JP4652151B2 - Heat-resistant polylactic acid resin composition and molded product thereof - Google Patents
Heat-resistant polylactic acid resin composition and molded product thereof Download PDFInfo
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Description
本発明は、ポリ乳酸系樹脂とポリオレフィンとの樹脂組成物において、ポリ乳酸系樹脂としてＬ−乳酸ユニットを有するポリＬ−乳酸とＤ−乳酸ユニットを有するポリＤ−乳酸とを用いたポリ乳酸系樹脂組成物、およびそれから得られる耐熱性の優れた成形体に関するものである。 The present invention relates to a polylactic acid-based resin composition comprising a polylactic acid-based resin and a polyolefin using poly-L-lactic acid having an L-lactic acid unit and poly-D-lactic acid having a D-lactic acid unit as the polylactic acid-based resin. The present invention relates to a resin composition and a molded article having excellent heat resistance obtained therefrom.
近年、原油に代表される化石原料の枯渇が問題視されている。そこで、化石原料に代わるプラスチックの原料として、植物が注目されている。ポリ乳酸はとうもろこし等の穀物資源から発酵により得られる乳酸を原料とし、しかも成形性・剛性に優れるために特に注目されている。しかしながら、ポリ乳酸は、耐熱性が低いために用途展開に限界があった。ポリ乳酸のガラス転移点（Tｇ）は６０℃程度であり、非晶状態では耐熱性が６０℃以下であるため、日常の使用環境下において、白化、変形等を生じやすいという問題点が指摘されている。また、ポリ乳酸は結晶性を有し、結晶化することによって耐熱性は６０℃を上回って大きく向上するが、結晶化速度が遅いために後結晶化工程が必要となるなど、通常の樹脂とは異なる成形法が必要となり、コスト高になるという問題点が指摘されている。 In recent years, depletion of fossil raw materials represented by crude oil has been regarded as a problem. Therefore, plants have attracted attention as a raw material for plastics that can replace fossil raw materials. Polylactic acid is particularly attracting attention because it uses lactic acid obtained by fermentation from corn and other cereal resources as a raw material and is excellent in moldability and rigidity. However, since polylactic acid has low heat resistance, its application development has been limited. Polylactic acid has a glass transition point (Tg) of about 60 ° C., and its heat resistance in an amorphous state is 60 ° C. or less. Therefore, it has been pointed out that it tends to cause whitening, deformation, etc. under daily use environment. ing. In addition, polylactic acid has crystallinity, and heat resistance is greatly improved by crystallization exceeding 60 ° C. However, since the crystallization rate is slow, a post-crystallization step is required, and the like, However, it has been pointed out that a different molding method is required and the cost becomes high.
ポリ乳酸の結晶化速度およびひいては耐熱性の改良は、従来より種々行われている。特にポリ乳酸のラセミ結晶を用いた結晶化速度の改良は良く知られている。ポリ乳酸を構成する乳酸は不斉炭素を有するため光学異性体であるＤ−乳酸とＬ−乳酸が存在する。Ｄ−乳酸のみを構成成分とするポリＤ―乳酸とＬ―乳酸のみを構成成分とするポリＬ―乳酸との間には強い相互作用が働き、両者をブレンドすることにより、融点が高く、結晶化速度が速いラセミ結晶が形成される。特許文献１には特定の分子量を有するポリＬ―乳酸とポリＤ―乳酸を溶融混合することにより、ラセミ結晶の形成が促進され、成形性の良好なポリ乳酸樹脂組成物が開示されている。しかしこのような方法によっても、ラセミ結晶の形成速度は十分に満足できるほどではなく、耐熱性に優れたポリ乳酸系樹脂組成物を得ることはできなかった。 Various improvements in polylactic acid crystallization speed and, in turn, heat resistance have been made. In particular, improvement of the crystallization rate using a racemic crystal of polylactic acid is well known. Since lactic acid constituting polylactic acid has an asymmetric carbon, D-lactic acid and L-lactic acid which are optical isomers exist. A strong interaction acts between poly-D-lactic acid containing only D-lactic acid as a constituent and poly-L-lactic acid containing only L-lactic acid as a constituent. Racemic crystals with a high conversion rate are formed. Patent Document 1 discloses a polylactic acid resin composition having a good moldability by promoting the formation of racemic crystals by melt-mixing poly L-lactic acid and poly D-lactic acid having a specific molecular weight. However, even with such a method, the formation rate of racemic crystals is not sufficiently satisfactory, and a polylactic acid resin composition having excellent heat resistance cannot be obtained.
また、特許文献２にはポリ乳酸樹脂とポリアセタール樹脂とを含有する結晶化特性と耐熱性に優れた樹脂組成物が開示されている。しかしながら、ポリアセタールは酸に弱く、ポリ乳酸とブレンドした際に分解して臭気を発するという欠点を有していた。
本発明の課題は耐熱性が向上し、成形性に優れたポリ乳酸系樹脂組成物およびその成形体の提供である。 An object of the present invention is to provide a polylactic acid resin composition having improved heat resistance and excellent moldability, and a molded product thereof.
本発明者らは、上記課題を達成するために鋭意検討した結果、ポリオレフィンとポリ乳酸系樹脂からなり、しかもポリ乳酸系樹脂中にＬ−乳酸ユニットを有するポリＬ−乳酸とＤ−乳酸ユニットを有するポリＤ−乳酸を含むことによって耐熱性が向上し、しかも成形性に優れたポリ乳酸系樹脂組成物を得られることを見出し、本発明に到達した。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have determined that poly L-lactic acid and D-lactic acid unit comprising a polyolefin and a polylactic acid-based resin and having an L-lactic acid unit in the polylactic acid-based resin. It has been found that a polylactic acid-based resin composition having improved heat resistance and excellent moldability can be obtained by including the poly-D-lactic acid having the present invention.
すなわち本発明はポリオレフィン（Ａ）１〜９０重量部とポリ乳酸系樹脂（Ｂ）１０〜９９重量部（ただし（Ａ）と（Ｂ）の合計を１００重量部とする）を含んでなるポリ乳酸系樹脂組成物であり、ポリ乳酸系樹脂（Ｂ）中のＬ−乳酸ユニットを有するポリＬ−乳酸（Ｂ−１）とＤ−乳酸ユニットを有するポリＤ−乳酸（Ｂ−２）の比が９９／１〜５０／５０であるポリ乳酸系樹脂組成物を提供する。 That is, the present invention is a polylactic acid comprising 1 to 90 parts by weight of a polyolefin (A) and 10 to 99 parts by weight of a polylactic acid resin (B) (provided that the total of (A) and (B) is 100 parts by weight). The ratio of poly L-lactic acid (B-1) having an L-lactic acid unit and poly D-lactic acid (B-2) having a D-lactic acid unit in the polylactic acid resin (B) A polylactic acid resin composition having a ratio of 99/1 to 50/50 is provided.
また、本発明においてポリ乳酸系樹脂組成物は好ましくは以下のような特徴をもつ。
１．ポリオレフィン（Ａ）がプロピレン系ポリオレフィン（Ａ１）である。
２．ポリオレフィン（Ａ）の降温結晶化温度が１００℃以上１４０℃以下である。
３．ポリ乳酸系樹脂（Ｂ）がＬ−乳酸ユニットを有するＬ−ポリ乳酸（Ｂ−１）とＤ−乳酸ユニットを有するポリＤ−乳酸（Ｂ−２）とが共有結合を介してブロック状およびまたはグラフト状およびまたはランダム状に結合している構造を有するポリ乳酸共重合体（Ｂ−３）を含む。
４．ポリ乳酸系樹脂（Ｂ）中のＬ−乳酸ユニットを有するポリＬ−乳酸（Ｂ−１）とＤ−乳酸ユニットを有するポリＤ−乳酸（Ｂ−２）との分子量の比が０．１〜１．４である。
In the present invention, the polylactic acid resin composition preferably has the following characteristics.
1. The polyolefin (A) is a propylene-based polyolefin (A1).
2. The cooling crystallization temperature of the polyolefin (A) is 100 ° C. or higher and 140 ° C. or lower.
3. The L-polylactic acid (B-1) having a polylactic acid-based resin (B) having an L-lactic acid unit and the poly-D-lactic acid (B-2) having a D-lactic acid unit are in a block form via a covalent bond and / or A polylactic acid copolymer (B-3) having a structure bonded in a graft form and / or a random form is included.
4). The ratio of the molecular weight of the poly L-lactic acid (B-1) having an L-lactic acid unit and the poly D-lactic acid (B-2) having a D-lactic acid unit in the polylactic acid resin (B) is 0.1 to 0.1. 1.4.
本発明に係るポリオレフィンとポリ乳酸系樹脂とからなる樹脂組成物により、耐熱性の優れたポリ乳酸系樹脂組成物が提供される。該樹脂組成物より形成される成形品は、従来のポリ乳酸では耐熱性が不十分であった分野に適用することができる。また該ポリ乳酸系樹脂組成物は、従来のポリ乳酸と比べて、成形性に優れる。 The resin composition comprising the polyolefin and the polylactic acid resin according to the present invention provides a polylactic acid resin composition having excellent heat resistance. Molded articles formed from the resin composition can be applied to fields where conventional polylactic acid has insufficient heat resistance. In addition, the polylactic acid-based resin composition is excellent in moldability as compared with conventional polylactic acid.
本発明で使用する「ポリ乳酸系樹脂（Ｂ）」なる言葉は、Ｌ−乳酸ユニットおよび／またはＤ−乳酸ユニットを少なくとも５０モル％以上含有する重合体およびそれを主成分とする重合体を意味するものであり、乳酸の重縮合や乳酸の環状二量体であるラクチドの開環重合によって合成される。乳酸と共重合可能な他のモノマーが共重合されたものでもよい。 The term “polylactic acid resin (B)” used in the present invention means a polymer containing at least 50 mol% of L-lactic acid units and / or D-lactic acid units and a polymer containing the same as a main component. It is synthesized by polycondensation of lactic acid or ring-opening polymerization of lactide, which is a cyclic dimer of lactic acid. Copolymerized with other monomers copolymerizable with lactic acid.
本発明で使用する「Ｌ−乳酸ユニットを有するポリＬ−乳酸（Ｂ−１）」または「Ｄ−乳酸ユニットを有するポリＤ−乳酸（Ｂ−２）」なる言葉は、それぞれＬ−乳酸ユニットまたはＤ―乳酸ユニットを８０モル％以上含有し、好ましくは９０モル％以上含有し、さらに好ましくは９５モル％以上含有する重合体を意味するものであり、乳酸の重縮合や乳酸の環状二量体であるラクチドの開環重合によって合成される。乳酸と共重合可能な他のモノマーが共重合されたものでもよい。 The terms “poly-L-lactic acid having an L-lactic acid unit (B-1)” or “poly-D-lactic acid having a D-lactic acid unit (B-2)” used in the present invention are L-lactic acid units or D- means a polymer containing 80 mol% or more, preferably 90 mol% or more, and more preferably 95 mol% or more of D-lactic acid unit, and is a polycondensation of lactic acid or a cyclic dimer of lactic acid. It is synthesized by ring-opening polymerization of lactide. Copolymerized with other monomers copolymerizable with lactic acid.
また、ポリ乳酸系樹脂（Ｂ）はＬ−乳酸ユニットを有するポリＬ−乳酸（Ｂ−１）とＤ−乳酸ユニットを有するポリＤ−乳酸（Ｂ−２）とは互いにブロック状、グラフト状、ランダム状に連結しているポリ乳酸共重合体（Ｂ−３）を含んでいても良い。Ｌ−乳酸ユニットを有するポリＬ−乳酸（Ｂ−１）とＤ−乳酸ユニットを有するポリＤ−乳酸（Ｂ−２）はそれぞれ分子量１万以上５０万以下が好ましく、より好ましくは分子量１万５千以上３０万以下である。 The polylactic acid-based resin (B) is composed of a poly-L-lactic acid (B-1) having an L-lactic acid unit and a poly-D-lactic acid (B-2) having a D-lactic acid unit, which are block-like, graft-like, The polylactic acid copolymer (B-3) connected at random may be included. The poly L-lactic acid (B-1) having an L-lactic acid unit and the poly D-lactic acid (B-2) having a D-lactic acid unit each preferably have a molecular weight of 10,000 to 500,000, and more preferably a molecular weight of 15,000. 1,000 to 300,000.
本発明で使用する「ポリオレフィン（Ａ）」なる言葉は、炭素原子数が２〜２０のオレフィンから導かれる繰返し単位からなる重合体を意味するものであり、具体的には炭素原子数が２〜２０のオレフィンから選ばれるオレフィンの単独重合体または共重合体である。このポリオレフィンセグメントが立体規則性を有する場合は、アイソタクティックポリオレフィン、シンジオタクティックポリオレフィンのいずれであってもよい。 The term “polyolefin (A)” used in the present invention means a polymer composed of a repeating unit derived from an olefin having 2 to 20 carbon atoms, specifically having 2 to 2 carbon atoms. An olefin homopolymer or copolymer selected from 20 olefins. When this polyolefin segment has stereoregularity, it may be either isotactic polyolefin or syndiotactic polyolefin.
炭素原子数が２〜２０のオレフィンとしては、例えば直鎖状または分岐状のα-オレフィン、環状オレフィン、芳香族ビニル化合物、共役ジエン、非共役ジエンなどが挙げられる。直鎖状または分岐状のα-オレフィンとして具体的には、例えばエチレン、プロピレン、1-ブテン、1-ペンテン、3-メチル-1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、3-メチル-1-ペンテン、3-エチル-1-ペンテン、4,4-ジメチル-1-ペンテン、4-メチル-1-ヘキセン、4,4-ジメチル-1-ヘキセン、4-エチル-1-ヘキセン、3-エチル-1-ヘキセン、1-オクテン、1-デセン、1-ドデセン、1-テトラデセン、1-ヘキサデセン、1-オクタデセン、1-エイコセンなどの炭素原子数２〜２０、好ましくは２〜１０のものが挙げられる。 Examples of the olefin having 2 to 20 carbon atoms include linear or branched α-olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, and nonconjugated dienes. Specific examples of the linear or branched α-olefin include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 -Methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene , 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc., 2 to 20, preferably 2 to 10 carbon atoms Can be mentioned.
環状オレフィンとしては、シクロペンテン、シクロヘプテン、ノルボルネン、５−メチル−２−ノルボルネン、テトラシクロドデセン、ビニルシクロヘキサンなどの炭素原子数が３〜２０、好ましくは５〜１５のものが挙げられる。芳香族ビニル化合物としては、例えばスチレン、およびα-メチルスチレン、o-メチルスチレン、m-メチルスチレン、p-メチルスチレン、ｏ，ｐ-ジメチルスチレン、o-エチルスチレン、m−エチルスチレン、p-エチルスチレンなどのモノまたはポリアルキルスチレンが挙げられる。 Examples of the cyclic olefin include those having 3 to 20 carbon atoms, preferably 5 to 15 such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and vinylcyclohexane. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p- Mono or polyalkyl styrenes such as ethyl styrene are mentioned.
共役ジエンとしては、例えば1,3-ブタジエン、イソプレン、クロロプレン、1,3-ペンタジエン、2,3-ジメチルブタジエン、4-メチル-1,3-ペンタジエン、1,3-ペンタジエン、1,3-ヘキサジエン、1,3-オクタジエンなどの炭素原子数が４〜２０、好ましくは４〜１０のものが挙げられる。非共役ジエンとしては、例えば1,4-ペンタジエン、1,4-ヘキサジエン、1,5-ヘキサジエン、1,4-オクタジエン、1,5-オクタジエン、1,6-オクタジエン、1,7-オクタジエン、2-メチル-1,5-ヘキサジエン、6-メチル-1,5-ヘプタジエン、7-メチル-1,6-オクタジエン、4-エチリデン-8-メチル-1,7-ノナジエン、4,8-ジメチル-1,4,8-デカトリエン（ＤＭＤＴ）、ジシクロペンタジエン、シクロヘキサジエン、ジシクロオクタジエン、メチレンノルボルネン、5-ビニルノルボルネン、5-エチリデン-2-ノルボルネン、5-メチレン-2-ノルボルネン、5-イソプロピリデン-2-ノルボルネン、6-クロロメチル-5-イソプロペンル-2-ノルボルネン、2,3-ジイソプロピリデン-5-ノルボルネン、2-エチリデン-3-イソプロピリデン-5-ノルボルネン、2-プロペニル-2,2-ノルボルナジエンなどの炭素原子数５〜２０、好ましくは５〜１０のものが挙げられる。 Examples of conjugated dienes include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,3-hexadiene. , 1,3-octadiene and the like having 4 to 20, preferably 4 to 10 carbon atoms. Non-conjugated dienes include, for example, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2 -Methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1 , 4,8-decatriene (DMDT), dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene -2-norbornene, 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2 -5 carbon atoms such as norbornadiene 0, preferably include the 5 to 10.
また、本発明で使用する「プロピレン系ポリオレフィン（Ａ１）」なる言葉は、重合体構成単位としてプロピレン単位が少なくとも５０モル％以上含有されるポリオレフィンを意味する。プロピレン単位が多いほどプロピレン系ポリオレフィン（Ａ１）の結晶性が向上し、ポリ乳酸系樹脂組成物の耐熱性が向上する。プロピレン単位の好ましい範囲は６０モル％以上１００モル％以下であり、より好ましくは７０モル％以上１００モル％以下である。 Further, the term “propylene-based polyolefin (A1)” used in the present invention means a polyolefin containing at least 50 mol% of propylene units as a polymer constituent unit. As the number of propylene units increases, the crystallinity of the propylene-based polyolefin (A1) improves, and the heat resistance of the polylactic acid-based resin composition improves. A preferable range of the propylene unit is 60 mol% or more and 100 mol% or less, and more preferably 70 mol% or more and 100 mol% or less.
本発明にかかるポリ乳酸系樹脂組成物は、ポリオレフィン（Ａ）１〜９０重量部とポリ乳酸系樹脂（Ｂ）１０〜９９重量部（ただし（Ａ）と（Ｂ）の合計を１００重量部とする）を含んでなり、ポリ乳酸系樹脂（Ｂ）中のＬ−乳酸ユニットを有するポリＬ−乳酸（Ｂ−１）とＤ−乳酸ユニットを有するポリＤ−乳酸（Ｂ−２）の比が９９／１〜５０／５０である樹脂組成物である。ポリＬ−乳酸（Ｂ−１）とポリＤ−乳酸（Ｂ−２）の比は好ましくは９８／２〜６０／４０であり、より好ましくは９７／３〜７０／３０である。 The polylactic acid resin composition according to the present invention comprises 1 to 90 parts by weight of polyolefin (A) and 10 to 99 parts by weight of polylactic acid resin (B) (however, the total of (A) and (B) is 100 parts by weight) The ratio of poly-L-lactic acid (B-1) having an L-lactic acid unit and poly-D-lactic acid (B-2) having a D-lactic acid unit in the polylactic acid resin (B) is It is a resin composition which is 99 / 1-50 / 50. The ratio of poly L- lactic acid (B-1) and poly D- lactic acid (B-2) is preferably 98 / 2-60 / 40, more preferably 97 / 3-70 / 30.
この樹脂組成物は、ポリオレフィン、ポリ乳酸系樹脂に加えて、架橋剤、架橋促進剤、架橋助剤、軟化剤、粘着付与剤、老化防止剤、発泡剤、加工助剤、密着性付与剤、無機充填剤、有機フィラー、結晶核剤、耐熱安定剤、耐候安定剤、帯電防止剤、着色剤、滑剤、難燃剤、ブルーミング防止剤などの添加剤を含んでいてもよい。また、架橋、発泡などの２次変性をしてもよい。 In addition to polyolefin and polylactic acid resins, this resin composition includes a crosslinking agent, a crosslinking accelerator, a crosslinking aid, a softener, a tackifier, an anti-aging agent, a foaming agent, a processing aid, an adhesion promoter, An additive such as an inorganic filler, an organic filler, a crystal nucleating agent, a heat stabilizer, a weather stabilizer, an antistatic agent, a colorant, a lubricant, a flame retardant, and an antiblooming agent may be contained. Further, secondary modification such as crosslinking and foaming may be performed.
また、ポリオレフィンとポリ乳酸系樹脂に加えて両者の相溶性を向上させる相容化剤が添加されていても良い。相溶化剤が含有されることにより、ポリオレフィン樹脂とポリ乳酸樹脂との相溶性が向上し、両者がよく分散した樹脂組成物となる。相溶性、分散性の向上は、たとえば樹脂組成物の断面を電子顕微鏡等で観察することにより確認できる。相溶化剤を添加することにより、ポリオレフィン樹脂かポリ乳酸樹脂のいずれかの相が２０μｍ以下の大きさ（直径、厚み等）になることが確認できる。好適な場合には１０μｍ以下になる。相溶化剤の添加によって、例えば衝撃強度の向上が期待される。 Moreover, in addition to polyolefin and a polylactic acid-type resin, the compatibilizer which improves compatibility of both may be added. By containing the compatibilizing agent, the compatibility between the polyolefin resin and the polylactic acid resin is improved, and a resin composition in which both are well dispersed is obtained. The improvement in compatibility and dispersibility can be confirmed, for example, by observing the cross section of the resin composition with an electron microscope or the like. By adding the compatibilizing agent, it can be confirmed that the phase of either the polyolefin resin or the polylactic acid resin has a size (diameter, thickness, etc.) of 20 μm or less. In the preferred case, it is 10 μm or less. By adding a compatibilizing agent, for example, an improvement in impact strength is expected.
特に耐熱性の向上したポリ乳酸系樹脂組成物を得る場合には、ポリオレフィン（Ａ）として、ポリエチレン、アイソタクティックポリプロピレン、アイソタクティックブロックポリプロピレンなどから選ばれる結晶化速度の速いポリオレフィン（Ｍｗ：５,０００〜１,０００,０００）を少なくとも１種用いる。また、ポリオレフィン（Ａ）の降温結晶化温度が高いほどポリ乳酸の結晶化が誘発され、耐熱性が向上する。降温結晶化温度は８０℃以上１４０℃以下が好ましく、１００℃以上１４０℃以下がさらに好ましく、１１０℃以上１４０℃以下がさらに好ましい。 In particular, when a polylactic acid resin composition having improved heat resistance is obtained, a polyolefin (A) having a high crystallization rate selected from polyethylene, isotactic polypropylene, isotactic block polypropylene and the like (Mw: 5) 1,000 to 1,000,000) is used. Moreover, the higher the temperature-lowering crystallization temperature of the polyolefin (A), the more crystallization of polylactic acid is induced and the heat resistance is improved. The temperature-falling crystallization temperature is preferably 80 ° C. or higher and 140 ° C. or lower, more preferably 100 ° C. or higher and 140 ° C. or lower, and further preferably 110 ° C. or higher and 140 ° C. or lower.
Ｌ−乳酸ユニットを有するポリＬ−乳酸（Ｂ−１）およびＤ−乳酸ユニットを有するポリＤ−乳酸（Ｂ−２）それぞれの光学純度は８０％以上であることがポリ乳酸系樹脂（Ｂ）の結晶性が高まる点から好ましく、さらに好ましくは９０％以上であり、さらに好ましくは９５％以上である。また、Ｌ−乳酸ユニットを有するポリＬ−乳酸（Ｂ−１）とＤ−乳酸ユニットを有するポリＤ−乳酸（Ｂ−２）とがブロック状またはグラフト状またはランダム状に連結していることにより、ポリ乳酸系樹脂（Ｂ）の結晶性がさらに高まる。また、ポリＬ−乳酸ユニットを有するポリＬ−乳酸（Ｂ−１）とＤ−乳酸ユニットを有するポリＤ−乳酸（Ｂ−２）との分子量の比は好ましくは０．０５〜２であり、さらに好ましくは０．１〜１．４である。 Polylactic acid-based resin (B) having an optical purity of 80% or more of poly L-lactic acid (B-1) having an L-lactic acid unit and poly D-lactic acid (B-2) having a D-lactic acid unit From the viewpoint of increasing the crystallinity, it is preferably 90% or more, and more preferably 95% or more. In addition, the poly L-lactic acid (B-1) having an L-lactic acid unit and the poly D-lactic acid (B-2) having a D-lactic acid unit are connected in a block shape, graft shape or random shape. The crystallinity of the polylactic acid resin (B) is further increased. Moreover, the ratio of the molecular weight of the poly L-lactic acid (B-1) having a poly L-lactic acid unit and the poly D-lactic acid (B-2) having a D-lactic acid unit is preferably 0.05 to 2. More preferably, it is 0.1-1.4.
このような樹脂組成物の調製方法としては、公知の任意の方法が採用でき、例えば、ポリオレフィン、ポリ乳酸系樹脂、必要に応じて上記添加剤を押出機、ニーダーなどを用いて溶融混練する方法が挙げられる。 As a method for preparing such a resin composition, any known method can be adopted. For example, polyolefin, polylactic acid resin, and if necessary, the above additives are melt-kneaded using an extruder, a kneader, or the like. Is mentioned.
本発明にかかる成形物は、上記の耐熱性の向上したポリ乳酸系樹脂組成物から形成される。 The molded product according to the present invention is formed from the above-described polylactic acid resin composition with improved heat resistance.
本発明に係る成形物の成形方法は、特に限定されないが、例えばカレンダー成形、押出し成形、射出成形、ブロー成形、プレス成形、スタンピングモールド成形などの方法により製造することができる。成形温度は好ましくは１８０℃以上２５０℃以下である。 Although the molding method of the molded product according to the present invention is not particularly limited, for example, it can be produced by a method such as calendar molding, extrusion molding, injection molding, blow molding, press molding, stamping molding or the like. The molding temperature is preferably 180 ° C. or higher and 250 ° C. or lower.
押出成形する際には、従来公知の押出装置および成形条件を採用することができ、例えば単軸スクリュー押出機、混練押出機、ラム押出機、ギヤ押出機などを用いて、溶融した樹脂組成物をＴダイなどから押出すことによりシートまたはフィルム（未延伸）などに成形することができる。 In the extrusion molding, a conventionally known extrusion apparatus and molding conditions can be employed. For example, a molten resin composition using a single screw extruder, a kneading extruder, a ram extruder, a gear extruder, or the like. Can be formed into a sheet or film (unstretched) by extruding from a T-die or the like.
延伸フィルムは、上記のような押出シートまたは押出フィルム（未延伸）を、たとえばテンター法（縦横延伸、横縦延伸）、同時二軸延伸法、一軸延伸法により延伸することにより得られる。 The stretched film is obtained by stretching an extruded sheet or an extruded film (unstretched) as described above, for example, by a tenter method (longitudinal and transverse stretching or transverse and longitudinal stretching), a simultaneous biaxial stretching method, or a uniaxial stretching method.
フィラメントは、例えば溶融した組成物を、紡糸口金を通して押出すことにより製造することができる。また、メルトブローン法で調製してもよい。射出成形物は、従来公知の射出成形装置を用いて公知の条件を採用して、種々の形状に射出成形することにより製造することができる。ブロー成形物は、従来公知のブロー成形装置を用いて公知の条件を採用して、製造することができる。 Filaments can be made, for example, by extruding the molten composition through a spinneret. Further, it may be prepared by a melt blown method. The injection-molded product can be manufactured by injection molding into various shapes using a conventionally known injection molding apparatus under known conditions. The blow molded product can be manufactured using a known blow molding apparatus and employing known conditions.
また、射出ブロー成形では、樹脂組成物を樹脂温度１８０℃〜２５０℃でパリソン金型に射出してパリソンを成形し、次いでパリソンを所望形状の金型中に保持した後空気を吹き込み、金型に着装することにより中空成形物を製造することができる。プレス成形物としてはモールドスタンピング成形物が挙げられる。 In injection blow molding, the resin composition is injected into a parison mold at a resin temperature of 180 ° C. to 250 ° C. to form a parison, and then the parison is held in a mold having a desired shape, and then air is blown into the mold. A hollow molded product can be produced by wearing on. Examples of the press-molded product include a mold stamping molded product.
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
なお、本発明において各種物性は下記の方法で測定した。
（Ａ）熱変形温度
得られたポリ乳酸系樹脂組成物を用いて射出成形を行い、得られた射出成形品（厚み３．２ｍｍ）についてＡＳＴＭ Ｄ６４８に準拠した条件で測定した。なお、荷重は０．４５ＭＰａ条件下で測定した。
（Ｂ）降温結晶化温度
ＤＳＣとしてPERKIN EＬMER社製ＤSC７を用い、２３０℃で５分間溶融した後、１０℃／ｍｉｎの速度で３０℃まで降温した際の結晶化温度を測定した。
（Ｃ）重量平均分子量
重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）により、ポリスチレンを標準として以下の条件で評価した。
装置 ：ＳｈｏＤｅｘ ＧＰＣｓｙｓｔｅｍ−１１
カラム：ＰＬｇｅＬ ５μｍ ＭＩＸＥＤ−Ｃ（ポリマーラボラトリー社製）
溶媒 ：クロロホルム
濃度 ：１重量％
注入量：２０μＬ
流速 ：１．０ｍＬ／ｍｉｎ
In the present invention, various physical properties were measured by the following methods.
(A) Thermal deformation temperature Injection molding was performed using the obtained polylactic acid-based resin composition, and the obtained injection molded product (thickness 3.2 mm) was measured under conditions based on ASTM D648. The load was measured under the condition of 0.45 MPa.
(B) Using a DSC7 manufactured by PERKIN ELMER as the temperature-falling crystallization temperature DSC, the crystallization temperature was measured when the temperature was lowered to 30 ° C at a rate of 10 ° C / min after melting at 230 ° C for 5 minutes.
(C) Weight average molecular weight The weight average molecular weight was evaluated by gel permeation chromatography (GPC) under the following conditions using polystyrene as a standard.
Apparatus: ShoDex GPC system-11
Column: PLgeL 5 μm MIXED-C (manufactured by Polymer Laboratory)
Solvent: Chloroform Concentration: 1% by weight
Injection volume: 20 μL
Flow rate: 1.0 mL / min
［製造例１］
Ｄ−ラクチド７５０ｇ、ラウリルアルコール１３．９５ｇ、オクタン酸スズ３７．５ｍｇ（５ｗｔ％キシレン溶液を０．７５ｇ添加）を５０００ｍＬセパラブルフラスコに入れ、窒素を流しながら１８０℃の条件下で４時間重合を行った。重合終了後、反応物をクロロホルム３０００ｍＬに溶解させ、メタノール中で撹拌しながら沈殿させて、よく撹拌して残存するＤ−ラクチドを除去し、吸引ろ過を行った。メタノールでリンス洗浄をして、６０℃、２ｋＰａで２４時間乾燥させて、標準ポリスチレン換算の重量平均分子量２１９００のポリＤ−乳酸を７１４ｇ得た。
[Production Example 1]
750 g of D-lactide, 13.95 g of lauryl alcohol, and 37.5 mg of tin octoate (0.75 g of 5 wt% xylene solution added) are placed in a 5000 mL separable flask and polymerized at 180 ° C. for 4 hours while flowing nitrogen. went. After completion of the polymerization, the reaction product was dissolved in 3000 mL of chloroform, precipitated in methanol, and stirred well to remove the remaining D-lactide and subjected to suction filtration. After rinsing with methanol and drying at 60 ° C. and 2 kPa for 24 hours, 714 g of poly D-lactic acid having a weight average molecular weight of 21,900 in terms of standard polystyrene was obtained.
[製造例２〜５]
製造例１においてラウリルアルコールの量を変えて重合を行った結果を表１に示す。
[Production Examples 2 to 5]
Table 1 shows the results of polymerization in Production Example 1 with varying amounts of lauryl alcohol.
[製造例６]
製造例３と同様な方法で製造したポリーＤ乳酸６７３ｇ、Ｌ−ラクチド１３４６ｇ、オクタン酸スズ６７．３ｍｇ（５ｗｔ％キシレン溶液を１．３５ｇ添加）をＳＵＳ製の反応釜に入れ、３Ｌ／分の流量で窒素を流しながら１４０℃で３０分、１８０℃で２時間、２１０℃で２時間重合を行った。重合終了後、反応物を反応釜の底部から抜き出し、室温まで冷却した後、ポリマーを粉砕した。その後、５Ｌのメタノールにポリマーを加え、よく撹拌して残存するＬ−ラクチドを除去し、吸引ろ過を行った。メタノールでリンス洗浄をして、６０℃、２ｋＰａで２４時間乾燥させて、ポリＬ−乳酸とポリＤ−乳酸のポリ乳酸共重合体を１７１０ｇ得た。
[Production Example 6]
673 g of poly-D lactic acid produced in the same manner as in Production Example 3, 1346 g of L-lactide and 67.3 mg of tin octoate (added 1.35 g of 5 wt% xylene solution) were placed in a reaction vessel made of SUS and 3 L / min. While flowing nitrogen at a flow rate, polymerization was carried out at 140 ° C. for 30 minutes, 180 ° C. for 2 hours, and 210 ° C. for 2 hours. After completion of the polymerization, the reaction product was taken out from the bottom of the reaction kettle, cooled to room temperature, and then the polymer was pulverized. Thereafter, the polymer was added to 5 L of methanol, and the remaining L-lactide was removed by stirring well, followed by suction filtration. After rinsing with methanol and drying at 60 ° C. and 2 kPa for 24 hours, 1710 g of a polylactic acid copolymer of poly L-lactic acid and poly D-lactic acid was obtained.
[参考例１] （樹脂組成物の調製および成形）
ポリオレフィンとしてプライムポリマー製ブロックポリプロピレン（登録商標プライムポリプロ 温度２３０℃、荷重２．１６ｋｇｆでのＭＦＲ：２５ｇ／１０分、比重：０．９０１、２３℃のパラキシレンに可溶な成分量：１０．８％、降温結晶化温度１１８℃）５０重量部、ポリＬ−乳酸として三井化学製ポリ乳酸（登録商標ＬＡＣＥＡ：重量平均分子量１７万、Ｌ−乳酸／Ｄ−乳酸＝９８．２／１．８）２５重量部、および製造例１で得られたポリＤ―乳酸２５重量部（三者の合計１００重量部とする）、およびタルク（富士タルク株式会社製：グレードＬＭＰ−３５０）１０重量部を混合し、テクノベル株式会社製ＫＺＷ１５二軸押出機にて温度２２０℃、回転数２００ｒｐｍの条件で溶融混練し、ペレット化した。溶融混練時に臭気などは発生せず、問題なく混練できた。
[ Reference Example 1] (Preparation and molding of resin composition)
Block Polypropylene made of prime polymer as polyolefin (registered trademark Prime Polypro, MFR at a temperature of 230 ° C., a load of 2.16 kgf: 25 g / 10 min, specific gravity: 0.901, amount of components soluble in paraxylene at 23 ° C .: 10.8 %, Temperature drop crystallization temperature 118 ° C.) 50 parts by weight, polylactic acid manufactured by Mitsui Chemicals as poly L-lactic acid (registered trademark LACEEA: weight average molecular weight 170,000, L-lactic acid / D-lactic acid = 98.2 / 1.8) 25 parts by weight, 25 parts by weight of poly-D-lactic acid obtained in Production Example 1 (total of 100 parts by weight of the three), and 10 parts by weight of talc (made by Fuji Talc Co., Ltd .: Grade LMP-350) are mixed. Then, it was melt-kneaded and pelletized with a KZW15 twin screw extruder manufactured by Technobel Co., Ltd. under the conditions of a temperature of 220 ° C. and a rotation speed of 200 rpm. No odor or the like was generated during melt kneading, and kneading was possible without problems.
得られた樹脂組成物を日本精工株式会社２０ｔ射出成型機にてシリンダー温度２３０℃、保圧と射出の合計１０ｓ、冷却８０℃、３０ｓの条件で成形し、射出成形品を得た。成形時の樹脂の流動性、離型性は問題なく成形できた。得られた射出成形品の熱変形温度は１０５℃だった。 The obtained resin composition was molded using a 20 t injection molding machine at Nippon Seiko Co., Ltd. under conditions of a cylinder temperature of 230 ° C., a total pressure and pressure of 10 s, cooling of 80 ° C., and 30 s to obtain an injection molded product. Resin fluidity and mold release during molding could be molded without any problems. The obtained injection molded product had a heat distortion temperature of 105 ° C.
[参考例２〜５、実施例１]
ポリオレフィンとしてプライムポリマー製ブロックポリプロピレン（登録商標プライムポリプロ 温度２３０℃、荷重２．１６ｋｇｆでのＭＦＲ：２５ｇ／１０分、比重：０．９０１、２３℃のパラキシレンに可溶な成分量：１０．８％、降温結晶化温度１１８℃）、ポリＬ−乳酸として三井化学製ポリ乳酸（登録商標ＬＡＣＥＡ：重量平均分子量１７万、Ｌ−乳酸／Ｄ−乳酸＝９８．２／１．８）、および製造例２〜６で得られたポリＤ―乳酸を表１に示した配合比で参考例１と同様に混練し、ペレット化し、射出成形を行った。得られた射出成形片の熱変形温度を表１に示した。
[Reference Examples 2 to 5, Example 1 ]
Block Polypropylene made of prime polymer as polyolefin (registered trademark Prime Polypro, MFR at a temperature of 230 ° C., a load of 2.16 kgf: 25 g / 10 min, specific gravity: 0.901, amount of components soluble in paraxylene at 23 ° C .: 10.8 %, Temperature-falling crystallization temperature 118 ° C.), polylactic acid manufactured by Mitsui Chemicals (registered trademark LACEEA: weight average molecular weight 170,000, L-lactic acid / D-lactic acid = 98.2 / 1.8), and production The poly-D-lactic acid obtained in Examples 2 to 6 was kneaded at the blending ratio shown in Table 1 in the same manner as in Reference Example 1, pelletized, and injection molded. Table 1 shows the heat distortion temperature of the obtained injection-molded piece.
[比較例１]
参考例１と同様な方法で三井化学製ポリ乳酸（登録商標ＬＡＣＥＡ：標準ポリスチレン換算の重量平均分子量１７万、Ｌ−乳酸／Ｄ−乳酸＝９８．２／１．８）の射出成形を行った。得られた射出成形片はポリ乳酸の結晶化度が低く、離型時に変形してしまい、成形片を得られなかった。
[Comparative Example 1]
Injection molding of Mitsui Chemicals polylactic acid (registered trademark LACEEA: standard polystyrene equivalent weight average molecular weight 170,000, L-lactic acid / D-lactic acid = 98.2 / 1.8) was performed in the same manner as in Reference Example 1. . The obtained injection-molded piece had a low crystallinity of polylactic acid and was deformed at the time of mold release, so that a molded piece could not be obtained.
[比較例２]
参考例１と同様な方法で三井化学製ポリ乳酸（登録商標ＬＡＣＥＡ：標準ポリスチレン換算の重量平均分子量１７万、Ｌ−乳酸／Ｄ−乳酸＝９８．２／１．８）１００重量部に対し、タルク（富士タルク株式会社製：グレードＬＭＰ−３５０）１０重量部を溶融混練し、ペレット化し、射出成形を行った。射出成形片のポリ乳酸の結晶化度が低いために射出成形片が変形しやすかった。得られた射出成形品の熱変形温度は５７℃だった。
[Comparative Example 2]
In the same manner as in Reference Example 1, with respect to 100 parts by weight of polylactic acid (registered trademark LACEEA: standard polystyrene equivalent weight average molecular weight 170,000, L-lactic acid / D-lactic acid = 98.2 / 1.8) manufactured by Mitsui Chemicals, Inc. Ten parts by weight of talc (Fuji Talc Co., Ltd .: Grade LMP-350) was melt-kneaded, pelletized, and injection molded. The injection molded piece was easily deformed due to the low crystallinity of polylactic acid in the injection molded piece. The heat deformation temperature of the obtained injection molded product was 57 ° C.
[比較例３]
参考例１と同様な方法でポリＬ−乳酸として三井化学製ポリ乳酸（登録商標ＬＡＣＥＡ：重量平均分子量１７万、Ｌ−乳酸／Ｄ−乳酸＝９８．２／１．８）５０重量部、ポリＤ−乳酸として製造例４で得られたポリＤ―乳酸５０重量部（ただしポリＬ−乳酸及びポリＤ−乳酸の合計を１００重量部とする）、およびタルク（富士タルク株式会社製：グレードＬＭＰ−３５０）１０重量部を溶融混練し、ペレット化し、射出成形を行った。射出成形片のポリ乳酸の結晶化度が低いために射出成形片が変形しやすかった。得られた射出成形品の熱変形温度は５８℃だった。
[Comparative Example 3]
Polylactic acid manufactured by Mitsui Chemicals (registered trademark LACEEA: weight average molecular weight 170,000, L-lactic acid / D-lactic acid = 98.2 / 1.8) 50 parts by weight as poly L-lactic acid in the same manner as in Reference Example 1 50 parts by weight of poly-D-lactic acid obtained in Production Example 4 as D-lactic acid (however, the total of poly-L-lactic acid and poly-D-lactic acid is 100 parts by weight), and talc (manufactured by Fuji Talc Co., Ltd .: Grade LMP) -350) 10 parts by weight was melt-kneaded, pelletized, and injection molded. The injection molded piece was easily deformed due to the low crystallinity of polylactic acid in the injection molded piece. The heat deformation temperature of the obtained injection molded product was 58 ° C.
[比較例４]
ポリオレフィンとしてプライムポリマー社製ブロックポリプロピレン（登録商標プライムポリプロ 温度２３０℃、荷重２．１６ｋｇｆでのＭＦＲ：２５ｇ／１０分、比重：０．９０１、２３℃のパラキシレンに可溶な成分量：１０．８％、降温結晶化温度１１８℃）５０重量部およびポリＬ−乳酸として三井化学製ポリ乳酸（登録商標ＬＡＣＥＡ：標準ポリスチレン換算の重量平均分子量１７万、Ｌ−乳酸／Ｄ−乳酸）５０重量部（ただしポリオレフィンとポリＬ−乳酸の合計１００重量部とする）、およびタルク（富士タルク株式会社製：グレードＬＭＰ−３５０）１０重量部を溶融混練し、ペレット化し、射出成形を行った。成形時の樹脂の流動性、離型性は問題なく成形できた。得られた射出成形品の熱変形温度は８１℃だった。
[Comparative Example 4]
Block Polypropylene manufactured by Prime Polymer Co., Ltd. as a polyolefin (registered trademark Prime Polypro, MFR at a temperature of 230 ° C., a load of 2.16 kgf: 25 g / 10 min, specific gravity: 0.901, amount of components soluble in paraxylene at 23 ° C .: 10. 50% by weight of 8%, crystallization temperature at 118 ° C.) and 50 parts by weight of polylactic acid (registered trademark LACEEA: weight average molecular weight of 170,000 L, L-lactic acid / D-lactic acid) in terms of standard polystyrene as poly L-lactic acid (However, a total of 100 parts by weight of polyolefin and poly-L-lactic acid) and 10 parts by weight of talc (Fuji Talc Co., Ltd .: Grade LMP-350) were melt-kneaded, pelletized, and injection molded. Resin fluidity and mold release during molding could be molded without any problems. The heat deformation temperature of the obtained injection molded product was 81 ° C.
実施例および比較例より明らかなようにポリオレフィンとＬ−乳酸ユニットを有するポリＬ−乳酸とＤ−乳酸ユニットを有するポリＤ−乳酸を所定の割合で配合し、混練することにより、成形性及び耐熱性に優れたポリ乳酸系樹脂組成物を得ることができる。 As is clear from the Examples and Comparative Examples, the moldability and heat resistance were obtained by blending and kneading the polyolefin, poly L-lactic acid having an L-lactic acid unit, and poly D-lactic acid having a D-lactic acid unit at a predetermined ratio. A polylactic acid resin composition having excellent properties can be obtained.
本発明にかかる、ポリオレフィンとＬ−乳酸ユニットを有するポリＬ−乳酸とＤ−乳酸ユニットを有するポリＤ−乳酸とからなる樹脂組成物から作られる成形物は耐熱性に優れ、電子・電気・通信機器の筐体、容器、医用材料その他各種産業資材として使用できる。 A molded product made from a resin composition comprising a polyolefin, a poly-L-lactic acid having an L-lactic acid unit, and a poly-D-lactic acid having a D-lactic acid unit is excellent in heat resistance and is electronic, electrical, and communication. Can be used as equipment casings, containers, medical materials and other industrial materials.
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| US20100120991A1 (en) | 2007-03-29 | 2010-05-13 | Teijin Limited | Polylactic acid composition |
| WO2008149995A1 (en) * | 2007-06-06 | 2008-12-11 | Mitsubishi Plastics, Inc. | Polylactic acid resin composition, polylactic acid film, molded articles, oriented film and heat-shrinkable labels made by using the polylactic acid film, and containers with the labels |
| US20110034607A1 (en) * | 2008-04-24 | 2011-02-10 | Polyone Corporation | Heat resistant polylactic acid compounds |
| US10087316B2 (en) | 2008-04-29 | 2018-10-02 | The Procter & Gamble Company | Polymeric compositions and articles comprising polylactic acid and polyolefin |
| CN107057307A (en) * | 2017-05-22 | 2017-08-18 | 安徽三义和能源科技有限公司 | A kind of ageing-resistant environmentally friendly composite polylactic acid plastics |
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| JPH0925400A (en) * | 1995-05-08 | 1997-01-28 | Mitsubishi Rayon Co Ltd | Polylactic acid resin composition and method of molding thereof |
| JPH10251498A (en) * | 1997-03-17 | 1998-09-22 | Kanebo Ltd | Naturally degradable resin composition and molded product thereof |
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| JP2003253106A (en) * | 2002-02-27 | 2003-09-10 | Toray Ind Inc | Resin composition and molded product made of the same |
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| WO2005035656A1 (en) * | 2003-10-09 | 2005-04-21 | Unitika Ltd. | Resin composition, molding thereof and process for producing the same |
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| JPH0925400A (en) * | 1995-05-08 | 1997-01-28 | Mitsubishi Rayon Co Ltd | Polylactic acid resin composition and method of molding thereof |
| JPH10251498A (en) * | 1997-03-17 | 1998-09-22 | Kanebo Ltd | Naturally degradable resin composition and molded product thereof |
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