JP2007308638A - Polylactic acid/polyolefin-based composition - Google Patents
Polylactic acid/polyolefin-based composition Download PDFInfo
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本発明は、例えばフィルム等のプラスチック製品を製造する際に使用されるポリ乳酸／ポリオレフィン系組成物に関する。 The present invention relates to a polylactic acid / polyolefin composition used for producing a plastic product such as a film.
近年、様々なプラスチック製品が日常生活において膨大な量使用され、これらプラスチック製品の使用後の処理などを含め、自然環境保護の見地から問題が発生している。例えば、スーパーマーケット等で使用される包装用のトレイや買い物袋，水切ネットや苗木用ポット等の押出成形法によって形成された、使い捨てプラスチック材料が家庭や事業所からゴミとして膨大な量が日常的に排出されている。これらの多くは焼却により廃棄されているのが現状である。ところで、これらの多くは化石資源由来の汎用プラスチック、主にポリオレフィン系樹脂が使用されている。 In recent years, various plastic products have been used in enormous amounts in daily life, and problems have arisen from the standpoint of protecting the natural environment, including treatment after use of these plastic products. For example, disposable plastic materials formed by extrusion methods such as packaging trays and shopping bags used in supermarkets, draining nets, pots for seedlings, etc. are routinely used as waste from homes and offices. It has been discharged. Most of these are disposed of by incineration. By the way, most of these use general-purpose plastics derived from fossil resources, mainly polyolefin resins.
また、従来からこれらのプラスチック材料は燃焼カロリーが高く焼却炉を傷めるという問題があると同時に最近では焼却処理で完全焼却された場合、物質中の炭素がＣＯ２として一気に放出され、地球温暖化の要因として問題になっている。 Conventionally, these plastic materials have a problem of high calorie burn and damage the incinerator. At the same time, when completely incinerated in recent years, carbon in the substance is released as CO 2 at a stretch, causing global warming. It is a problem as a factor.
この問題を解決する手段として、ここ十数年、炭酸カルシウム等の無機物をポリオレフィン系樹脂中に数十％添加して、発熱量を低減させる手段が採られてきた。しかし、添加した無機物が灰として残留してしまうことが、逆に埋立処理とも絡んで問題視される様になってきており、更にＣＯ２の発生の点ではなんら解決には至っていない状況である。 As means for solving this problem, in recent decades, means for reducing calorific value by adding several tens of percent of an inorganic substance such as calcium carbonate to a polyolefin resin have been adopted. However, the fact that the added inorganic substance remains as ash has been regarded as a problem on the contrary in connection with landfill treatment, and further, there is no solution in terms of the generation of CO 2. .
解決策として、燃焼させた時の発熱量を小さくすることができ、しかも燃焼後灰分として大量の残渣を残さない材料が求められている。その一つとして、不飽和カルボン酸もしくはその誘導体で変性されたポリオレフィン樹脂、または不飽和カルボン酸若しくはその誘導体で変性されたポリオレフィン樹脂と未変性ポリオレフィン樹脂との混合物及びデンプン系材料を含有するポリオレフィン−デンプン系成形用組成物が提案されている（特許文献１）。このポリオレフィン−デンプン系成形用組成物は、加工性、熱流動性及び光分解性に優れ、実用上十分な機械的強度を有する事を特徴としている。 As a solution, there is a demand for a material that can reduce the amount of heat generated when burned, and that does not leave a large amount of residue as ash after combustion. One of them is a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, or a polyolefin resin containing a mixture of a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof and an unmodified polyolefin resin, and a starch-based material. A starch-based molding composition has been proposed (Patent Document 1). This polyolefin-starch molding composition is excellent in processability, heat fluidity and photodegradability, and has a mechanical strength sufficient for practical use.
また、ポリオレフィン−デンプン系成形用組成物以外の対応策として、ポリ乳酸樹脂に不飽和カルボン酸若しくはその誘導体で変性されたポリオレフィン樹脂を含有するポリ乳酸−変性ポリオレフィン系樹脂組成物が提案されている（特許文献２，３）。これらのポリ乳酸−変性ポリオレフィン系樹脂組成物は、強度、耐衝撃性に優れ、且つ生分解性を有する事を特徴としている。
ところで、上記の様なポリオレフィン−デンプン系組成物を、一般的なフィルム用途に使用した場合、組成中にデンプン系が含有される為、ゴミとして廃棄され焼却処分された際、燃焼時のカロリー低減、灰分残渣の問題は解決されるが、以下のような問題がある。 By the way, when the above-mentioned polyolefin-starch-based composition is used for general film applications, since the starch-based composition is contained in the composition, when it is discarded as waste and incinerated, the calorie reduction during combustion is reduced. Although the problem of ash residue is solved, there are the following problems.
（１）組成中にデンプン系が含有されている影響で、成形時の「焼け」、「臭気」、「ガス発生」等の要因があるため、成形時の温度制御に注意しなければならない。 (1) Due to the influence of the starch system in the composition, there are factors such as “burning”, “odor”, and “gas generation” at the time of molding, so care must be taken in temperature control at the time of molding.
（２）組成中にデンプン系が含有されている影響で、成形時の温度制御を注意しても、デンプン系組成は、成形の際の熱影響を受けて変色が起こり、透明なフィルムを得ることができない。 (2) Even if the temperature control at the time of molding is careful due to the influence of the starch system in the composition, the starch system composition is discolored due to the heat effect at the time of molding, and a transparent film is obtained. I can't.
（３）家庭や事業所から発生するゴミの回収袋としては適しているが、組成中にデンプン系組成が含有されているため、直接口にするような食品の梱包フィルムには適さない。 (3) Although it is suitable as a collection bag for garbage generated from households and business establishments, it is not suitable for a packaging film for foods that are directly taken into mouth because it contains a starch-based composition.
一方、上記のポリ乳酸／変性ポリオレフィン系樹脂組成物は、ポリ乳酸の含有率が多いために自然環境下で完全に分解可能である。従って、使用後にゴミとして廃棄する場合、従来の焼却廃棄とは別に埋立廃棄を有利に利用することができるが、以下の問題がある。 On the other hand, the polylactic acid / modified polyolefin resin composition described above can be completely decomposed in a natural environment due to the high content of polylactic acid. Therefore, when it is discarded as garbage after use, landfill disposal can be advantageously used separately from conventional incineration disposal, but there are the following problems.
（４）構成されている樹脂成分がポリ乳酸、変性ポリオレフィンの２成分構成であり、各々の樹脂価格は、オレフィン系樹脂価格の２．５〜１０倍と価格が高い。従って、廃棄処理の点では有効であるが、製品価格のコストアップ要因を含んでいる。 (4) The resin component is a two-component structure of polylactic acid and modified polyolefin, and the price of each resin is 2.5 to 10 times the price of the olefin resin, and the price is high. Therefore, it is effective in terms of disposal processing, but includes a factor for increasing the product price.
（５）成形に際しての各々の樹脂を１度別工程である２軸押出混練機にて混練して溶融押出し、ストランド化、ペレタイズ化したものを主原料としなければならないため、主原料の更なるコストアップ化の要因を含んでいる。 (5) Since each resin at the time of molding must be kneaded once in a biaxial extrusion kneader, which is a separate process, melt extruded, formed into a strand and pelletized, the main raw material must be used. It includes factors that increase costs.
本発明は、こうした事情を考慮したもので、前記ポリオレフィン／デンプン系組成物で成形を行った際の問題点（１）〜（３）と、ポリ乳酸／変性ポリオレフィン系樹脂組成物で成形を行った際の問題点（４）、（５）を克服し、ポリ乳酸の特徴である剛性を生かし、かつ耐衝撃性に優れ、成形性、及び高い機械的強度を有するポリ乳酸／ポリオレフィン系組成物を提供するものである。 The present invention has been made in consideration of such circumstances, and the molding is performed with the problems (1) to (3) when the molding is performed with the polyolefin / starch-based composition and the polylactic acid / modified polyolefin-based resin composition. Polylactic acid / polyolefin-based composition that overcomes problems (4) and (5), and has excellent impact resistance, moldability, and high mechanical strength, making use of the rigidity characteristic of polylactic acid Is to provide.
１．本発明のポリ乳酸／ポリオレフィン系組成物は、ポリ乳酸樹脂とポリオレフィン樹脂と変性ポリオレフィン化合物の組み合わせによる３成分で構成され、ポリ乳酸樹脂を４．５〜３０質量部、ポリオレフィン樹脂を２５〜８８．７５質量部、変性ポリオレフィン化合物を６．７５〜４５質量部含有し、３成分の総量が１００質量部であることを特徴とする。 1. The polylactic acid / polyolefin composition of the present invention is composed of three components by a combination of a polylactic acid resin, a polyolefin resin, and a modified polyolefin compound, 4.5-30 parts by mass of the polylactic acid resin, and 25-88. 75 parts by mass, 6.75 to 45 parts by mass of the modified polyolefin compound are contained, and the total amount of the three components is 100 parts by mass.
２．また、本発明のポリ乳酸／ポリオレフィン系組成物は、上記１、において、ポリ乳酸樹脂に対して変性ポリオレフィン化合物が１．５倍以上含有されていることを特徴とする。 2. The polylactic acid / polyolefin-based composition of the present invention is characterized in that, in the above 1, the modified polyolefin compound is contained 1.5 times or more with respect to the polylactic acid resin.
更に、本発明のポリ乳酸／ポリオレフィン系組成物は、上記１．又は２．において、前記ポリ乳酸樹脂は、植物デンプンを乳酸化、重合化して得られた樹脂であることを特徴とする。 Further, the polylactic acid / polyolefin composition of the present invention is the above-mentioned 1. Or 2. The polylactic acid resin is characterized in that it is a resin obtained by lactating and polymerizing plant starch.
本発明によれば、ポリ乳酸樹脂の特徴である剛性を生かし、且つ耐衝撃性に優れ、成形性、高い機械的強度を有するポリ乳酸／ポリオレフィン系組成物が得られる。また、ポリ乳酸樹脂を植物デンプンを乳酸化、重合化して得られた樹脂とすることにより、ＣＯ２の発生量を１．５〜１０％の割合で抑制することができる。 According to the present invention, a polylactic acid / polyolefin-based composition can be obtained that makes use of the rigidity characteristic of a polylactic acid resin, is excellent in impact resistance, has moldability, and high mechanical strength. Further, lactated polylactic acid resin plant starch, by a resin obtained by polymerization, the generation amount of CO 2 can be suppressed in a proportion 1.5 to 10%.
以下、本発明について更に詳しく説明する。
本発明において、ポリ乳酸樹脂としては、トウモロコシ、ジャガイモ、サツマイモ等の植物デンプンを乳酸化、重合化された樹脂で、その構造はＬ−乳酸及び／又はＤ−乳酸由来のモノマー単位のみで構成されているポリマーを指す。
Hereinafter, the present invention will be described in more detail.
In the present invention, the polylactic acid resin is a resin obtained by lactating and polymerizing plant starch such as corn, potato, and sweet potato, and its structure is composed only of monomer units derived from L-lactic acid and / or D-lactic acid. Refers to the polymer.
ポリ乳酸樹脂の製造は、既知の任意の重合方法を採用することででき、最も代表的な方法としては、乳酸の無水環状２量体であるラクチドを開環重合する方法（ラクチド法）であるが、乳酸を直接縮合重合しても構わない。 The production of the polylactic acid resin can be performed by adopting any known polymerization method, and the most typical method is a method of ring-opening polymerization of lactide which is an anhydrous cyclic dimer of lactic acid (lactide method). However, lactic acid may be subjected to direct condensation polymerization.
ポリ乳酸樹脂が、Ｌ−乳酸樹脂及び／又はＤ−乳酸樹脂に由来するモノマー単位からなる場合、重合体は結晶性で高融点を有し、Ｌ−乳酸樹脂、Ｄ−乳酸樹脂由来のモノマー単位の比率（以下、Ｌ／Ｄと呼ぶ）を変化させることにより、結晶性・融点を自在に調節することができる。これらのポリ乳酸樹脂としては、例えば三井化学（株）製の商品名：ＬＡＣＥＡ、トヨタ自動車（株）製のＥｃｏ Ｐｌａｓｔｉｃｓ Ｕ’ｚ、ネイチャーワーク社製の商品名：ネイチャーワークスが市販されており、本発明においてはいずれの樹脂を使用してもよい。 When the polylactic acid resin is composed of monomer units derived from L-lactic acid resin and / or D-lactic acid resin, the polymer is crystalline and has a high melting point, and monomer units derived from L-lactic acid resin and D-lactic acid resin By changing the ratio (hereinafter referred to as L / D), the crystallinity and melting point can be freely adjusted. As these polylactic acid resins, for example, trade names: LACEA manufactured by Mitsui Chemical Co., Ltd., Eco Plastics U'z manufactured by Toyota Motor Co., Ltd., and trade names manufactured by Nature Work: Nature Works are commercially available. Any resin may be used in the present invention.
前記ポリ乳酸樹脂の添加量は、４．５〜３０質量部であることが必須であり、より好ましくは、使用の際に十分な機械的特性に優れ、且つＣＯ２削減効果に寄与することから１０〜２０質量部である。ここで、ポリ乳酸樹脂の添加量が４．５質量部未満の場合、オレフィン系樹脂の含有量が多いため、機械的特性は十分に保たれて、酸素透過率も高い効果が得られる。しかし、微生物による崩壊性を付与することができなく、燃焼カロリーの低減効果も認められない。また、ＣＯ２削減効果も１．０％以下と少なく、好ましくない。一方、ポリ乳酸樹脂の添加量が３０質量部を越えると、微生物による崩壊性効果が寄与するが、硬くて脆いフィルムが得られ、酸素透過率の低下、更にはフィルム質感が硬いために成形の際に折れジワ等が発生して安定な成形ができないという問題が生じる。 It is essential that the amount of the polylactic acid resin added is 4.5 to 30 parts by mass, and more preferably, it is excellent in sufficient mechanical properties during use and contributes to the CO 2 reduction effect. 10 to 20 parts by mass. Here, when the addition amount of the polylactic acid resin is less than 4.5 parts by mass, since the content of the olefin resin is large, the mechanical characteristics are sufficiently maintained and the effect of high oxygen permeability is obtained. However, disintegration by microorganisms cannot be imparted, and no reduction effect of burned calories is recognized. Also, the CO 2 reduction effect is as low as 1.0% or less, which is not preferable. On the other hand, when the addition amount of the polylactic acid resin exceeds 30 parts by mass, the disintegration effect by microorganisms contributes, but a hard and brittle film is obtained, the oxygen permeability is lowered, and the film texture is hard, so At this time, a problem arises that wrinkles or the like occur and stable molding cannot be performed.
本発明において、オレフィン系樹脂としては種々のものが使用でき、例えばポリプロピレン、高密度ポリエチレン（以後、ＨＤＰＥと呼ぶ）、中密度ポリエチレン（以後、ＬＬＤＰＥと呼ぶ）、低密度ポリエチレン（以後、ＬＤＰＥと呼ぶ）、ポリブテン、ポリ−４−メチルペンテン等のモノオレフィンポリマーあるいはエチレン−プロピレンコポリマー、エチレン−ピロピレンコポリマー、エチレン−塩化ビニルコポリマー、プロピレン−塩化ビニルコポリマー又はこれらのポリマーの混合物が好適に挙げられる。 In the present invention, various types of olefin resins can be used. For example, polypropylene, high density polyethylene (hereinafter referred to as HDPE), medium density polyethylene (hereinafter referred to as LLDPE), and low density polyethylene (hereinafter referred to as LDPE). And monoolefin polymers such as polybutene and poly-4-methylpentene, or ethylene-propylene copolymers, ethylene-propylene copolymers, ethylene-vinyl chloride copolymers, propylene-vinyl chloride copolymers or mixtures of these polymers.
前記オレフィン系樹脂の添加量は２５〜８８．７５質量部であることが必須であるが、より好ましくは、ポリ乳酸の特徴を持ちつつ、ＣＯ２削減効果と燃焼カロリーの低減効果に寄与することから５０〜７５質量部である。ここで、オレフィン系樹脂の添加量が２５質量部未満の場合、ポリ乳酸の特徴が強く、ＣＯ２削減効果は著しく大きく、生分解性・崩壊性の効果や透明性に優れたフィルムを得ることができる。しかし、ポリ乳酸の特徴が強く影響するため硬くて脆いフィルムが得られ、耐衝撃性試験においても１０回以下で破損する状況でフィルム用途に適しないという問題が生じる。一方、オレフィン系樹脂の添加量が８８．７５質量部を超えると、オレフィン系樹脂含有が多い影響でヒートシール強度値も高い値を示し、耐衝撃性においては３０回以上の衝撃を与えても底抜けや本体からの裂けも起り難い,機械的特性に優れたフィルムを得ることができるが、燃焼カロリーの低減効果は得られない。 The addition amount of the olefin resin is essential to be 25 to 88.75 parts by mass, and more preferably, it contributes to the CO 2 reduction effect and the combustion calorie reduction effect while having the characteristics of polylactic acid. To 50 to 75 parts by mass. Here, when the addition amount of the olefin resin is less than 25 parts by mass, the characteristics of polylactic acid are strong, the CO 2 reduction effect is remarkably large, and a film excellent in biodegradability / disintegration effect and transparency is obtained. Can do. However, since the characteristics of polylactic acid are strongly influenced, a hard and brittle film can be obtained, and in the impact resistance test, there is a problem that it is not suitable for film use in a situation where the film is broken 10 times or less. On the other hand, when the addition amount of the olefin resin exceeds 88.75 parts by mass, the heat seal strength value also shows a high value due to the large content of the olefin resin, and even in the impact resistance, an impact of 30 times or more is given. Although a film with excellent mechanical properties can be obtained without causing bottom-out or tearing from the main body, the effect of reducing calories burned cannot be obtained.
本発明において、変性ポリオレフィン系化合物としては、以下の（１）〜（６）の共重合体が挙げられる。
(1)α−オレフィンとアクリル酸エステルの共重合体に（メタ）アクリル酸エステルもしくはスチレンをグラフト反応させた共重合体
(2)α−オレフィンと酢酸ビニル共重合体に（メタ）アクリル酸エステルもしくはスチレンをグラフと反応させた共重合体
(3)α− オレフィンとエチレン性不飽和結合を有するグリシル基含有単量体との共重合体
(4)α−オレフィンとエチレンとアクリル酸エステル及び酸無水物をグラフト反応させた共重合体
(5)α−オレフィンとエチレン−プロピレン共重合体にマレイン酸がグラフト重合した共重合体
(6)エチレンとエチレン以外のα−オレフィンからなるエチレン系共重合体不飽和カルボン酸またはその誘導体をグラフト重合させた共重合体
上述した共重合体におけるα−オレフィンとしては、エチレン、ピロピレン、ブテン−１、ヘキセン−１、４−メチルブテン−１、４−メチルペンテン−１が挙げられるが、エチレン、ピロピレンが好ましい。
In the present invention, examples of the modified polyolefin compound include the following copolymers (1) to (6).
(1) Copolymer obtained by graft reaction of (meth) acrylate ester or styrene to copolymer of α-olefin and acrylate ester
(2) Copolymer obtained by reacting α-olefin and vinyl acetate copolymer with (meth) acrylate or styrene with graph
(3) Copolymer of α-olefin and glycyl group-containing monomer having ethylenically unsaturated bond
(4) Copolymer obtained by graft reaction of α-olefin, ethylene, acrylic ester and acid anhydride
(5) Copolymer in which maleic acid is graft polymerized to α-olefin and ethylene-propylene copolymer
(6) Ethylene copolymer comprising ethylene and α-olefin other than ethylene Copolymer obtained by graft polymerization of unsaturated carboxylic acid or derivative thereof As the α-olefin in the above-mentioned copolymer, ethylene, pyropyrene, butene -1, hexene-1,4-methylbutene-1,4-methylpentene-1, and ethylene and pyropyrene are preferable.
上述したエチレン性不飽和結合を有するグリシル基含有単量体としては、例えば、アクリル酸ジグリシジル、メタクリル酸ジグリシジル、イタコン酸モノグリシジルエステル、ブテントリカルボン酸ジグリシジルエステル、ブテントリカルボン酸モノグリシジルエステル、ブテントリカルボン酸トリグリシジルエステル等のグリシジルエステル類、またはビニルグリシジルエーテル、アリルグリシジルエステル、グリシジルオキシエチルエーテル類が挙げられる。（メタ）アクリル酸エステルとしては、例えばアクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチルが挙げられるが、耐衝撃改質剤としてはメタクリル酸メチルが特に好ましい。 Examples of the glycyl group-containing monomer having an ethylenically unsaturated bond include diglycidyl acrylate, diglycidyl methacrylate, itaconic acid monoglycidyl ester, butenetricarboxylic acid diglycidyl ester, butenetricarboxylic acid monoglycidyl ester, and butenetricarboxylic acid. Examples thereof include glycidyl esters such as acid triglycidyl ester, vinyl glycidyl ether, allyl glycidyl ester, and glycidyloxyethyl ether. Examples of the (meth) acrylic acid ester include methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate. As the impact modifier, methyl methacrylate is particularly preferable.
前記変性オレフィン化合物としては、次の（１）〜（６）の商品名で市販されている。
(1)(エチレン＋無水マレイン酸)グラフト共重合体（商品名：アドマー、三井化学（株）製）
(2)α−エチレン−プロピレン共重合体（商品名：タフマー、三井化学（株）製））
(3)エチレン−グリシジルメタクリレート共重合体グラフト化ＰＭＭＡ（商品名：モディバーＡ４２００、日本油脂（株）製）
(4)エチレン−エチルアクリレート共重合体グラフト化ＰＭＭＡ（商品名：モディバーＡ５２００、日本油脂（株）製）
(5)エチレン−酢酸ビニル共重合体グラフト化ＰＭＭＡ（商品名：モディバーＡ６２００、日本油脂（株）製）
(6)エチレン−エチルアクリレート−無水マレイン酸共重合体化ＰＭＭＡ（商品名：モディバーＡ８２００、日本油脂（株）製）
前記変性オレフィン系化合物の添加量は６．７５〜４５質量部であることが必須であるが、より好ましくは、フィルム表面の樹脂ムラや光沢性に寄与する点から１５〜３０質量部である。更に詳しくは、ポリ乳酸樹脂に対して変性ポリオレフィン化合物が１．５倍以上の質量部で構成されていることが好ましい。
As said modified | denatured olefin compound, it is marketed by the brand name of following (1)-(6).
(1) (Ethylene + maleic anhydride) graft copolymer (trade name: Admer, manufactured by Mitsui Chemicals, Inc.)
(2) α-ethylene-propylene copolymer (trade name: Tafmer, manufactured by Mitsui Chemicals, Inc.)
(3) Ethylene-glycidyl methacrylate copolymer grafted PMMA (trade name: Modivar A4200, manufactured by NOF Corporation)
(4) Ethylene-ethyl acrylate copolymer grafted PMMA (trade name: Modivar A5200, manufactured by NOF Corporation)
(5) Ethylene-vinyl acetate copolymer grafted PMMA (trade name: Modivar A6200, manufactured by NOF Corporation)
(6) Ethylene-ethyl acrylate-maleic anhydride copolymerized PMMA (trade name: Modivar A8200, manufactured by NOF Corporation)
The amount of the modified olefinic compound added is necessarily 6.75 to 45 parts by mass, and more preferably 15 to 30 parts by mass from the viewpoint of contributing to unevenness of the resin on the film surface and glossiness. More specifically, it is preferable that the modified polyolefin compound is composed of 1.5 parts by mass or more with respect to the polylactic acid resin.
変性ポリオレフィン系化合物の添加量が６．７５質量部未満の場合、添加による物性の向上及び相溶性の効果が認められない。また、ポリ乳酸樹脂成分に対する変性ポリオレフィン系化合物の質量部割合１．５倍以上に相当するポリ乳酸樹脂を含んだ時のＣＯ２削減率（％）が１．５倍以下と本発明に見出されたＣＯ２削減率（％）を満たすことができなくなる。一方、変性オレフィン系化合物の添加量が４５質量部を越えると、ポリ乳酸樹脂とオレフィン系樹脂との相溶性効果が認められる。しかし、全体的にポリオレフィン系化合物の含有率が増し、生物体をエネルギー源又は工業原料として利用した植物由来の効果を奏することができなく、変性ポリオレフィン系化合物の原料価格がポリオレフィン系樹脂と比較すると２．５倍以上高く、変性ポリオレフィン系化合物の転化率が増加すると成形品のコストアップとなるという問題が生じる。 When the addition amount of the modified polyolefin compound is less than 6.75 parts by mass, the improvement of physical properties and the compatibility effect due to the addition are not recognized. Further, the present invention finds that the CO 2 reduction rate (%) is 1.5 times or less when the polylactic acid resin corresponding to 1.5 parts or more by mass part ratio of the modified polyolefin compound to the polylactic acid resin component is contained. The reduced CO 2 reduction rate (%) cannot be satisfied. On the other hand, when the addition amount of the modified olefinic compound exceeds 45 parts by mass, a compatibility effect between the polylactic acid resin and the olefinic resin is recognized. However, as a whole, the content of the polyolefin-based compound increases, and it is not possible to produce a plant-derived effect using a living organism as an energy source or an industrial raw material, and the raw material price of the modified polyolefin-based compound is compared with that of a polyolefin-based resin. When the conversion rate of the modified polyolefin compound is increased by 2.5 times or more, there is a problem that the cost of the molded product is increased.
本発明において、特に限定するものではないが、成形の際に開口性や原反滑り性等の問題がある様であれば、必要に応じて可塑剤を添加しても構わない。
可塑剤としては、ポリ乳酸や変性ポリオレフィン等全てに対する相溶性及び可塑化能の点から、脂肪族二塩基酸エステル系、フタル酸エステル系、アジピン酸エステル系、ヒドロキシ多価カルボン酸エステル系、ギリコール酸誘導体、エーテルエステル誘導体、グリセリン誘導体、アルキル燐酸エステル系、ジアルキレーテル系、ジエステル系、トリカルボン酸エステル系、ポリエステル系、エポキシ系、スルホン酸アミド系、エーテルエステル系、ソベンソエート系、ポリグリコールジエステル、アルキルアルキレーテルジエステル、脂肪酸エステル、アルキレーテルモノエステル、クエン酸エステル可塑剤からなる群から選ばれた少なくとも１種類以上からなることが好ましい。
In the present invention, although not particularly limited, a plasticizer may be added as necessary as long as there is a problem such as openability and raw fabric slippage during molding.
Plasticizers include aliphatic dibasic acid esters, phthalic acid esters, adipic acid esters, hydroxy polycarboxylic acid esters, and glycol from the viewpoint of compatibility with all of polylactic acid and modified polyolefins and plasticizing ability. Acid derivatives, ether ester derivatives, glycerin derivatives, alkyl phosphate esters, dialalkylates, diesters, tricarboxylic esters, polyesters, epoxies, sulfonic acid amides, ether esters, sobensoates, polyglycol diesters, alkyl alkyls It is preferably composed of at least one selected from the group consisting of a latex diester, a fatty acid ester, an alkylate monoester, and a citrate plasticizer.
本発明において、必要に応じて、顔料、酸化防止剤、可塑剤、帯電防止剤、艶消剤、劣化防止剤、蛍光増白剤、紫外線吸収剤、紫外線安定剤、滑剤、結晶核剤、金属粉、無機フィラー、カーボンブラック、増粘剤、粘度安定剤等を任意の割合で添加することができる。 In the present invention, as necessary, pigments, antioxidants, plasticizers, antistatic agents, matting agents, deterioration inhibitors, fluorescent brighteners, ultraviolet absorbers, ultraviolet stabilizers, lubricants, crystal nucleating agents, metals Powder, an inorganic filler, carbon black, a thickener, a viscosity stabilizer, etc. can be added in arbitrary ratios.
本発明において、本発明を実施し、本発明に係るポリ乳酸／ポリオレフィン系組成物を得るには、一般的なフィルム成形法であるインフレーション法、Ｔダイ法、二軸延伸フィルム成形体の代表的な成形法である射出成形法，ブロー成形法や水切ネットに見られる押出ネットの成形法等の成形方法が挙げられるが、本発明においては一般的なフィルム成形法に基づいて説明を行う。 In the present invention, in order to carry out the present invention and obtain the polylactic acid / polyolefin-based composition according to the present invention, a typical film forming method such as an inflation method, a T-die method, or a biaxially stretched film molded product. Examples of molding methods include injection molding methods, blow molding methods, and extrusion net molding methods found in drained nets. In the present invention, description will be made based on a general film molding method.
本発明において、ポリ乳酸樹脂、オレフィン系樹脂、変性ポリオレフィン系化合物等の混合方法や混合装置は、特に限定されないが、連続的に処理できるものが工業的には有利で好ましい。例えば、次の（１）、（２）の方法がある。
（１）２種類以上のペレットを所定比率で混合し、そのままインフレーション法、Ｔダイ法、二軸延伸フィルム等の押出成形機のホッパー内に樹脂を投入し、溶融させ、直ちに成形する方法。
（２）夫々の樹脂を２軸押出機の成形機にて溶融混合した後、一旦ペレット化し、このペレットをインフレーション法、Ｔダイ法、二軸延伸フィルム等の押出機のホッパー内に投入し、溶融させ、成形する方法。
In the present invention, a mixing method and a mixing apparatus for polylactic acid resin, olefin resin, modified polyolefin compound and the like are not particularly limited, but those that can be continuously processed are industrially advantageous and preferable. For example, there are the following methods (1) and (2).
(1) A method in which two or more types of pellets are mixed at a predetermined ratio, and the resin is put into an hopper of an extrusion molding machine such as an inflation method, a T-die method, or a biaxially stretched film as it is, melted, and immediately molded.
(2) Each resin was melt-mixed in a twin-screw extruder molding machine, and then pelletized, and the pellets were put into an hopper of an extruder such as an inflation method, a T-die method, or a biaxially stretched film. A method of melting and molding.
前記（１）の混合方法は、樹脂の熱劣化を少なくすることができ、工程的にも一括して成形を行えることができる為、成形におけるコストアップも殆どない状態である。前記（２）の混合方法は、フィルム等の成形を行う前に一旦溶融押出にてペレット化を行う為、ポリマーの劣化、変質を実質的に防ぐ必要があり、更に成形品を得るに当たってペレット成形品と工程が２工程に分けて行う必要がある。従って、成形におけるコストアップにつながる。 The mixing method (1) can reduce the thermal deterioration of the resin and can be molded all at once in the process, so there is almost no increase in molding cost. In the mixing method (2), since pelletization is performed by melt extrusion once before forming a film or the like, it is necessary to substantially prevent deterioration and deterioration of the polymer, and further, pellet molding is performed to obtain a molded product. The product and the process must be divided into two steps. Therefore, it leads to a cost increase in molding.
以下に実施例を挙げて本発明を更に具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
（比較例１）
ポリ乳酸（商品名：Ｅco plastic Ｕ’z Ｂ−２、トヨタ自動車（株）製）例えばＰＬＡ １０重量％、オレフィン系樹脂（商品名：エボリューＳＰ２５２０、日本ポリエチレン（株）例えばメタルセン−中密度ポリエチレン（以後、メタルセンＬＬＤＰＥと呼ぶ）９０重量％をドライブレンド法にて混合し、インフレーション成形機を用いてブロー比２．５倍、厚み２５μｍのフィルムを製膜した。このときの成形温度は１５０〜２００℃、室内温度は２５℃で一定に保持した。
The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.
(Comparative Example 1)
Polylactic acid (trade name: Eco plastic U'z B-2, manufactured by Toyota Motor Corporation), for example, PLA 10% by weight, olefin-based resin (trade name: Evolue SP2520, Nippon Polyethylene Co., Ltd., for example, Metalsen-Medium density polyethylene ( 90% by weight (hereinafter referred to as “Metalsen LLDPE”) was mixed by a dry blend method, and a film having a blow ratio of 2.5 times and a thickness of 25 μm was formed using an inflation molding machine at a molding temperature of 150 to 200. The room temperature was kept constant at 25 ° C.
（比較例２）
ポリ乳酸（商品名：Ｅco plastic Ｕ’z Ｂ−２、トヨタ自動車（株）製）例えばＰＬＡ ２．５重量％、オレフィン系樹脂（商品名：エボリューＳＰ２５２０、日本ポリエチレン（株）例えばメタルセンＬＬＤＰＥ ９３．７５重量％、及び変性ポリオレフィン（商品名：アドマーＬＢ５４８、三井化学（株）製）例えばＥＥＤＣＡ ３．７５重量％をドライブレンド法にて混合し、インフレーション成形機を用いてブロー比２．５倍、厚み２５μｍのフィルムを製膜した。このときの成形温度は１５０〜２００℃、室内温度は２５℃で一定に保持した。
(Comparative Example 2)
Polylactic acid (trade name: Eco plastic U'z B-2, manufactured by Toyota Motor Corporation), for example, PLA 2.5% by weight, olefin resin (trade name: Evolu SP2520, Nippon Polyethylene Co., Ltd., for example, Metalsen LLDPE 93. 75% by weight, and modified polyolefin (trade name: Admer LB548, manufactured by Mitsui Chemicals, Inc.), for example, 3.75% by weight of EEDCA are mixed by a dry blend method, and a blow ratio is 2.5 times using an inflation molding machine. A film having a thickness of 25 μm was formed, and the molding temperature at this time was kept constant at 150 to 200 ° C. and the room temperature was 25 ° C.
（実施例１）
ポリ乳酸（商品名：Ｅco plastic Ｕ’z Ｂ−２、トヨタ自動車（株）製）例えばＰＬＡ ４．５重量％、オレフィン系樹脂（商品名：エボリューＳＰ２５２０、日本ポリエチレン（株）例えばメタルセンＬＬＤＰＥ ８８．７５重量％、及び変性ポリオレフィン（商品名：アドマーＬＢ５４８、三井化学（株）製）例えばＥＥＤＣＡ ６．７５重量％をドライブレンド法にて混合し、インフレーション成形機を用いてブロー比２．５倍、厚み２５μｍのフィルムを製膜した。このときの成形温度は１５０〜２００℃、室内温度は２５℃で一定に保持した。
Example 1
Polylactic acid (trade name: Eco plastic U'z B-2, manufactured by Toyota Motor Corporation), for example, PLA 4.5% by weight, olefin resin (trade name: Evolu SP2520, Nippon Polyethylene Co., Ltd., for example, Metalsen LLDPE 88. 75% by weight and modified polyolefin (trade name: Admer LB548, manufactured by Mitsui Chemicals), for example, EEDCA 6.75% by weight are mixed by a dry blend method, and a blow ratio is 2.5 times using an inflation molding machine. A film having a thickness of 25 μm was formed, and the molding temperature at this time was kept constant at 150 to 200 ° C. and the room temperature was 25 ° C.
（実施例２）
ポリ乳酸（商品名：Ｅco plastic Ｕ’z Ｂ−２、トヨタ自動車（株）製）例えばＰＬＡ １０重量％、オレフィン系樹脂（商品名：エボリューＳＰ２５２０、日本ポリエチレン（株）例えばメタルセンＬＬＤＰＥ ８０重量％、及び変性ポリオレフィン（商品名：アドマーＬＢ５４８、三井化学（株）製）例えばＥＥＤＣＡ １０重量％をドライブレンド法にて混合し、インフレーション成形機を用いてブロー比２．５倍、厚み２５μｍのフィルムを製膜した。このときの成形温度は１５０〜２００℃、室内温度は２５℃で一定に保持した。
(Example 2)
Polylactic acid (trade name: Eco plastic U'z B-2, manufactured by Toyota Motor Corporation), for example, PLA 10% by weight, olefin resin (trade name: Evolu SP2520, Nippon Polyethylene Co., Ltd., for example, Metalsen LLDPE 80% by weight, And modified polyolefin (trade name: Admer LB548, manufactured by Mitsui Chemicals, Inc.) For example, EEDCA 10% by weight is mixed by a dry blend method, and a film having a blow ratio of 2.5 times and a thickness of 25 μm is manufactured using an inflation molding machine. The molding temperature at this time was kept constant at 150 to 200 ° C. and the room temperature was kept at 25 ° C.
（実施例３）
ポリ乳酸（商品名：Ｅco plastic Ｕ’z Ｂ−２、トヨタ自動車（株）製）例えばＰＬＡ １０重量％、オレフィン系樹脂（商品名：エボリューＳＰ２５２０、日本ポリエチレン（株）例えばメタルセンＬＬＤＰＥ ７５重量％、及び変性ポリオレフィン（商品名：アドマーＬＢ５４８、三井化学（株）製）例えばＥＥＤＣＡ １５重量％をドライブレンド法にて混合し、インフレーション成形機を用いてブロー比２．５倍、厚み２５μｍのフィルムを製膜した。このときの成形温度は１５０〜２００℃、室内温度は２５℃で一定に保持した。
(Example 3)
Polylactic acid (trade name: Eco plastic U'z B-2, manufactured by Toyota Motor Corporation), for example, PLA 10% by weight, olefin resin (trade name: Evolue SP2520, Nippon Polyethylene Co., Ltd., for example, Metalsen LLDPE 75% by weight, And modified polyolefin (trade name: Admer LB548, manufactured by Mitsui Chemicals Co., Ltd.) For example, EEDCA 15% by weight is mixed by a dry blend method, and a film having a blow ratio of 2.5 times and a thickness of 25 μm is manufactured using an inflation molding machine. The molding temperature at this time was kept constant at 150 to 200 ° C. and the room temperature was kept at 25 ° C.
（実施例４）
ポリ乳酸（商品名：Ｅco plastic Ｕ’z Ｂ−２、トヨタ自動車（株）製）例えばＰＬＡ ３０重量％、オレフィン系樹脂（商品名：エボリューＳＰ２５２０、日本ポリエチレン（株）例えばメタルセンＬＬＤＰＥ ２５重量％、及び変性ポリオレフィン（商品名：アドマーＬＢ５４８、三井化学（株）製）例えばＥＥＤＣＡ ４５重量％をドライブレンド法にて混合し、インフレーション成形機を用いてブロー比２．５倍、厚み２５μｍのフィルムを製膜した。このときの成形温度は１５０〜２００℃、室内温度は２５℃で一定に保持した。
Example 4
Polylactic acid (trade name: Eco plastic U'z B-2, manufactured by Toyota Motor Corporation), for example, PLA 30% by weight, olefin resin (trade name: Evolu SP2520, Nippon Polyethylene Co., Ltd., for example, Metalsen LLDPE 25% by weight, And modified polyolefin (trade name: Admer LB548, manufactured by Mitsui Chemicals, Inc.), for example, 45% by weight of EEDCA is mixed by a dry blend method, and a film having a blow ratio of 2.5 times and a thickness of 25 μm is manufactured using an inflation molding machine. The molding temperature at this time was kept constant at 150 to 200 ° C. and the room temperature was kept at 25 ° C.
（比較例３）
ポリ乳酸（商品名：Ｅco plastic Ｕ’z Ｂ−２、トヨタ自動車（株）製）例えばＰＬＡ ３５重量％、オレフィン系樹脂（商品名：エボリューＳＰ２５２０、日本ポリエチレン（株）例えばメタルセンＬＬＤＰＥ １２．５重量％、及び変性ポリオレフィン（商品名：アドマーＬＢ５４８、三井化学（株）製）例えばＥＥＤＣＡ ５２．５重量％をドライブレンド法にて混合し、インフレーション成形機を用いてブロー比２．５倍、厚み２５μｍのフィルムを製膜した。このときの成形温度は１５０〜２００℃、室内温度は２５℃で一定に保持した。
(Comparative Example 3)
Polylactic acid (trade name: Eco plastic U'z B-2, manufactured by Toyota Motor Corporation), for example, PLA 35% by weight, olefin resin (trade name: Evolue SP2520, Nippon Polyethylene Co., Ltd., for example, Metalsen LLDPE, 12.5% by weight % And modified polyolefin (trade name: Admer LB548, manufactured by Mitsui Chemicals, Inc.), for example, EEDCA 52.5% by weight is mixed by a dry blend method, and blow ratio is 2.5 times and thickness is 25 μm using an inflation molding machine. At this time, the molding temperature was 150 to 200 ° C., and the room temperature was kept constant at 25 ° C.
（比較例４）
オレフィン系樹脂（商品名：ノバテックＵＦ４２１、日本ポリエチレン（株）製）例えばＬＬＤＰＥ １００重量％を、インフレーション成形機を用いてブロー比２．５倍、厚み２５μｍのフィルムを製膜した。
(Comparative Example 4)
An olefin resin (trade name: Novatec UF421, manufactured by Nippon Polyethylene Co., Ltd.), for example, LLDPE 100% by weight was formed into a film having a blow ratio of 2.5 times and a thickness of 25 μm using an inflation molding machine.
（比較例５）
オレフィン系樹脂（商品名：ノバテックＵＦ４２１、日本ポリエチレン（株）製）例えば低密度ポリエチレン（以後、ＬＤＰＥと呼ぶ） １００重量％を、インフレーション成形機を用いてブロー比２．５倍、厚み２５μｍのフィルムを製膜した。
(Comparative Example 5)
Olefin-based resin (trade name: Novatec UF421, manufactured by Nippon Polyethylene Co., Ltd.), for example, low-density polyethylene (hereinafter referred to as LDPE) 100% by weight using a blow molding machine with a blow ratio of 2.5 times and a thickness of 25 μm Was formed.
前記実施例１〜４、比較例１〜５の材料を、夫々以下の評価項目及び評価方法で比較評価した。その結果を下記表１、表２に示す。
（評価項目及び評価方法）
（１）加工性
加工性は、実施例に基づいて成形を行う、相溶性、連続成形における吐出、製膜性、フロストラインの安定性、巻取り安定性、並びにフィルム開口性やシワや透明性の成形品状態を確認した。
（２）比重
比重は、ＪＩＳ−Ｋ−７１１２記載のプラスチックの密度と比重の測定方法に準拠して測定を行った。
(Evaluation items and evaluation methods)
(1) Workability
Processability is based on the example, compatibility, discharge in continuous molding, film forming, frost line stability, winding stability, film opening, wrinkle and transparent molded product state confirmed.
(2) Specific gravity
The specific gravity was measured in accordance with the plastic density and specific gravity measurement method described in JIS-K-7112.
（３）融点
融点は、ＪＩＳ−Ｋ−７１２１記載の熱分析測定法に準拠した示差熱分析装置（（株）島津製作所製のＤＳＣ−５０型）で測定を行った。
（４）引張破断強度及び破断伸度
引張破断強度及び破断伸度は、ＪＩＳ−Ｋ−１７０２記載の引張試験法に準拠して測定を行った。試験片はＪＩＳ−Ｋ−７１２７に記載されている４号形試験片形状を用いた。
(3) Melting point
The melting point was measured with a differential thermal analyzer (DSC-50 type, manufactured by Shimadzu Corporation) based on the thermal analysis measurement method described in JIS-K-7121.
(4) Tensile breaking strength and breaking elongation
The tensile breaking strength and breaking elongation were measured according to the tensile test method described in JIS-K-1702. The test piece used the shape of No. 4 type test piece described in JIS-K-7127.
（５）引裂強度
引裂強度は、ＪＩＳ−Ｋ−７１２８Ｃ法（直角形引裂法）記載の引裂試験法に準拠して測定を行った。
（６）ヒートシール強度
ヒートシール強度は、ＪＩＳ−Ｚ−１７１１記載のヒートシール強度測定法に準拠して測定を行った。一般的な製袋機にて温度２００℃、ショット数５０枚／ｍｉｎの条件で製袋加工した袋のシール部を測定した。
(5) Tear strength
The tear strength was measured according to the tear test method described in JIS-K-7128C method (right angle tear method).
(6) Heat seal strength
The heat seal strength was measured according to the heat seal strength measurement method described in JIS-Z-1711. The sealing part of the bag made by bag making was measured with a general bag making machine under the conditions of a temperature of 200 ° C. and a shot number of 50 sheets / min.
（７）耐衝撃性
任意の大きさの袋状に製袋加工した後、全容積量の１／２容量の水を入れ、上下に激しく震動させて底抜けや袋本体からの裂け性等の状態を確認した。
(7) Impact resistance
After making into a bag of any size, half the total volume of water was added and vigorously shaken up and down to check the state of bottoming and tearing from the bag body.
（８）燃焼カロリー
検討に使用した原材料の燃焼カロリー、ポリ乳酸１９ｋＪ／ｇ、ポリエチレン４６ｋＪ／ｇ、変性ポリオレフィン４６ｋＪ／ｇより、理論的に下記の式より算出した。
燃焼カロリー（ｋＪ／ｇ）＝１９×Ｘ＋４６×Ｙ＋４６×Ｚ／１００
但し、Ｘ：ポリ乳酸樹脂の質量部、Ｙ：オレフィン系樹脂の質量部、
Ｚ：変性ポリオレフィン化合物の質量部
（９）燃焼時のＣＯ２発生量
燃焼時のＣＯ２発生量は、実施例、比較例で成形したフィルム１ｋｇ当りのＣＯ２発生量を算出した。算出方法は、「Ｈｅａｌｔｈ Ｄｉｇｅｓｔ．１４（１）．１（１９９９、小原仁実著）」より、「プラスチックが酸化分解時に発生するＣＯ２量（化学構造由来分）」に記載されているＣＯ２発生量の計算法に基づき算出した。計算法は次の通りである。
ＣＯ２発生量（ｋｇ−ＣＯ２／ｋｇ−Ｒｅｓｉｎ）
＝（化石資源由来の成分量）×３ｋｇ／ＣＯ２＋（バイオマス由来の成分量）×２ｋｇ／ＣＯ２
更に、「Ｈｅａｌｔｈ Ｄｉｇｅｓｔ．１４（１）．１（１９９９、小原仁実著）」の「プラスチックが酸化分解時に発生するＣＯ２量（化学構造由来分）」によれば、ＬＬＤＰＥ，ＬＤＰＥ等のポリエチレンの燃焼時のＣＯ２発生量は、１ｋｇ当りに対して３．０ｋｇであることから、実施例１〜５、比較例１〜４で得られた成形品の１Ｋｇ当りのＣＯ２発生削減率（％）を、次の計算式より算出した。
ＣＯ２発生削減率（％）
＝１００−｛（実施例、比較例組成のＣＯ２発生／３．０ｋｇ／ＣＯ２）×１００｝
上記表１は、実施例１〜４、比較例１〜５におけるポリ乳酸／ポリオレフィン系組成物の組成及びその組成比、ブロー比等の条件、並びに相溶性、吐出安定性、製膜安定性等の成形状況と成形品の機械的特性等の結果を示す。
(8) Burning calories
From the calorie of the raw materials used in the study, polylactic acid 19 kJ / g, polyethylene 46 kJ / g, and modified polyolefin 46 kJ / g, the theoretical calculation was performed from the following formula.
Burning calories (kJ / g) = 19 × X + 46 × Y + 46 × Z / 100
However, X: parts by mass of polylactic acid resin, Y: parts by mass of olefin resin,
Z: parts by mass of the modified polyolefin compound (9) CO 2 generation amount during combustion
As the amount of CO 2 generated during combustion, the amount of CO 2 generated per 1 kg of the film formed in Examples and Comparative Examples was calculated. The calculation method is “Health Digest. 14 (1). 1 (1999, written by Hitomi Ohara)” and “CO 2 generation described in“ Amount of CO 2 Generated during Plastic Oxidation Decomposition (Chemical Structure Origin) ”. It was calculated based on the amount calculation method. The calculation method is as follows.
CO 2 generation amount (kg-CO 2 / kg-Resin)
= (Component amount derived from fossil resources) x 3 kg / CO2 + (component amount derived from biomass) x 2 kg / CO2
Furthermore, according to “Health Digest. 14 (1) .1 (1999, by Hitomi Ohara)”, “the amount of CO 2 generated during oxidative degradation of plastics (derived from the chemical structure)”, it can be seen that polyethylene such as LLDPE and LDPE Since the CO 2 generation amount during combustion is 3.0 kg per kg, the CO 2 generation reduction rate (%) per kg of the molded products obtained in Examples 1 to 5 and Comparative Examples 1 to 4 Was calculated from the following formula.
CO 2 emission reduction rate (%)
= 100-{(CO 2 generation of example, comparative example composition / 3.0 kg / CO 2 ) × 100}
Table 1 shows the composition of the polylactic acid / polyolefin composition in Examples 1 to 4 and Comparative Examples 1 to 5 and the composition ratio, conditions such as the blow ratio, and compatibility, ejection stability, film formation stability, etc. The results of molding conditions and mechanical properties of molded products are shown.
表１の結果によれば、本発明を実施するのに必要な条件であるポリ乳酸樹脂、ポリオレフィン系樹脂、変性ポリオレフィン系化合物の組合せによる３成分で構成され、ポリ乳酸樹脂が４．５〜３０質量部、ポリオレフィン樹脂が２５〜８８．７５質量部、変性ポリオレフィン化合物が６．７５〜４５質量部含有し、ポリ乳酸樹脂に対して変性ポリオレフィン系化合物が１．５倍以上含まれており、且つ、３成分の総量が１００質量部で製膜するという条件に従って製作された実施例１、実施例３、実施例４は、植物由来の樹脂成分を含んだバイオマス型フィルムの成形が安定していることが分かる。 According to the result of Table 1, it is comprised by three components by the combination of the polylactic acid resin which is the conditions required for implementing this invention, polyolefin resin, and a modified polyolefin compound, and polylactic acid resin is 4.5-30. Part by mass, 25 to 88.75 parts by mass of a polyolefin resin, 6.75 to 45 parts by mass of a modified polyolefin compound, 1.5 times or more of the modified polyolefin compound relative to the polylactic acid resin, and In Example 1, Example 3, and Example 4 manufactured according to the condition that the total amount of the three components is 100 parts by mass, the molding of the biomass type film containing the plant-derived resin component is stable. I understand that.
一方、ポリ乳酸樹脂に対して変性ポリオレフィン系化合物が１．５倍以下含まれた比較例１、実施例２は、吐出量や製膜性等の成形は比較的良好な状況ではあるが、成形で得られたフィルム表面に樹脂ムラが見受けられ外観的にも好ましくなく、更にフィルム層間にて層間剥離現象も見受けられ、本発明の植物由来の樹脂成分を含んだバイオマス型フィルムとしての特性を備えていない。 On the other hand, Comparative Example 1 and Example 2 in which the modified polyolefin compound is contained 1.5 times or less with respect to the polylactic acid resin are in a relatively good situation in terms of molding such as discharge amount and film forming property. Resin unevenness is found on the surface of the film obtained in 1), which is not preferable in terms of appearance, and further, a delamination phenomenon is observed between the film layers, and it has characteristics as a biomass type film containing the plant-derived resin component of the present invention. Not.
更に、比較例３は、ＣＯ２削減効果は大きいが、成形の際に部分的に折れジワが発生する傾向が見受けられ、ポリ乳酸樹脂成分の増加に伴い、変性ポリオレフィン化合物成分の割合も増加する傾向にあるため、原料コストがポリオレフィン樹脂価格に対して２．５倍以上と高くなる。 Furthermore, although Comparative Example 3 has a large CO 2 reduction effect, it can be seen that there is a tendency to partially crease during molding, and as the polylactic acid resin component increases, the proportion of the modified polyolefin compound component also increases. Due to the tendency, the raw material cost is 2.5 times or more higher than the polyolefin resin price.
なお、この発明は、上記実施形態そのままに限定されるものではなく、実施段階ではその要旨を逸脱しない範囲で構成要素を変形して具体化できる。また、上記実施形態に開示されている複数の構成要素の適宜な組合せにより種々の発明を形成できる。例えば、実施形態のポリ乳酸／ポリオレフィン系組成物はインフレーション法により成形する場合であるが、これに限定されない。更に、異なる実施形態に亘る構成要素を適宜組み合せてもよい。 Note that the present invention is not limited to the above-described embodiment as it is, and can be embodied by modifying the constituent elements without departing from the scope of the invention in the implementation stage. In addition, various inventions can be formed by appropriately combining a plurality of components disclosed in the embodiment. For example, the polylactic acid / polyolefin composition of the embodiment is a case of molding by an inflation method, but is not limited thereto. Furthermore, you may combine suitably the component covering different embodiment.
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