JP4636173B2 - Method for producing polylactic acid biaxially stretched film - Google Patents
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本発明は、新規なポリ乳酸二軸延伸フィルムの製造方法に関する。 The present invention relates to a method for producing a novel polylactic acid biaxially stretched film.
従来、ポリ乳酸をはじめとする脂肪族ポリエステル系フィルムは、自然環境下に棄却された場合に容易に分解されること、例えばポリ乳酸フィルムは土壌中において自然に加水分解されたのち微生物によって無害な分解物となることを利点として、種々開発されてきた。 Conventionally, aliphatic polyester-based films including polylactic acid are easily decomposed when discarded in a natural environment. For example, polylactic acid films are naturally hydrolyzed in soil and then harmless by microorganisms. Various developments have been made with the advantage of being a decomposition product.
このような生分解性フィルムとして、ポリ乳酸系重合体からなり、面配向度ΔＰが３．０×１０-3以上であり、且つフィルムを昇温したときの結晶化融解熱量ΔＨｍと昇温中の結晶化により発生する結晶化熱量ΔＨｃとの差(ΔＨｍ−ΔＨｃ)が２０Ｊ／ｇ以上である、実用的な強度及び熱寸法安定性を有するフィルムが知られている（特開平７−２０７０４１号公報）。 Such a biodegradable film is made of a polylactic acid-based polymer, has a plane orientation degree ΔP of 3.0 × 10 −3 or more, and is heated during crystallization melting heat ΔHm when the film is heated. A film having practical strength and thermal dimensional stability in which the difference (ΔHm−ΔHc) from the crystallization heat amount ΔHc generated by crystallization of 20 J / g or more is known (Japanese Patent Laid-Open No. 7-207041). Publication).
しかしながら、上記ポリ乳酸系フィルムは、自然界で分解させることを優先して開発を進めた結果、本来脂肪族ポリエステルが持つ優れた特性を十分に引き出すことが出来ていなかった。即ち、生分解性を重視するために、フィルムの配向・結晶化が十分ではなく、強度や熱寸法安定性が不十分なものとなった。 However, as a result of the development of the polylactic acid film with priority given to degrading it in nature, the excellent properties inherent in aliphatic polyesters could not be fully exploited. That is, in order to attach importance to biodegradability, the film was not sufficiently oriented and crystallized, and the strength and thermal dimensional stability were insufficient.
その結果、生鮮食品、加工食品、医薬品、医療機器、電子部品等の包装用フィルムとして用いる場合、このようなフィルムでは、包装用途のフィルムとして必要とされる印刷やラミネートの加工工程において寸法変化を生じたり、しわが発生する等の問題点があることが明らかになった。 As a result, when used as a packaging film for fresh foods, processed foods, pharmaceuticals, medical equipment, electronic parts, etc., such films may undergo dimensional changes in the printing and laminating processes required as packaging films. It has become clear that there are problems such as generation and wrinkles.
本発明の目的は、上述の問題点が解消され、印刷やラミネートの加工工程において優れた加工適性を有する新規なポリ乳酸二軸延伸フィルムの製造方法を提供することにある。 An object of the present invention is to provide a novel method for producing a polylactic acid biaxially stretched film that solves the above-mentioned problems and has excellent processability in a printing or laminating process.
本発明者は、前記従来技術の問題点を解消すべく、鋭意研究した。その結果、特定の脂肪族ポリエステルを主成分とするポリマーから成る二軸延伸フィルムの長手方向の厚みむら及び熱収縮率をそれぞれ特定値以下とすることによって、印刷やラミネートの加工工程において寸法変化を生じたり、しわを発生したりすることがない優れた加工適性を持つ、一般包装用基材として有用なフィルムが得られることを見出し、本発明を完成するに至った。 The present inventor has intensively studied to solve the problems of the prior art. As a result, the thickness variation in the longitudinal direction and the heat shrinkage rate of the biaxially stretched film made of a polymer containing a specific aliphatic polyester as a main component are reduced to a specific value or less, respectively, so that a dimensional change can be made in a printing or laminating process. The inventors have found that a film useful as a general packaging base material having excellent processability that does not generate or wrinkle can be obtained, and the present invention has been completed.
即ち、本発明は、長手方向の厚みむらが１０％以下であり、且つ１２０℃における長手方向の熱収縮率が５％以下であり、生鮮食品、加工食品、医薬品、医療機器、電子部品の包装用フィルムとして用いられるポリ乳酸二軸延伸フィルムの製造方法であって、重量平均分子量が２５万以上５０万以下であるポリ乳酸に、シリカを０．００５重量％以上０．０６重量％以下配合し、二段以上の、かつ少なくとも１回は１２０００％／分以上の速度で縦延伸を施し、１５５℃以上ポリマーの融解温度（Ｔｍ）以下の温度で熱固定することを特徴とするポリ乳酸二軸延伸フィルムの製造方法に係る。 That is, the present invention, the longitudinal thickness unevenness is not less than 10%, and Ri der longitudinal thermal shrinkage rate of 5% or less at 120 ° C., perishables, processed foods, medicines, medical equipment, electronic components a method for producing a biaxially stretched polylactic acid film that is used as a packaging film, the weight average molecular weight polylactic acid is 250,000 to 500,000, silica 0.005 wt% or more 0.06 wt% or less blended, two or more stages, and at least once to facilities longitudinal stretching at 12000% / min or faster, characterized in that heat-set at the melting temperature (Tm) below the temperature of 155 ° C. or higher poly The present invention relates to a method for producing a lactic acid biaxially stretched film.
本発明により得られるポリ乳酸フィルムは、生鮮食品、加工食品、医薬品、医療機器、電子部品の包装用フィルムにおいて重要な特性である印刷やラミネートの加工工程において寸法変化やしわを発生することが無く、平面性悪化や印刷ずれ等の発生しない優れた加工適性を有しており、一般包装用フィルムとして極めて有用である。 Polylactic acid film obtained by the present invention, fresh food, processed food, drugs, medical devices, is possible to generate a dimensional change and wrinkles in an important characteristic printing and lamination processing steps in the packaging film of electronic components It has excellent processability that does not cause deterioration of flatness or printing misalignment, and is extremely useful as a general packaging film.
本発明における脂肪族ポリエステルとしては、主たる繰り返し単位が、一般式（Ｉ）で表される単位である脂肪族ポリエステル、例えばポリ乳酸、ポリグリコール酸、ポリ（２−オキシ酪酸）等を挙げることができるが、これらに限定されるものではない。 Examples of the aliphatic polyester in the present invention include an aliphatic polyester whose main repeating unit is a unit represented by the general formula (I), such as polylactic acid, polyglycolic acid, poly (2-oxybutyric acid), and the like. However, it is not limited to these.
また、これら脂肪族ポリエステルの単独でも良く、或いは混合物でも良い。また、上記一般式（Ｉ）の単位の共重合体を使用しても構わない。脂肪族ポリエステル中に不斉炭素を有する場合は、Ｌ−体、ＤＬ−体、Ｄ−体といった光学異性体が存在するが、それらのいずれでも良く、また、それら異性体の混合物でも良い。更に、本発明の効果を阻害しない範囲で、他の高分子材料が混入されても構わない。 These aliphatic polyesters may be used alone or as a mixture. Moreover, you may use the copolymer of the unit of the said general formula (I). When the aliphatic polyester has an asymmetric carbon, optical isomers such as L-form, DL-form, and D-form exist, and any of them may be used, or a mixture of these isomers may be used. Furthermore, other polymer materials may be mixed as long as the effects of the present invention are not impaired.
これらのフィルムの素材となる上述した脂肪族ポリエステル（以下、単に「ポリマー」ということがある。）は、対応するα−オキシ酸の脱水環状エステル化合物を開環重合等の公知の方法に供して製造される。 The above-mentioned aliphatic polyesters (hereinafter sometimes simply referred to as “polymers”) that serve as materials for these films are prepared by subjecting the corresponding α-oxyacid dehydrated cyclic ester compounds to known methods such as ring-opening polymerization. Manufactured.
本発明において、用いられる脂肪族ポリエステルは、重量平均分子量で、１万以上５０万以下である。１万未満であると、得られたフィルムの物性が著しく劣り、且つ、分解速度が速すぎ本発明の目的を達し得ない。また、フィルム製造時の押出し性、二軸延伸性も低下することから重量平均分子量は１万以上である必要がある。一方、重量平均分子量が５０万以上の高粘度重合体になると溶融押出しが困難になるという問題がある。好ましい範囲は、５万以上３０万以下である。 In the present invention, the aliphatic polyester used has a weight average molecular weight of 10,000 to 500,000. If it is less than 10,000, the physical properties of the obtained film are remarkably inferior, and the decomposition rate is too high to achieve the object of the present invention. Moreover, since the extrudability at the time of film manufacture and biaxial stretching property also fall, a weight average molecular weight needs to be 10,000 or more. On the other hand, when it becomes a high viscosity polymer having a weight average molecular weight of 500,000 or more, there is a problem that melt extrusion becomes difficult. A preferable range is 50,000 or more and 300,000 or less.
本発明により得られるポリ乳酸からなるフィルムは、押出成形、二軸延伸後に熱固定されたフィルムであることが好ましく、製膜し延伸され製造される。 Film made of polylactic acid obtained by the present invention, extrusion molding, it is heat-set film after biaxial stretching is preferably a film stretched prepared.
本発明におけるフィルムを押出成形する方法は、公知のＴ−ダイ法、インフレーション法等が適用でき、これらの方法により未延伸フィルムを得ることができる。押出し温度は、用いるポリマーの融解温度（Ｔｍ）〜Ｔｍ＋７０℃の範囲、より好ましくは、Ｔｍ＋２０〜Ｔｍ＋５０℃の範囲である。 How extruding a film of the present invention, known T- die method, can inflation method is applied, it is possible to obtain an unstretched film by these methods. The extrusion temperature is in the range of the melting temperature (Tm) to Tm + 70 ° C. of the polymer used, and more preferably in the range of Tm + 20 to Tm + 50 ° C.
押出し温度が低すぎると押出し安定性が得難く、又過負荷に陥りやすい。また、逆に高すぎるとポリマーの分解が激しくなるので好ましくない。本発明で用いる押出機のダイは、環状又は線状のスリットを有するものでよい。ダイの温度は押出温度範囲と同じ程度で良い。 If the extrusion temperature is too low, it is difficult to obtain extrusion stability, and overload tends to occur. On the other hand, if it is too high, the decomposition of the polymer becomes severe, such being undesirable. The die of the extruder used in the present invention may have an annular or linear slit. The die temperature may be about the same as the extrusion temperature range.
未延伸フィルムの二軸延伸は、一軸目の延伸と二軸目の延伸を逐次に行っても、同時に行っても良い。 The biaxial stretching of the unstretched film may be performed sequentially or simultaneously with the first and second axes.
尚、本発明により得られる二軸延伸フィルムにおける長手方向とは縦延伸方向を意味し、又幅方向とは横延伸方向を意味する。 In the biaxially stretched film obtained by the present invention, the longitudinal direction means the longitudinal stretching direction, and the width direction means the transverse stretching direction.
延伸温度は、用いるポリマーのガラス転移温度（Ｔｇ）〜Ｔｇ＋５０℃の範囲が好ましい。より好ましくはＴｇ＋１０〜Ｔｇ＋４０℃の範囲である。延伸温度がＴｇ未満では延伸が困難であり、Ｔｇ＋５０℃を越えると厚み均一性や得られたフィルムの機械的強度が低下し好ましくない。 The stretching temperature is preferably in the range of glass transition temperature (Tg) to Tg + 50 ° C. of the polymer used. More preferably, it is the range of Tg + 10-Tg + 40 degreeC. If the stretching temperature is less than Tg, stretching is difficult, and if it exceeds Tg + 50 ° C., the thickness uniformity and the mechanical strength of the obtained film are undesirably lowered.
縦、横の延伸は１段階でも多段階に分けて行っても良いが、それぞれの延伸方向に最終的には少なくとも３倍以上、更に好ましくは、３．５倍以上、又縦・横面積倍率で９倍以上、更に好ましくは１２倍以上延伸することが厚みの均一性や機械的性質の点から必要である。縦、横延伸比がそれぞれ３倍未満、又面積倍率が９倍未満では、厚み均一性の良いフィルムは得られず、又機械的強度等の物性の向上も乏しい。延伸倍率の上限は、製膜中にフィルムの破断が生じない限り、限定されない。 Longitudinal and lateral stretching may be carried out in one step or in multiple stages, but in the final stretching direction, at least 3 times or more, more preferably 3.5 times or more, and longitudinal / lateral area magnification. It is necessary to stretch 9 times or more, more preferably 12 times or more from the viewpoint of thickness uniformity and mechanical properties. When the longitudinal and lateral stretch ratios are each less than 3 times and the area magnification is less than 9 times, a film having good thickness uniformity cannot be obtained, and improvement in physical properties such as mechanical strength is poor. The upper limit of the draw ratio is not limited as long as the film does not break during film formation.
本発明における厚みむら及び熱収縮率を所定の範囲とするため重要なことは、縦延伸を二段以上で行い、少なくとも一回はＴｇ＋２０〜Ｔｇ＋４０℃の範囲で延伸速度が１００００％／分、好ましくは１５０００％／分、さらに好ましくは２００００％／分以上で延伸する工程を含むことである。延伸速度の上限は、製膜中にフィルムの破断が生じない限り、限定されない。 What is important for making the thickness unevenness and heat shrinkage ratio in the present invention within a predetermined range is that longitudinal stretching is performed in two or more stages, and at least once, the stretching speed is 10,000% / min in the range of Tg + 20 to Tg + 40 ° C., preferably Includes a step of stretching at 15000% / min, more preferably 20000% / min or more. The upper limit of the stretching speed is not limited as long as the film does not break during film formation.
上記フィルムの二軸延伸をした後、通常、１５０℃以上Ｔｍ以下好ましくは１５５℃以上Ｔｍ以下の温度で熱固定を行い、更に１２０℃以上熱固定温度以下の温度で１〜１０％程度好ましくは２〜８％程度横弛緩処理を行う。 After biaxial stretching of the above film, it is usually heat-set at a temperature of 150 ° C. or more and Tm or less, preferably 155 ° C. or more and Tm or less, and further at a temperature of 120 ° C. or more and the heat setting temperature or less, preferably about 1 to 10%. Perform lateral relaxation treatment about 2-8%.
本発明により得られるポリ乳酸二軸延伸フィルムは、製造工程において共押出し法やコーティング法によって複層化されてもよい。また、本発明のフィルムは、表面エネルギーを向上する目的で、コロナ処理、プラズマ処理、火炎処理等を施しても良い。 The polylactic acid biaxially stretched film obtained by the present invention may be multilayered by a coextrusion method or a coating method in the production process. Further, the film of the present invention may be subjected to corona treatment, plasma treatment, flame treatment, etc. for the purpose of improving the surface energy.
本発明における原料脂肪族ポリエステルには、公知の添加剤を必要に応じて含有させることができる。例えば、滑剤、ブロッキング防止剤、熱安定剤、酸化防止剤、帯電防止剤、耐光剤、耐衝撃性改良剤等を含有させてもよい。但し、本発明の脂肪族ポリエステル系二軸延伸フィルムは、ヒートシール層を形成された後、透明で内容物が見える必要があるので、ヒートシール層を形成された後においても高い透明性を保持できる範囲内での使用が必要となる。 The raw material aliphatic polyester in the present invention may contain known additives as necessary. For example, a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a light resistance agent, an impact resistance improver, and the like may be contained. However, since the aliphatic polyester biaxially stretched film of the present invention needs to be transparent and visible after the heat seal layer is formed, it retains high transparency even after the heat seal layer is formed. Use within the possible range is required.
滑剤としては、例えばシリカ、二酸化チタン、タルク、カオリナイト等の金属酸化物、炭酸カルシウム、リン酸カルシウム、硫酸バリウム等の金属の塩、又は架橋ポリスチレン樹脂、架橋アクリル樹脂、シリコン樹脂、架橋ポリエステル樹脂等の有機樹脂からなる粒子等の脂肪族ポリエステルに対し不活性な粒子が例示できる。 Examples of the lubricant include metal oxides such as silica, titanium dioxide, talc, and kaolinite, metal salts such as calcium carbonate, calcium phosphate, and barium sulfate, or crosslinked polystyrene resins, crosslinked acrylic resins, silicone resins, crosslinked polyester resins, and the like. Examples thereof include particles inert to aliphatic polyesters such as particles made of organic resin.
これらの滑剤は、いずれか一種を単独で用いてもよく、又２種以上を併用してもよいが、使用する滑剤の平均粒子径は０．０１μｍ以上３．０μｍ以下が好ましく、０．０５μｍ以上２．５μｍ以下がより好ましい。その添加量としては、０．００５重量％以上２重量％以下含有していることが好ましく、０．０１重量％以上１．０重量％以下含有していることがフィルムの透明性及び滑り性を両立するためにより好ましい。 These lubricants may be used alone or in combination of two or more. The average particle size of the lubricant used is preferably 0.01 μm to 3.0 μm, preferably 0.05 μm. More preferably, it is 2.5 μm or less. The addition amount is preferably 0.005 wt% or more and 2 wt% or less, and 0.01 wt% or more and 1.0 wt% or less contains the transparency and slipperiness of the film. It is more preferable to achieve both.
また、特に透明性と滑り性を両立する為には２種以上の滑剤を併用することが好ましい。特に、フィルムの製膜中に変形する滑剤粒子（例えば、架橋ポリスチレン樹脂、架橋アクリル樹脂等の架橋度の低い有機滑剤、一次粒子の凝集体であるシリカ等の無機滑剤）とフィルム製膜中に変形しない通常の滑剤粒子を組み合わせることが好ましい。 In particular, in order to achieve both transparency and slipperiness, it is preferable to use two or more lubricants in combination. In particular, lubricant particles that deform during film formation (for example, organic lubricants with a low degree of crosslinking such as crosslinked polystyrene resin and crosslinked acrylic resin, inorganic lubricants such as silica, which are aggregates of primary particles) and film formation. It is preferable to combine ordinary lubricant particles that do not deform.
本発明により得られるポリ乳酸二軸延伸フィルムの長手方向の厚みむらは、１０％以下である必要があり、好ましくは８％以下、更に好ましくは５％以下である。この厚みむらは、フィルム長手方向の厚みを連続して測定し、厚みの平均値に対する最大値と最小値の差の百分率として、表されるものである。厚みむらが１０％より大きいと印刷やラミネート等の加工工程において搬送張力が加わった状態でフィルムが加熱されるとフィルムの長手方向に平面性の良好な場所と不良な場所が混在した状態のフィルムとなり、最終製品の収率（歩留り）の低下が発生するため好ましくない。ここで、本発明フィルムの厚さは、通常、５〜５０μｍ程度とするのが良い。 The thickness unevenness in the longitudinal direction of the polylactic acid biaxially stretched film obtained by the present invention needs to be 10% or less, preferably 8% or less, more preferably 5% or less. This thickness unevenness is expressed as a percentage of the difference between the maximum value and the minimum value with respect to the average value of the thickness, continuously measuring the thickness in the film longitudinal direction. If the thickness unevenness is greater than 10%, when the film is heated in the processing process such as printing or laminating, the film is heated and the film is in a state where both good and bad flatness are mixed in the longitudinal direction of the film. This is not preferable because the yield (yield) of the final product is reduced. Here, the thickness of the film of the present invention is usually preferably about 5 to 50 μm.
また、本発明により得られるポリ乳酸二軸延伸フィルムの１２０℃における長手方向の熱収縮率は、５％以下である必要があり、好ましくは３％以下である。熱収縮率が５％より大きいと印刷工程においては印刷ずれが発生し、ヒートシール時にはしわが発生するため好ましくない。 Further, the heat shrinkage rate in the longitudinal direction at 120 ° C. of the polylactic acid biaxially stretched film obtained by the present invention needs to be 5% or less, preferably 3% or less. If the thermal shrinkage rate is larger than 5%, printing deviation occurs in the printing process, and wrinkles occur during heat sealing, which is not preferable.
また、本発明により得られるポリ乳酸二軸延伸フィルムの厚み方向の屈折率（Ｎｚ）は、好ましくは１．４４０以上１．４５５以下であり、より好ましくは１．４４５以上１．４５５以下である。Ｎｚが１．４４０未満ではフィルムを製膜する工程において破断が発生しやすくなる。また、１．４５５を越えると印刷やラミネートの工程等でフィルムが加熱された場合に平面性の乱れを発生するため好ましくない。 Further, the refractive index (Nz) in the thickness direction of the polylactic acid biaxially stretched film obtained by the present invention is preferably 1.440 or more and 1.455 or less, more preferably 1.445 or more and 1.455 or less. . If Nz is less than 1.440, breakage is likely to occur in the step of forming a film. On the other hand, if it exceeds 1.455, the flatness is disturbed when the film is heated in the printing or laminating process or the like.
更に、本発明により得られるポリ乳酸二軸延伸フィルムにおいて、その長手方向の屈折率(Ｎｘ)から幅方向の屈折率(Ｎｙ)を差し引いた値(Ｎｘ−Ｎｙ)が、−０．０２０以上０以下であるのが好ましく、−０．０１５以上０以下であるのがより好ましい。Ｎｘ−Ｎｙが−０．０２０未満では印刷やラミネートの工程等でフィルムが加熱された場合に、フィルムの搬送張力により引き伸ばされ、印刷ずれ及び波うちを発生し平面性が悪化するため好ましくない。また、Ｎｘ−Ｎｙが０以上では厚みむらが大きくなりやすい。 Further, in the polylactic acid biaxially stretched film obtained by the present invention, the value (Nx−Ny) obtained by subtracting the refractive index (Ny) in the width direction from the refractive index (Nx) in the longitudinal direction is −0.020 or more and 0 Or less, more preferably −0.015 or more and 0 or less. When Nx-Ny is less than -0.020, when the film is heated in the printing or laminating process, the film is stretched by the conveyance tension of the film, and printing misalignment and waviness are generated, resulting in poor flatness. Further, when Nx−Ny is 0 or more, the thickness unevenness tends to increase.
以下、実施例及び比較例を挙げて、本発明の内容及び効果を更に具体的に説明するが、本発明は、その要旨を逸脱しない限り以下の実施例に限定されるものではない。 Hereinafter, although an example and a comparative example are given and the contents and effect of the present invention are explained more concretely, the present invention is not limited to the following examples, unless it deviates from the gist.
以下の実施例及び比較例における物性の評価方法は以下の通りである。 The evaluation methods of physical properties in the following examples and comparative examples are as follows.
（１）長手方向の厚みむらアンリツ株式会社製の「フィルム厚み連続測定器」を用い、フィルムの長手方向に連続して３ｍの厚みを計測し、下式から厚みむらを算出した。 (1) Uneven thickness in the longitudinal direction Using a “film thickness continuous measuring device” manufactured by Anritsu Corporation, a thickness of 3 m was measured continuously in the longitudinal direction of the film, and the uneven thickness was calculated from the following equation.
厚みむら(％)＝〔(厚みの最大値−厚みの最小値)／厚みの平均値〕×１００ Unevenness of thickness (%) = [(maximum thickness−minimum thickness) / average thickness] × 100
（２）長手方向の熱収縮率フィルムを幅１０ｍｍ、長さ２５０ｍｍ取り、２００ｍｍ間隔で印をつけ５ｇの一定張力で間隔Ａを測る。続いて、無荷重で３０分間、１２０℃の雰囲気中のオーブンに入れた後の印の間隔Ｂを、５ｇの一定張力で測り、以下の式により熱収縮率を求めた。 (2) Take a heat shrinkage film of 10 mm in width and 250 mm in length in the longitudinal direction, mark it at intervals of 200 mm, and measure the interval A with a constant tension of 5 g. Subsequently, the interval B between marks after being placed in an oven in an atmosphere of 120 ° C. for 30 minutes with no load was measured with a constant tension of 5 g, and the thermal shrinkage rate was determined by the following equation.
熱収縮率（％）＝〔（Ａ−Ｂ）／Ａ〕×１００ Thermal contraction rate (%) = [(A−B) / A] × 100
（３）厚み方向、長手方向及び幅方向の屈折率（Ｎｚ、Ｎｘ、Ｎｙ）
株式会社アタゴ製の「アッベ屈折計１Ｔ」を用いて、それぞれの屈折率を測定した。
(3) Refractive index (Nz, Nx, Ny) in thickness direction, longitudinal direction and width direction
Each refractive index was measured using “Abbe refractometer 1T” manufactured by Atago Co., Ltd.
（４）加工適性各実施例及び比較例で得られた熱可塑性フィルムの上にグラビアインキ（「ラミエース６１白二液タイプ」、東洋インキ社製）をグラビア印刷して印刷インキ層を形成し、次いで接着剤「ＡＤ５８５／ＣＡＴ−１０」（東洋モートン社製）を２ｇ／ｍ2塗布した後、常法に従って６０μｍの未延伸ポリプロピレンフィルム（「Ｐ１１２０」、東洋紡績製）をドライラミネート法にて貼り合わせてシーラント層を設け、脂肪族ポリエステル系フィルム積層体を得た。この工程においてフィルムの状態を観察し、印刷及びラミネートの工程における加工適性を、しわ及び印刷ずれの各項目について、下記基準に基づき、三段階評価した。 (4) Processing suitability Gravure printing (“Ramiace 61 white two-component type”, manufactured by Toyo Ink Co., Ltd.) is formed on the thermoplastic films obtained in each Example and Comparative Example to form a printing ink layer. Next, an adhesive “AD585 / CAT-10” (manufactured by Toyo Morton) was applied at 2 g / m 2, and then a 60 μm unstretched polypropylene film (“P1120”, manufactured by Toyobo Co., Ltd.) was bonded by a dry laminating method according to a conventional method. A sealant layer was provided to obtain an aliphatic polyester film laminate. In this process, the state of the film was observed, and the processing suitability in the printing and laminating processes was evaluated in three stages based on the following criteria for each item of wrinkles and printing misalignment.
しわ：○；しわが無く、フィルムの状態良好、
△；しわが若干発生、
×；平面性悪化が見られ、しわが発生。
Wrinkle: ○: No wrinkle, good film condition,
Δ: Some wrinkles occur,
X: The flatness was deteriorated and wrinkles were generated.
印刷ずれ：○；印刷ずれが無く、フィルムの状態良好、
△；印刷ずれが若干発生、
×；平面性悪化が見られ、印刷ずれが発生。
Print misalignment: ○: No print misalignment, good film condition,
Δ: Some printing misalignment occurred,
X: Deterioration of flatness was observed and printing misalignment occurred.
（５）製膜状況
二軸延伸を連続３時間実施したとき、フィルムの破断が発生しない又は１回発生を良好とし、フィルムの破断が２回以上発生を破断発生とした。
(5) Film-forming situation When biaxial stretching was carried out for 3 hours continuously, the film did not break or the occurrence of one occurrence was considered good, and the occurrence of the film breaking twice or more was regarded as the occurrence of breakage.
実施例１
重量平均分子量２５万のポリ−Ｌ−乳酸（Ｔｇ＝６１．６℃、Ｔｍ＝１７０℃）１００重量部に対し、表面突起を形成するための滑剤として平均粒子径１．８μｍの凝集体シリカ粒子を０．０６重量部添加した組成物を、Ｔダイ付き口径３０ｍｍ押出機を使用して、樹脂温度２１０℃で押出した後、２０℃のチルロールで冷却し、厚さ３００μｍの未延伸フィルムを得た。複数本のセラミックロールによりフィルム温度を９６℃に予熱しロール間で３００００％／分の延伸速度で縦方向に１．５倍延伸し、更に９８℃で２．７倍縦方向に延伸した。次いで、テンター式延伸機で横方向に８０℃で３．８倍延伸した後、１５５℃で熱固定した後、１３５℃で３％横弛緩処理を行った。かくして、厚さ２０μｍの本発明二軸延伸フィルムを得た。表１にその物性を示す。
Example 1
Aggregated silica particles having an average particle diameter of 1.8 μm as a lubricant for forming surface protrusions with respect to 100 parts by weight of poly-L-lactic acid having a weight average molecular weight of 250,000 (Tg = 61.6 ° C., Tm = 170 ° C.) Was extruded at a resin temperature of 210 ° C. using a 30 mm diameter extruder with a T-die and cooled with a chill roll at 20 ° C. to obtain an unstretched film having a thickness of 300 μm. It was. The film temperature was preheated to 96 ° C. with a plurality of ceramic rolls, stretched 1.5 times in the machine direction between the rolls at a stretching speed of 30000% / min, and further stretched 2.7 times in the machine direction at 98 ° C. Next, the film was stretched 3.8 times in the transverse direction at 80 ° C. by a tenter type stretching machine, heat-set at 155 ° C., and then subjected to a 3% transverse relaxation treatment at 135 ° C. Thus, a biaxially stretched film of the present invention having a thickness of 20 μm was obtained. Table 1 shows the physical properties.
比較例１
実施例１において縦延伸を複数本のセラミックロールによりフィルム温度９６℃に予熱しロール間で３００００％／分の延伸速度で縦方向に２．５倍に一段延伸で実施した以外は実施例１とまったく同様の方法で、比較用の二軸延伸フィルムを得た。表１にその物性を示す。
Comparative Example 1
Example 1 is the same as Example 1 except that the longitudinal stretching was carried out by a single-stage stretching of 2.5 times in the longitudinal direction at a stretching speed of 30000% / min between rolls by preheating to a film temperature of 96 ° C. with a plurality of ceramic rolls. A biaxially stretched film for comparison was obtained in exactly the same manner. Table 1 shows the physical properties.
比較例２
実施例１において縦延伸を６８℃で３．５倍に一段延伸で実施した以外は実施例１とまったく同様の方法で、比較用の二軸延伸フィルムを得た。表１にその物性を示す。
Comparative Example 2
A biaxially stretched film for comparison was obtained in the same manner as in Example 1 except that the longitudinal stretching in Example 1 was carried out by single-stage stretching at 3.5 times at 68 ° C. Table 1 shows the physical properties.
実施例２
実施例１において縦延伸を１２０００％／分で実施した以外は実施例１とまったく同様の方法で、本発明の二軸延伸フィルムを得た。表１にその物性を示す。
Example 2
A biaxially stretched film of the present invention was obtained in the same manner as in Example 1 except that longitudinal stretching was performed at 12000% / min in Example 1. Table 1 shows the physical properties.
比較例３
実施例１において熱固定を１４０℃で実施した以外は実施例１とまったく同様の方法で、比較用の二軸延伸フィルムを得た。表１にその物性を示す。
Comparative Example 3
A biaxially stretched film for comparison was obtained in the same manner as in Example 1 except that heat setting was performed at 140 ° C. in Example 1. Table 1 shows the physical properties.
参考例１
実施例１において熱固定を１５０℃で実施した以外は実施例１とまったく同様の方法で、本発明の二軸延伸フィルムを得た。表１にその物性を示す。
Reference example 1
A biaxially stretched film of the present invention was obtained in the same manner as in Example 1 except that heat setting was performed at 150 ° C. in Example 1. Table 1 shows the physical properties.
本発明により得られるポリ乳酸フィルムは、生鮮食品、加工食品、医薬品、医療機器、電子部品の包装用フィルムにおいて重要な特性である印刷やラミネートの加工工程において寸法変化やしわを発生することが無く、平面性悪化や印刷ずれ等の発生しない優れた加工適性を有しており、一般包装用フィルムとして極めて有用である。 Polylactic acid film obtained by the present invention, fresh food, processed food, drugs, medical devices, is possible to generate a dimensional change and wrinkles in an important characteristic printing and lamination processing steps in the packaging film of electronic components It has excellent processability that does not cause deterioration of flatness or printing misalignment, and is extremely useful as a general packaging film.
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| JPH09208817A (en) * | 1995-11-30 | 1997-08-12 | Mitsui Toatsu Chem Inc | Oriented lactic acid base polymer film |
| JPH09278997A (en) * | 1996-04-16 | 1997-10-28 | Mitsui Toatsu Chem Inc | Lactic acid-based polymer film |
| JPH09286908A (en) * | 1996-04-19 | 1997-11-04 | Mitsui Toatsu Chem Inc | Lactic acid-based polymer film |
| JPH10315318A (en) * | 1997-05-16 | 1998-12-02 | Mitsui Chem Inc | Lactate polymer biaxially oriented film |
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| JPH09208817A (en) * | 1995-11-30 | 1997-08-12 | Mitsui Toatsu Chem Inc | Oriented lactic acid base polymer film |
| JPH09278997A (en) * | 1996-04-16 | 1997-10-28 | Mitsui Toatsu Chem Inc | Lactic acid-based polymer film |
| JPH09286908A (en) * | 1996-04-19 | 1997-11-04 | Mitsui Toatsu Chem Inc | Lactic acid-based polymer film |
| JPH10315318A (en) * | 1997-05-16 | 1998-12-02 | Mitsui Chem Inc | Lactate polymer biaxially oriented film |
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