JP2006070224A - Polylactic-based resin composition for calendar molding - Google Patents
Polylactic-based resin composition for calendar molding Download PDFInfo
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この発明は、耐熱性、耐衝撃性の改善されたポリ乳酸を含むシートを成形加工するためのカレンダー成形用ポリ乳酸系樹脂組成物に関する。 The present invention relates to a polylactic acid resin composition for calendering for molding a sheet containing polylactic acid having improved heat resistance and impact resistance.
ポリ乳酸系樹脂組成物は、植物由来のポリ乳酸を主成分として含み、石油による原料依存が少なく燃焼エネルギーも低いため、そのシートは環境保護の観点から、ポリプロピレン、ポリスチレン、ポリ塩化ビニル樹脂などの石油系のシートに替わる材料として期待されている。 The polylactic acid-based resin composition contains plant-derived polylactic acid as a main component, is less dependent on raw materials due to petroleum and has low combustion energy, so the sheet is made of polypropylene, polystyrene, polyvinyl chloride resin, etc. from the viewpoint of environmental protection. It is expected as a material to replace petroleum-based sheets.
ポリ乳酸はＬ−乳酸とＤ−乳酸の含有比率によって成形後の結晶化のしやすさが異なり、Ｌ−乳酸またはＤ−乳酸の含有比率がおよそ９５％以上のポリ乳酸は結晶化しやすく実質上結晶性のポリ乳酸といわれ、それがほぼ単独で配合された樹脂組成物は、押出成形法により溶融状態で押出して、溶融樹脂を急冷して一旦固化させた後、ニ軸延伸法で延伸する方法によってシート成形されている。 Polylactic acid differs in the ease of crystallization after molding depending on the content ratio of L-lactic acid and D-lactic acid, and polylactic acid having a content ratio of L-lactic acid or D-lactic acid of about 95% or more is easily crystallized. A resin composition called crystalline polylactic acid, which is blended almost alone, is extruded in a molten state by an extrusion molding method, the molten resin is rapidly cooled and solidified, and then stretched by a biaxial stretching method. The sheet is formed by the method.
しかし、この成形方法は生産性が低く、得られたポリ乳酸系シートはコストが高く、経済性が重要視される上記石油系のシートに替わる材料とはなりにくいといった問題がある。 However, this molding method has a problem that productivity is low, and the obtained polylactic acid-based sheet is high in cost and is unlikely to be a material to replace the above-described petroleum-based sheet, where economics are important.
そこで、押出法、ニ軸延伸法に比べてシート状物を成形するのに生産効率がよく、経済性に優れたカレンダー成形によるポリ乳酸系樹脂組成物からなるシート化の検討がなされている。 Therefore, the production of a sheet made of a polylactic acid-based resin composition by calender molding has been studied, which is more efficient for forming a sheet-like material than the extrusion method and the biaxial stretching method, and is excellent in economy.
一般的には、上記結晶性のポリ乳酸は、溶融時における温度依存性が大きく、溶融粘度によって成形性が左右されるカレンダー成形法にとってはシート成形が難しいと考えられている。また、熱成形時の粘度が低く、カレンダー機の金属ロールへの粘着度合も強く剥離がしにくいことからも、カレンダー成形が難しいと考えられている。 In general, the crystalline polylactic acid has a large temperature dependency at the time of melting, and it is considered that sheet molding is difficult for a calendar molding method in which moldability is affected by melt viscosity. In addition, it is considered that calendar molding is difficult because the viscosity at the time of thermoforming is low, the degree of adhesion to the metal roll of the calender machine is strong, and it is difficult to peel off.
このようなカレンダー成形を可能とするポリ乳酸系樹脂組成物としては、例えば、ポリ乳酸にシリコンと他の滑剤が配合されたポリ乳酸系樹脂組成物（特許文献１）や、ポリ乳酸樹脂に脂肪族リン酸エステル化合物など含有するポリ乳酸系樹脂組成物（特許文献２）が公知である。
しかしながら、このような結晶化しやすい結晶性のポリ乳酸系樹脂組成物を用いてカレンダー成形されたシートは、押出法、ニ軸延伸法で成形されたような縦横方向に均等に延伸された結晶構造とならず、また結晶が形成されていない脆い非結晶部分が混在するため、耐衝撃性が著しく劣るという問題を抱えている。 However, the sheet formed by calendering using such a crystalline polylactic acid resin composition that is easily crystallized has a crystal structure that is uniformly stretched in the vertical and horizontal directions as formed by an extrusion method or a biaxial stretching method. In addition, there is a problem that the impact resistance is remarkably inferior because a brittle non-crystalline portion where no crystal is formed is mixed.
そこで、ポリ乳酸のうちＬ−乳酸とＤ−乳酸の含有比率を変更して、すなわちＬ−乳酸またはＤ−乳酸の含有比率がおよそ９３％未満になるように調整して、結晶化しにくくしたいわゆる非晶性のポリ乳酸樹脂組成物の使用が考えられるが、そのような樹脂組成物からなるカレンダー成形シートは結晶部分と非晶部分の混在による悪影響はなくなるものの、常温において柔軟で、耐熱性に劣るという問題を抱えている。 Therefore, the content ratio of L-lactic acid and D-lactic acid in polylactic acid is changed, that is, the content ratio of L-lactic acid or D-lactic acid is adjusted to be less than about 93% to make it difficult to crystallize. The use of an amorphous polylactic acid resin composition can be considered, but a calendered sheet made of such a resin composition eliminates the adverse effects of mixing of crystalline and amorphous parts, but is flexible at room temperature and heat resistant. I have the problem of being inferior.
それに対し、ポリ乳酸の耐熱性、耐衝撃性を改善させる組成物として、ポリ乳酸よりも耐熱温度の高い樹脂であるポリカーボネートをポリ乳酸に配合した技術（特開平１１−１４０２９２）が開示されている。 On the other hand, as a composition for improving the heat resistance and impact resistance of polylactic acid, a technique in which polycarbonate, which is a resin having a higher heat resistance temperature than polylactic acid, is blended with polylactic acid (JP-A-11-140292) is disclosed. .
しかし、ポリ乳酸にこのような耐熱性の高いポリカーボネートを所定量配合した組成物は、ポリカーボネートがポリ乳酸の溶融時の実用温度環境にとっては温度依存性が過剰に大きいものであるため、カレンダー成形する際には、成形温度のわずかな変化でも溶融粘度が著しく変動するものとなり、シート成形性が困難なものであるという問題がある。 However, a composition in which a predetermined amount of such heat-resistant polycarbonate is blended with polylactic acid is calendered because the polycarbonate is excessively temperature dependent for the practical temperature environment when polylactic acid is melted. In some cases, even a slight change in the molding temperature causes the melt viscosity to fluctuate remarkably, and sheet formability is difficult.
そこで、本発明は、カレンダー成形法によるシート成形が可能で、耐衝撃性、耐熱性の改善されたカレンダー成形用ポリ乳酸系樹脂組成物を提供することを目的とする。 Therefore, an object of the present invention is to provide a polylactic acid-based resin composition for calender molding that can be molded by a calender molding method and has improved impact resistance and heat resistance.
本発明者は鋭意研究をすることによって、ポリ乳酸としてＬ−乳酸とＤ−乳酸の含有比率が９２：８〜８：９２の実質上非晶性のポリ乳酸を特定して、それにポリ乳酸の溶融時の実用温度環境にとって温度依存性が緩やかなＡＢＳ系樹脂を特定し所定量配合するとともに、さらに脂肪酸エステルであるモンタン酸ワックスを特定し所定量配合した組成物が、カレンダー成形が可能で、しかも耐衝撃性、耐熱性の改善された組成物となることを見出した。 The present inventor conducted intensive research to identify a substantially non-crystalline polylactic acid having a content ratio of L-lactic acid to D-lactic acid of 92: 8 to 8:92 as polylactic acid. A specific amount of ABS-based resin that is moderately temperature-dependent for the practical temperature environment at the time of melting is specified and blended in a predetermined amount, and a montanic acid wax that is a fatty acid ester is specified and blended in a predetermined amount, and a calendar molding is possible. Moreover, it has been found that the composition has improved impact resistance and heat resistance.
すなわち、本発明は、Ｌ−乳酸とＤ−乳酸の含有比率が９２：８〜８：９２であるポリ乳酸１００重量部に対し、ＡＢＳ系樹脂３０〜９９重量部と、脂肪酸エステル系のモンタン酸ワックス０．０５〜５重量部とを配合してなるカレンダー成形用ポリ乳酸系樹脂組成物を要旨とする。 That is, according to the present invention, the amount of L-lactic acid and D-lactic acid is 92: 8 to 8:92, and the polylactic acid is 100 parts by weight. The gist is a polylactic acid-based resin composition for calendering formed by blending 0.05 to 5 parts by weight of a wax.
この発明に係るポリ乳酸系樹脂組成物は、Ｌ−乳酸とＤ−乳酸の含有比率を９２：８〜８：９２に特定した実質上非晶性のポリ乳酸と、同じく非晶質でポリ乳酸の溶融時の実用温度環境にとって温度依存性が緩やかなＡＢＳ樹脂とから構成されているため、溶融混合時においても非晶性で温度依存性の緩やかな特性を示し、カレンダー成形に適した組成物となる。同時に耐衝撃性、耐熱性の優れたＡＢＳ樹脂が、ポリ乳酸の柔軟性と脆さを改善することとなり、カレンダー成形されたシートにおいては耐熱性と耐衝撃性の改善されたものになるという効果がある。 The polylactic acid-based resin composition according to the present invention includes substantially non-crystalline polylactic acid in which the content ratio of L-lactic acid and D-lactic acid is specified as 92: 8 to 8:92, as well as amorphous polylactic acid. Because it is composed of an ABS resin that is moderately temperature-dependent for the practical temperature environment at the time of melting, it is a non-crystalline and temperature-dependent property that is suitable for calendar molding even during melt mixing. It becomes. At the same time, ABS resin with excellent impact resistance and heat resistance will improve the flexibility and brittleness of polylactic acid, and the effect that heat resistance and impact resistance will be improved in calendered sheets. There is.
また、この樹脂組成物は、特定量のモンタン酸ワックスが配合されることによって、非晶質のポリ乳酸とＡＢＳ樹脂の両方の樹脂に適度な滑性を付与し得るものとなり、カレンダー機の金属ロールからの剥離性がよく、カレンダー成形が可能であるといった効果がある。 In addition, this resin composition can impart appropriate lubricity to both amorphous polylactic acid and ABS resin by blending a specific amount of montanic acid wax. It has the effect that it has good releasability from the roll and can be calendered.
そしてこのポリ乳酸系樹脂組成物によるシートは、カレンダー成形することによって得られるため、経済性に優れたものであり、さらに植物由来の樹脂が主成分であることから燃焼エネルギーが低く、環境保護上からも好適なものであるといった効果がある。 And since the sheet made of this polylactic acid resin composition is obtained by calender molding, it is excellent in economic efficiency, and furthermore, since the plant-derived resin is the main component, the combustion energy is low, and in terms of environmental protection. Therefore, there is an effect that it is suitable.
本発明におけるポリ乳酸は、Ｌ−乳酸、Ｄ−乳酸、ＤＬ−乳酸、またはこれら混合物を脱水縮合して得られるか、あるいは乳酸のラクチドを開環重合して得られたものが採用されるが、そのＬ−乳酸とＤ−乳酸の含有比率は９２：８〜８：９２に特定される。好ましくは９１：９〜９：９１に特定されるのが望ましい。このような成分比率に調整されたポリ乳酸は、カレンダー成形の溶融時には結晶化しにくいものとなり、またＡＢＳ樹脂との相溶性もよく溶融時の温度依存性の少ないものとなり、カレンダー成形性の良好なものとなる。反対に上記の範囲を逸脱するポリ乳酸は、溶融時に結晶化しやすく、ＡＢＳ樹脂との相溶性が悪く、カレンダー成形時の温度依存性が大きくなり、シート成形性が著しく低下するため好ましくない。 The polylactic acid in the present invention is obtained by dehydration condensation of L-lactic acid, D-lactic acid, DL-lactic acid, or a mixture thereof, or one obtained by ring-opening polymerization of lactide of lactic acid. The content ratio of L-lactic acid and D-lactic acid is specified as 92: 8 to 8:92. Preferably, it is desirable to specify 91: 9 to 9:91. Polylactic acid adjusted to such a component ratio becomes difficult to crystallize at the time of melting in calendar molding, has good compatibility with ABS resin, and has little temperature dependency at the time of melting, and has good calendar moldability. It will be a thing. On the other hand, polylactic acid that deviates from the above range is not preferable because it easily crystallizes at the time of melting, has poor compatibility with the ABS resin, increases temperature dependency at the time of calender molding, and remarkably reduces sheet moldability.
本発明におけるＡＢＳ樹脂は、アクリロニトリル・ブタジエン・スチレン共重合体をいい、一般的には、スチレン・アクリロニトリル樹脂と、ゴム成分とを混合したものであり、その選定にはとくに制限はない。ここで、ゴム成分としては、ポリブタジエン、ブタジエン・アクリロニトリルゴム（ＮＢＲ）、スチレン・ブタジエンゴム（ＳＢＲ）等のブタジエン系ゴムの他、アクリルゴム（ＡＲ）、エチレン・プロピレンゴム（ＥＰＲ）、塩素化ポリエチレン（ＣＰＥ）等を例示することができ、これらが単独で混合されていても、２種以上のものが併用されて混合されていても良い。ＭＦＲ（メルトフローレート）は、ＡＳＴＭ Ｄ１２３８、ＪＩＳ Ｋ７２１０に規定された押出型プラストメータとを用いて、一定の温度及び圧力でオリフィスから熱可塑性材料を押し出し、押し出された量を１０分間当たりのグラム数に換算して表した数値によって特定されるものであるが、２２０℃、１０ｋｇの条件において、５〜４０の範囲であるのが好ましい。 The ABS resin in the present invention refers to an acrylonitrile / butadiene / styrene copolymer, and is generally a mixture of a styrene / acrylonitrile resin and a rubber component, and there is no particular limitation on the selection thereof. Here, the rubber component includes polybutadiene, butadiene-acrylonitrile rubber (NBR), butadiene rubber such as styrene-butadiene rubber (SBR), acrylic rubber (AR), ethylene-propylene rubber (EPR), chlorinated polyethylene. (CPE) etc. can be illustrated and these may be mixed independently, or 2 or more types may be used together and mixed. MFR (melt flow rate) is measured by extruding a thermoplastic material from an orifice at a constant temperature and pressure using ASTM D1238, an extrusion type plastometer specified in JIS K7210, and the amount extruded is expressed in grams per 10 minutes. Although it is specified by a numerical value converted into a number, it is preferably in the range of 5 to 40 under the conditions of 220 ° C. and 10 kg.
本発明に係るＡＢＳ樹脂は、非晶性ポリ乳酸の耐熱性と耐衝撃性とを向上させる作用をするものであるため、その耐熱性と耐衝撃性は考慮されることが好ましい。すなわち、荷重たわみ温度は、ＡＳＴＭ Ｄ６４８に準拠して、１８．５ＭＰａの条件のもとで７０〜８５℃であるものが採用されるのが好ましい。また、アイゾット衝撃強さは、ＡＳＴＭ Ｄ２５６に準拠して、１０〜２５ｋｇｆｃｍ／ｃｍであるものが採用されるのが好ましい。 Since the ABS resin according to the present invention functions to improve the heat resistance and impact resistance of amorphous polylactic acid, the heat resistance and impact resistance are preferably taken into consideration. That is, it is preferable that the deflection temperature under load is 70 to 85 ° C. under the condition of 18.5 MPa in accordance with ASTM D648. Moreover, it is preferable that what is 10-25 kgfcm / cm is employ | adopted for Izod impact strength based on ASTMD256.
本発明に係るＡＢＳ樹脂の添加量は、上記ポリ乳酸１００重量部に対し、３０〜９９重量部の範囲である。３０重量部未満では、非晶性ポリ乳酸の耐熱性と耐衝撃性を十分に改善させることができず、すなわち、成形されたシートは、耐熱性、耐衝撃性の改善されない柔軟で脆いものとなり好ましくない。一方９９重量部を超過する場合では、ポリ乳酸系の含有比率が少なくなりすぎて、混合樹脂の石油による原料依存度を増やし、また燃焼エネルギーも増加させ、環境保護の観点から好ましくない。 The addition amount of the ABS resin according to the present invention is in the range of 30 to 99 parts by weight with respect to 100 parts by weight of the polylactic acid. If it is less than 30 parts by weight, the heat resistance and impact resistance of the amorphous polylactic acid cannot be sufficiently improved, that is, the molded sheet is flexible and brittle with no improvement in heat resistance and impact resistance. It is not preferable. On the other hand, when the amount exceeds 99 parts by weight, the content ratio of the polylactic acid is too small, increasing the dependency of the mixed resin on the raw material by petroleum and increasing the combustion energy, which is not preferable from the viewpoint of environmental protection.
つぎに、この発明において上記混合樹脂とともに用いられる滑剤には、モンタン酸とアルコールとのエステル化合物である脂肪酸エステル系のモンタン酸ワックスが適用される。この場合のアルコールは、エチレングリコール、１，２−ブタンジオール、１，３−ブタンジオール、２，３−ブタンジオール、グリセロール等である。また、モンタン酸ワックスは、部分鹸化されたものであってもよい。 Next, a fatty acid ester-based montanic acid wax which is an ester compound of montanic acid and alcohol is applied to the lubricant used together with the mixed resin in the present invention. The alcohol in this case is ethylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, glycerol or the like. The montanic acid wax may be partially saponified.
このモンタン酸ワックスの配合量については、モンタン酸ワックスを上記ポリ乳酸１００重量部に対して、０．０５〜５重量部とする必要がある。好ましくは０．０５〜３重量部である。モンタン酸ワックスの配合量が０．０５重量部未満では、カレンダー機の金属ロール表面へのカレンダー成形用樹脂組成物の粘着が激しく、これをシート状にして金属ロールから引き剥がすことができない。一方５重量部を超えると、金属ロール表面へのカレンダー成形用樹脂組成物の粘着の度合いは弱まるが、逆に溶融時の粘度が低下して、一旦シート状に金属ロール表面から剥がれるものの、それ自体の自重で過剰に伸びを生じ、結果としてシート状に成形することができない。 About the compounding quantity of this montanic acid wax, it is necessary to make a montanic acid wax into 0.05-5 weight part with respect to 100 weight part of said polylactic acid. Preferably it is 0.05-3 weight part. When the amount of the montanic acid wax is less than 0.05 parts by weight, the calender molding resin composition is so strongly adhered to the surface of the metal roll of the calender machine that it cannot be made into a sheet and peeled off from the metal roll. On the other hand, when the amount exceeds 5 parts by weight, the degree of adhesion of the resin composition for calendering to the surface of the metal roll is weakened, but conversely, the viscosity at the time of melting is lowered and the sheet is once peeled off from the surface of the metal roll. It grows excessively by its own weight, and as a result, it cannot be formed into a sheet.
なお、この発明のカレンダー成形用樹脂組成物の成分として、前記必須成分であるポリ乳酸、ＡＢＳ樹脂、及びモンタン酸ワックスのほか、カレンダー機の金属ロールに対する剥離助剤として、他の滑剤を添加することも可能であり、例えばパラフィンワックス等の炭化水素系の滑剤、ステアリン酸等の脂肪酸系の滑剤、ステアリルアミド等の脂肪酸アミド系の滑剤、及び脂肪酸エステル系、アルコール系、金属石鹸系等の各滑剤を併用することができる。 In addition to the essential components polylactic acid, ABS resin, and montanic acid wax, other lubricants are added as components for the calender molding resin composition of the present invention as a peeling aid for the metal roll of the calender machine. For example, hydrocarbon lubricants such as paraffin wax, fatty acid lubricants such as stearic acid, fatty acid amide lubricants such as stearyl amide, fatty acid esters, alcohols, metal soaps, etc. A lubricant can be used in combination.
また、その他の添加剤として、フェノール系、ヒンダードアミン系、リン系等の酸化防止剤、各種加工助剤、各種充填剤、各種顔料等を、この発明の目的を逸脱しない範囲で添加することができる。 Moreover, as other additives, antioxidants such as phenols, hindered amines, and phosphoruss, various processing aids, various fillers, various pigments, and the like can be added without departing from the object of the present invention. .
本発明の樹脂組成物は、上記の配合物を各成分が均一になるまで混合して、成形材料を得、そしてその成形材料を用いて、カレンダー成形によりシート状等の成形品を得るものである。さらに本発明においては、そのシートを一次成形品として、真空成形、圧空成形、ブロー成形等の二次成形を行って、最終製品としての二次成形品を得ることも可能である。 The resin composition of the present invention is a mixture obtained by mixing the above-mentioned blend until the respective components are uniform to obtain a molding material, and using the molding material, a molded product such as a sheet is obtained by calendar molding. is there. Furthermore, in the present invention, it is also possible to obtain a secondary molded product as a final product by performing secondary molding such as vacuum molding, pressure forming, blow molding or the like using the sheet as a primary molded product.
つぎに以下に、本発明に関連した実施例、及びその効果を立証するための比較例について説明する。 Below, the Example relevant to this invention and the comparative example for demonstrating the effect are described.
＜実施例１〜５＞
ポリ乳酸として、Ｌ−乳酸とＤ−乳酸の含有比率が８８：１２である、実質上非晶性のポリ乳酸（品番：レイシアＨ−２８０、三井化学社製）を準備した。
<Examples 1-5>
As polylactic acid, a substantially amorphous polylactic acid (product number: Lacia H-280, manufactured by Mitsui Chemicals, Inc.) having a content ratio of L-lactic acid and D-lactic acid of 88:12 was prepared.
またＡＢＳ樹脂として市販の透明帯電防止グレード品（品番：クララスチックＴＥ−２２００、日本エイアンドエル社製）を準備した。 Moreover, a commercially available transparent antistatic grade product (product number: Clarastic TE-2200, manufactured by Nippon A & L Co., Ltd.) was prepared as an ABS resin.
モンタン酸ワックスとしては、構成されるモンタン酸とアルコールとのエステル化合物において、アルコールが１，３―ブタンジオールであるものを準備した。 As the montanic acid wax, a constituent ester compound of montanic acid and alcohol in which the alcohol was 1,3-butanediol was prepared.
上記で用意したポリ乳酸、ＡＢＳ樹脂、及びモンタン酸ワックスの各成分を、表１に示す割合で実施例別に混合し、まず前処理として２軸の押出機により予め加熱混練したのち、ついでロール径２５０ｍｍの金属ロール４本からなるＬ型カレンダー機に移して、ロール温度１５５〜１７０℃の条件下で圧延して厚さ０．５ｍｍのシートを成形加工した。 The components of polylactic acid, ABS resin, and montanic acid wax prepared above were mixed according to the examples in the proportions shown in Table 1, and after pre-heating and kneading in advance using a twin-screw extruder, the roll diameter The sheet was transferred to an L-shaped calender machine consisting of four 250 mm metal rolls and rolled under a roll temperature of 155 to 170 ° C. to form a 0.5 mm thick sheet.
上記のカレンダー機によるシートの成形加工において、その成形加工性を評価し、かつ得られたシートについて、耐熱性及び耐衝撃性を評価した結果を、成形加工性においてはシートの成形加工が可能の場合を良好（○で示す）、不可能の場合を不良（×で示す）とし、また耐熱性においてはビカット軟化温度の測定値がＩＳＯ−３０６（Ｂ法）に準拠して、５８℃を超えるものを良好（○で示す）、５８℃以下のものを不良（×で示す）として表し、耐衝撃性においては引張衝撃強さの測定値がＩＳＯ−８２５６（Ａ法 ３形）に準拠して、８０ｋＪ／ｍ２を超えるものを良好（○で示す）、８０ｋＪ／ｍ２以下のものを不良（×で示す）として表し、各実施例について表１に併記した。 In the molding process of the sheet by the calendering machine, the molding processability was evaluated, and the results of evaluating the heat resistance and impact resistance of the obtained sheet were obtained. The case is good (indicated by ◯), the case incapable is defective (indicated by x), and the measured value of the Vicat softening temperature exceeds 58 ° C. in accordance with ISO-306 (Method B) in heat resistance. Good (indicated by ◯), and those below 58 ° C. are indicated as defective (indicated by ×). In terms of impact resistance, the measured value of tensile impact strength conforms to ISO-8256 (Method A, Type 3). Those exceeding 80 kJ / m 2 were indicated as good (indicated by ◯), those below 80 kJ / m 2 were indicated as defective (indicated by ×), and each example was also shown in Table 1.
＜比較例１、２＞
表２に示したＡＢＳとモンタン酸ワックスの重量部数以外は実施例１と同様にして、厚さ０．５ｍｍのシートを成形加工した。また実施例１と同様にして、成形加工性、耐熱性、及び耐衝撃性の評価を行った。その結果を併せて表２に記す。
<Comparative Examples 1 and 2>
A sheet having a thickness of 0.5 mm was formed in the same manner as in Example 1 except for the parts by weight of ABS and montanic acid wax shown in Table 2. Further, in the same manner as in Example 1, molding processability, heat resistance, and impact resistance were evaluated. The results are also shown in Table 2.
＜比較例３＞
実質上結晶性のポリ乳酸として、Ｌ−乳酸とＤ−乳酸の含有比率が９８：２であるポリ乳酸（品番：レイシアＨ−４００、三井化学社製）を準備した。
<Comparative Example 3>
As substantially crystalline polylactic acid, polylactic acid (product number: Lacia H-400, manufactured by Mitsui Chemicals) having a content ratio of L-lactic acid and D-lactic acid of 98: 2 was prepared.
これをＬ−乳酸とＤ−乳酸の含有比率が８８：１２のポリ乳酸に替えて用いた以外は、実施例１と同様にして厚さ０．５ｍｍのシートの成形加工を行った。また実施例１と同様にして、成形加工性、耐熱性、及び耐衝撃性の評価を行った。その結果を併せて表２に記す。 A sheet having a thickness of 0.5 mm was formed in the same manner as in Example 1 except that this was used instead of polylactic acid having a content ratio of L-lactic acid and D-lactic acid of 88:12. Further, in the same manner as in Example 1, molding processability, heat resistance, and impact resistance were evaluated. The results are also shown in Table 2.
＜比較例４、５＞
表２に示したＡＢＳとモンタン酸ワックスの重量部数以外は実施例１と同様にして、厚さ０．５ｍｍのシートの成形加工を試みた。しかし比較例４においては、押出機によってゲル化され、カレンダー機へ移送された溶融樹脂が、カレンダー機の金属ロールに混合樹脂が強く粘着して剥離することができずシートを得ることができなかった。一方比較例５においては、カレンダー機の金属ロールに混合樹脂が粘着せず、一旦シート状に金属ロール表面から剥がれるものの、それ自体の自重で過剰に伸びを生じシートを圧延することができなかった。
<Comparative Examples 4 and 5>
Except for the parts by weight of ABS and montanic acid wax shown in Table 2, an attempt was made to form a 0.5 mm thick sheet in the same manner as in Example 1. However, in Comparative Example 4, the molten resin gelled by the extruder and transferred to the calender machine cannot be peeled off because the mixed resin strongly adheres to the metal roll of the calender machine, and a sheet cannot be obtained. It was. On the other hand, in Comparative Example 5, the mixed resin did not adhere to the metal roll of the calender and once peeled off from the surface of the metal roll in the form of a sheet, the sheet could not be rolled due to excessive elongation due to its own weight. .
表１から明らかなように、上記実施例１〜５によれば、所望の０．５ｍｍのシートを難なく得ることができ、いずれもカレンダー機による成形加工性が良好であり、またいずれも耐熱性及び耐衝撃性が良好であった。一方、表２に示された比較例１〜５における発明の範囲を逸脱するものは、いずれかの評価結果に劣るものであった。 As apparent from Table 1, according to the above Examples 1 to 5, a desired 0.5 mm sheet can be obtained without difficulty, and all have good molding processability by a calender, and all have heat resistance. And the impact resistance was good. On the other hand, what deviated from the scope of the invention in Comparative Examples 1 to 5 shown in Table 2 was inferior to any of the evaluation results.
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| JP2004257909A JP4622397B2 (en) | 2004-09-06 | 2004-09-06 | Polylactic acid resin composition and sheet for calendar molding |
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| WO2007083820A1 (en) * | 2006-01-18 | 2007-07-26 | Teijin Chemicals Ltd. | Resin composition, molded article and their production methods |
| EP1835409A2 (en) | 2006-03-15 | 2007-09-19 | Hitachi, Ltd. | Storage system and storage system control method |
| JP2008031321A (en) * | 2006-07-28 | 2008-02-14 | Mitsui Chemicals Inc | Sheet comprising lactic acid-based resin composition and molded product of the sheet |
| JP2008037940A (en) * | 2006-08-03 | 2008-02-21 | Mitsui Chemicals Inc | Thermoplastic resin composition |
| JP2009173715A (en) * | 2008-01-22 | 2009-08-06 | Lonseal Corp | Polylactic acid-based sheet or film and method for producing the same |
| EP2133392A1 (en) | 2008-06-05 | 2009-12-16 | Cheil Industries Inc. | Polylactic acid resin composition |
| DE102009029035A1 (en) | 2008-09-02 | 2010-03-04 | Cheil Industries, Inc., Gumi | Environmentally friendly polylactic acid resin composition |
| EP2204417A2 (en) | 2008-12-30 | 2010-07-07 | Cheil Industries Inc. | Polylactic acid resin composition and molded product using the same |
| WO2013118408A1 (en) | 2012-02-10 | 2013-08-15 | 日東電工株式会社 | Protective film |
| US8618191B2 (en) | 2010-12-31 | 2013-12-31 | Cheil Industries Inc. | Acrylic based resin composition and molded product using the same |
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| WO2007083820A1 (en) * | 2006-01-18 | 2007-07-26 | Teijin Chemicals Ltd. | Resin composition, molded article and their production methods |
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| WO2013118408A1 (en) | 2012-02-10 | 2013-08-15 | 日東電工株式会社 | Protective film |
| WO2013118407A1 (en) | 2012-02-10 | 2013-08-15 | 日東電工株式会社 | Separator |
| WO2013118406A1 (en) | 2012-02-10 | 2013-08-15 | 日東電工株式会社 | Polylactic acid-based film or sheet, and adhesive tape or sheet |
| US10118999B2 (en) | 2012-02-10 | 2018-11-06 | Nitto Denko Corporation | Polylactic acid film or sheet, and pressure-sensitive adhesive tape or sheet |
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