica, calcium silicate, white carbon, asbestos, porcelain clay (fired), glass fiber and the like can be added.
【００１１】ポリ乳酸（Ａ）とε−カプロラクトン
（Ｂ）の混練方法は、一般的な方法が好ましく使用で
き、具体的にはヘンシェルミキサーやリボンミキサーで
混合し、単軸や２軸の押出機、バンバリーミキサー、ニ
ーダー、ミキシングロールなどの公知の溶融混合機に供
給して溶融混練することができる。As a method for kneading the polylactic acid (A) and the ε-caprolactone (B), a general method can be preferably used. Specifically, mixing is performed with a Henschel mixer or a ribbon mixer, and a single-screw or twin-screw extruder is used. The mixture can be supplied to a known melt mixer such as a Banbury mixer, a kneader, or a mixing roll to perform melt kneading.
【００１２】本発明の透明成形品用ポリ乳酸樹脂組成物
の成形方法としては、従来の押し出し成形、射出成形、
圧空成形、真空成形またはインフレーション成形等が使
用できる。The method of molding the polylactic acid resin composition for a transparent molded article of the present invention includes conventional extrusion molding, injection molding,
Compressed air molding, vacuum molding or inflation molding can be used.
【００１３】本発明で提供される透明性ポリ乳酸樹脂組
成物は、下記ＪＩＳ Ｋ６９５０で規定する都市下水汚
泥中での４週間培養後の分解率が２０％、好ましくは３
０％を上回る。また本発明で提供されるポリ乳酸樹脂組
成物は、従来のポリオレフィンの代替として広範な用途
に使用することができる。特に環境に放置されやすい物
品用途に用いることが好ましい。サンプルの生分解性評
価方法は、ＪＩＳ Ｋ６９５０に準じた活性汚泥を使用
する方法や、土壌中の埋設、海水中や河川中への浸漬、
コンポストでの評価など種々あるが、以下の実施例で
は、一般フィールドでの分解性と相関関係があるとされ
るＪＩＳ Ｋ６９５０に準じて行った。The transparent polylactic acid resin composition provided by the present invention has a decomposition rate of 20%, preferably 3%, after cultivation in municipal sewage sludge specified in JIS K6950 below for 4 weeks.
More than 0%. Further, the polylactic acid resin composition provided by the present invention can be used for a wide range of applications as an alternative to conventional polyolefins. In particular, it is preferable to use it for articles that are easily left in the environment. Methods for evaluating the biodegradability of samples include methods using activated sludge according to JIS K6950, burying in soil, immersion in seawater and rivers,
Although there are various methods such as evaluation by compost, in the following examples, the evaluation was performed according to JIS K6950, which is considered to have a correlation with the degradability in a general field.
【００１４】[0014]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明はこれらに限定されるものではない。な
お、機械物性の測定はＪＩＳ Ｋ７１２７により、以下
の条件で行った。 テンシロン：島津製作所性オートグラフ。 サンプル：３号ダンベル。 引張速度（Ｅ）：２００ｍｍ／ｍｉｎ．EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. The mechanical properties were measured under the following conditions according to JIS K7127. Tensilon: Shimadzu Autograph. Sample: No. 3 dumbbell. Tensile speed (E): 200 mm / min.
【００１５】（実施例１〜２）ポリ乳酸（Ａ）としてラ
クティ１０１２（島津製作所製，数平均分子量７０，０
００）を、ε−カプロラクトン（Ｂ）として市販の試薬
特級品を蒸留して使用した。ポリ乳酸系樹脂（Ａ）とε
−カプロラクトン（Ｂ）を表１に示す割合で混合し、ラ
ボプラストミルにより１８０℃で５分間混練した。得ら
れた樹脂組成物を加熱プレス成形し、１５０×１５０×
１．０ｍｍシートを作製した。加熱プレス成形は、金型
に必要量の樹脂組成物を入れて予熱（１８０℃，１０分
間）し、加圧成形（１８０℃，１００ｋｇ／ｃｍ2，１
０分間）した後、自然放冷し、金型からシートを取り出
す方法で行った。結果を表１に示す。なお、表において
ラクティ１０１２はラクティと、ε−カプロラクトンは
CL-Mと略載した。表からわかるように、透明性、生分解
性および靱性に優れたポリ乳酸樹脂成形物が得られた。Examples 1 and 2 Lacty 1012 (manufactured by Shimadzu Corporation, number average molecular weight 70,0) was used as polylactic acid (A).
00) was used by distilling a special grade reagent commercially available as ε-caprolactone (B). Polylactic acid resin (A) and ε
-Caprolactone (B) was mixed at the ratio shown in Table 1, and kneaded at 180 ° C for 5 minutes by Labo Plastomill. The obtained resin composition was subjected to hot press molding, and 150 × 150 ×
A 1.0 mm sheet was produced. In hot press molding, a required amount of the resin composition is put into a mold, preheated (180 ° C., 10 minutes), and pressure molded (180 ° C., 100 kg / cm 2 , 1).
(0 min), then allowed to cool naturally and take out the sheet from the mold. Table 1 shows the results. In the table, Lacty 1012 is Lacty, and ε-caprolactone is Lacty.
Abbreviated as CL-M. As can be seen from the table, a polylactic acid resin molded product having excellent transparency, biodegradability and toughness was obtained.
【００１６】（比較例１〜２）ポリ乳酸系樹脂（Ａ）に
対するε−カプロラクトン（Ｂ）の割合を表１に示すよ
うに低くした他は実施例１と同様に行った。結果を表１
に示す。表からわかるように、透明性はあるが伸びが小
さい。(Comparative Examples 1 and 2) The same procedure as in Example 1 was carried out except that the ratio of ε-caprolactone (B) to the polylactic acid resin (A) was reduced as shown in Table 1. Table 1 shows the results
Shown in As can be seen from the table, there is transparency but low elongation.
【００１７】（比較例３〜１０）比較のためε−カプロ
ラクトンの代わりに種々の重合度のポリカプロラクトン
樹脂を使用した他は実施例１と同様に行った。PCL303は
トリメチロールプロパンを開始剤にしてε−カプロラク
トンを重合したものであり、数平均分子量Ｍｎ３００で
ある。PCL202はエチレングリコールを開始剤にしてε−
カプロラクトンを重合したものであり、数平均分子量Ｍ
ｎ２００である。PCL205はエチレングリコールを開始剤
にしてε−カプロラクトンを重合したものであり、数平
均分子量Ｍｎ５００である。PCL220はエチレングリコー
ルを開始剤にしてε−カプロラクトンを重合したもので
あり、数平均分子量Ｍｎ２０００である。PCL220ALはエ
チレングリコールを開始剤にしてε−カプロラクトンと
ブチレンアジペートとの共重合体であり、数平均分子量
Ｍｎ２０００である。結果を表２に示す。(Comparative Examples 3 to 10) For comparison, the same procedures as in Example 1 were carried out except that polycaprolactone resins having various degrees of polymerization were used instead of ε-caprolactone. PCL303 is obtained by polymerizing ε-caprolactone using trimethylolpropane as an initiator, and has a number average molecular weight Mn300. PCL202 uses ε-
Caprolactone polymerized, number average molecular weight M
n200. PCL205 is obtained by polymerizing ε-caprolactone using ethylene glycol as an initiator, and has a number average molecular weight Mn500. PCL220 is obtained by polymerizing ε-caprolactone using ethylene glycol as an initiator, and has a number average molecular weight Mn2000. PCL220AL is a copolymer of ε-caprolactone and butylene adipate using ethylene glycol as an initiator, and has a number average molecular weight Mn2000. Table 2 shows the results.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【表２】 [Table 2]
【００２０】[0020]
【発明の効果】ポリ乳酸にカプロラクトンモノマーを加
えることにより、生分解性、靱性および透明性に優れた
ポリ乳酸成形物が得られた。By adding a caprolactone monomer to polylactic acid, a molded product of polylactic acid having excellent biodegradability, toughness and transparency was obtained.
Claims (1)
ε−カプロラクトン（Ｂ）１５〜３０重量％からなる透
明成形品用ポリ乳酸樹脂組成物。1. A polylactic acid resin composition for transparent molded articles, comprising 85 to 70% by weight of polylactic acid (A) and 15 to 30% by weight of ε-caprolactone (B).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29117396A JPH10120890A (en) | 1996-10-14 | 1996-10-14 | Polylactic resin composition for transparent molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29117396A JPH10120890A (en) | 1996-10-14 | 1996-10-14 | Polylactic resin composition for transparent molding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10120890A true JPH10120890A (en) | 1998-05-12 |
Family
ID=17765405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29117396A Pending JPH10120890A (en) | 1996-10-14 | 1996-10-14 | Polylactic resin composition for transparent molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10120890A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002087851A1 (en) * | 2001-04-30 | 2002-11-07 | Trespaphan Gmbh | Method for the production of biologically-degradable packagings made from biaxially-drawn films |
| WO2005085351A1 (en) * | 2004-02-27 | 2005-09-15 | Cereplast, Inc. | Biodegradable poly(lactic acid) polymer composition and films, coatings and products comprising biodegradable poly(lactic acid) polymer composition |
| US20110136988A1 (en) * | 2008-04-18 | 2011-06-09 | Commonwealth Scientific an dIndustrial Research Organisation | Condensation polymers with modified properties |
| CN113563570A (en) * | 2021-07-21 | 2021-10-29 | 湖南聚仁化工新材料科技有限公司 | Polylactic acid transparent toughening agent and preparation method thereof |
-
1996
- 1996-10-14 JP JP29117396A patent/JPH10120890A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002087851A1 (en) * | 2001-04-30 | 2002-11-07 | Trespaphan Gmbh | Method for the production of biologically-degradable packagings made from biaxially-drawn films |
| WO2005085351A1 (en) * | 2004-02-27 | 2005-09-15 | Cereplast, Inc. | Biodegradable poly(lactic acid) polymer composition and films, coatings and products comprising biodegradable poly(lactic acid) polymer composition |
| US20110136988A1 (en) * | 2008-04-18 | 2011-06-09 | Commonwealth Scientific an dIndustrial Research Organisation | Condensation polymers with modified properties |
| CN113563570A (en) * | 2021-07-21 | 2021-10-29 | 湖南聚仁化工新材料科技有限公司 | Polylactic acid transparent toughening agent and preparation method thereof |
| CN113563570B (en) * | 2021-07-21 | 2023-07-28 | 湖南聚仁化工新材料科技有限公司 | Polylactic acid transparent toughening agent and preparation method thereof |
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