JP2006316172A - Resin composition - Google Patents
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- JP2006316172A JP2006316172A JP2005140403A JP2005140403A JP2006316172A JP 2006316172 A JP2006316172 A JP 2006316172A JP 2005140403 A JP2005140403 A JP 2005140403A JP 2005140403 A JP2005140403 A JP 2005140403A JP 2006316172 A JP2006316172 A JP 2006316172A
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Abstract
Description
本発明は、ポリヒドロキシブチレートを含む樹脂組成物に関し、具体的には、射出成形体とした際に、衝撃強度及び耐熱性に優れる樹脂組成物に関する。 The present invention relates to a resin composition containing polyhydroxybutyrate, and specifically relates to a resin composition excellent in impact strength and heat resistance when formed into an injection-molded product.
一般に、自動車の内装等に用いられる樹脂材料では、物性向上のために改質剤をブレンドしたものが用いられている。改質剤の選定では、バルク材料との相溶性が重要な観点の一つである。しかし、実際には改質剤に加えて相溶化剤を添加して改質剤の高分散状態を実現するケースが殆どであり、これが高コストの主要因となっている。 In general, resin materials used for automobile interiors are blended with modifiers to improve physical properties. In selecting a modifier, compatibility with the bulk material is one of the important viewpoints. However, in most cases, a compatibilizing agent is added in addition to the modifying agent to realize a highly dispersed state of the modifying agent, which is a main factor of high cost.
また、改質剤のうち、柔軟化剤と呼ばれるものは、総じて耐熱性が低い。従って、改質剤を多く含有させると樹脂組成物の耐熱性が低下してしまうことから、少量の改質剤をいかに高分散させて耐熱性の低下を最小限に抑えるかが重要になっている。 Of the modifiers, those called softening agents generally have low heat resistance. Therefore, since the heat resistance of the resin composition decreases when a large amount of the modifier is contained, it is important how to disperse a small amount of the modifier to minimize the decrease in heat resistance. Yes.
樹脂組成物に用いられるバルク材料としては、耐熱性の高いポリヒドロキシブチレート（以下、「ＰＨＢ」という場合がある。）が挙げられる。但し、ＰＨＢは、耐熱性に優れるものの衝撃性にやや劣るため、多くの場合には衝撃強度を向上させるために、改質剤が用いられる。 Examples of the bulk material used for the resin composition include polyhydroxybutyrate (hereinafter sometimes referred to as “PHB”) having high heat resistance. However, although PHB is excellent in heat resistance, it is slightly inferior in impact properties. Therefore, in many cases, a modifier is used to improve impact strength.
ポリヒドロキシブチレートを用いた例としては、例えば、生分解性を有する脂肪族ポリエステルとセルロースエステルとの２成分系ブレンドしたものに第三成分として重合体を添加したポリマー成分であって、前記脂肪族ポリエステルの一つとしてＰＨＢを用いたものが提案されている（例えば、特許文献１参照。）。しかし、このポリマー成分は、フィルム成形を目的とするものであり、樹脂成形体用途については記載がなく、衝撃強度の向上を目的とするものではない。 Examples of using polyhydroxybutyrate include, for example, a polymer component obtained by adding a polymer as a third component to a two-component blend of a biodegradable aliphatic polyester and a cellulose ester, The thing using PHB as one of the group polyester is proposed (for example, refer patent document 1). However, this polymer component is intended for film molding, and there is no description about the use of a resin molded product, and it is not intended to improve impact strength.
以上のように、衝撃強度の向上と耐熱性との両立を目的とするＰＨＢを用いた樹脂組成物は未だ提供されておらず、このような樹脂組成物の開発が望まれていた。 As described above, a resin composition using PHB for the purpose of improving both impact strength and heat resistance has not been provided, and development of such a resin composition has been desired.
本発明は、射出成形体に好適に用いることができ、衝撃強度と耐熱性とに優れた樹脂組成物を提供することを目的とする。 An object of this invention is to provide the resin composition which can be used suitably for an injection molded object and was excellent in impact strength and heat resistance.
本発明は、ポリヒドロキシブチレートと、エチレン−酢酸ビニルコポリマーとを含み、前記ポリヒドロキシブチレートの含有量が全固形分に対して７０質量％以上であることを特徴とする樹脂組成物である。また、本発明の樹脂組成物は、前記エチレン−酢酸ビニルコポリマーの含有量が全固形分に対して６質量％〜２０質量％であることが好ましい。更に、本発明の樹脂組成物は射出成形用であることが好ましい。 The present invention is a resin composition comprising polyhydroxybutyrate and an ethylene-vinyl acetate copolymer, wherein the content of the polyhydroxybutyrate is 70% by mass or more based on the total solid content. . In the resin composition of the present invention, the content of the ethylene-vinyl acetate copolymer is preferably 6% by mass to 20% by mass with respect to the total solid content. Furthermore, the resin composition of the present invention is preferably used for injection molding.
本発明の樹脂組成物は、ポリヒドロキシブチレート（ＰＨＢ）に改質剤としてエチレン−酢酸ビニルコポリマーを添加した組成物であり、高い衝撃強度と耐熱性とを両立させることができる。これは、エチレン−酢酸コポリマーはＰＨＢとの相溶性がよく、相溶化剤を用いなくても微細に分散させることができることから、ポリヒドロキシブチレートの耐熱性を低下させることなく衝撃強度を高めることができるためであると推測される。 The resin composition of the present invention is a composition obtained by adding an ethylene-vinyl acetate copolymer as a modifier to polyhydroxybutyrate (PHB), and can achieve both high impact strength and heat resistance. This is because the ethylene-acetic acid copolymer has good compatibility with PHB and can be finely dispersed without using a compatibilizing agent, thus increasing the impact strength without reducing the heat resistance of polyhydroxybutyrate. This is presumed to be possible.
本発明によれば、射出成形体に好適に用いることができ、衝撃強度と耐熱性とに優れた樹脂組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can be used suitably for an injection molded object and was excellent in impact strength and heat resistance can be provided.
以下、本発明の樹脂組成物について説明する。本発明の樹脂組成物は、ポリヒドロキシブチレートと、エチレン−酢酸ビニルコポリマーとを含み、前記ポリヒドロキシブチレートの含有量が全固形分に対して７０質量％以上であり、前記エチレン−酢酸ビニルコポリマーの含有量が全固形分に対して６質量％〜２０質量％であることを特徴とする。 Hereinafter, the resin composition of the present invention will be described. The resin composition of the present invention comprises polyhydroxybutyrate and an ethylene-vinyl acetate copolymer, and the content of the polyhydroxybutyrate is 70% by mass or more based on the total solid content. The content of the copolymer is 6% by mass to 20% by mass with respect to the total solid content.
本発明の樹脂組成物はポリヒドロキシブチレート（ＰＨＢ）を主成分とする樹脂組成物であって、ＰＨＢを全固形分に対して７０質量％以上含む。ＰＨＢの含有量が７０質量％未満であると十分な耐熱性を維持することができない。前記ＰＨＢの含有量は、全固形分に対して８０〜９５質量％であることが好ましく、８５〜９０質量％が更に好ましい。 The resin composition of the present invention is a resin composition containing polyhydroxybutyrate (PHB) as a main component, and contains PHB in an amount of 70% by mass or more based on the total solid content. If the PHB content is less than 70% by mass, sufficient heat resistance cannot be maintained. The PHB content is preferably 80 to 95% by mass, more preferably 85 to 90% by mass, based on the total solid content.
本発明におけるＰＨＢの重量平均分子量（Ｍｗ）としては、射出成形時の流動性と結晶化速度の観点から、１０万〜４０万が好ましく、１５万〜２５万が更に好ましい。 The weight average molecular weight (Mw) of PHB in the present invention is preferably 100,000 to 400,000, more preferably 150,000 to 250,000 from the viewpoints of fluidity and crystallization speed during injection molding.
また、本発明におけるポリヒドロキシブチレートには、ポリヒドロキシブチレートの誘導体も含まれる。ポリヒドロキシブチレートの誘導体としては、例えば、ポリヒドロキシアルカン酸が挙げられ、例えば、ポリヒドロキシヘキサン酸、ポリヒドロキシバレン酸、及び、これらの共重合体等が挙げられる。 The polyhydroxybutyrate in the present invention also includes polyhydroxybutyrate derivatives. Examples of the polyhydroxybutyrate derivative include polyhydroxyalkanoic acid, and examples thereof include polyhydroxyhexanoic acid, polyhydroxyvaleric acid, and copolymers thereof.
本発明の樹脂組成物には、改質剤としてエチレン−酢酸ビニルコポリマーが含まれる。エチレン−酢酸コポリマーは、ＰＨＢとの相溶性が高いことから、本発明の樹脂組成物を射出成形した際に、結晶性を維持したまま微細に分散させることができる。 The resin composition of the present invention contains an ethylene-vinyl acetate copolymer as a modifier. Since the ethylene-acetic acid copolymer is highly compatible with PHB, it can be finely dispersed while maintaining the crystallinity when the resin composition of the present invention is injection molded.
本発明の樹脂組成物中における前記エチレン−酢酸ビニルコポリマーの含有量は、衝撃強度と耐熱性との両立を図る観点から、６質量％〜２０質量％であることが好ましく、１０質量％〜２０質量％がさらに好ましい。 The content of the ethylene-vinyl acetate copolymer in the resin composition of the present invention is preferably 6% by mass to 20% by mass from the viewpoint of achieving both impact strength and heat resistance, and is preferably 10% by mass to 20%. More preferred is mass%.
前記エチレン−酢酸ビニルコポリマーの共重合比（エチレン／酢酸ビニル）は、ＰＨＢとの相溶性の観点から、８０／２０〜５０／５０が好ましく、６５／３５〜５５／４５が更に好ましい。 The copolymerization ratio (ethylene / vinyl acetate) of the ethylene-vinyl acetate copolymer is preferably 80/20 to 50/50, more preferably 65/35 to 55/45, from the viewpoint of compatibility with PHB.
また、前記エチレン−酢酸ビニルコポリマーの、１５０℃、荷重２１．１８Ｎの条件に基づいて測定されたメルトフローレート（ＭＦＲ）は、ＰＨＢとの溶解差や温度差の観点から、１５〜７５ｇ／１０ｍｉｎが好ましく、５５〜７７ｇ／１０ｍｉｎが更に好ましい。 Moreover, the melt flow rate (MFR) measured based on the conditions of 150 degreeC and load 21.18N of the said ethylene- vinyl acetate copolymer is 15-75 g / 10min from a viewpoint of a melt | dissolution difference with PHB, or a temperature difference. Is preferable, and 55-77 g / 10min is still more preferable.
本発明におけるエチレン−酢酸ビニルコポリマーとしては、例えば、酢酸ビニル含有量（ＪＩＳ Ｋ６７３０−１９８１）が、４．５質量％、５質量％、６質量％、７．５質量％、１０質量％、１３質量％、１５質量％、１６質量％、１９質量％、２０質量％、２５質量％、２８質量％、３２質量％、４１質量％のものを用いることができる。また、本発明におけるエチレン−酢酸ビニルコポリマーは、本発明の効果を損なわない範囲で、エチレン及び酢酸ビニル以外の構成成分を含むものであってもよい。 As an ethylene-vinyl acetate copolymer in the present invention, for example, vinyl acetate content (JIS K6730-1981) is 4.5 mass%, 5 mass%, 6 mass%, 7.5 mass%, 10 mass%, 13 The thing of the mass%, 15 mass%, 16 mass%, 19 mass%, 20 mass%, 25 mass%, 28 mass%, 32 mass%, and 41 mass% can be used. Moreover, the ethylene-vinyl acetate copolymer in this invention may contain structural components other than ethylene and vinyl acetate in the range which does not impair the effect of this invention.
また、ＰＨＢ中に分散した本発明におけるエチレン−酢酸ビニルコポリマーの平均粒径は、５μｍ以下程度が好ましく、１μｍ以下程度が更に好ましい。 Further, the average particle size of the ethylene-vinyl acetate copolymer dispersed in PHB in the present invention is preferably about 5 μm or less, and more preferably about 1 μm or less.
本発明の樹脂組成物は、本発明の効果を損なわない範囲でＰＨＢ及びエチレン−酢酸ビニルコポリマー以外の第三成分を含んでいてもよい。前記第三成分としては、例えば、本発明の樹脂組成物のブレンド状態を良好にするための可塑剤が挙げられ、該可塑剤としては、例えば、脂肪族二塩基酸エステル、フタル酸エステル、ヒドロキシ多価カルボン酸エステル、ポリエステル系可塑剤、脂肪酸エステル、エポキシ系可塑剤、及び、これらの混合物を挙げることができる。具体的には、フタル酸ジ２−エチルヘキシル（ＤＯＰ）、フタル酸ジブチル（ＤＢＰ）、フタル酸ジイソデシル（ＤＩＤＰ）等のフタル酸エステル；アジピン酸ジ２−エチルヘキシル（ＤＯＡ）、アジピン酸ジイソデシル（ＤＩＤＡ）等のアジピン酸エステル；アゼライン酸ジ２−エチルヘキシル（ＤＯＺ）等のアゼライン酸エステル、アセチルクエン酸トリ２−エチルヘキシル、アセチルクエン酸トリブチル等のヒドロキシ多価カルボン酸エステル、ポリプロピレングリコールアジピン酸エステル等のポリエステル系可塑剤が挙げられ、これらは一種又は２種以上の混合物で用いることができる。 The resin composition of the present invention may contain a third component other than PHB and ethylene-vinyl acetate copolymer as long as the effects of the present invention are not impaired. Examples of the third component include a plasticizer for improving the blend state of the resin composition of the present invention. Examples of the plasticizer include aliphatic dibasic acid esters, phthalic acid esters, hydroxy compounds, and the like. Examples thereof include polyvalent carboxylic acid esters, polyester plasticizers, fatty acid esters, epoxy plasticizers, and mixtures thereof. Specifically, phthalic acid esters such as di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diisodecyl phthalate (DIDP); di-2-ethylhexyl adipate (DOA), diisodecyl adipate (DIDA) Adipic acid esters such as azelaic acid di-2-ethylhexyl (DOZ), azelaic acid esters such as tri-acetylhexyl citrate, tributyl acetyl citrate, and polyesters such as polypropylene glycol adipic acid ester These include plasticizers, which can be used alone or as a mixture of two or more.
本発明の樹脂組成物中における第三成分の含有量は、目的によって異なるが、１〜２０質量％が好ましく、５〜１５質量％が更に好ましい。 Although content of the 3rd component in the resin composition of this invention changes with purposes, 1-20 mass% is preferable and 5-15 mass% is still more preferable.
本発明の樹脂組成物は、成形体用途に用いられることが好ましい。成型方法としては公知の成形方法を適宜用いることができ、例えば、射出成形、ブロー成形、インフレーション成形、Ｔダイ押出し成形、カレンダー成形等を用いることができる。本発明の樹脂組成物は、結晶性を保ったままエチレン−酢酸ビニルコポリマーの分散状態を良好にする観点から、射出成形用であることが好ましい。 It is preferable that the resin composition of this invention is used for a molded object use. As a molding method, a known molding method can be appropriately used. For example, injection molding, blow molding, inflation molding, T-die extrusion molding, calendar molding, or the like can be used. The resin composition of the present invention is preferably for injection molding from the viewpoint of improving the dispersion state of the ethylene-vinyl acetate copolymer while maintaining crystallinity.
樹脂組成物の耐熱性は、例えば、ＪＩＳ Ｋ６７３０−１９８１に基づくビカット軟化温度（℃）を指標とすることができる。本発明の樹脂組成物のビカット軟化温度は、１４０〜１７０℃であることが好ましく、１５０〜１７０℃であることが更に好ましい。 The heat resistance of the resin composition can be determined using, for example, the Vicat softening temperature (° C.) based on JIS K6730-1981. The Vicat softening temperature of the resin composition of the present invention is preferably 140 to 170 ° C, and more preferably 150 to 170 ° C.
また、樹脂組成物の衝撃強度は、例えば、ＪＩＳ−Ｋ７１１０に基づくノッチ付Ｉｚｏｄ衝撃強度(Ｊ／ｍ)を指標とすることができる。本発明の樹脂組成物のノッチ付Ｉｚｏｄ衝撃強度は、１０Ｊ／ｍ以上であることが好ましく、２０Ｊ／ｍ以上が更に好ましい。 Moreover, the impact strength of the resin composition can use, for example, a notched Izod impact strength (J / m) based on JIS-K7110 as an index. The notched Izod impact strength of the resin composition of the present invention is preferably 10 J / m or more, and more preferably 20 J / m or more.
本発明の樹脂組成物は、各材料を任意の割合でブレンドすることによって作製することができる。具体的には、まず、各材料をペレタイズ（チップ化）し、それをブレンドした後、例えば、射出成形機等で射出成形することで、本発明の組成物（射出成形体）を作製することができる。 The resin composition of the present invention can be produced by blending each material at an arbitrary ratio. Specifically, first, each material is pelletized (chips), blended, and then, for example, injection molded with an injection molding machine or the like to produce the composition (injection molded body) of the present invention. Can do.
本発明の樹脂組成物の用途としては、例えば、自動車用材料、家電製品用材料、包装材、建築資材、及びその他種々の樹脂組成物が用いられる分野で利用することができる。 As a use of the resin composition of this invention, it can utilize in the field | area where the material for motor vehicles, the material for household appliances, a packaging material, building materials, and other various resin compositions are used, for example.
以下に本発明の樹脂組成物について実施例により具体的に説明する。但し、本発明はこれに限定されるものではない。 The resin composition of the present invention will be specifically described below with reference to examples. However, the present invention is not limited to this.
［実施例１］
２軸押出機にてＰＨＢをペレタイズした後、同機にてエチレン−ビニルアセテート共重合体とブレンドし、その後、射出成形により、実施例１の樹脂成形体を作製した。各条件を下記に示す。
[Example 1]
After pelletizing PHB with a twin screw extruder, it was blended with an ethylene-vinyl acetate copolymer in the same machine, and then a resin molded article of Example 1 was produced by injection molding. Each condition is shown below.
〔材料〕
・ＰＨＢ… 商品名：＃１０００、ブラジルのＰＨＢ Ｉｎｄｓｔｒｉａｌ ＳＡ社製、重量平均分子量（Ｍｗ）：１９万、数平均分子量（Ｍｎ）：７．６万、Ｍｗ／Ｍｎ：２．４
・エチレン−ビニルアセテート共重合体… 商品名Ｒ５０１１、住友化学（株）製、酢酸ビニル含有量（ＪＩＳ Ｋ６７３０−１９８１）４１質量％、メルトフローレート（ＪＩｓ Ｋ６７３０−１９８１）６０ｇ／１０ｍｉｎ
・ブレンド比率：（全固形分に対するエチレン−ビニルアセテート共重合体の含有率）＝５質量％
〔material〕
-PHB ... Product name: # 1000, manufactured by PHB Industrial SA, Brazil, weight average molecular weight (Mw): 190,000, number average molecular weight (Mn): 76,000, Mw / Mn: 2.4
-Ethylene-vinyl acetate copolymer ... Trade name R5011, manufactured by Sumitomo Chemical Co., Ltd., vinyl acetate content (JIS K6730-1981) 41% by mass, melt flow rate (JIS K6730-1981) 60 g / 10 min
Blend ratio: (content of ethylene-vinyl acetate copolymer relative to the total solid content) = 5% by mass
・ペレタイズ条件：１４５℃〜１７３℃（ノズルヘッド温度１６０℃、スクリュー回転速度１５０ｒｐｍ）
・ブレンド条件：１６０℃〜１７０℃（ノズルヘッド温度１６０℃、スクリュー回転速度５０ｒｐｍ）
・射出成形条件：１４５℃〜１６５℃（ノズルヘッド温度１６３℃）、型温５０〜５３℃（実測）、射出・保圧時間１０ｓｅｃ、冷却時間３０ｓｅｃ、射出圧（一次）約３ＭＰａ、保圧約２．３ＭＰａ
Pelletizing conditions: 145 ° C to 173 ° C (nozzle head temperature 160 ° C, screw rotation speed 150 rpm)
Blend condition: 160 ° C to 170 ° C (nozzle head temperature 160 ° C, screw rotation speed 50 rpm)
Injection molding conditions: 145 ° C. to 165 ° C. (nozzle head temperature 163 ° C.), mold temperature 50 to 53 ° C. (actual measurement), injection / holding time 10 sec, cooling time 30 sec, injection pressure (primary) about 3 MPa, holding pressure about 2 .3 MPa
［実施例２〜３］
実施例１において、ＰＨＢとエチレン−ビニルアセテート共重合体とのブレンド量を、下記表１に示すように変更した以外は実施例１と同様にして各樹脂組成物を作製した。
[Examples 2-3]
Each resin composition was prepared in the same manner as in Example 1 except that the blend amount of PHB and ethylene-vinyl acetate copolymer was changed as shown in Table 1 below.
［比較例１］
実施例１において、エチレン−ビニルアセテート共重合体を用いなかった以外は実施例１と同様にして樹脂組成物を作製した。
[Comparative Example 1]
In Example 1, a resin composition was prepared in the same manner as in Example 1 except that the ethylene-vinyl acetate copolymer was not used.
［比較例２〜４］
実施例１において、エチレン−ビニルアセテート共重合体をエチレン−アクリル共重合体（商品名：アクリフトＷＨ４０１、住友化学（株）製、アクリル含有量：２０質量％）に変更し、更に、ブレンド量を下記表１に示すように変更した以外は実施例１と同様にして樹脂組成物を作製した。
[Comparative Examples 2 to 4]
In Example 1, the ethylene-vinyl acetate copolymer was changed to an ethylene-acrylic copolymer (trade name: ACLIFT WH401, manufactured by Sumitomo Chemical Co., Ltd., acrylic content: 20% by mass), and the blend amount was further changed. A resin composition was prepared in the same manner as in Example 1 except that the changes were made as shown in Table 1 below.
〔評価〕
−ノッチ付Ｉｚｏｄ衝撃強度−
実施例１〜３、比較例１〜４を用いて、ＪＩＳ−Ｋ７１１０の条件で、樹脂成形体のノッチ付Ｉｚｏｄ衝撃強度を測定した。結果を下記表１に示す。
[Evaluation]
-Izod impact strength with notch-
Using Examples 1 to 3 and Comparative Examples 1 to 4, the notched Izod impact strength of the resin molded body was measured under the conditions of JIS-K7110. The results are shown in Table 1 below.
−ビカット軟化温度−
実施例１〜３、比較例１〜４を用いて、ＪＩＳ−Ｋ６７３０−１９８１）の条件で、樹脂成形体のビカット軟化温度を測定した。結果を下記表１に示す。
−Vicat softening temperature−
Using Examples 1 to 3 and Comparative Examples 1 to 4, the Vicat softening temperature of the resin molded body was measured under the conditions of JIS-K6730-1981). The results are shown in Table 1 below.
表１からわかるように、実施例１〜３の樹脂成形体は、Ｉｚｏｄ衝撃強度とビカット軟化温度との両立が図られていた。特に、実施例２の樹脂成形体は、Ｉｚｏｄ衝撃強度及びビカット軟化温度共に優れていた。 As can be seen from Table 1, the resin molded bodies of Examples 1 to 3 achieved both the Izod impact strength and the Vicat softening temperature. In particular, the resin molded product of Example 2 was excellent in both Izod impact strength and Vicat softening temperature.
また、実施例２及び比較例３の樹脂成形体の断面をＳＥＭで観察した。図１は実施例２の樹脂成形体の断面を示すＳＥＭ画像であり、図２は、比較例３の樹脂成形体の断面を示すＳＥＭ画像である。図１に示すように、実施例２の樹脂成形体は、エチレン−ビニルアセテート共重合体がＰＨＢに微細に分散され分散状態が良好であり、エチレン−ビニルアセテート共重合体の粒径が約１μｍと小さいことがわかる。これに対し、図２に示すように比較例３の樹脂成型体は、エチレン−アクリル共重合体のの粒径が大きく、分散状態が悪いことがわかる。 Moreover, the cross section of the resin molding of Example 2 and Comparative Example 3 was observed with SEM. FIG. 1 is an SEM image showing a cross section of the resin molded body of Example 2, and FIG. 2 is an SEM image showing a cross section of the resin molded body of Comparative Example 3. As shown in FIG. 1, in the resin molded product of Example 2, the ethylene-vinyl acetate copolymer is finely dispersed in PHB and the dispersion state is good, and the particle size of the ethylene-vinyl acetate copolymer is about 1 μm. I understand that it is small. On the other hand, as shown in FIG. 2, it can be seen that the resin molded body of Comparative Example 3 has a large particle size of the ethylene-acrylic copolymer and a poor dispersion state.
Claims (3)
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| JP2005140403A JP2006316172A (en) | 2005-05-12 | 2005-05-12 | Resin composition |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014002417A1 (en) * | 2012-06-29 | 2014-01-03 | 株式会社カネカ | Poly-3-hydroxyalkanoate resin composition and molded body |
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| JPH06503847A (en) * | 1990-07-25 | 1994-04-28 | モンサント・カンパニー | Biodegradable polymer blend containing 3-hydroxybutyrate/3-hydroxyvalerate copolymer |
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| WO2014002417A1 (en) * | 2012-06-29 | 2014-01-03 | 株式会社カネカ | Poly-3-hydroxyalkanoate resin composition and molded body |
| JPWO2014002417A1 (en) * | 2012-06-29 | 2016-05-30 | 株式会社カネカ | POLY-3-HYDROXYALKANOATE RESIN COMPOSITION AND MOLDED ARTICLE |
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