JPH083432A - Polylactic acid resin composition - Google Patents
Polylactic acid resin compositionInfo
- Publication number
- JPH083432A JPH083432A JP13902394A JP13902394A JPH083432A JP H083432 A JPH083432 A JP H083432A JP 13902394 A JP13902394 A JP 13902394A JP 13902394 A JP13902394 A JP 13902394A JP H083432 A JPH083432 A JP H083432A
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- JP
- Japan
- Prior art keywords
- polylactic acid
- particle size
- acid
- resin composition
- molecular 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.)
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- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はポリ乳酸系樹脂組成物に
関する。更に詳しくは生分解性があり、成形性に優れた
ポリ乳酸系樹脂組成物に関する。TECHNICAL FIELD The present invention relates to a polylactic acid resin composition. More specifically, it relates to a polylactic acid-based resin composition having biodegradability and excellent in moldability.
【０００２】[0002]
【従来の技術】ポリ乳酸は、生分解性の高分子として注
目され、例えば、縫合糸等の医用材料、医薬、農薬、肥
料等の徐放性材料等多方面に利用されている。更には生
分解性汎用プラスチックとして容器やフィルム等の包装
材料としても期待されている。これら用途のためには一
般的に成形性および機械的物性が高いことが好ましい。
そのため、高分子量のこれらポリマーを得るために、従
来は乳酸からラクチドを製造し、これらを開環重合して
高分子量のポリ乳酸を製造していた。この方法では高分
子量のポリマーが得られるが２段反応であり、ラクチド
を得るために多大な労力がかかり、経済的とはいえなか
った。一方、乳酸を直接重縮合反応させる方法は、経済
的であるが、その反面、高分子量化できないという欠点
があり、工業化されていない。例えば、高分子量化の試
みとして重縮合触媒としてスズ化合物を用い、重縮合時
に流動パラフィンを添加させる方法（特開昭６２−６４
８２３）等も提案されているが、工業的利用を考えた場
合には必ずしも充分な分子量とはいえない。また、Ｃｅ
Ｏ2 等の無機ゲルマニウム化合物を触媒とすることも提
案されている（特開平５−４３６６５号公報）が、得ら
れるポリマーの色調及び分子量の点で必ずしも充分とは
言えなかった。また、これらの製造方法で高分子量のポ
リ乳酸を製造しても、ポリ乳酸の結晶化速度が遅いた
め、成形性に問題があり、一般的な射出成形等を採用す
ることが困難であるという問題点があった。2. Description of the Related Art Polylactic acid has attracted attention as a biodegradable polymer and is used in various fields such as medical materials such as sutures, sustained-release materials such as medicines, agricultural chemicals and fertilizers. Furthermore, it is expected as a biodegradable general-purpose plastic as a packaging material for containers and films. For these purposes, it is generally preferable that the moldability and mechanical properties are high.
Therefore, in order to obtain these high molecular weight polymers, conventionally, lactide was produced from lactic acid, and ring-opening polymerization thereof was performed to produce high molecular weight polylactic acid. Although a high molecular weight polymer can be obtained by this method, it is a two-step reaction, and a great deal of labor is required to obtain lactide, which is not economical. On the other hand, the method of directly subjecting lactic acid to a polycondensation reaction is economical, but on the other hand, it has a drawback that it cannot be made into a high molecular weight compound and has not been industrialized. For example, in an attempt to increase the molecular weight, a tin compound is used as a polycondensation catalyst, and liquid paraffin is added during polycondensation (JP-A-62-64).
823) and the like have been proposed, but they cannot be said to have a sufficient molecular weight when considering industrial use. Also, Ce
It has been proposed to use an inorganic germanium compound such as O 2 as a catalyst (Japanese Patent Laid-Open No. 5-43665), but it was not always sufficient in terms of color tone and molecular weight of the obtained polymer. Further, even if a high-molecular-weight polylactic acid is produced by these production methods, the polylactic acid has a slow crystallization rate, which causes a problem in moldability, and it is difficult to adopt general injection molding or the like. There was a problem.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、優れ
た機械的物性を有し、かつ十分な結晶化速度を有するポ
リ乳酸系樹脂組成物を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a polylactic acid resin composition having excellent mechanical properties and a sufficient crystallization rate.
【０００４】[0004]
【課題を解決するための手段】本発明は上述の目的を達
成するためになされたものであり、その要旨は、平均粒
度が５μｍ以下のタルク及び／又は平均粒度が３０μｍ
以下の窒化ホウ素からなる無機粒子を０．５〜５重量％
含有することを特徴とする数平均分子量が１万〜１０万
のポリ乳酸系樹脂組成物に存する。以下、本発明につ
き、詳細に説明する。本発明のポリ乳酸系樹脂組成物に
おけるポリマー成分としては、ポリ乳酸あるいは、乳酸
から誘導される繰り返し単位と乳酸と共重合しうる他の
共重合成分から誘導される繰り返し単位とを有する共重
合体が挙げられる。The present invention has been made to achieve the above object, and its gist is to provide talc having an average particle size of 5 μm or less and / or an average particle size of 30 μm.
0.5 to 5% by weight of the following inorganic particles made of boron nitride
The polylactic acid-based resin composition has a number average molecular weight of 10,000 to 100,000, which is characterized in that it is contained. Hereinafter, the present invention will be described in detail. As the polymer component in the polylactic acid-based resin composition of the present invention, polylactic acid or a copolymer having a repeating unit derived from lactic acid and a repeating unit derived from another copolymerizable component copolymerizable with lactic acid Is mentioned.
【０００５】本発明におけるポリ乳酸としては特に限定
されるものではないが、例えば、乳酸のＤ、Ｌ、ラセミ
体等を直接重縮合させたものあるいはラクチドを開環重
合させたもの、あるいはこれらの混合物等が挙げられ
る。これらのポリ乳酸の分子量は、充分な機械的強度を
得るために数平均分子量として通常１万以上好ましくは
３万以上である。上限としては製造方法の問題および成
形性の低下の恐れがあるので数平均分子量として通常１
０万以下好ましくは７万以下である。The polylactic acid in the present invention is not particularly limited, but examples thereof include those obtained by directly polycondensing lactic acid D, L and racemates, those obtained by ring-opening polymerization of lactide, or these. A mixture etc. are mentioned. The molecular weight of these polylactic acids is usually 10,000 or more, preferably 30,000 or more, as a number average molecular weight in order to obtain sufficient mechanical strength. The upper limit is usually 1 as the number average molecular weight because of problems in the production method and a decrease in moldability.
It is at most 0,000, preferably at most 70,000.
【０００６】上記ポリ乳酸の製造方法を直接重縮合する
方法を例にして説明する。原料の乳酸はＤ、Ｌ、ラセミ
体等特に限定なく使用でき、その形態も特に限定されな
いが、溶融状態で反応を行なうことが好ましく、そのた
め、高濃度の乳酸水溶液が好ましい。使用する触媒は通
常のポリエステル重合触媒が使用可能であるが、好まし
くはアンチモン系、スズ系触媒、ゲルマニウム系触媒、
チタン系触媒が挙げられる。特に好ましいのは重合速
度、着色の点から酸化ゲルマニウムやテトラエトキシゲ
ルマニウム、テトラブトキシゲルマニウム等のゲルマニ
ウムアルコキシド等のゲルマニウム系触媒である。A method of directly polycondensing the above-mentioned method for producing polylactic acid will be described as an example. Lactic acid as a raw material can be used without particular limitation such as D, L and racemates, and the form thereof is not particularly limited, but it is preferable to carry out the reaction in a molten state, and therefore, a high concentration lactic acid aqueous solution is preferable. The catalyst used may be a usual polyester polymerization catalyst, but preferably an antimony-based catalyst, a tin-based catalyst, a germanium-based catalyst,
Examples include titanium-based catalysts. Particularly preferred are germanium-based catalysts such as germanium alkoxides such as germanium oxide, tetraethoxygermanium, and tetrabutoxygermanium from the viewpoint of polymerization rate and coloring.
【０００７】触媒の反応系への添加は重縮合反応以前で
あれば、特に限定されるものではないが、好ましくは原
料仕込み時に原料中に分散させた状態で、あるいは原料
仕込み後減圧開始時に分散処理した状態で添加する方法
である。触媒の使用量は使用するモノマー量に対して
０．０１〜３重量％より好ましくは０．０５〜１．５重
量％である。The addition of the catalyst to the reaction system is not particularly limited as long as it is before the polycondensation reaction, but it is preferably dispersed in the raw material at the time of charging the raw material or at the start of decompression after charging the raw material. It is a method of adding in a treated state. The amount of the catalyst used is 0.01 to 3% by weight, preferably 0.05 to 1.5% by weight, based on the amount of the monomer used.
【０００８】重合条件としては重合温度が１５０〜２６
０℃、好ましくは１８０〜２３０℃の範囲であり、反応
時間は２時間以上、好ましくは４時間以上、更に好まし
くは１０時間以上が重合度を挙げるためには好ましい。
しかし、あまり長時間ではポリマーの着色、劣化の問題
等が生じるため、４〜１５時間である。減圧度は５０ｍ
ｍＨｇ以下、好ましくは３０ｍｍＨｇ以下である。The polymerization conditions are such that the polymerization temperature is 150 to 26.
The temperature is 0 ° C, preferably 180 to 230 ° C, and the reaction time is preferably 2 hours or longer, preferably 4 hours or longer, more preferably 10 hours or longer in order to increase the degree of polymerization.
However, if the time is too long, problems such as coloration and deterioration of the polymer may occur, so that it is 4 to 15 hours. Decompression degree is 50m
mHg or less, preferably 30 mmHg or less.
【０００９】本発明における乳酸から誘導される繰り返
し単位と乳酸と共重合しうる他の共重合体成分から誘導
される繰り返し単位とを有する共重合体における他の共
重合体成分としては脂肪族ジオール、脂肪族ジカルボン
酸等が挙げられる。脂肪族ジオールとして直鎖アルキレ
ン基の両末端に水酸基を有するものが好ましく、具体的
に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。得られる共
重合体の物性からは特に１，４−ブタンジオールが好ま
しい。The other copolymer component in the copolymer having a repeating unit derived from lactic acid and a repeating unit derived from another copolymerizable component with lactic acid in the present invention is an aliphatic diol. , Aliphatic dicarboxylic acids and the like. As the aliphatic diol, those having a hydroxyl group at both ends of a linear alkylene group are preferable, and specifically, ethylene glycol, 1,3-propanediol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol etc. are mentioned. From the physical properties of the resulting copolymer, 1,4-butanediol is particularly preferable.
【００１０】脂肪族ジカルボン酸としては特に限定され
ないが、直鎖アルキレン基の両末端にカルボン酸基を有
するものが好ましく、具体的にはシュウ酸、マロン酸、
コハク酸、グルタル酸、アジピン酸等が挙げられる。得
られる共重合体の物性からは特にコハク酸が好ましい。
上述の２成分の組成比は脂肪族ジオールと脂肪族ジカル
ボン酸のモル比が実質的に等しく添加することが必要で
あり、これにより、分子量の増大、機械的物性の改良が
行えるため特に好ましい。その他の共重合体成分として
はヒドロキシ安息香酸等の芳香族オキシカルボン酸類、
ビスフェノールＡ等の芳香族ジオール類、テレフタル
酸、イソフタル酸等の芳香族ジカルボン酸、あるいは３
官能以上の脂肪族ポリオール、脂肪族ポリカルボン酸等
を導入することも可能である。The aliphatic dicarboxylic acid is not particularly limited, but those having a carboxylic acid group at both ends of a linear alkylene group are preferable, and specifically, oxalic acid, malonic acid,
Examples thereof include succinic acid, glutaric acid and adipic acid. From the physical properties of the resulting copolymer, succinic acid is particularly preferable.
Regarding the composition ratio of the above-mentioned two components, it is necessary to add the aliphatic diol and the aliphatic dicarboxylic acid in a substantially equal molar ratio, and this is particularly preferable because the molecular weight can be increased and the mechanical properties can be improved. As other copolymer components, aromatic oxycarboxylic acids such as hydroxybenzoic acid,
Aromatic diols such as bisphenol A, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, or 3
It is also possible to introduce a functional or higher aliphatic polyol, aliphatic polycarboxylic acid, or the like.
【００１１】本発明における無機粒子としては、タルク
及び／又は窒化ホウ素が挙げられる。本発明におけるタ
ルクは特に限定されるものではないが、例えば、タルク
鉱石を選鉱、公知の方法で分級したものなどがあげられ
る。この場合、平均粒度が５μｍ以下である。５μｍを
越えるとポリ乳酸内での均一な分散が難しいためか、添
加の効果が少ない。粒度の上限は好ましくは４μｍ以
下、特に好ましくは３μｍ以下であり、粒度の下限は通
常０．３μｍ以上好ましくは１μｍ以上である。この場
合の添加量は通常０．５〜５重量％、好ましくは１〜３
重量％である。０．５重量％未満では結晶化速度の向上
効果が少なく、５重量％を越えると破断強度等の機械的
物性の低下がある。Examples of the inorganic particles in the present invention include talc and / or boron nitride. The talc in the present invention is not particularly limited, and examples thereof include beneficiation of talc ore and classification by a known method. In this case, the average particle size is 5 μm or less. If it exceeds 5 μm, it is difficult to uniformly disperse it in polylactic acid, and the effect of addition is small. The upper limit of the particle size is preferably 4 μm or less, particularly preferably 3 μm or less, and the lower limit of the particle size is usually 0.3 μm or more, preferably 1 μm or more. The addition amount in this case is usually 0.5 to 5% by weight, preferably 1 to 3
% By weight. If it is less than 0.5% by weight, the effect of improving the crystallization rate is small, and if it exceeds 5% by weight, mechanical properties such as breaking strength are deteriorated.
【００１２】本発明における窒化ホウ素は特に限定され
るものではないが、例えば、尿素、ジシアンジアミド、
塩化アンモニウム等をホウ酸に添加し、アンモニア中で
高温で還元窒化し、公知の方法で分級することなどによ
って得られる。この場合、平均粒度は３０μｍ以下であ
る。３０μｍを越えるとポリ乳酸内での均一な分散が難
しいためか、添加の効果が小さい。粒度の上限は通常３
０μｍ以下、好ましくは２０μｍ以下であり、粒度の下
限は通常１μｍ以上、好ましくは２μｍ以上である。こ
の場合の添加量は０．５〜５重量％、好ましくは１〜３
重量％である。０．５重量％未満では結晶化速度の向上
効果が少なく、５重量％を越えると破断強度等の機械的
物性の低下がある。尚、ここでいう平均粒度とはレーザ
ー法、光透過法、ＪＩＳ篩法などで粒子の粒度分布を求
め、累積分布が５０％に対応する粒径を意味する。The boron nitride in the present invention is not particularly limited, but for example, urea, dicyandiamide,
It can be obtained by adding ammonium chloride or the like to boric acid, reducing and nitriding in ammonia at a high temperature, and classifying by a known method. In this case, the average particle size is 30 μm or less. If it exceeds 30 μm, the effect of addition is small, probably because it is difficult to uniformly disperse it in polylactic acid. The upper limit of particle size is usually 3
It is 0 μm or less, preferably 20 μm or less, and the lower limit of the particle size is usually 1 μm or more, preferably 2 μm or more. In this case, the addition amount is 0.5 to 5% by weight, preferably 1 to 3
% By weight. If it is less than 0.5% by weight, the effect of improving the crystallization rate is small, and if it exceeds 5% by weight, mechanical properties such as breaking strength are deteriorated. The average particle size as used herein means a particle size corresponding to a cumulative distribution of 50% when the particle size distribution of particles is determined by a laser method, a light transmission method, a JIS sieving method or the like.
【００１３】無機粒子のポリ乳酸あるいは乳酸系共重合
体への添加については公知の方法が特に限定なく採用で
きる。例えば、混練機等を使用する方法、マスターバッ
チの方法、重合前に添加する方法、ポリ乳酸等のポリマ
ーを溶媒を用いて溶液としてから混合し、溶媒を除去す
る方法等が可能である。この場合の溶媒としてはポリ乳
酸あるいは乳酸系共重合体を溶解するものが使用でき、
例えば、四塩化炭素、クロロホルム等のハロゲン化炭化
水素、テトラハイドロフラン等が挙げられる。For adding the inorganic particles to the polylactic acid or the lactic acid-based copolymer, known methods can be adopted without particular limitation. For example, a method of using a kneader, a method of masterbatch, a method of adding before polymerization, a method of mixing a polymer such as polylactic acid as a solution with a solvent and then removing the solvent are possible. As the solvent in this case, a solvent that dissolves polylactic acid or a lactic acid-based copolymer can be used,
Examples thereof include halogenated hydrocarbons such as carbon tetrachloride and chloroform, and tetrahydrofuran.
【００１４】以上のように、特定の粒度のタクル及び／
又は窒化ホウ素を数平均分子量が１万〜１０万のポリ乳
酸あるいは乳酸系共重合体に０．５〜５重量％配合する
ことにより、結晶核剤として作用しポリマーの結晶化速
度が増大し、成形性及び機械的物性に優れたポリ乳酸系
組成物が得られる。本発明のポリ乳酸系組成物は結晶化
速度が向上するため、射出成形、押し出し成形、圧縮成
形等の通常の成形方法が採用でき、破断強度、伸度等の
機械的強度にも優れており、通常の汎用プラスチックあ
るいはエンジニアリングプラスチックと同様の種々の用
途に使用可能である。As described above, the tuckle having a specific grain size and / or
Alternatively, by adding 0.5 to 5% by weight of boron nitride to polylactic acid or a lactic acid-based copolymer having a number average molecular weight of 10,000 to 100,000, it acts as a crystal nucleating agent to increase the crystallization rate of the polymer, A polylactic acid-based composition having excellent moldability and mechanical properties can be obtained. Since the polylactic acid-based composition of the present invention has an improved crystallization rate, it can be subjected to ordinary molding methods such as injection molding, extrusion molding and compression molding, and is excellent in mechanical strength such as breaking strength and elongation. It can be used for various purposes similar to ordinary general-purpose plastics or engineering plastics.
【００１５】また、本発明のポリ乳酸系組成物には、本
発明の効果を損なわない範囲において、他のポリアミ
ド、ポリエステル、ポリオレフィン等の重合体を配合で
き、通常の汎用プラスチック、エンジニアリングプラス
チックに用いられるのと同様の着色剤、安定剤、充填
剤、難燃剤等の添加剤を使用することも可能である。更
に本発明のポリ乳酸系組成物を用いた成形品は通常の成
形品と同様に帯電防止、酸化防止や染色等の表面処理も
可能である。Further, the polylactic acid composition of the present invention may be blended with other polymers such as polyamide, polyester and polyolefin within a range that does not impair the effects of the present invention, and is used for ordinary general-purpose plastics and engineering plastics. It is also possible to use the same additives such as colorants, stabilizers, fillers, flame retardants and the like. Further, the molded product using the polylactic acid-based composition of the present invention can be subjected to surface treatment such as antistatic, antioxidation and dyeing as in the case of a normal molded product.
【００１６】[0016]
【実施例】以下に本発明を実施例によりさらに具体的に
説明するが、本発明はその要旨を越えない限りこれら実
施例に限定されるものではない。 測定法： 数平均分子量：５ｍｇのサンプルを５ｇのＴＨＦに溶解
し、東ソー製ＧＰＣ ＨＬＣ−８０２０を用いてポリス
チレン換算により測定した。カラムには、ＰＬｇｅｌ
５μ ＭＩＸ−Ｃを使用した。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. Measurement method: A sample having a number average molecular weight of 5 mg was dissolved in 5 g of THF, and measured by polystyrene conversion using GPC HLC-8020 manufactured by Tosoh Corporation. PLgel for the column
5μ MIX-C was used.
【００１７】Ｔｃ及びΔＨ：Ｔｃは、降温時に検出され
る結晶化に伴う発熱ピークである。成形性の面から、融
溶後、冷却により結晶化しやすくするためには、Ｔｃは
より高いことが好ましい。また、ピーク面積ΔＨは、結
晶化に伴う発熱量であり、この値が大きい程、結晶性が
良好となる。成形性の点ではΔＨは大きい方が好まし
い。 溶液粘度（ηｓｐ／ｃ）：ポリマー０．１２５ｇをフェ
ノール／トリクロロエタン（１／１ｗｔ％）混合溶媒２
５ｍｌに溶解し、自動粘度測定器により３０℃で測定し
た。Tc and ΔH: Tc are exothermic peaks associated with crystallization, which are detected when the temperature is lowered. From the viewpoint of formability, it is preferable that Tc is higher in order to facilitate crystallization by cooling after melting. The peak area ΔH is the amount of heat generated by crystallization, and the larger this value, the better the crystallinity. From the viewpoint of moldability, it is preferable that ΔH is large. Solution viscosity (ηsp / c): 0.125 g of polymer and phenol / trichloroethane (1/1 wt%) mixed solvent 2
It was dissolved in 5 ml and measured at 30 ° C. with an automatic viscosity meter.
【００１８】実施例１〜５ ポリ乳酸（数平均分子量３万２千）のクロロホルム溶液
４ｗｔ％に表−１に示す粒径のミクロンホワイト（タル
ク粒子 林化成製）又はショウビーエヌＵＨＰ（窒化ホ
ウ素粒子 昭和電工製）を加え、均一に分散させた。次
いで、該溶液からクロロホルムを室温で揮発、さらに８
０℃で８時間以上真空乾燥して、各サンプルを得た。各
サンプルをＤＳＣ ＴＡ２０００（ＤＳＣ装置 Ｄｕｐ
ｏｎｔ社製）で昇温温度速度１６℃／分で測定しＴｃ及
びΔＨを求めた。その結果を表−１に示した。Examples 1 to 5 Micron white (talc particles manufactured by Hayashi Kasei) or Showbi N UHP (boron nitride) having a particle size shown in Table 1 in 4 wt% of a chloroform solution of polylactic acid (number average molecular weight 32,000) Particles (manufactured by Showa Denko) were added and uniformly dispersed. Then, chloroform was volatilized from the solution at room temperature, and further 8
Each sample was obtained by vacuum drying at 0 ° C. for 8 hours or more. DSC TA2000 (DSC device Dup
The temperature rise rate was 16 ° C./min, and Tc and ΔH were determined. The results are shown in Table-1.
【００１９】比較例１ 実施例１において核剤を加えない以外は実施例１と全く
同様にしてサンプルを得、実施例１と同様にしてＴｃ及
びΔＨを求めた。その結果を表−１に示した。Comparative Example 1 A sample was obtained in the same manner as in Example 1 except that the nucleating agent was not added, and Tc and ΔH were determined in the same manner as in Example 1. The results are shown in Table-1.
【００２０】比較例２ 実施例１において核剤として表−１に示す平均粒度が４
０μｍのＢＮ（窒化ホウ素）粒子を用いる以外は実施例
１と全く同様にしてサンプルを得、実施例１と同様にし
てＴｃ及びΔＨを求めた。その結果を表−１に示した。Comparative Example 2 The average particle size shown in Table 1 as the nucleating agent in Example 1 was 4
A sample was obtained in exactly the same manner as in Example 1 except that 0 μm BN (boron nitride) particles were used, and Tc and ΔH were determined in the same manner as in Example 1. The results are shown in Table-1.
【００２１】[0021]
【表１】 表 − １ 核剤 平均粒度* 添加量 Ｔｃ ピーク面積（ΔＨ） （μｍ） （ｗｔ％） （℃） （Ｊ／ｇ） 実施例１ タルク １．６ ２ ９７ １０．５ ２ タルク ２．９ ２ ９８ １２．２ ３ タルク ３．９ ２ ９９ ５．０ ４ ＢＮ １．５ ２ ９６ ２．２ ５ ＢＮ ８．５ ２ ９２ ４．８ 比較例１ − − ０ − ０ ２ ＢＮ ４０ ２ − ０ ＊平均粒度測定方法 実施例１〜３ 遠心沈降式自動粒度分布測定装置ＣＡＰＡ−３００により 測定 ４ 光透過法により測定 ５ レーザー法により測定 比較例２ ＪＩＳ篩法により測定[Table 1] Table-1 Nucleating agent Average particle size * Addition amount Tc Peak area (ΔH) (μm) (wt%) (° C) (J / g) Example 1 Talc 1.6 2 97 10.5 2 Talc 2 9.9 2 98 12.2 3 Talc 3.9 2 99 5.0 4 BN 1.5 2 96 22.5 5 BN 8.5 5 2 92 4.8 Comparative Example 1--0-0 0 2 BN 40 2- 0 * Mean particle size measurement method Examples 1 to 3 Measured by centrifugal sedimentation type automatic particle size distribution analyzer CAPA-300 4 Measured by light transmission method 5 Measured by laser method Comparative example 2 Measured by JIS sieve method
【００２２】[0022]
【発明の効果】本発明によって得られたポリ乳酸系樹脂
組成物は、生分解性があり、結晶化速度が高く成形性に
優れており、しかも充分満足できる機械的物性を有す
る。The polylactic acid resin composition obtained according to the present invention is biodegradable, has a high crystallization rate, is excellent in moldability, and has sufficiently satisfactory mechanical properties.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 宮崎 景子 神奈川県横浜市緑区鴨志田町1000番地 三 菱化成株式会社総合研究所内 (72)発明者 石井 由希子 神奈川県横浜市緑区鴨志田町1000番地 三 菱化成株式会社総合研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Keiko Miyazaki, 1000 Kamoshida-cho, Midori-ku, Yokohama, Kanagawa Sanryoh Kasei Co., Ltd. Ryokasei Co., Ltd.
Claims (3)
は平均粒度が３０μｍ以下の窒化ホウ素からなる無機粒
子を０．５〜５重量％含有することを特徴とする数平均
分子量が１万〜１０万のポリ乳酸系樹脂組成物。1. A number-average molecular weight of 10,000 to 10 characterized by containing 0.5 to 5% by weight of inorganic particles composed of talc having an average particle size of 5 μm or less and / or boron nitride having an average particle size of 30 μm or less. Many polylactic acid based resin compositions.
ルクであることを特徴とする請求項１に記載のポリ乳酸
系樹脂組成物。2. The polylactic acid resin composition according to claim 1, wherein the inorganic particles are talc having an average particle size of 5 μm or less.
窒化ホウ素であることを特徴とする請求項１に記載のポ
リ乳酸系樹脂組成物。3. The polylactic acid-based resin composition according to claim 1, wherein the inorganic particles are boron nitride having an average particle size of 30 μm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13902394A JP3334338B2 (en) | 1994-06-21 | 1994-06-21 | Polylactic acid based resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13902394A JP3334338B2 (en) | 1994-06-21 | 1994-06-21 | Polylactic acid based resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH083432A true JPH083432A (en) | 1996-01-09 |
| JP3334338B2 JP3334338B2 (en) | 2002-10-15 |
Family
ID=15235674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13902394A Ceased JP3334338B2 (en) | 1994-06-21 | 1994-06-21 | Polylactic acid based resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3334338B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08120165A (en) * | 1994-10-25 | 1996-05-14 | Nippon Shokubai Co Ltd | Polyester resin composition |
| JP2001226571A (en) * | 2000-02-14 | 2001-08-21 | C I Kasei Co Ltd | Polylactic acid based resin material and heat-shrinkabl film |
| JP2006111747A (en) * | 2004-10-15 | 2006-04-27 | Sony Corp | Composite composition and molded product using the composite composition |
| WO2008032484A1 (en) | 2006-09-13 | 2008-03-20 | Panasonic Corporation | Method of molding polylactic acid resin |
| US7531585B2 (en) | 2004-03-30 | 2009-05-12 | Nissan Chemical Industries, Ltd. | Polyactic acid resin composition |
| WO2010131678A1 (en) | 2009-05-12 | 2010-11-18 | 日産化学工業株式会社 | Method for producing phosphonic acid metal salt fine particles |
| US8236904B2 (en) | 2005-12-28 | 2012-08-07 | Ethicon, Inc. | Bioabsorbable polymer compositions exhibiting enhanced crystallization and hydrolysis rates |
| WO2014148555A1 (en) | 2013-03-22 | 2014-09-25 | 日産化学工業株式会社 | Polyester resin composition containing amino-triazine derivative |
-
1994
- 1994-06-21 JP JP13902394A patent/JP3334338B2/en not_active Ceased
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5843573A (en) * | 1994-10-25 | 1998-12-01 | Nippon Shokubai Co., Ltd. | Polyester resin composition |
| JPH08120165A (en) * | 1994-10-25 | 1996-05-14 | Nippon Shokubai Co Ltd | Polyester resin composition |
| JP4583537B2 (en) * | 2000-02-14 | 2010-11-17 | シーアイ化成株式会社 | Polylactic acid resin material and heat shrinkable film |
| JP2001226571A (en) * | 2000-02-14 | 2001-08-21 | C I Kasei Co Ltd | Polylactic acid based resin material and heat-shrinkabl film |
| US7531585B2 (en) | 2004-03-30 | 2009-05-12 | Nissan Chemical Industries, Ltd. | Polyactic acid resin composition |
| JP2006111747A (en) * | 2004-10-15 | 2006-04-27 | Sony Corp | Composite composition and molded product using the composite composition |
| US9173980B2 (en) | 2005-12-28 | 2015-11-03 | Ethicon, Inc. | Bioabsorbable polymer compositions exhibiting enhanced crystallization and hydrolysis rates |
| US8236904B2 (en) | 2005-12-28 | 2012-08-07 | Ethicon, Inc. | Bioabsorbable polymer compositions exhibiting enhanced crystallization and hydrolysis rates |
| US8450431B2 (en) | 2005-12-28 | 2013-05-28 | Ethicon, Inc. | Bioabsorbable polymer compositions exhibiting enhanced crystallization and hydrolysis rates |
| US9238094B2 (en) | 2005-12-28 | 2016-01-19 | Ethicon, Inc. | Bioabsorbable polymer compositions exhibiting enhanced crystallization and hydrolysis rates |
| WO2008032484A1 (en) | 2006-09-13 | 2008-03-20 | Panasonic Corporation | Method of molding polylactic acid resin |
| WO2010131678A1 (en) | 2009-05-12 | 2010-11-18 | 日産化学工業株式会社 | Method for producing phosphonic acid metal salt fine particles |
| US8445718B2 (en) | 2009-05-12 | 2013-05-21 | Nissan Chemical Industries, Ltd. | Method for producing phosphonic acid metal salt fine particles |
| WO2014148555A1 (en) | 2013-03-22 | 2014-09-25 | 日産化学工業株式会社 | Polyester resin composition containing amino-triazine derivative |
| US9683090B2 (en) | 2013-03-22 | 2017-06-20 | Nissan Chemical Industries, Ltd. | Polyester resin composition containing amino-triazine derivative |
| US10899720B2 (en) | 2013-03-22 | 2021-01-26 | Nissan Chemical Industries, Ltd. | Polyester resin composition containing amino-triazine derivative |
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| Publication number | Publication date |
|---|---|
| JP3334338B2 (en) | 2002-10-15 |
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