JP4652803B2 - Polylactic acid biaxially stretched film with excellent antistatic properties - Google Patents
Polylactic acid biaxially stretched film with excellent antistatic properties Download PDFInfo
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims description 44
- 239000004626 polylactic acid Substances 0.000 title claims description 43
- 239000004094 surface-active agent Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 22
- 239000004327 boric acid Substances 0.000 claims description 22
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- -1 glycerin stearic acid ester Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 description 25
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 12
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 12
- CKQVRZJOMJRTOY-UHFFFAOYSA-N octadecanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCCCCCCCCCCCC(O)=O CKQVRZJOMJRTOY-UHFFFAOYSA-N 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 239000004594 Masterbatch (MB) Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229930182843 D-Lactic acid Natural products 0.000 description 6
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229940022769 d- lactic acid Drugs 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000009998 heat setting Methods 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 2
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229940075529 glyceryl stearate Drugs 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- UTWVENOYOROSRG-UHFFFAOYSA-N 1,4-didodecoxy-1,4-dioxobutane-2-sulfonic acid;sodium Chemical compound [Na].CCCCCCCCCCCCOC(=O)CC(S(O)(=O)=O)C(=O)OCCCCCCCCCCCC UTWVENOYOROSRG-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229960000878 docusate sodium Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Description
本発明は、帯電防止性に優れたポリ乳酸系二軸延伸フィルムに関するものである。 The present invention relates to a polylactic acid biaxially stretched film having excellent antistatic properties.
現在、機械的強度、耐熱性、寸法安定性に優れる材料としてポリエチレンテレフタレート延伸フィルム、ポリプロピレン系延伸フィルム等が知られており、産業界で幅広く使用されている。 Currently, polyethylene terephthalate stretched films, polypropylene stretched films and the like are known as materials having excellent mechanical strength, heat resistance, and dimensional stability, and are widely used in industry.
しかしながら、これらのプラスチックフィルムは自然環境中に廃棄されると、その化学的安定性のため分解せず、ゴミとして蓄積する一方である。将来的にはゴミ処分場、埋立地の確保が益々困難になり、また、自然環境、野生動物に悪影響を及ぼすなどの問題が懸念されている。これらのプラスチックフィルムに代わり、土壌中において加水分解され、次いで微生物分解により無害な分解物となり得るものにポリ乳酸を材料としたフィルムがある。 However, when these plastic films are disposed in the natural environment, they are not decomposed due to their chemical stability, but are accumulated as garbage. In the future, it will become more difficult to secure garbage disposal sites and landfill sites, and there are concerns about problems such as adverse effects on the natural environment and wild animals. In place of these plastic films, there is a film made of polylactic acid that can be hydrolyzed in soil and then become a harmless degradation product by microbial degradation.
ポリ乳酸の無延伸フィルムあるいはシートは、強度、伸度が低く、耐衝撃性に劣る材料であり、そのままでは成形体として実用性が不足していた。そこで、脆性を向上させるため、一軸あるいは二軸延伸し、配向させる方法が知られている。ポリ乳酸二軸延伸フィルムは、情報記録材料（磁気カード）、工業用パッケージ、食品包装などに展開され、一部は実用化に至っているものもある。 An unstretched film or sheet of polylactic acid is a material having low strength and elongation and inferior impact resistance, and as it is, its practicality is insufficient. Therefore, in order to improve brittleness, a method of aligning by uniaxial or biaxial stretching is known. Polylactic acid biaxially stretched films have been developed in information recording materials (magnetic cards), industrial packages, food packaging, etc., and some have been put into practical use.
しかしながら、これらのポリ乳酸延伸フィルムにおいては、ポリ乳酸樹脂自体が高度な電気絶縁性を有していることから極めて帯電しやすく、静電気の発生、蓄積により、印刷、製袋等の２次加工において、様々な問題を引き起こしている。また、容易にゴミ、ホコリを吸着するため、外観を損ねるという問題も生じる。 However, in these polylactic acid stretched films, the polylactic acid resin itself has a high degree of electrical insulation, so it is very easy to be charged. Due to the generation and accumulation of static electricity, secondary processing such as printing and bag making, etc. , Causing various problems. Moreover, since dust and dust are easily adsorbed, there is a problem that the appearance is impaired.
一般的に、プラスチックフィルム及びシートに帯電防止性を付与する方法として、アニオン系のアルキルスルホン酸塩をポリ乳酸に添加することが知られている。また、特許文献１には、非イオン系のグリセリン脂肪酸エステル類をポリ乳酸系重合体に添加することが開示されている。 In general, as a method for imparting antistatic properties to plastic films and sheets, it is known to add an anionic alkyl sulfonate to polylactic acid. Patent Document 1 discloses that nonionic glycerin fatty acid esters are added to a polylactic acid polymer.
ところが、これら従来方法では満足な帯電防止性が得られないばかりでなく、透明性の悪化、加水分解誘因による機械的物性の低下を招き、実用性に乏しかった。 However, these conventional methods are not only satisfactory in antistatic properties, but also have poor practicality due to deterioration of transparency and deterioration of mechanical properties caused by hydrolysis.
また、特許文献２には、ポリ乳酸系樹脂フィルムの表面にコーティング組成物を塗布することが開示されている。 Patent Document 2 discloses that a coating composition is applied to the surface of a polylactic acid resin film.
しかしながら、フィルム表面にコーティング組成物を塗布する方法では、塗布されていない面の帯電防止性が乏しく、また、両面に塗布するに至っては、設備上複雑となり容易に実施できなかった。
本発明の目的は、このような問題点を解決しようとするものであり、透明性を有し、かつ帯電防止性に優れたポリ乳酸系二軸延伸フィルムを提供しようとするものである。 An object of the present invention is to solve such problems, and to provide a polylactic acid biaxially stretched film having transparency and excellent antistatic properties.
本発明に係るポリ乳酸系二軸延伸フィルムは、ポリ乳酸系樹脂に、（Ａ）ジアルキルスルホコハク酸塩９０〜１０質量％と（Ｂ）グリセリンステアリン酸エステルと硼酸との反応物１０〜９０質量％とを含む界面活性剤組成物を０．１〜１０質量％含有させたことを特徴とするものである。 The polylactic acid biaxially stretched film according to the present invention comprises (A) 90 to 10% by mass of a dialkylsulfosuccinate and (B) a reaction product of glyceryl stearate and boric acid in an amount of 10 to 90% by mass. Is contained in an amount of 0.1 to 10% by mass.
本発明によれば、透明性を有し、かつ帯電防止性に優れたポリ乳酸系二軸延伸フィルムを提供することができる。 According to the present invention, a polylactic acid biaxially stretched film having transparency and excellent antistatic properties can be provided.
本発明者らは、上記課題を解決するため鋭意研究を行った結果、ポリ乳酸系樹脂に、（Ａ）ジアルキルスルホコハク酸塩、及び、（Ｂ）グリセリンステアリン酸エステルと硼酸との反応物を含む界面活性剤組成物を含有させることにより、透明性を有意に劣化させることなく、二軸延伸フィルムに優れた帯電防止性を付与できることを見出し、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventors include (A) a dialkylsulfosuccinate and (B) a reaction product of glycerin stearate and boric acid in a polylactic acid resin. It has been found that the inclusion of the surfactant composition can impart excellent antistatic properties to the biaxially stretched film without significantly degrading the transparency, leading to the present invention.
以下、本発明の種々の実施形態を説明する。 Hereinafter, various embodiments of the present invention will be described.
本発明において、ポリ乳酸系樹脂には、Ｌ−乳酸を主構成単位とするホモポリマー、及びＬ−乳酸とＤ−乳酸とを主構成単位とするコポリマーが含まれる。二軸延伸による配向結晶化を促進させ、実用強度を発現させるため、ポリ乳酸系樹脂は、Ｌ−乳酸／Ｄ−乳酸＝１００／０〜９４／６（モル比）の組成比を満足することが好ましい。Ｄ−乳酸が６モル％を超えると、融点が極端に低くなり結晶性に乏しい物となり、得られるフィルムの耐熱性、寸法安定性が劣化する恐れがある。Ｌ−乳酸とＤ−乳酸との組成比は、Ｌ−乳酸／Ｄ−乳酸＝９９／１〜９６／４（モル比）がさらに好ましい。 In the present invention, the polylactic acid resin includes a homopolymer having L-lactic acid as a main structural unit and a copolymer having L-lactic acid and D-lactic acid as main structural units. In order to promote orientation crystallization by biaxial stretching and to develop practical strength, the polylactic acid resin should satisfy the composition ratio of L-lactic acid / D-lactic acid = 100/0 to 94/6 (molar ratio). Is preferred. When D-lactic acid exceeds 6 mol%, the melting point becomes extremely low and the crystallinity is poor, and the heat resistance and dimensional stability of the resulting film may be deteriorated. The composition ratio of L-lactic acid and D-lactic acid is more preferably L-lactic acid / D-lactic acid = 99/1 to 96/4 (molar ratio).
また、ポリ乳酸系樹脂の数平均分子量は、５万〜３０万の範囲にあることが好ましい。数平均分子量が５万未満の場合、得られるフィルムの機械的強度が不十分となり、かつ延伸、巻き取り工程中での切断も頻繁に起こり操業性の低下を招く。一方、数平均分子量が３０万を超えると、加熱溶融時の流動性が乏しくなって製膜性が低下する。ポリ乳酸系樹脂の数平均分子量のさらに好ましい範囲は、８万〜１５万である。 The number average molecular weight of the polylactic acid resin is preferably in the range of 50,000 to 300,000. When the number average molecular weight is less than 50,000, the resulting film has insufficient mechanical strength, and also frequently undergoes cutting during the stretching and winding processes, resulting in a decrease in operability. On the other hand, when the number average molecular weight exceeds 300,000, the fluidity at the time of heating and melting becomes poor, and the film forming property is lowered. A more preferable range of the number average molecular weight of the polylactic acid resin is 80,000 to 150,000.
ポリ乳酸系樹脂を得るための重合法としては、縮合重合法及び開環重合法のいずれの方法を採用することも可能であり、分子量増大を目的として少量の鎖延長剤、例えばジイソシアネート化合物、ジエポキシ化合物、酸無水物等を使用してもよい。 As a polymerization method for obtaining a polylactic acid-based resin, any of a condensation polymerization method and a ring-opening polymerization method can be adopted, and a small amount of chain extender such as a diisocyanate compound or diepoxy is used for the purpose of increasing the molecular weight. Compounds, acid anhydrides and the like may be used.
本発明において、ポリ乳酸系樹脂に配合される界面活性剤組成物は、（Ａ）ジアルキルスルホコハク酸塩、及び、（Ｂ）グリセリンステアリン酸エステルと硼酸との反応物を配合したものである。 In the present invention, the surfactant composition blended in the polylactic acid-based resin is a blend of (A) a dialkylsulfosuccinate and (B) a reaction product of glycerin stearate and boric acid.
本発明において、（Ａ）ジアルキルスルホコハク酸塩としては、下記一般式（１）で示されるアニオン系界面活性剤を好適に使用することができる。
（但し、Ｒ１、Ｒ２はアルキル基、Ｍは対イオン）
ここで一般式（１）のＲ１及びＲ２は同一もしくは異なるアルキル基であり、Ｒ１及びＲ２の炭素数は６〜２０が望ましく、更に好ましくは８〜１６である。具体的には、ジアルキルスルホコハク酸塩として、ジオクチルスルホコハク酸塩（Ｒ１、Ｒ２の炭素数８）が好適に使用できる。−ＳＯ３Ｍで示される塩としては、ナトリウム、カリウム、カルシウム、マグネシウム等のアルカリ金属、アルカリ土類金属、又はジエタノールアミン、トリエタノールアミン等のスルホン酸塩が好適に使用できる。
(However, R 1 and R 2 are alkyl groups, M is a counter ion)
Here, R 1 and R 2 in the general formula (1) are the same or different alkyl groups, and R 1 and R 2 preferably have 6 to 20 carbon atoms, and more preferably 8 to 16 carbon atoms. Specifically, dioctylsulfosuccinate (carbon number of R 1 and R 2 having 8 carbon atoms) can be suitably used as the dialkylsulfosuccinate. As the salt represented by —SO 3 M, alkali metals such as sodium, potassium, calcium and magnesium, alkaline earth metals, or sulfonates such as diethanolamine and triethanolamine can be preferably used.
本発明において、ジアルキルスルホコハク酸塩は公知の方法で得ることができる。具体的には、例えば、無水マレイン酸１モルに対し、例えばオクチルアルコール２モルを塩基性条件下にて１２０℃で反応させた後、亜硫酸ナトリウムを加え、透明な液が得られるまで５０℃で撹拌し溶媒を留去する方法が挙げられるが、これに限定されるものではない。 In the present invention, dialkylsulfosuccinate can be obtained by a known method. Specifically, for example, 1 mol of maleic anhydride is reacted with, for example, 2 mol of octyl alcohol under basic conditions at 120 ° C., then sodium sulfite is added, and at 50 ° C. until a transparent liquid is obtained. Although the method of stirring and distilling a solvent off is mentioned, it is not limited to this.
本発明において、（Ｂ）グリセリンステアリン酸エステルと硼酸との反応物は、グリセリンステアリン酸エステルに対して硼酸を反応させた界面活性剤である。グリセリンステアリン酸エステル中の脂肪酸は、ステアリン酸であることが望ましいが、炭素数１２〜２０の脂肪酸が含まれていても好適に使用できる。グリセリンステアリン酸エステルは、グリセリンとステアリン酸とのエステル化反応によって得ることができる。このエステル化反応から、グリセリンとステアリン酸との反応モル比によりモノエステル、ジエステル、トリエステルが得られる。分子蒸留によりモノエステルの純度を高くする方が望ましいが、特にエステル化度に限定はない。グリセリンステアリン酸エステルに対する硼酸の反応モル比は、グリセリンステアリン酸エステル１モルに対して、硼酸０．１〜１モルが望ましく、更に好ましくは０．２〜０．５モルである。 In the present invention, (B) a reaction product of glycerin stearate and boric acid is a surfactant obtained by reacting glycerin stearate with boric acid. The fatty acid in the glycerin stearic acid ester is desirably stearic acid, but can be suitably used even if a fatty acid having 12 to 20 carbon atoms is contained. Glycerin stearate can be obtained by esterification reaction of glycerin and stearic acid. From this esterification reaction, monoesters, diesters, and triesters are obtained depending on the reaction molar ratio of glycerin and stearic acid. Although it is desirable to increase the purity of the monoester by molecular distillation, the degree of esterification is not particularly limited. The reaction molar ratio of boric acid to glycerin stearate is preferably 0.1 to 1 mol, more preferably 0.2 to 0.5 mol, of boric acid with respect to 1 mol of glycerin stearate.
本発明において、グリセリンステアリン酸エステルと硼酸との反応物は公知の方法で得ることができる。具体的には、例えば、グリセリン１モルに対してステアリン酸１モルを塩基性触媒下にて２３０℃でエステル化させ、グリセリンステアリン酸エステルを得た後、続いてその化合物１モルに対し硼酸０．５モルを２３０℃で反応させることで目的物を得ることができる。 In the present invention, a reaction product of glycerin stearic acid ester and boric acid can be obtained by a known method. Specifically, for example, 1 mol of stearic acid per 1 mol of glycerin is esterified at 230 ° C. under a basic catalyst to obtain a glycerin stearic acid ester, and then boric acid is added to 1 mol of the compound. The desired product can be obtained by reacting 5 mol at 230 ° C.
本発明において、界面活性剤組成物は、（Ａ）ジアルキルスルホコハク酸塩９０〜１０質量％と（Ｂ）グリセリンステアリン酸エステルと硼酸との反応物１０〜９０質量％とを含む。（Ａ）ジアルキルスルホコハク酸塩が１０質量％未満であると、十分な帯電防止効果が得られないだけでなく、ポリ乳酸系樹脂に対する相溶性が悪くなり、フィルム白化等の外観不良を招く。（Ａ）ジアルキルスルホコハク酸塩が９０質量％を超えると、ポリ乳酸系樹脂への相溶性は向上するが十分な帯電防止効果は得られない。界面活性剤組成物は、（Ａ）ジアルキルスルホコハク酸塩９０〜５０質量％と（Ｂ）グリセリンステアリン酸エステルと硼酸との反応物１０〜５０質量％とから構成されることが更に好ましい。 In the present invention, the surfactant composition includes (A) 90 to 10% by mass of a dialkylsulfosuccinate and (B) 10 to 90% by mass of a reaction product of glycerin stearate and boric acid. When the (A) dialkylsulfosuccinate is less than 10% by mass, not only a sufficient antistatic effect cannot be obtained, but the compatibility with the polylactic acid resin is deteriorated, resulting in poor appearance such as whitening of the film. When (A) dialkyl sulfosuccinate exceeds 90% by mass, the compatibility with the polylactic acid resin is improved, but a sufficient antistatic effect cannot be obtained. The surfactant composition is more preferably composed of (A) 90 to 50% by mass of a dialkylsulfosuccinate and (B) 10 to 50% by mass of a reaction product of glycerin stearic acid ester and boric acid.
本発明のポリ乳酸系二軸延伸フィルムに含有される界面活性剤組成物の含有量は、０．１〜１０質量％の範囲である。界面活性剤組成物の含有量が０．１質量％未満であると、十分な帯電防止効果が得られない。一方、界面活性剤組成物の含有量が１０質量％を超えると、帯電防止効果が飽和に達するため、帯電防止性能に対して含有量が過剰であるばかりでなく、透明性の悪化、高温高湿度下におけるフィルム同士のブロッキング現象、製膜時の押し出し不良など様々な問題を引き起こす。界面活性剤組成物の含有量の好ましい範囲は、０．５〜２質量％である。この範囲内とすると、特に優れた帯電防止性を提供することができる。 The content of the surfactant composition contained in the polylactic acid biaxially stretched film of the present invention is in the range of 0.1 to 10% by mass. When the content of the surfactant composition is less than 0.1% by mass, a sufficient antistatic effect cannot be obtained. On the other hand, when the content of the surfactant composition exceeds 10% by mass, the antistatic effect reaches saturation, so that not only is the content excessive with respect to the antistatic performance, but also the transparency deteriorates, the high temperature increases. It causes various problems such as blocking phenomenon between films under humidity and poor extrusion during film formation. A preferable range of the content of the surfactant composition is 0.5 to 2% by mass. When it is within this range, particularly excellent antistatic properties can be provided.
本発明において、ポリ乳酸系樹脂と界面活性剤組成物を含有するフィルム原料は、押出機の中でポリ乳酸系樹脂と界面活性剤組成物とを加熱混練する等により得ることができる。（Ａ）ジアルキルスルホコハク酸塩と（Ｂ）グリセリンステアリン酸エステルと硼酸との反応物とは、別々にポリ乳酸系樹脂に添加しても良いし、予め混合してからポリ乳酸系樹脂に添加しても良い。ポリ乳酸系樹脂の量に対し添加する界面活性剤組成物の量が少ないと、これらが樹脂中で均一に分散され難くなる。このため、予め高濃度の（Ａ）ジアルキルスルホコハク酸塩及び／又は（Ｂ）グリセリンステアリン酸エステルと硼酸との反応物を含むマスターバッチを作製し、これを界面活性剤組成物を含まないポリ乳酸系樹脂と混練して所定含有量とするマスターバッチ法を採用することが好ましい。 In the present invention, the film raw material containing the polylactic acid resin and the surfactant composition can be obtained by heating and kneading the polylactic acid resin and the surfactant composition in an extruder. The reaction product of (A) dialkylsulfosuccinate and (B) glycerin stearic acid ester and boric acid may be added separately to the polylactic acid resin, or mixed in advance and then added to the polylactic acid resin. May be. When the amount of the surfactant composition to be added is small relative to the amount of the polylactic acid-based resin, it becomes difficult to uniformly disperse them in the resin. For this reason, a master batch containing a reaction product of (A) dialkylsulfosuccinate and / or (B) glyceryl stearate and boric acid in a high concentration was prepared in advance, and this was used as a polylactic acid containing no surfactant composition. It is preferable to employ a master batch method in which a predetermined content is obtained by kneading with a resin.
本発明のポリ乳酸系二軸延伸フィルムの製造方法としては、Ｔダイ法、インフレーション法、カレンダー法等が例示できるが、中でも、Ｔダイを用いて溶融混練して押し出すＴダイ法が好ましい。Ｔダイ法の製法例としては、上記フィルム原料、及び、必要に応じて可塑剤、滑剤を適量配合したポリ乳酸系樹脂組成物を押出機ホッパーに供給し、押出機を例えばシリンダー温度１８０〜２４０℃、Ｔダイ温度２００〜２３０℃に加熱し、溶融混練して押し出し、２０〜４０℃に制御された冷却ロールで冷却し、厚さ１００〜５００μｍの未延伸シートを得る。 Examples of the method for producing the polylactic acid-based biaxially stretched film of the present invention include a T-die method, an inflation method, a calendar method, and the like. Among these, a T-die method in which a T-die is melt-kneaded and extruded is preferable. As an example of the production method of the T-die method, the film raw material and, if necessary, a polylactic acid resin composition containing an appropriate amount of a plasticizer and a lubricant are supplied to an extruder hopper, and the extruder has a cylinder temperature of 180 to 240, for example. C., T-die temperature 200-230.degree. C., melt kneaded and extruded, cooled with a cooling roll controlled at 20-40.degree. C. to obtain an unstretched sheet having a thickness of 100-500 .mu.m.
未延伸シートの二軸延伸方法としては、テンター方式による同時二軸延伸法、ロールとテンターによる逐次二軸延伸法のいずれでもよい。同時二軸延伸の代表例としては、上述の如く得られた未延伸シートを予熱・延伸温度７０〜９０℃、熱固定温度１００〜１５０℃のテンターにて面倍率９〜１６倍に延伸しフィルムを得る。また、逐次二軸延伸の代表例としては、未延伸シートを駆動ロールの回転速度比によって縦方向にロール表面温度５０〜８０℃、延伸倍率１．５〜５倍で延伸し、引き続き連続して横方向に延伸温度５０〜９０℃、延伸倍率１．５〜８倍、熱固定温度１００〜１５０℃の条件下で延伸しフィルムを得る。 As a biaxial stretching method of the unstretched sheet, any of a simultaneous biaxial stretching method using a tenter method and a sequential biaxial stretching method using a roll and a tenter may be used. As a typical example of simultaneous biaxial stretching, an unstretched sheet obtained as described above is stretched to a surface magnification of 9 to 16 times with a tenter having a preheating / stretching temperature of 70 to 90 ° C. and a heat setting temperature of 100 to 150 ° C. Get. As a representative example of sequential biaxial stretching, an unstretched sheet is stretched in the longitudinal direction at a roll surface temperature of 50 to 80 ° C. and a stretch ratio of 1.5 to 5 times according to the rotational speed ratio of the drive roll, and continuously. A film is obtained by stretching in the transverse direction under conditions of a stretching temperature of 50 to 90 ° C., a stretching ratio of 1.5 to 8 times, and a heat setting temperature of 100 to 150 ° C.
本発明に係るポリ乳酸系二軸延伸フィルムの厚みは特に制限なく、用途、要求性能、価格等によって適宜設定すればよい。一般的には、１０〜１００μｍ程度の厚さを例示できる。さらに、フィルムの印刷性、ラミネート性、コーティング適性等を向上させる目的で、表面処理を施してもよい。表面処理の方法としては、コロナ放電処理、プラズマ処理、酸処理等が挙げられ、いずれの方法も用いることができる。これらの中では、簡便さの点からコロナ放電処理が最も好ましいものとして例示できる。 The thickness of the polylactic acid biaxially stretched film according to the present invention is not particularly limited, and may be set as appropriate depending on the application, required performance, price, and the like. Generally, a thickness of about 10 to 100 μm can be exemplified. Furthermore, surface treatment may be performed for the purpose of improving the printability, laminating property, coating suitability, etc. of the film. Examples of the surface treatment method include corona discharge treatment, plasma treatment, and acid treatment, and any method can be used. Among these, the corona discharge treatment can be exemplified as the most preferable from the viewpoint of simplicity.
本発明のポリ乳酸系二軸延伸フィルムには、本発明の目的を損なわない範囲で、必要により上述した本発明の界面活性剤以外の公知のアニオン界面活性剤、カチオン界面活性剤、ノニオン界面活性剤、両性界面活性剤を単独或いは２種以上を含有させても良い。 In the polylactic acid-based biaxially stretched film of the present invention, a known anionic surfactant other than the above-described surfactant of the present invention, a cationic surfactant, and a nonionic surfactant, as long as the object of the present invention is not impaired. Agents and amphoteric surfactants may be used alone or in combination of two or more.
本発明のポリ乳酸系二軸延伸フィルムに、必要に応じて顔料、酸化防止剤、可塑剤、紫外線吸収剤、滑剤、結晶核剤等を任意の割合で含有させることができる。また、さらなる帯電防止性能が必要な場合、フィルム表面に帯電防止剤をさらに塗布することもできる。なお、２次加工などを容易にするために必要に応じて、易接着コート剤などのコート液もフィルム表面に塗布することも可能である。 The polylactic acid-based biaxially stretched film of the present invention can contain a pigment, an antioxidant, a plasticizer, an ultraviolet absorber, a lubricant, a crystal nucleating agent, and the like as required. If further antistatic performance is required, an antistatic agent can be further applied to the film surface. In addition, in order to make secondary processing etc. easy, it is also possible to apply | coat coating liquids, such as an easily bonding coating agent, to a film surface as needed.
本発明のポリ乳酸系二軸延伸フィルムの表面固有抵抗値（Ω／□）は低い方が望ましいが、フィルムの巻き取り、スリット工程では感電、また印刷、製袋等の２次加工ではロールへの巻き付き、あるいは蛇行によりしわの発生など生産時の問題が発生しない範囲であれば良い。目安としては、表面固有抵抗値は１０１５Ω／□以下が好ましく、１０１４Ω／□以下であればさらに好ましい。 The surface resistivity (Ω / □) of the polylactic acid-based biaxially stretched film of the present invention is preferably low, but it is an electric shock in the film winding and slitting process, and in the secondary processing such as printing and bag making, to the roll. As long as it does not cause production problems such as wrinkling or wrinkling due to meandering. As a guide, the surface resistivity is preferably 10 15 Ω / □ or less, more preferably 10 14 Ω / □ or less.
本発明のポリ乳酸系二軸延伸フィルムは、カレンダー、文具、衣料、食品等の包装用フィルムとして好適であるが、その他はＯＡメディア商品等のオーバーラップシュリンクフィルム、封筒の窓貼りフィルム、電気・電子部品等のラッピング、プリントラミネート等が例示でき、特に制限されず使用できる。 The polylactic acid-based biaxially stretched film of the present invention is suitable as a packaging film for calendars, stationery, clothing, foods, etc., but others are overlap shrink films such as OA media products, envelope window pasting films, Examples include wrapping of electronic parts and the like, print lamination, and the like, which can be used without any particular limitation.
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み合せにより種々の発明を形成できる。例えば、実施形態に示される全構成要素から幾つかの構成要素を削除してもよい。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 constituent elements disclosed in the embodiment. For example, some components may be deleted from all the components shown in the embodiment. Furthermore, you may combine suitably the component covering different embodiment.
［実施例］
以下、本発明を実施例により説明するが、本発明は下記実施例により制限されるものでない。
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not restrict | limited by the following Example.
（実施例１）
Ｌ−乳酸とＤ−乳酸とをＬ体／Ｄ体＝９９／１（モル比）で含有し、数平均分子量が９５，０００、ＭＦＲが５．０ｇ／１０分（２１０℃）であるポリ乳酸樹脂（カーギル・ダウ社製、ネイチャーワークス）を用意した。また、（（Ａ）−１）ジオクチルスルホコハク酸ナトリウム８０質量％と、（（Ｂ）−１）グリセリンモノステアレートと硼酸との反応物（反応モル比（グリセリンモノステアレート：硼酸）１：０.５）２０質量％とを配合した界面活性剤組成物を得た。
Example 1
Polylactic acid containing L-lactic acid and D-lactic acid in L-form / D-form = 99/1 (molar ratio), having a number average molecular weight of 95,000 and MFR of 5.0 g / 10 min (210 ° C.) Resin (manufactured by Cargill Dow, Nature Works) was prepared. Further, ((A) -1) sodium dioctylsulfosuccinate 80% by mass and ((B) -1) a reaction product of glycerol monostearate and boric acid (reaction molar ratio (glycerol monostearate: boric acid) 1: 0 .5) A surfactant composition containing 20% by mass was obtained.
ポリ乳酸樹脂の数平均分子量は以下に説明するようにして測定した。 The number average molecular weight of the polylactic acid resin was measured as described below.
すなわち、（株）島津製作所製ＬＣ１０ＡＤを用い、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により数平均分子量を求めた。このとき、カラム温度４０℃、クロロホルム溶媒により測定を行い、ポリスチレン換算法により計算した。 That is, the number average molecular weight was determined by gel permeation chromatography (GPC) using LC10AD manufactured by Shimadzu Corporation. At this time, measurement was performed with a column temperature of 40 ° C. and a chloroform solvent, and calculation was performed by a polystyrene conversion method.
上述のポリ乳酸樹脂９０．０質量％に対して得られた界面活性剤組成物を１０．０質量％添加して、２軸押出機を用いて溶融混練し、得られたストランドをカッティングしてペレット化し、マスターバッチａを作製した。 10.0% by mass of the surfactant composition obtained with respect to 90.0% by mass of the polylactic acid resin described above was added, melt-kneaded using a twin screw extruder, and the resulting strand was cut. Pelletized to prepare master batch a.
上述のポリ乳酸樹脂９０質量％にマスターバッチａを１０質量％添加し、コートハンガータイプのＴダイを具備した５０ｍｍφ押出機を使用して、滞留時間５分、Ｔダイ温度２３０℃で溶融押出し、２５℃に温度制御されたキャストロールに密着急冷し、厚さ１５０μｍの未延伸シートを得た。得られた未延伸シートを予熱ロール６０℃、延伸ロール７０℃で３．０倍に縦方向に延伸した。次いでテンター内において、８０℃の延伸温度で横方向に３．５倍延伸した後、横方向の弛緩率を５％として１５０℃で熱処理を施し、厚さ１５μｍの逐次二軸延伸フィルムを得た。 Add 10% by mass of masterbatch a to 90% by mass of the polylactic acid resin described above, and use a 50 mmφ extruder equipped with a coat hanger type T die, and melt extrude at a T die temperature of 230 ° C. for 5 minutes. The cast roll was temperature-controlled at 25 ° C., and was closely adhered and cooled to obtain an unstretched sheet having a thickness of 150 μm. The obtained unstretched sheet was stretched in the longitudinal direction 3.0 times at a preheating roll 60 ° C. and a stretching roll 70 ° C. Next, in the tenter, the film was stretched 3.5 times in the transverse direction at a stretching temperature of 80 ° C., and then subjected to heat treatment at 150 ° C. with a transverse relaxation rate of 5% to obtain a sequentially biaxially stretched film having a thickness of 15 μm. .
（実施例２〜８）
マスターバッチの種類（界面活性剤（Ａ），（Ｂ）の種類、配合割合）及びその添加量（界面活性剤組成物含有量）を表１に示すように変更する以外には、実施例１と同様にして逐次二軸延伸フィルムを得た。
(Examples 2 to 8)
Example 1 except that the type of masterbatch (types of surfactants (A) and (B), blending ratio) and the amount added (surfactant composition content) were changed as shown in Table 1. In the same manner, a biaxially stretched film was obtained sequentially.
（実施例９）
実施例１と同様のポリ乳酸樹脂９０質量％にマスターバッチａを１０質量％添加し、コートハンガータイプのＴダイを具備した５０ｍｍφ押出機を使用して、滞留時間５分、Ｔダイ温度２３０℃で溶融押出し、２５℃に温度制御されたキャストロールに密着急冷し、厚さ１５０μｍの未延伸シートを得た。続いて、予熱８０℃、延伸７８℃のテンターへ未延伸シートを導入し、面倍率１０倍にて延伸後、弛緩率４％、熱固定温度１５０℃にて熱処理を行い、厚み１５μｍの同時二軸延伸フィルムを得た。
Example 9
10% by mass of masterbatch a was added to 90% by mass of the polylactic acid resin similar to Example 1, and a residence time of 5 minutes and a T-die temperature of 230 ° C. using a 50 mmφ extruder equipped with a coat hanger type T-die. The resulting mixture was melt-extruded and cooled tightly on a cast roll whose temperature was controlled at 25 ° C. to obtain an unstretched sheet having a thickness of 150 μm. Subsequently, an unstretched sheet was introduced into a tenter having a preheating of 80 ° C. and a stretching of 78 ° C., and after stretching at a surface magnification of 10 times, heat treatment was performed at a relaxation rate of 4% and a heat setting temperature of 150 ° C. An axially stretched film was obtained.
（比較例１〜３）
マスターバッチの種類（界面活性剤（Ａ），（Ｂ）の種類、配合割合）及びその添加量（界面活性剤組成物含有量）を表１に示すように変更する以外には、実施例１と同様にして逐次二軸延伸フィルムを得た。
(Comparative Examples 1-3)
Example 1 except that the type of masterbatch (types of surfactants (A) and (B), blending ratio) and the amount added (surfactant composition content) were changed as shown in Table 1. In the same manner, a biaxially stretched film was obtained sequentially.
表１中に示す界面活性剤の種類（Ａ）−１，（Ａ）−２，（Ｂ）−１，（Ｂ）−２は、下記のとおりである。 The types (A) -1, (A) -2, (B) -1, and (B) -2 of the surfactants shown in Table 1 are as follows.
（Ａ）−１：ジオクチルスルホコハク酸ナトリウム
（Ａ）−２：ジラウリルスルホコハク酸ナトリウム
（Ｂ）−１：グリセリンモノステアレートと硼酸との反応物（反応モル比（グリセリンモノステアレート：硼酸）１：０．５）
（Ｂ）−２：グリセリンモノステアレートと硼酸との反応物（反応モル比（グリセリンモノステアレート：硼酸）１：１．０）
(B) -2: Reaction product of glycerol monostearate and boric acid (reaction molar ratio (glycerol monostearate: boric acid) 1: 1.0)
得られた実施例１〜９及び比較例１〜３の二軸延伸フィルムについて、以下に説明する評価を行った。各評価方法は下記のとおりである。これらの結果を表２に示す。 About the obtained biaxially stretched film of Examples 1-9 and Comparative Examples 1-3, evaluation demonstrated below was performed. Each evaluation method is as follows. These results are shown in Table 2.
（１）表面固有抵抗値
表面固有抵抗値を、温度２３℃、相対湿度５０％の条件下に１日放置した後、同条件下でＪＩＳ−Ｋ６９１１に準じて測定装置（製造元；川口電気製作所、機器名；超絶縁計（型式Ｐ−６１６））を用いて測定した。本発明においては、生産（フィルム製造）に支障が生じなかったものを合格（帯電防止性能に優れるもの）とした。
(1) Surface resistivity value The surface resistivity value was allowed to stand for 1 day under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, and then measured according to JIS-K6911 under the same conditions (manufacturer: Kawaguchi Electric Works, Device name: Measured using a super insulation meter (model P-616). In the present invention, a product that did not hinder production (film production) was determined to be acceptable (excellent in antistatic performance).
（２）摩擦耐電圧力
温度２３℃、相対湿度５０％の条件下に１日放置した後、同条件下でインテックス社製の摩擦耐電圧測定器（型式：ＥＣ−３Ｎ）にて綿／ポリエステル＝６０／４０の白布とフィルムのコロナ処理面とを接触させ、６０秒間の最高耐電圧を評価した。本発明においては、３ｋｖ以下を合格とした。
(2) Friction Withstand Voltage After standing for 1 day under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, cotton / polyester was measured with a friction withstand voltage measuring instrument (model: EC-3N) manufactured by Intex under the same conditions. A 60/40 white cloth was brought into contact with the corona-treated surface of the film, and the maximum withstand voltage for 60 seconds was evaluated. In the present invention, 3 kv or less was accepted.
（３）引張強度及び伸度
ＪＩＳ−Ｋ７１２７の測定法に準じて、長さ１０ｃｍ、幅１０ｍｍの試料で測定した。
(3) Tensile strength and elongation It measured with the sample of length 10cm and width 10mm according to the measuring method of JIS-K7127.
（４）ヘーズ
ＪＩＳ−Ｋ７１０５に準じて測定した。
表１に示したように、本発明に従う実施例１〜９の二軸延伸フィルムは、表面固有抵抗値、摩擦耐電圧力共に低く、帯電防止性能に優れていただけでなく、同時に機械的強度（引張強度，引張伸度）にも優れていた。また、界面活性剤組成物の含有量が０．５〜２質量％という好ましい範囲にある実施例１〜３，６〜９は、実施例４，５に比較してヘーズがより低く、透明性に特に優れていた。 As shown in Table 1, the biaxially stretched films of Examples 1 to 9 according to the present invention have low surface resistivity and friction withstand voltage, and are not only excellent in antistatic performance, but at the same time mechanical strength (tensile It was also excellent in strength and tensile elongation. In addition, Examples 1 to 3 and 6 to 9 in which the content of the surfactant composition is in a preferable range of 0.5 to 2% by mass have lower haze than Examples 4 and 5, and are transparent. Was particularly good.
これに対して、ジアルキルスルホコハク酸塩を含有しない界面活性剤組成物を用いた比較例１のフィルム、グリセリンステアリン酸エステルと硼酸との反応物を含有しない界面活性剤組成物を用いた比較例２のフィルム、及び、界面活性剤組成物（ジアルキルスルホコハク酸塩及びグリセリンステアリン酸エステルと硼酸との反応物）を含有しない比較例３のフィルムは、実施例１〜９に比較して摩擦耐電圧力が高く、帯電防止性能に劣っていた。特に、比較例３のフィルムは、摩擦耐電圧力が非常に高かっただけでなく表面固有抵抗値も高く、静電気を帯びていた。 On the other hand, the film of the comparative example 1 using the surfactant composition which does not contain a dialkyl sulfosuccinate, the comparative example 2 which used the surfactant composition which does not contain the reaction material of glycerol stearic acid ester and boric acid And the film of Comparative Example 3 that does not contain a surfactant composition (a reaction product of dialkylsulfosuccinate and glycerin stearic acid ester and boric acid) have a friction withstand voltage as compared with Examples 1-9. High and antistatic performance was poor. In particular, the film of Comparative Example 3 was not only very high in friction withstand voltage, but also high in surface resistivity, and was static.
本発明のポリ乳酸系二軸延伸フィルムは、透明性を有し、機械的強度、特に帯電防止性に優れているため、衣料、文具、食品、医薬品等の包装材料として有用性が高い。また、ゴミとして廃棄された場合、土壌中で微生物により分解され、自然環境、野生動物に対する環境負荷を軽減することができる。 Since the polylactic acid biaxially stretched film of the present invention has transparency and excellent mechanical strength, particularly antistatic properties, it is highly useful as a packaging material for clothing, stationery, food, pharmaceuticals and the like. Moreover, when discarded as garbage, it is decomposed by microorganisms in the soil, and the environmental load on the natural environment and wild animals can be reduced.
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