WO2002034818A1 - Biaxially oriented aliphatic polyester film and process for producing the same - Google Patents

Biaxially oriented aliphatic polyester film and process for producing the same Download PDF

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Publication number
WO2002034818A1
WO2002034818A1 PCT/JP2000/007397 JP0007397W WO0234818A1 WO 2002034818 A1 WO2002034818 A1 WO 2002034818A1 JP 0007397 W JP0007397 W JP 0007397W WO 0234818 A1 WO0234818 A1 WO 0234818A1
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WO
WIPO (PCT)
Prior art keywords
film
aliphatic polyester
biaxially oriented
polylactic acid
acid
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PCT/JP2000/007397
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French (fr)
Japanese (ja)
Inventor
Shigenori Terada
Jun Takagi
Original Assignee
Mitsubishi Plastics Inc.
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Publication date
Priority to JP11235075A priority Critical patent/JP2001059029A/en
Application filed by Mitsubishi Plastics Inc. filed Critical Mitsubishi Plastics Inc.
Priority to PCT/JP2000/007397 priority patent/WO2002034818A1/en
Publication of WO2002034818A1 publication Critical patent/WO2002034818A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function

Definitions

  • the present invention relates to a biaxially oriented aliphatic polyester film and a method for producing the same.
  • plastics for general packaging include polyethylene, polypropylene, PET, etc., but these materials generate a large amount of heat during combustion and may damage the combustion furnace during the combustion process.
  • polyvinyl chloride which is still widely used, cannot burn because of its self-extinguishing properties.
  • plastic products, including materials that cannot be incinerated are often landfilled.However, due to their chemical and biological stability, they remain with little decomposition and shorten the life of the landfill. I'm having a problem.
  • Polylactic acid has a calorific value of combustion less than half that of polyethylene, and hydrolyses naturally in soil and water, and then becomes harmless degradation products by microorganisms.
  • research is being conducted to obtain molded articles, specifically, containers such as films, sheets, and bottles, using polylactic acid.
  • the film when a film made of polylactic acid is manufactured, if the film does not slip smoothly, the film may be wound continuously during the production of the film or in the secondary processing such as printing and laminating with a winder or the like. This causes problems such as meandering and wrinkling.
  • an object of the present invention is to improve the slip of a film made of polylactic acid, to suppress the meandering and wrinkling of the film, and to obtain the film's waist, strength, low heat shrinkage, and It is an object of the present invention to provide a slippery aliphatic polyester film while maintaining transparency according to the conditions. Disclosure of the invention
  • the present invention comprises an aliphatic polyester having a polylactic acid-based polymer as a main component, is blended with inorganic particles, and has an average roughness Ra of the film surface of 0.01 ⁇ Ra ⁇ 0.08.
  • the biaxially oriented aliphatic polyester film according to the present invention is made of an aliphatic polyester mainly containing a polylactic acid polymer, is blended with inorganic particles, and has a film surface with a predetermined average roughness Ra. .
  • the above-mentioned polylactic acid-based polymer refers to a polymer mainly composed of L-, D- or DL-lactic acid units, and is a polymer of only polylactic acid, or L-, D- or DL-lactic acid and hydro- Copolymers with xycarboxylic acid, aliphatic dicarboxylic acid (including alicyclic groups; the same applies hereinafter) and / or aliphatic diols, and those containing 50% or more of a polylactic acid component.
  • the ratio of L-lactic acid to D-lactic acid in the polylactic acid-based polymer should be 100: 0 to 94: 6 or 6:94 to 0: 1 in order to obtain a desirable surface roughness. 0 0 is preferred. If the ratio is smaller than 94: 6 and larger than 6:94, the film cannot be sufficiently crystallized by heat treatment after stretching, and the heat shrinkage of the film cannot be suppressed. In addition, the orientation is relaxed, and no improvement in physical properties due to the effect of the orientation is observed. As described later, the inorganic particles blended during stretching protrude, the surface is roughened, and the slip of the film is improved.
  • the film is subjected to heat treatment.
  • the inorganic particles protruding with the relaxation of the orientation are buried in the film again, and a film with good slip cannot be obtained.
  • the present invention it is extremely important to use a polylactic acid-based polymer having a high crystallinity in the above range together with the blending of the inorganic particles in the production of the oriented film through the heat treatment step.
  • the polymerization method a known method such as a condensation polymerization method or a ring-opening polymerization method can be employed.
  • L-lactic acid, D-lactic acid, or these and other monomers described above are used.
  • a polylactic acid-based polymer having an arbitrary composition can be obtained.
  • lactide which is a cyclic dimer of lactic acid
  • lactide method lactide method
  • a polymerization regulator and the like By mixing and polymerizing the other monomers, a polylactic acid-based polymer can be obtained.
  • the preferred range of the weight average molecular weight of the polylactic acid polymer used in the present invention is 60,000 to 700,000, more preferably 80,000 to 400,000, and particularly preferably 100,000. ⁇ 300,000. If the molecular weight is smaller than 60,000, practical physical properties such as mechanical properties and heat resistance are hardly exhibited, and if it is larger than 70,000, the melt viscosity is too high and the moldability may be poor.
  • Examples of other monomers copolymerized with polylactic acid include the following.
  • lactic acid having a predetermined optical isomer lactic acid having another optical isomer (for example, D-lactic acid for L-lactic acid and L-lactic acid for D-lactic acid) Monolactic acid).
  • Hydroxycarboxylic acids include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxy-1-n-butyric acid, 2-hydroxy-3-, 3-dimethylbutyric acid, 2—Hydroxy-1 3—Methylbutyric acid, 2-Methyllactate, 2-Hydroxycaproic acid and other bifunctional aliphatic hydroxycarboxylic acids, and lactones such as hydroprolactone, petyrolactone, and norrelactonekind.
  • aliphatic dicarboxylic acids examples include aliphatic dicarponic acids such as succinic acid, adipic acid, suberic acid, sebacic acid, dodecandioic acid, and anhydrides and derivatives thereof.
  • aliphatic diol examples include aliphatic diols such as ethylene glycol, butanediol, hexanediol, octanediol, cyclopentenediol, cyclohexanediol, and cyclohexanedimethanol; Derivatives thereof.
  • those having a bifunctional compound as a main component having an alkylene group or a cycloalkylene group having 2 to 10 carbon atoms are preferable.
  • two or more of these carboxylic acid components and alcohol components may be used.
  • the unit of the above (a) is used for the purpose of providing a branch in the polymer to improve the melt viscosity, and specifically, malic acid, tartaric acid, citric acid, trimellitic acid, and pyromellitic acid.
  • a polyfunctional component such as erythritol pentotrimethylolpropane. If these components are used in large amounts, the resulting polymer will have a crosslinked structure and will not be thermoplastic, or even if it is a thermoplastic, a microgel with a partially highly crosslinked structure will be formed. There is a possibility that.
  • the proportion of these polyfunctional components contained in the polymer is very small, and is limited to a level that does not greatly affect the chemical and physical properties of the polymer.
  • specific examples of the non-aliphatic dicarboxylic acid include terephthalic acid and the like
  • examples of the non-aliphatic diol include an ethylene oxide adduct of bisphenol A and the like. Is raised.
  • the aliphatic polyester contains a polylactic acid-based polymer as a main component, but may contain other resin components (hereinafter, referred to as “other resin components”).
  • the resin component include aliphatic polyesters other than the polylactic acid-based polymer.
  • the aliphatic polyester other than the polylactic acid-based polymer include a polymer of hydroxycarboxylic acid other than lactic acid, and a polyester composed of an aliphatic dicarboxylic acid and / or an aliphatic diol.
  • the hydroxycarboxylic acids, aliphatic dicarboxylic acids and aliphatic diols used herein are the same as described above.
  • the aliphatic polyester may contain the same small amount of copolymerized units as described above, and may also contain a small amount of a chain extender residue.
  • the direct method is a method of directly polymerizing an aliphatic carboxylic acid and an aliphatic diol while removing water contained in these components or generated during the polymerization to obtain a high molecular weight product.
  • the indirect method is an indirect production method in which a small amount of a chain extender is used to increase the molecular weight after polymerization to the degree of an oligomer, as in the case of the polylactic acid-based polymer.
  • the other resin component preferably has a weight average molecular weight of 50,000 to 250,000. If the weight-average molecular weight is less than 50,000, the properties as a polymer are inferior, and not only does not improve the heat sealing property, but also causes problems such as temporary bleeding on the film surface. Also, if it is larger than 250,000, the melt viscosity becomes too high. This leads to a decrease in the mixing property with polylactic acid and a decrease in extrudability when forming a film like polylactic acid.
  • the other resin component has a glass transition point (T g) of 0 ° C. or less from the viewpoint of the effect of improving impact resistance and cold resistance.
  • Particularly suitable other resin components include, for example, polyethylene suberate, polyethylene sebacate, polyethylene decane dicarboxylate, polybutylene succinate, polybutylene adipate, polybutylene sebacate, polybutylene succinate acetate. Copolymers.
  • a block copolymer of a polylactic acid-based polymer and another resin component may be used together with or instead of the other resin component.
  • products containing can be used.
  • This block copolymer can be prepared by any method. For example, either a polylactic acid-based polymer or another resin component is separately prepared as a polymer, and the other constituent monomer is polymerized in the presence of the polymer.
  • a block copolymer of polylactic acid and another resin component is obtained by polymerizing lactide in the presence of another resin component prepared in advance.
  • the polymerization can be carried out in the same manner as in the case of preparing a polylactic acid-based polymer by the lactide method, only with the difference that other resin components coexist. ⁇ At this time, if the polymerization of lactide proceeds At the same time, an appropriate transesterification reaction occurs between polylactic acid and other resin components, and a copolymer having relatively high randomness can be obtained.
  • an aliphatic polyester urethane having a urethane bond is used as a starting material Also produces ester-amide exchange.
  • the inorganic particles refer to particles of an inorganic substance.
  • the inorganic material constituting the inorganic particles include silicon dioxide such as silica, calcium carbonate, magnesium carbonate, silica, titanium dioxide, kaolin, and alumina, and preferably silicon dioxide such as silica, calcium carbonate, and the like. Examples thereof include magnesium carbonate, talc, titanium dioxide, and kaolin. Particularly preferred is silicon dioxide such as silica.
  • silicon dioxide such as silica.
  • One of the above-mentioned inorganic particles may be used alone, or a mixture of two or more thereof may be used.
  • the mixing amount of the inorganic particles is preferably from 0.01 to 120 parts by weight, more preferably from 0.01 to 5 parts by weight, based on 100 parts by weight of the aliphatic polyester. If the amount is less than 0.01 parts by weight, the effect of imparting lubricity is not obtained. On the other hand, if the amount is more than 120 parts by weight, the film cannot be stretched normally, and even if the film can be stretched, defects such as holes are generated.
  • the average particle diameter of the inorganic particles is preferably from 0.1 to 5 m. These inorganic particles can be measured using a sedimentation balance measurement method, a Coal-Yuichi counter measurement method, a light scattering method, or the like.
  • the same effect is obtained as the number of blending parts increases.
  • the average particle size is too large, the smoothness of the surface is reduced, so that printing loss occurs when printing on a film, or scratches occur when the inorganic particles having high hardness rub against each other between the film surfaces. .
  • the number of blending parts is much larger than that of the resin component, the film may not be stretched. Even if it can be stretched, it may cause defects such as holes.
  • the average particle size is too small, the effect of providing lubricity is too low.
  • Haze can be used as a definition of transparency. This can be measured by JISK 7105.
  • the haze is preferably 10% or less, and if the haze exceeds 10%, sufficient transparency may not be obtained.
  • the content be at most about 0.5 part, though it depends on the type and particle size of the inorganic particles to be blended and the thickness of the film. Film If the haze exceeds 10%, it lacks clearness.
  • these formulations can roughen the surface of the film and impart lubricity, and more specifically, lower the coefficient of friction of the film.
  • the average particle diameter of the inorganic particles should be 0.1 to 4 m and the number of parts should be 0.01 to 3 parts by weight.
  • the average particle diameter is 0.5. More preferably, the mixing amount is in the range of 0.02 to 1 part by weight.
  • the biaxially oriented polylactic acid film according to the present invention can be manufactured by the following method.
  • the above-mentioned aliphatic polyester and inorganic particles including the polylactic acid-based polymer and the aliphatic polyester are charged into the same extruder and mixed.
  • a film can be directly produced.
  • a pellet can be produced by extruding the film into a strand shape, and the film can be produced again by an extruder.
  • the reduction in molecular weight due to decomposition must be taken into consideration, but the latter is better to be selected for uniform mixing. After fully drying the aliphatic polyester to remove water, it is melted by an extruder.
  • the melt extrusion temperature of the polylactic acid-based polymer is appropriately selected in consideration of the fact that the melting point changes depending on the composition ratio of the L-lactic acid structure and the D-lactic acid structure, and the melting point and mixing ratio of the aliphatic polyester. In practice, a temperature range of 100-250 ° C is usually chosen.
  • a heat stabilizer for the purpose of adjusting various physical properties, a heat stabilizer, a light stabilizer, a light absorber, a plasticizer, an inorganic filler, a colorant, a pigment, and the like can be added to these mixtures.
  • an oriented film (hereinafter, referred to as a “biaxially oriented polylactic acid-based film”) is preferably obtained by biaxial stretching.
  • the index of orientation at this time is preferably 3.0 ⁇ 10—3 or more in plane orientation ⁇ . In order to achieve this, it is necessary to stretch at least 1.5 times in the uniaxial direction.
  • This biaxially stretched oriented polylactic acid-based film is stretched biaxially, and then heat-treated while being fixed.
  • a heat-set biaxially oriented polylactic acid film can be obtained. It is preferable that at least one of the longitudinal and lateral directions of the film has a shrinkage ratio at 80 ° C. of 10% or less. If the shrinkage exceeds 10%, heat shrinks relatively easily, and a problem is likely to occur.
  • an adhesive is applied on the film surface and bonded to paper, a metal thin film, or other plastic films. Such heat causes the film to shrink, impairing the appearance such as wrinkles, and causing the laminating body to roll easily.
  • the surface roughness Ra (center line average roughness) of the obtained biaxially oriented polylactic acid-based film is preferably 0.01 ⁇ Ra ⁇ 0.08. (Ten-point average roughness) is more preferably 2.0 or less.
  • Rz can be used as an index of smoothness. As this value is larger than Ra, the unevenness (roughness) of the film is sparser, and there is no uniformity. As the value approaches Ra, the size of the unevenness is more uniform.
  • the measurement of Ra and Rz can be measured in accordance with JISB0601,
  • the coefficient of friction of the biaxially oriented polylactic acid film is preferably 0.8 or less in static friction coefficient, more preferably -0.5 or less, and more preferably 0.3 or less.
  • static friction coefficient There are two types of friction coefficient: static friction coefficient and dynamic friction coefficient. In general, the smaller the static friction coefficient, the smaller the dynamic friction.
  • the coefficient of static friction is larger than the coefficient of dynamic friction.
  • Films are produced continuously and are usually rolled. At this time, since the films come into contact with each other-If the coefficient of friction of the film is large, it does not slip and cannot be taken up uniformly and uniformly, and it is also a problem in film processing, for example, printing, laminating, and bag making. In some cases, static electricity is generated and productivity may be significantly reduced. Therefore, it is better to satisfy the above requirements by evaluating the coefficient of static friction.
  • More preferred embodiments of the method for producing a biaxially oriented polylactic acid film according to the present invention are as follows. That is, the polylactic acid-based polymer 10 in which the ratio of L-lactic acid to D-lactic acid is in the range of 100: 0 to 94: 6 or in the range of 6: 94-0: 100. 0 In other words, 0.01 to 120 parts by weight of an inorganic particle having an average particle diameter of 0.1 to 5 ⁇ m is blended with respect to parts by weight, and the biaxial direction is stretched. This makes it possible to produce a biaxially oriented polylactic acid film having an average surface roughness Ra of 0.01 ⁇ Ra ⁇ 0.08.
  • Example 1 Example 1
  • the methods for measuring various physical properties and characteristics in the present invention are as follows.
  • the particle size distribution was measured and calculated by sedimentation balance measurement method, Cole-Yuichi counter measurement method, light scattering method, etc.
  • the refractive index ( ⁇ , ⁇ , y) in three orthogonal directions was measured by Abbe refractometer and calculated by the following formula.
  • ⁇ ⁇ ⁇ ( ⁇ +?) / 2 ⁇ — ( ⁇ 3 ⁇ )
  • Refractive index in the direction perpendicular to the film plane
  • Refractive index in the thickness direction of the film
  • Static friction coefficient According to JISK 712, measurement was made in the machine direction (MD), taking into account the roll of film. The front and back of the film were measured three times each, for a total of six times, and the average was taken.
  • Heat shrinkage (%) [(dimension before shrinkage) one (dimension after shrinkage)] / (dimension before shrinkage) X100
  • X Cannot be used as a product.
  • the obtained sheet is brought into contact with a hot water circulation type roll while Heated together, 3.0 times at 75 ° C vertically between the peripheral speed difference rolls.
  • the film was stretched 3.0 times at 75 ° C. and then heat-treated at 120 ° C. for about 15 seconds to produce a film having a thickness of 40 mm.
  • the film was wound up by a winder. Observation of the occurrence of wrinkles in the film at this time revealed that a roll sample could be obtained without any particular problems. Table 1 shows the evaluation results of the obtained films.
  • a film having a thickness of 40 m was produced in the same manner as in Example 1 except that polylactic acid having a molecular weight of about 180,000 and a ratio of L-lactic acid component to D-lactic acid component of 92: 8 was used. .
  • the winding condition of the film tends to be slightly wrinkled, but it has been used as a product.
  • Table 1 shows the evaluation results of the obtained films.
  • NS # 250 Average particle size of about 0.9 ⁇ m
  • Example 2 The pellet was dried again, put into a ⁇ 40 mm co-axial twin screw extruder, set at a temperature of 210 ° C, and then biaxially oriented to a thickness of 40 mm in the same manner as in Example 1.
  • a film was prepared. The film was wound up with a winder. Observation of the wrinkles of the film at this time showed that a roll-shaped sample could be obtained without any particular problem, but the film lacked transparency. Table 1 shows the evaluation results of the obtained films.
  • a biaxially oriented film having a thickness of 40 m was produced in the same manner as in Example 1 with the number of particles blended as shown in Table 1. However, in Example 4, the heat treatment temperature was set to 50 ° C. or lower, which was lower than the glass transition temperature, to produce a biaxially oriented film that was not substantially thermally fixed. In Example 5, a uniaxially oriented film having a thickness of 60 / m, which was stretched 2.5 times in the vertical direction without longitudinal stretching, was produced. In winding with a winder, Example 4 tended to be good and Example 5 tended to wrinkle slightly. did it. Table 1 shows the evaluation results of the obtained films.
  • L Monolactic acid component D—The ratio of lactic acid component is 9 9: 1 Polylactic acid with a molecular weight of about 220,000 and polybutylene succinate / adipate (manufactured by Showa Kogyo Co., Ltd., trade name: Biono Ile # 3003) and granulated silicon dioxide (silica) manufactured by Fuji Silica Chemical Co., Ltd. with an average particle size of about 2.5 m (trade name: Silicia 430) 0.1 part by weight After drying each of them to remove water sufficiently, they are put into a ⁇ 40 mm co-rotating twin-screw extruder, melt-mixed at about 210 ° C, extruded into strands, and cooled.
  • Example 1 I cut it in a pellet shape while rejecting it.
  • the pellet was dried again and charged into a ⁇ 40 ⁇ ⁇ co-rotating twin-screw extruder at a set temperature of 210 ° C. Thereafter, the pellet having a thickness of 40 ⁇ m was formed in the same manner as in Example 1.
  • An axially oriented film was produced.
  • Table 1 shows the vertical and horizontal stretching temperatures, stretching ratios, and heat treatment temperatures. The film was taken up by a winder and the wrinkles of the film were observed at this time. As a result, a roll sample could be obtained without any particular problem.
  • the evaluation results of the obtained film are shown in Table 1, (Comparative Example 1).
  • Example 2 shows the evaluation results.
  • a biaxially oriented film was prepared in the same manner as in Example 1 except that the particles to be blended were changed to fine particles of titanium dioxide (average particle size: 0.05 m) (trade name: TAF-110, manufactured by Fuji Titanium Co., Ltd.) I got The film is wound up by a winder. Observation of the occurrence of wrinkles on the film at this time reveals that wrinkles are remarkable and the product is judged to be insufficient. Table 2 shows the evaluation results.
  • the number of parts of granular silicon dioxide (silica) having an average particle size of 2.5 ⁇ m was A biaxially oriented film was obtained in the same manner as in Example 1 except that the amount was changed to parts by weight. The occurrence of wrinkles in winding is remarkable, and it is judged that the product is insufficient. Table 2 shows the evaluation results.
  • Example 3 In the same manner as in Example 3 except that the number of parts of calcium carbonate (trade name: NS # 250000) manufactured by Nitto Powder Chemical Co., Ltd. having an average particle size of about 0.9 zm was changed to 140 parts by weight. An attempt was made to produce a biaxially oriented film. However, during production, holes were frequently formed in the film during longitudinal stretching and breakage occurred frequently, and a stable film could not be obtained.
  • NS # 250000 manufactured by Nitto Powder Chemical Co., Ltd. having an average particle size of about 0.9 zm
  • Comparative Example 5 the stretching temperature and the magnification were changed as shown in Table 1.
  • Comparative Example 6 the ratio between the L-lactic acid component and the D-lactic acid component was approximately 80:20, and the molecular weight was about 16
  • a biaxially oriented film was produced in the same manner as in Example 1 except that the polylactic acid was changed to 100,000 and the heat treatment temperature was set to 100 ° C. In each case, the occurrence of wrinkles in winding was remarkable, and it was judged that the product was insufficient. Table 2 shows the evaluation results. Industrial applicability
  • the biaxially oriented aliphatic polyester film since the biaxially oriented aliphatic polyester film has a predetermined surface roughness, the biaxially oriented aliphatic polyester film has good slip and suppresses the meandering and wrinkling of the film.
  • the biaxially oriented aliphatic polyester film has a predetermined composition, it can maintain stiffness, strength, and low heat shrinkage.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

An aliphatic polyester film which has satisfactory slip properties better than those of polylactic acid films, is inhibited from meandering or creasing, retains stiffness, strength, and low heat shrinkability, and optionally has transparency. The film comprises an aliphatic polyester consisting mainly of a polylactic acid polymer, contains inorganic particles, and has an average surface roughness (Ra) of 0.01 < Ra ≤ 0.08.

Description

明 細 書  Specification
2軸配向脂肪族ポリエステル系フィルム及びその製造方法 技術分野 Biaxially oriented aliphatic polyester film and method for producing the same
この発明は、 2軸配向脂肪族ポリエステル系フィルム及びその製造方法に関す る。 背景技術  The present invention relates to a biaxially oriented aliphatic polyester film and a method for producing the same. Background art
従来のプラスチック製品の多く、 特にプラスチック包装材は、 使用後すぐに棄 却されることが多く、 その処理の問題が指摘されている。 一般包装用プラスチヅ クとして代表的なものとしては、 ポリエチレン、 ポリプロピレン、 P E T等が挙 げられるが、 これら材料は燃焼時の発熱量が多く、 燃焼処理中に燃焼炉を傷める 恐れがある。 さらに、 現在でも使用量の多いポリ塩化ビニルは、 自己消火性のた め燃焼することができない。 また、 このような焼却できない材料も含めプラスチ ック製品は埋め立て処理されることが多いが、 その化学的、 生物的安定性のため ほとんど分解せず残留し、 埋立地の寿命を短くする等の問題を起こしている。 こ れに対し、 燃焼熱量が低く、 土壌中で分解し、 かつ安全であるものが望まれ、 多 くの研究がされている。  Many conventional plastic products, especially plastic packaging materials, are often discarded immediately after use, and problems with their disposal have been pointed out. Typical plastics for general packaging include polyethylene, polypropylene, PET, etc., but these materials generate a large amount of heat during combustion and may damage the combustion furnace during the combustion process. In addition, polyvinyl chloride, which is still widely used, cannot burn because of its self-extinguishing properties. In addition, plastic products, including materials that cannot be incinerated, are often landfilled.However, due to their chemical and biological stability, they remain with little decomposition and shorten the life of the landfill. I'm having a problem. On the other hand, there is a demand for one that has a low calorific value, decomposes in soil, and is safe, and much research has been conducted.
その一例として、 ポリ乳酸があげられる。 ポリ乳酸は、 燃焼熱量はポリエチレ ンの半分以下であり、 土中 · 水中で自然に加水分解が進行し、 次いで微生物によ り無害な分解物となる。 現在、 ポリ乳酸を用いて成形物、 具体的にはフィルム · シートゃボトルなどの容器等を得る研究がなされている。  One example is polylactic acid. Polylactic acid has a calorific value of combustion less than half that of polyethylene, and hydrolyses naturally in soil and water, and then becomes harmless degradation products by microorganisms. At present, research is being conducted to obtain molded articles, specifically, containers such as films, sheets, and bottles, using polylactic acid.
ところで、 ポリ乳酸からなるフィルムを製造する場合、 フイルムの滑りが悪い と、 フィルムの生産中、 あるいは印刷やラ ミネート等の二次加工において、 ワイ ンダ一等で連続して巻き取る際に、 フィルムの蛇行や、 しわが入るなどの問題を 生じる。  By the way, when a film made of polylactic acid is manufactured, if the film does not slip smoothly, the film may be wound continuously during the production of the film or in the secondary processing such as printing and laminating with a winder or the like. This causes problems such as meandering and wrinkling.
そこで、 この発明の課題は、 ポリ乳酸からなるフィルムの滑り を良く し、 フィ ルムの蛇行や、 しわ発生を抑制し、 フィルムの腰、 強度、 低熱収縮性、 また必要 に応じて透明性を保持しつつ滑りの良好な脂肪族ポリエステル系フィルムを提供 することである。 発明の開示 Therefore, an object of the present invention is to improve the slip of a film made of polylactic acid, to suppress the meandering and wrinkling of the film, and to obtain the film's waist, strength, low heat shrinkage, and It is an object of the present invention to provide a slippery aliphatic polyester film while maintaining transparency according to the conditions. Disclosure of the invention
この発明は、 ポリ乳酸系重合体を主成分とする脂肪族ポリエステルからなり、 無機系粒子が配合され、 フィルム表面の平均粗さ R aが 0 . 0 1 < R a≤ 0 . 0 8 とすることにより、 上記の課題を解決したのである。  The present invention comprises an aliphatic polyester having a polylactic acid-based polymer as a main component, is blended with inorganic particles, and has an average roughness Ra of the film surface of 0.01 <Ra≤0.08. Thus, the above problem was solved.
得られる脂肪族ポリエステル系フィルムの粗さを所定の範囲内としたので、 適 度の滑り性を有するフィルムが得られる。 このため、 フ ィルムの蛇行や、 しわ発 生を抑制することができる。 発明を実施するための最良の形態  Since the resulting aliphatic polyester-based film has a roughness within a predetermined range, a film having an appropriate sliding property can be obtained. For this reason, the meandering and wrinkling of the film can be suppressed. BEST MODE FOR CARRYING OUT THE INVENTION
この発明にかかる 2軸配向脂肪族ポリエステル系フィ ルムは、 ポリ乳酸系重合 体を主成分とする脂肪族ポリエステルからなり、 無機系粒子が配合され、 所定の 平均粗さ R aのフィルム表面を有する。  The biaxially oriented aliphatic polyester film according to the present invention is made of an aliphatic polyester mainly containing a polylactic acid polymer, is blended with inorganic particles, and has a film surface with a predetermined average roughness Ra. .
上記ポリ乳酸系重合体とは、 L一、 D—又は D L —乳酸単位を主成分とする重 合体をいい、 ポリ乳酸のみの重合体、 又は、 L一、 D—又は D L —乳酸とヒ ドロ キシカルボン酸、 脂肪族ジカルボン酸 (脂環族も含む。 以下同じ。 ) 及び/又は 脂肪族ジオールとの共重合体でありポリ乳酸成分を 5 0 %以上含むものがあげら れる。  The above-mentioned polylactic acid-based polymer refers to a polymer mainly composed of L-, D- or DL-lactic acid units, and is a polymer of only polylactic acid, or L-, D- or DL-lactic acid and hydro- Copolymers with xycarboxylic acid, aliphatic dicarboxylic acid (including alicyclic groups; the same applies hereinafter) and / or aliphatic diols, and those containing 50% or more of a polylactic acid component.
ポリ乳酸系重合体中の L—乳酸と D —乳酸の割合は、 好ま しい表面粗さを得る ためには、 1 0 0 : 0〜9 4 : 6 も しくは 6 : 9 4〜0 : 1 0 0が好ま しい。 9 4 : 6 よ り小さ く、 6 : 9 4より大きい場合は、 延伸後の熱処理において十分に 結晶化させるこ とができず、 フィルムの熱収縮率を抑制することができない。 ま た、 配向の緩和が起こ り、 配向の効果による物性向上が見られなくなる。,さらに. 後述するように延伸時に配合した無機粒子が突起して、 表面が粗され、 フィルム の滑りが向上するが、 結晶性の低いあるいは結晶化しないポリ乳酸系重合体では 熱処理工程でフィルムの配向緩和とともに突起した無機粒子が再び、 フィルム内 部に埋没してしまい、 滑りの良好なフィルムを得ることができない。 本発明にお いては、 熱処理工程を経る配向フィルムの製造における無機粒子の配合と共に 結晶性の高い上記範囲のポリ乳酸系重合体を使用することは極めて重要である。 重合法と しては、 縮重合法、 開環重合法等公知の方法を採用することができる < 例えば、 縮重合法では、 L 一乳酸、 D—乳酸、 あるいは、 これらと上記他のモノ マーの混合物を直接脱水縮重合することにより、 任意の組成を持ったポリ乳酸系 重合体を得ることができる。 The ratio of L-lactic acid to D-lactic acid in the polylactic acid-based polymer should be 100: 0 to 94: 6 or 6:94 to 0: 1 in order to obtain a desirable surface roughness. 0 0 is preferred. If the ratio is smaller than 94: 6 and larger than 6:94, the film cannot be sufficiently crystallized by heat treatment after stretching, and the heat shrinkage of the film cannot be suppressed. In addition, the orientation is relaxed, and no improvement in physical properties due to the effect of the orientation is observed. As described later, the inorganic particles blended during stretching protrude, the surface is roughened, and the slip of the film is improved. However, in the case of a polylactic acid-based polymer having low crystallinity or not crystallizing, the film is subjected to heat treatment. The inorganic particles protruding with the relaxation of the orientation are buried in the film again, and a film with good slip cannot be obtained. The present invention In addition, it is extremely important to use a polylactic acid-based polymer having a high crystallinity in the above range together with the blending of the inorganic particles in the production of the oriented film through the heat treatment step. As the polymerization method, a known method such as a condensation polymerization method or a ring-opening polymerization method can be employed. <For example, in the condensation polymerization method, L-lactic acid, D-lactic acid, or these and other monomers described above are used. By directly dehydrating and condensing the mixture of the above, a polylactic acid-based polymer having an arbitrary composition can be obtained.
また、 開環重合法 (ラクチ ド法) では、 乳酸の環状 2量体であるラクチ ドを、 必要に応じて重合調節剤等を用いながら、 選ばれた触媒を使用して、 必要に応じ て上記他のモノマーを混合して重合させることによ り、 ポリ乳酸系重合体を得る ことができる。  In the ring-opening polymerization method (lactide method), lactide, which is a cyclic dimer of lactic acid, is converted into lactide using a selected catalyst, if necessary, using a polymerization regulator and the like. By mixing and polymerizing the other monomers, a polylactic acid-based polymer can be obtained.
本発明において使用されるポリ乳酸系重合体の重量平均分子量の好ま しい範囲 と しては 6万〜 7 0万であり、 よ り好ましくは 8万〜 4 0万、 特に好ま しくは 1 0万〜 3 0万である。 分子量が 6万よ り小さいと機械物性や耐熱性等の実用物性 がほとんど発現されず、 7 0万より大きいと溶融粘度が高すぎ成形加工性に劣る 場合がある。  The preferred range of the weight average molecular weight of the polylactic acid polymer used in the present invention is 60,000 to 700,000, more preferably 80,000 to 400,000, and particularly preferably 100,000. ~ 300,000. If the molecular weight is smaller than 60,000, practical physical properties such as mechanical properties and heat resistance are hardly exhibited, and if it is larger than 70,000, the melt viscosity is too high and the moldability may be poor.
ポリ乳酸に共重合される他のヒ ドロキシカルボン酸、 脂肪族ジカルポン酸及び /又は脂肪族ジオール等の他のモノマーと しては、 次のものがあげられる。 すな わち、 乳酸と して所定の光学異性体を有する乳酸を持つ場合は、 他の光学異性体 を有する乳酸 (例えば、 L 一乳酸に対して D —乳酸、 D—乳酸に対して L 一乳 酸) があげられる。 また、 ヒ ドロキシカルボン酸と しては、 グリ コール酸、 3— ヒ ドロキシ酪酸、 4 —ヒ ドロキシ酪酸、 2 —ヒ ドロキシ一 n —酪酸、 2—ヒ ドロ キシ— 3 , 3 —ジメチル酪酸、 2 —ヒ ドロキシ一 3 —メチル酪酸、 2—メチル乳 酸、 2—ヒ ドロキシカブロン酸等の 2官能脂肪族ヒ ドロキシカルボン酸や力プロ ラク トン、 プチロラク ト ン、 ノ レロラク ト ン等のラク トン類があげられる。  Examples of other monomers copolymerized with polylactic acid, such as other hydroxycarboxylic acids, aliphatic dicarbonic acids and / or aliphatic diols, include the following. In other words, when lactic acid has lactic acid having a predetermined optical isomer, lactic acid having another optical isomer (for example, D-lactic acid for L-lactic acid and L-lactic acid for D-lactic acid) Monolactic acid). Hydroxycarboxylic acids include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxy-1-n-butyric acid, 2-hydroxy-3-, 3-dimethylbutyric acid, 2—Hydroxy-1 3—Methylbutyric acid, 2-Methyllactate, 2-Hydroxycaproic acid and other bifunctional aliphatic hydroxycarboxylic acids, and lactones such as hydroprolactone, petyrolactone, and norrelactone Kind.
上記脂肪族ジカルボン酸と しては、 コハク酸、 アジピン酸、 スベリ ン酸、 セバ シン酸、 ドデカン二酸等の脂肪族ジカルポン酸、 又はこれらの無水物や誘導体が あげられる。 また、 脂肪族ジオールと しては、 エチレングリコール、 ブタンジォ ール、 へキサンジオール、 オクタンジオール、 シクロペン夕ンジオール、 シクロ へキサンジオール、 シクロへキサンジメタノール等の脂肪族ジオール、 又はこれ らの誘導体があげられる。 いずれも、 炭素数 2〜 1 0のアルキレン基又はシクロ アルキレン基を持つ、 2官能性化合物を主成分とするものが好ま しい。 もちろん、 これらカルボン酸成分あるいはアルコール成分のいずれにおいても、 2種類以上 用いても構わない。 Examples of the aliphatic dicarboxylic acids include aliphatic dicarponic acids such as succinic acid, adipic acid, suberic acid, sebacic acid, dodecandioic acid, and anhydrides and derivatives thereof. Examples of the aliphatic diol include aliphatic diols such as ethylene glycol, butanediol, hexanediol, octanediol, cyclopentenediol, cyclohexanediol, and cyclohexanedimethanol; Derivatives thereof. In any case, those having a bifunctional compound as a main component having an alkylene group or a cycloalkylene group having 2 to 10 carbon atoms are preferable. Of course, two or more of these carboxylic acid components and alcohol components may be used.
さらに、 上記脂肪族ポリエステルには少量共重合として、  Further, the aliphatic polyester as a small amount copolymerization,
( a ) 3官能基以上のカルボン酸、 アルコール又はヒ ドロキシカルボン酸単位、 (a) carboxylic acid, alcohol or hydroxycarboxylic acid unit having three or more functional groups,
( b ) 非脂肪族ジカルボン酸単位及び/又は非脂肪族ジオール単位、 (b) non-aliphatic dicarboxylic acid units and / or non-aliphatic diol units,
を含んでもよく、 また少量の鎖延長剤残基を含んでもよい。 Or a small amount of a chain extender residue.
上記 ( a ) の単位は、 溶融粘度の向上のためポリマー中に分岐を設ける目的で 用いられ、 具体的には、 リンゴ酸、 酒石酸、 クェン酸、 ト リメ リ ッ ト酸、 ピロメ リ ッ ト酸あるいはペン夕エリスリ ヅ トゃト リメチロールプロパン等の多官能性成 分があげられる。 これらの成分は多量に用いると、 得られるポリマーが架橋構造 を持ち、 熱可塑性でなくなったり、 熱可塑性であっても部分的に高度に架橋構造 を持ったミクロゲルが生じ、 フィルムにしたときフイ ツシュアィ となる恐れがあ る。 従って、 これら多官能性成分が、 ポリマー中に含まれる割合は、 ごくわずか で、 ポリマーの化学的性質、 物理的性質を大きく左右しない程度に制限される。 また、 上記 ( b ) においては、 非脂肪族ジカルボン酸の具体例としては、 テレ フタル酸等があげられ、 また、 非脂肪族ジオールと しては、 ビスフエノール Aの エチレンォキサイ ド付加物等があげられる。  The unit of the above (a) is used for the purpose of providing a branch in the polymer to improve the melt viscosity, and specifically, malic acid, tartaric acid, citric acid, trimellitic acid, and pyromellitic acid. Alternatively, there may be mentioned a polyfunctional component such as erythritol pentotrimethylolpropane. If these components are used in large amounts, the resulting polymer will have a crosslinked structure and will not be thermoplastic, or even if it is a thermoplastic, a microgel with a partially highly crosslinked structure will be formed. There is a possibility that. Therefore, the proportion of these polyfunctional components contained in the polymer is very small, and is limited to a level that does not greatly affect the chemical and physical properties of the polymer. In the above (b), specific examples of the non-aliphatic dicarboxylic acid include terephthalic acid and the like, and examples of the non-aliphatic diol include an ethylene oxide adduct of bisphenol A and the like. Is raised.
上記脂肪族ポリエステルは、 ポリ乳酸系重合体を主成分として含有するが、 こ れ以外の樹脂成分 (以下、 「他樹脂成分」 と称する。 ) を含んでもよい。 この他 樹脂成分の例と しては、 ポリ乳酸系重合体以外の脂肪族ポリエステルがあげられ る。 ポリ乳酸系重合体以外の脂肪族ポリエステルとは、 乳酸以外のヒ ドロキシカ ルボン酸の重合体、 脂肪族ジカルボン酸及び/又は脂肪族ジオールからなるポリ エステル等があげられる。 ここで使用されるヒ ドロキシカルボン酸、 脂肪族ジカ ルボン酸及び脂肪族ジオールは、 それそれ上記と同様である。  The aliphatic polyester contains a polylactic acid-based polymer as a main component, but may contain other resin components (hereinafter, referred to as “other resin components”). In addition, examples of the resin component include aliphatic polyesters other than the polylactic acid-based polymer. Examples of the aliphatic polyester other than the polylactic acid-based polymer include a polymer of hydroxycarboxylic acid other than lactic acid, and a polyester composed of an aliphatic dicarboxylic acid and / or an aliphatic diol. The hydroxycarboxylic acids, aliphatic dicarboxylic acids and aliphatic diols used herein are the same as described above.
さらに、 上記脂肪族ポリエステルには上記の同様の少量共重合単位を含んでも よく、 また少量の鎖延長剤残基を含んでもよい。  Further, the aliphatic polyester may contain the same small amount of copolymerized units as described above, and may also contain a small amount of a chain extender residue.
上記の脂肪族カルボン酸と脂肪族ジオールからなるポリエステルを調整するに は、 直接法、 間接法等公知の方法を採用することができる。 例えば、 直接法は、 脂肪族カルボン酸と脂肪族ジオールとを、 これらの成分中に含まれる、 あるいは 重合中に発生する水分を除去しながら、 直接重合して高分子量物を得る方法であ る。 間接法は、 オリゴマー程度に重合した後、 上記ポリ乳酸系重合体の場合と同 様、 少量の鎖延長剤を使用して高分子量化する間接的な製造方法である。 To adjust the polyester consisting of the above aliphatic carboxylic acid and aliphatic diol Any known method such as a direct method and an indirect method can be employed. For example, the direct method is a method of directly polymerizing an aliphatic carboxylic acid and an aliphatic diol while removing water contained in these components or generated during the polymerization to obtain a high molecular weight product. . The indirect method is an indirect production method in which a small amount of a chain extender is used to increase the molecular weight after polymerization to the degree of an oligomer, as in the case of the polylactic acid-based polymer.
上記の他樹脂成分の重量平均分子量は、 5万〜 2 5万が好ましい。 重量平均分 子量が 5万より小さいとポリマーとしての性質が劣り、 特にヒートシール性の向 上につながらないばかりか、 絰時的にフィルム表面にブリードするなどの不具合 を生じさせる。 また、 2 5万より大きいと溶融粘度が高くなりすぎて、。ポリ乳酸 との混合性の低下や、 ポリ乳酸と同様にフイルムにするときの押出成形性の低下 を招く。  The other resin component preferably has a weight average molecular weight of 50,000 to 250,000. If the weight-average molecular weight is less than 50,000, the properties as a polymer are inferior, and not only does not improve the heat sealing property, but also causes problems such as temporary bleeding on the film surface. Also, if it is larger than 250,000, the melt viscosity becomes too high. This leads to a decrease in the mixing property with polylactic acid and a decrease in extrudability when forming a film like polylactic acid.
なお、 耐衝撃性の改良効果、 耐寒性の点から、 他樹脂成分は、 ガラス転移点 ( T g ) が 0 °C以下であることが好ま しい。  It is preferable that the other resin component has a glass transition point (T g) of 0 ° C. or less from the viewpoint of the effect of improving impact resistance and cold resistance.
特に好適な他樹脂成分としては、 例えばポリエチレンスべレート、 ポリエチレ ンセバケート、 ポリエチレンデカンジカルボキシレート、 ポリブチレンサクシネ —ト、 ポリ プチレンアジペート、 ポリ ブチレンセバケ一ト、 ポリ ブチレンサクシ ネートアジぺートゃこれらの共.重合体が挙げられる。  Particularly suitable other resin components include, for example, polyethylene suberate, polyethylene sebacate, polyethylene decane dicarboxylate, polybutylene succinate, polybutylene adipate, polybutylene sebacate, polybutylene succinate acetate. Copolymers.
本発明においては、 上記他樹脂成分とともに、 又は他樹脂成分に代えて、 ポリ 乳酸系重合体と他樹脂成分とのプロヅク共重合体 (その一部エステル交換生成物、 少量の鎖延長剤残基を含んだ生成物も含む。 ) を使用することもできる。 このブ ロック共重合体は、 任意の方法で調整することができる。 例えば、 ポリ乳酸系重 合体又は他樹脂成分のいずれか一方を別途重合体として準備しておき、 この重合 体の存在下に他方の構成モノマーを重合させる。 通常は、 予め準備した他樹脂成 分の存在下でラクチ ドの重合を行うことにより、 ポリ乳酸と他樹脂成分のプロッ ク共重合体を得る。 基本的には、 他樹脂成分を共存させる点が相違するだけで、 ラクチド法でポリ乳酸系重合体を調整する場合と同様に重合を行うことができる < この時、 ラクチ ドの重合が進行すると同時に、 ポリ乳酸と他樹脂成分の間で適度 なエステル交換反応が起こ り、 比較的ランダム性が高い共重合体が得られる。 出 発物質として、 ウレタン結合を有する脂肪族ポリエステルウレタンを用いた場合 には、 エステル一アミ ド交換も生成する。 In the present invention, a block copolymer of a polylactic acid-based polymer and another resin component (partially transesterified product, a small amount of chain extender residue) may be used together with or instead of the other resin component. Also, products containing) can be used. This block copolymer can be prepared by any method. For example, either a polylactic acid-based polymer or another resin component is separately prepared as a polymer, and the other constituent monomer is polymerized in the presence of the polymer. Usually, a block copolymer of polylactic acid and another resin component is obtained by polymerizing lactide in the presence of another resin component prepared in advance. Basically, the polymerization can be carried out in the same manner as in the case of preparing a polylactic acid-based polymer by the lactide method, only with the difference that other resin components coexist. <At this time, if the polymerization of lactide proceeds At the same time, an appropriate transesterification reaction occurs between polylactic acid and other resin components, and a copolymer having relatively high randomness can be obtained. When an aliphatic polyester urethane having a urethane bond is used as a starting material Also produces ester-amide exchange.
上記無機系粒子とは、 無機物質の粒子をいう。 この無機粒子を構成する無機物 質としては、 シリカ等の二酸化ケイ素、 炭酸カルシウム、 炭酸マグネシウム、 夕 ルク、 二酸化チタン、 カオリ ン、 アルミナ等が挙げられ、 好ましくは、 シリカ等 の二酸化ケイ素、 炭酸カルシウム、 炭酸マグネシウム、 タルク、 二酸化チタン、 カオリ ンが挙げられ、 特に好ましくは、 シリカ等の二酸化ケイ素である。 上記無 機粒子は上記のうち 1種のみを使用してもよいし、 2種以上を混合して使用して もよい。  The inorganic particles refer to particles of an inorganic substance. Examples of the inorganic material constituting the inorganic particles include silicon dioxide such as silica, calcium carbonate, magnesium carbonate, silica, titanium dioxide, kaolin, and alumina, and preferably silicon dioxide such as silica, calcium carbonate, and the like. Examples thereof include magnesium carbonate, talc, titanium dioxide, and kaolin. Particularly preferred is silicon dioxide such as silica. One of the above-mentioned inorganic particles may be used alone, or a mixture of two or more thereof may be used.
上記脂肪族ポ リエステル 1 0 0重量部に対し、 無機系粒子の配合部数は、 0 . 0 1 ~ 1 2 0重量部が好ましく、 0 . 0 1 ~ 5重量部がより好ま しい。 0 . 0 1 重量部より少ないと滑性を与える効果が出ない。 また、 1 2 0重量部よ り多いと 通常はフィ ルムの延伸ができず、 延伸できても、 穴があ くなどの欠陥を生じる。 無機粒子の平均粒子径は 0 . 1〜 5 mが好ましい。 この無機粒子は、 沈降天 秤式測定法、 コール夕一カウンター測定法、 光散乱法等を用いて測定することが できる。  The mixing amount of the inorganic particles is preferably from 0.01 to 120 parts by weight, more preferably from 0.01 to 5 parts by weight, based on 100 parts by weight of the aliphatic polyester. If the amount is less than 0.01 parts by weight, the effect of imparting lubricity is not obtained. On the other hand, if the amount is more than 120 parts by weight, the film cannot be stretched normally, and even if the film can be stretched, defects such as holes are generated. The average particle diameter of the inorganic particles is preferably from 0.1 to 5 m. These inorganic particles can be measured using a sedimentation balance measurement method, a Coal-Yuichi counter measurement method, a light scattering method, or the like.
上記平均粒子径は、 大きいほどフィ ルムの表面は粗され滑り性は向上し、 摩擦 係数が小さ くなる。 また、 配合部数が多いほど同様の効果がある。 しかし、 平均 粒子径が大きすぎると表面の平滑性は低下するので、 フィルムに印刷するときの 印刷抜けが発生した り、 硬度の高い無機粒子ではフィルム面同士でこすれあった とき傷等が発生する。 また、 配合部数が樹脂成分に比べて非常に多い時は、 フィ ルムの延伸ができない場合が生ずる。 延伸できても、 穴があくなどの欠陥を生じ る場合がある。 一方、 平均粒子径が小さすぎると滑性を与える効果が低すぎる。 また、 透明性が必要なフィルムにおいては極力配合部数を減ら しておく必要が ある。 また、 配合部数を少なく しても、 粒子径が大きいと透明なフィルムが得難 い。 透明性の定義と してはヘーズを用いることができる。 これは、 J I S K 7 1 0 5で測定することができる。 このヘーズは、 1 0 %以下のものが好ま しい, ヘーズが 1 0 %を越えると十分な透明性が得られない場合がある。  The larger the average particle diameter is, the rougher the surface of the film is, the better the slipperiness is, and the smaller the coefficient of friction is. The same effect is obtained as the number of blending parts increases. However, if the average particle size is too large, the smoothness of the surface is reduced, so that printing loss occurs when printing on a film, or scratches occur when the inorganic particles having high hardness rub against each other between the film surfaces. . When the number of blending parts is much larger than that of the resin component, the film may not be stretched. Even if it can be stretched, it may cause defects such as holes. On the other hand, if the average particle size is too small, the effect of providing lubricity is too low. In the case of a film that requires transparency, it is necessary to reduce the number of compounding parts as much as possible. Also, even if the number of parts is small, it is difficult to obtain a transparent film if the particle diameter is large. Haze can be used as a definition of transparency. This can be measured by JISK 7105. The haze is preferably 10% or less, and if the haze exceeds 10%, sufficient transparency may not be obtained.
また、 透明性を得たいときは、 配合する無機系粒子の種類や粒子径、 フィルム の厚みにもよるが、 多く とも 0 . 5部程度にすることが重要である。 フィルムの ヘーズが 1 0 %を超えると、 ク リァ感に欠ける。 When it is desired to obtain transparency, it is important that the content be at most about 0.5 part, though it depends on the type and particle size of the inorganic particles to be blended and the thickness of the film. Film If the haze exceeds 10%, it lacks clearness.
また、 これらの処方により フィルムの表面を粗く し、 滑性を付与、 具体的には フィルムの摩擦係数を低下させることができる。  In addition, these formulations can roughen the surface of the film and impart lubricity, and more specifically, lower the coefficient of friction of the film.
フィルムの機械強度等の諸物性を著しく低下することないようにする という観 点から、 無機粒子は、 平均粒子径 0 . 1〜 4 m、 配合部数は 0 . 0 1 〜 3重量 部にするのが好ま しく、 また、 特に透明性の高いフ ィルム (具体的にはヘーズが 1 0 %以下) であり、 かつ滑性の優れたフ ィルムを得るという観点から、 平均粒 子径は 0 . 5〜 3 Λί πι、 配合部数は 0 . 0 2〜 1重量部の範囲にするのがよ り好 ま しい。  In terms of preventing the physical properties such as mechanical strength of the film from being significantly reduced, the average particle diameter of the inorganic particles should be 0.1 to 4 m and the number of parts should be 0.01 to 3 parts by weight. In addition, from the viewpoint of obtaining a film with high transparency (specifically, a haze of 10% or less) and a film with excellent lubricity, the average particle diameter is 0.5. More preferably, the mixing amount is in the range of 0.02 to 1 part by weight.
この発明にかかる 2軸配向ポリ乳酸フィルムは、 下記の方法で製造することが できる。 上記のポリ乳酸系重合体や脂肪族ポリエステル等を含む脂肪族ポリエス テルや無機粒子等を、 同一の押出機にそれそれの原料を投入して混合する。 そし て、 そのまま口金よ り押出すと、 直接フィルムを作製することができる。 また、 ス トラ ン ド形状に押し出してペレ ツ トを作製し、 再度押出機にてフイルムを製造 することができる。 いずれも、 分解による分子量の低下を考慮しなければならな いが、 均一に混合させるには後者を選択する方がよい。 脂肪族ポリエステルを充 分に乾燥し、 水分を除去した後、 押出機で溶融する。 ポリ乳酸系重合体は、 L 一 乳酸構造と D —乳酸構造の組成比によって融点が変化することや、 脂肪族ポリエ ステルの融点と混合の割合を考慮して、 適宜溶融押出温度を選択する。 実際には 1 0 0 - 2 5 0 °Cの温度範囲が通常選ばれる。  The biaxially oriented polylactic acid film according to the present invention can be manufactured by the following method. The above-mentioned aliphatic polyester and inorganic particles including the polylactic acid-based polymer and the aliphatic polyester are charged into the same extruder and mixed. Then, by directly extruding through a die, a film can be directly produced. In addition, a pellet can be produced by extruding the film into a strand shape, and the film can be produced again by an extruder. In each case, the reduction in molecular weight due to decomposition must be taken into consideration, but the latter is better to be selected for uniform mixing. After fully drying the aliphatic polyester to remove water, it is melted by an extruder. The melt extrusion temperature of the polylactic acid-based polymer is appropriately selected in consideration of the fact that the melting point changes depending on the composition ratio of the L-lactic acid structure and the D-lactic acid structure, and the melting point and mixing ratio of the aliphatic polyester. In practice, a temperature range of 100-250 ° C is usually chosen.
これらの混合物には、 諸物性を調整する 目的で、 熱安定剤、 光安定剤、 光吸収 剤、 可塑剤、 無機充填材、 着色剤、 顔料等を添加するこ ともできる。  For the purpose of adjusting various physical properties, a heat stabilizer, a light stabilizer, a light absorber, a plasticizer, an inorganic filler, a colorant, a pigment, and the like can be added to these mixtures.
このようにして得られたフィルムは、 延伸倍率が低いとフィルム表面上に粒子 が突起しない。 このため、 粒子を突起させて、 フィルムの表面の粗さを向上させ るためには、 十分フィルムを配向させておく ことが必要である。 具体的には、 2 軸延伸することによ り、 配向されたフ ィルム (以下、 「 2軸配向ポリ乳酸系フィ ルム」 と称する。 ) を得るのがよい。 このときの配向の指標は、 面配向 Δ Ρで 3 . 0 x 1 0 — 3 以上がよい。 これを達成するには少なく とも 1軸方向に 1 . 5倍以上 延伸させることが必要である。 この 2軸延伸配向ポリ乳酸系フィルムは、 2軸方向に延伸し、 次いで、 固定し ながら熱処理を行う。 これにより、 熱固定された 2軸延伸配向ポリ乳酸系フ ィル ムが得られる。 このフィルムの縦方向又は横方向の少なく とも一方の 8 0 °Cでの 収縮率が 1 0 %以下であることが好ま しい。 この収縮率が 1 0 %を越えると、 相 対的に熱収縮しやすく、 問題を生じやすい。 例えば、 これらフィ ルムの用途とし て、 フィルム表面上に接着剤を塗布して紙や金属薄膜、 他のプラスチックフ ィル ム等と貼り合わせることがあるが、 熱収縮率が高いと工程内でかかる温熱により 上記フィルムが収縮してしまい、 しわ等の外観を損なったり、 ラ ミネート体が力 ールする等の問題が起こ りやすくなる。 In the film thus obtained, when the stretching ratio is low, the particles do not project on the film surface. For this reason, it is necessary to sufficiently orient the film in order to protrude the particles and improve the surface roughness of the film. Specifically, an oriented film (hereinafter, referred to as a “biaxially oriented polylactic acid-based film”) is preferably obtained by biaxial stretching. The index of orientation at this time is preferably 3.0 × 10—3 or more in plane orientation ΔΡ. In order to achieve this, it is necessary to stretch at least 1.5 times in the uniaxial direction. This biaxially stretched oriented polylactic acid-based film is stretched biaxially, and then heat-treated while being fixed. As a result, a heat-set biaxially oriented polylactic acid film can be obtained. It is preferable that at least one of the longitudinal and lateral directions of the film has a shrinkage ratio at 80 ° C. of 10% or less. If the shrinkage exceeds 10%, heat shrinks relatively easily, and a problem is likely to occur. For example, as an application of these films, an adhesive is applied on the film surface and bonded to paper, a metal thin film, or other plastic films. Such heat causes the film to shrink, impairing the appearance such as wrinkles, and causing the laminating body to roll easily.
得られた 2軸配向ポリ乳酸系フィルムの表面粗さ R a (中心線平均粗さ) は、 0 . 0 1 < R a≤ 0 . 0 8であることが好ましく、 さらにこの範囲においては R z (十点平均粗さ) が 2 . 0以下であることがより好ま しい。 R aが大きいほど フ ィ ルムの表面が粗く、 滑り性が高くなる。 しかし、 R aが大きすぎるとフ ィ ル ムの平滑性が劣ることとなる。 平滑性の指標としては、 R zを用いることができ る。 R aに比してこの数値が大きいほど、 フィルムの凹凸 (粗さ) がまばらであ り、 均一性がな く、 R aの数値に近づくほど凹凸の大きさも均一であることを示 す。 R aや R zの測定は、 J I S B 0 6 0 1 に従って測定することができる , The surface roughness Ra (center line average roughness) of the obtained biaxially oriented polylactic acid-based film is preferably 0.01 <Ra≤0.08. (Ten-point average roughness) is more preferably 2.0 or less. The larger the Ra, the rougher the film surface and the higher the slipperiness. However, if Ra is too large, the film will have poor smoothness. Rz can be used as an index of smoothness. As this value is larger than Ra, the unevenness (roughness) of the film is sparser, and there is no uniformity. As the value approaches Ra, the size of the unevenness is more uniform. The measurement of Ra and Rz can be measured in accordance with JISB0601,
2軸配向ポリ乳酸系フ ィルムのの摩擦係数は、 静摩擦係数で 0 . 8以下がよく - 0 . 5以下が好ましく、 0 . 3以下がより好ま しい。 摩擦係数には、 静摩擦係数 と動摩擦係数がある。 一般的には、 静摩擦係数が小さいと動摩擦も小さ くなる。 また、 静摩擦係数の方が動摩擦係数よ り も大きな数値を示す。 フ ィルムは連続的 に生産され、 通常はロール状にされる。 このとき、 フィルム同士が接触するので- フィルムの摩擦係数が大きいと滑らず、 一様にきれいに巻き取ることはできない, また、 フィ ルムの加工、 例えば印刷やラミネート、 製袋においても同様に問題と なり、 場合によっては静電気を発生させ、 生産性を著しく低下させるこ ともある, このため、 静摩擦係数で評価すると、 上記の要件を満たすのがよい。 The coefficient of friction of the biaxially oriented polylactic acid film is preferably 0.8 or less in static friction coefficient, more preferably -0.5 or less, and more preferably 0.3 or less. There are two types of friction coefficient: static friction coefficient and dynamic friction coefficient. In general, the smaller the static friction coefficient, the smaller the dynamic friction. The coefficient of static friction is larger than the coefficient of dynamic friction. Films are produced continuously and are usually rolled. At this time, since the films come into contact with each other-If the coefficient of friction of the film is large, it does not slip and cannot be taken up uniformly and uniformly, and it is also a problem in film processing, for example, printing, laminating, and bag making. In some cases, static electricity is generated and productivity may be significantly reduced. Therefore, it is better to satisfy the above requirements by evaluating the coefficient of static friction.
この発明にかかる 2軸配向ポリ乳酸フィルム製造法のより好ま しい態様は、 下 記の通りである。 すなわち、 L —乳酸と D —乳酸の割合が 1 0 0 : 0〜 9 4 : 6 の範囲内も しく は 6 : 9 4 - 0 : 1 0 0の範囲内であるポリ乳酸系重合体 1 0 0 重量部に対し、 平均粒子径が 0. 1 m~ 5〃 mの無機系粒子を 0. 0 1〜 1 2 0重量部配合し、 2軸方向に延伸することである。 これにより、 表面の平均粗さ R aが 0. 0 1 <R a≤ 0. 0 8である 2軸配向ポリ乳酸フィルムを製造するこ とができる。 実施例 More preferred embodiments of the method for producing a biaxially oriented polylactic acid film according to the present invention are as follows. That is, the polylactic acid-based polymer 10 in which the ratio of L-lactic acid to D-lactic acid is in the range of 100: 0 to 94: 6 or in the range of 6: 94-0: 100. 0 In other words, 0.01 to 120 parts by weight of an inorganic particle having an average particle diameter of 0.1 to 5 μm is blended with respect to parts by weight, and the biaxial direction is stretched. This makes it possible to produce a biaxially oriented polylactic acid film having an average surface roughness Ra of 0.01 <Ra≤0.08. Example
以下、 本発明を実施例によりさらに詳細に説明する。 なお、 本発明はその本旨 を越えない限り、 以下の実施例に限定されるものではない。  Hereinafter, the present invention will be described in more detail with reference to Examples. It should be noted that the present invention is not limited to the following examples unless the gist of the present invention is exceeded.
なお、 本発明における各種の物性及び特性の測定方法は下記のとおりである。  The methods for measuring various physical properties and characteristics in the present invention are as follows.
( 1 ) 平均粒子径  (1) Average particle size
沈降天秤式測定法、 コール夕一カウンター測定法、 光散乱法等により粒度分布 を測定し、 算出した。  The particle size distribution was measured and calculated by sedimentation balance measurement method, Cole-Yuichi counter measurement method, light scattering method, etc.
( 2 ) フィルム厚み  (2) Film thickness
(株) テク口ヅク製ダイヤルゲージ S M— 1 2 0 1で十点測定を行い、 その平 均値で厚みとした。 単位は mである。  Ten-point measurements were made with a dial gauge S M-1201 manufactured by Tec Kokukoku Co., Ltd., and the average value was used as the thickness. The unit is m.
( 3 ) 面配向度  (3) Plane orientation degree
アッベ屈折計によって直交 3軸方向の屈折率 (α、 β、 y ) を測定し、 次式で 算出した。  The refractive index (α, β, y) in three orthogonal directions was measured by Abbe refractometer and calculated by the following formula.
△ Ρ = { (ァ + ? ) / 2 } — (《< 3<ァ)  △ Ρ = {(α +?) / 2} — (<<< 3 <α)
ァ : フ ィルム面内の最大屈折率  A: Maximum refractive index in the film plane
β : それに直交するフィルム面内方向の屈折率 α : フ ィルム厚さ方向の屈折率  β: Refractive index in the direction perpendicular to the film plane α: Refractive index in the thickness direction of the film
なお、 表中に示す値は、 0. 0 0 1単位で現し、 1 0 0 0倍した値である。  The values shown in the table are expressed in 0.001 units and are multiplied by 1000.
( 4 ) 表面粗さ  (4) Surface roughness
測定は、 J I S Β 0 6 0に記載される方法に基づいて行った。 (株) 小坂 研究所製表面粗さ測定器 (S E— 3 F) を用い、 R a (中心線平均粗さ) と R z The measurement was performed based on the method described in JISΒ060. Ra (centerline average roughness) and Rz were measured using a surface roughness tester (SE-3F) manufactured by Kosaka Laboratory Co., Ltd.
(十点平均粗さ) を求めた。 測定器の触針先端半径は 2 zm、 荷重は 3 0 m gと し、 測定長さは 8 mm, 力ッ トオフ値は 0. 0 8 mmと した。 (Ten point average roughness) was determined. The stylus tip radius of the measuring instrument was 2 zm, the load was 30 mg, the measurement length was 8 mm, and the force-off value was 0.08 mm.
( 5 ) 静摩擦係数 J I S K 7 1 2 5に従い、 フィルムの巻き物を考慮し、 長手方向 (MD) について測定した。 フィルムの表及び裏をそれそれ 3回、 計 6回測定し、 その平 均値をとつた。 (5) Static friction coefficient According to JISK 712, measurement was made in the machine direction (MD), taking into account the roll of film. The front and back of the film were measured three times each, for a total of six times, and the average was taken.
( 6 ) 熱収縮率  (6) Heat shrinkage
フィルムサンプルを長手方向 (MD) 、 その直行方向 (TD) にそれそれ 1 4 0 mm (幅 1 0 mm) に切り出し、 その間に 1 0 0 mm間の表線を入れ、 8 0 °C の温水バスに 5分浸漬した後、 その評線間の寸法を計り、 次式にしたがって熱収 縮率を算出した。  Cut the film sample in the longitudinal direction (MD) and in the direction perpendicular to it (TD), each with a length of 140 mm (width 10 mm), with a 100 mm line between them, and hot water at 80 ° C. After immersion in the bath for 5 minutes, the dimension between the evaluation lines was measured, and the heat shrinkage was calculated according to the following equation.
熱収縮率 (%) = 〔 (収縮前の寸法) 一 (収縮後の寸法) 〕 / (収縮前の寸 法) X 1 0 0  Heat shrinkage (%) = [(dimension before shrinkage) one (dimension after shrinkage)] / (dimension before shrinkage) X100
( 7 ) ヘーズ  (7) Haze
J I S K 7 1 0 5にしたがって測定した。 値が小さいほど、 透明性が高い ことを示す。  The measurement was performed according to JIS K 7105. The smaller the value, the higher the transparency.
( 8 ) 総合評価  (8) Comprehensive evaluation
上記の各物性を総合し、 下記の基準で評価した。  The above properties were combined and evaluated according to the following criteria.
◎ : 特に良好  ◎: Particularly good
〇 : 良好  〇: Good
△ : やや良好で、 製品と して使用できる  △: Slightly good and can be used as a product
X : 製品と して使用できない。  X: Cannot be used as a product.
(実施例 1 )  (Example 1)
L一乳酸成分と D—乳酸成分との割合が 9 5 : 5である分子量約 2 0万のポリ 乳酸と、 平均粒径約 2. 5 mの富士シリ シァ化学 (株) 製粒状二酸化ケイ素 Polylactic acid with a molecular weight of about 200,000 with a ratio of L-lactic acid component to D-lactic acid component of 95: 5, and granular silicon dioxide manufactured by Fuji Silicon Chemical Co., Ltd. with an average particle size of about 2.5 m
(シリカ) (商品名 : サイ リ シァ 4 3 0 ) 1重量部をそれぞれ乾燥して十分に水 分を除去した後、 Φ 4 0 mm同方向二軸押出機に投入して、 約 2 0 0 °Cに設定し て溶融混合し、 ス トラン ドにして押出し、 冷却しながらペレッ ト状にカヅ ト した < このペレッ トをマスターバッチと し、 再度乾燥して、 同じく乾燥した上記ポリ乳 酸に 1 0 %混合し、 Φ 4 0 mm同方向二軸押出機に投入し設定温度 2 1 0 °Cで、 シート状に押出し、 回転する冷却ドラムで急冷固化させ、 実質的に非晶質のシ一 トを得た。 得られたシートて温水循環式ロールと接触させつつ赤外線ヒー夕一で 併用して加熱し、 周速差ロール間で縦方向に 7 5 °Cで 3 . 0倍、 次いでこの縦延 伸シートをクリ ップで把持しながらテン夕一に導き、 フィルム流れの垂直方向に 7 5 °Cで 3 . 0倍に延伸した後、 1 2 0 °Cで約 1 5秒間熱処理し、 4 0 ΠΙ厚み のフィルムを作製した。 フィルムはワインダ一にて卷き取られ、 このときのフィ ルムのしわの発生具合等を観察したところ、 特に問題なく ロール状サンプルを得 ることができた。 この得られたフィルムの評価結果を表 1 に示す。 (Silica) (Product name: Silica 430) After drying 1 part by weight of each to remove water sufficiently, the mixture was put into a φ40 mm co-rotating twin-screw extruder, and about 200 The mixture was melt-mixed at a temperature of ° C, extruded into strands, extruded into pellets with cooling. <The pellets were used as master batches, dried again, and dried again with the above-mentioned polylactic acid. 10%, mixed into a twin-screw extruder with a diameter of 40 mm, extruded into a sheet at a set temperature of 210 ° C, and quenched and solidified by a rotating cooling drum. I got one. The obtained sheet is brought into contact with a hot water circulation type roll while Heated together, 3.0 times at 75 ° C vertically between the peripheral speed difference rolls. The film was stretched 3.0 times at 75 ° C. and then heat-treated at 120 ° C. for about 15 seconds to produce a film having a thickness of 40 mm. The film was wound up by a winder. Observation of the occurrence of wrinkles in the film at this time revealed that a roll sample could be obtained without any particular problems. Table 1 shows the evaluation results of the obtained films.
(実施例 2 )  (Example 2)
L—乳酸成分と D—乳酸成分との割合が 9 2 : 8である分子量約 1 8万のポリ 乳酸を使用した以外は、 実施例 1 と同様にして厚み 4 0 mのフィルムを作製し た。 フィルムの卷取り具合は、 若干しわが入る傾向にあるが、 製品として使用で きた。 この得られたフィルムの評価結果を表 1 に示す。  A film having a thickness of 40 m was produced in the same manner as in Example 1 except that polylactic acid having a molecular weight of about 180,000 and a ratio of L-lactic acid component to D-lactic acid component of 92: 8 was used. . The winding condition of the film tends to be slightly wrinkled, but it has been used as a product. Table 1 shows the evaluation results of the obtained films.
(実施例 3 )  (Example 3)
L—乳酸成分と D—乳酸成分との割合が 9 5 : 5である分子量約 2 0万のポリ 乳酸と、 平均粒径約 0 . 9〃mの日東粉化工業 (株) 製炭酸カルシウム (商品 名 : N S # 2 5 0 0 ) 5 0重量部をそれぞれ乾燥して十分に水分を除去した後、 Φ 4 0 m m同方向二軸押出機に投入して、 約 2 1 0 °Cに設定して溶融混合し、 ス トラン ドにして押出し、 冷却しながらペレッ ト状にカッ ト した。 このペレヅ トを 再度乾燥して、 Φ 4 0 m m同方向二軸押出機に投入し設定温度 2 1 0 °Cで、 後は 実施例 1 と同様にして 4 0〃mの厚みの二軸配向フィルムを作製した。 フィルム はワイ ンダ一にて巻き取られ、 このときのフィルムのしわの発生具合等を観察し たところ、 特に問題なく ロール状サンプルを得ることができたが、 やや透明性に 欠けた。 この得られたフィルムの評価結果を表 1 に示す。  Polylactic acid with a molecular weight of about 200,000 with a ratio of L-lactic acid component to D-lactic acid component of 95: 5, and calcium carbonate manufactured by Nitto Powder Chemical Co., Ltd. with an average particle size of about 0.9〃m ( Product name: NS # 250) After drying 50 parts by weight to remove water sufficiently, put it into a φ40 mm co-rotating twin-screw extruder and set it at about 210 ° C. The mixture was melt-mixed, extruded into strands, and cut into pellets while cooling. The pellet was dried again, put into a Φ40 mm co-axial twin screw extruder, set at a temperature of 210 ° C, and then biaxially oriented to a thickness of 40 mm in the same manner as in Example 1. A film was prepared. The film was wound up with a winder. Observation of the wrinkles of the film at this time showed that a roll-shaped sample could be obtained without any particular problem, but the film lacked transparency. Table 1 shows the evaluation results of the obtained films.
(実施例 4、 5 )  (Examples 4 and 5)
粒子の配合部数を表 1 に示すようにして、 実施例 1 と同様の方法で 4 0 mの 厚みの二軸配向フィルムを作製した。 ただし、 実施例 4では熱処理温度をガラス 転移温度以下の 5 0 °Cに設定して、 実質熱固定されない二軸配向フィルムを作製 した。 また、 実施例 5では縦延伸をせず、 垂直方向に 2 . 5倍延伸した厚み 6 0 / mの一軸配向フィルムを作製した。 ワイ ンダ一での巻き取りにおいて実施例 4 では、 良好に、 実施例 5では若干しわが入る傾向にあつたが、 製品としては使用 できた。 この得られたフィルムの評価結果を表 1 に示す。 A biaxially oriented film having a thickness of 40 m was produced in the same manner as in Example 1 with the number of particles blended as shown in Table 1. However, in Example 4, the heat treatment temperature was set to 50 ° C. or lower, which was lower than the glass transition temperature, to produce a biaxially oriented film that was not substantially thermally fixed. In Example 5, a uniaxially oriented film having a thickness of 60 / m, which was stretched 2.5 times in the vertical direction without longitudinal stretching, was produced. In winding with a winder, Example 4 tended to be good and Example 5 tended to wrinkle slightly. did it. Table 1 shows the evaluation results of the obtained films.
(実施例 6 )  (Example 6)
L 一乳酸成分と: D —乳酸成分との割合が 9 9 : 1である分子量約 2 2万のポリ 乳酸にポリ ブチレンサクシネート/アジペート (昭和高分子 (株) 製、 商品名 : ビオノ一レ # 3 0 0 3 ) を 1 5部、 さらに平均粒径約 2 . 5 mの富士シリシァ 化学 (株) 製粒状二酸化ケイ素 (シリカ) (商品名 : サイ リ シァ 4 3 0 ) 0 . 1 重量部をそれぞれ乾燥して十分に水分を除去した後、 Φ 4 0 m m同方向二軸押出 機に投入して、 約 2 1 0 °Cに設定して溶融混合し、 ス トラン ドにして押出し、 冷 却しながらペレヅ ト状にカッ ト した。 このペレッ トを再度乾燥して、 Φ 4 0 πι ιη 同方向二軸押出機に投入し設定温度 2 1 0 °Cで、 後は実施例 1 と同様の方法で 4 0 〃mの厚みの二軸配向フィルムを作製した。 縦横の延伸温度、 延伸倍率ならび に熱処理温度は表 1 に示すとおりである。 フィルムはワインダ一にて卷き取られ このときのフ ィ ルムのしわの発生具合等を観察したところ、 特に問題なく ロール 状サンプルを得ることができた。 この得られたフィルムの評価結果を表 1 に示す, (比較例 1 )  L Monolactic acid component: D—The ratio of lactic acid component is 9 9: 1 Polylactic acid with a molecular weight of about 220,000 and polybutylene succinate / adipate (manufactured by Showa Kogyo Co., Ltd., trade name: Biono Ile # 3003) and granulated silicon dioxide (silica) manufactured by Fuji Silica Chemical Co., Ltd. with an average particle size of about 2.5 m (trade name: Silicia 430) 0.1 part by weight After drying each of them to remove water sufficiently, they are put into a φ40 mm co-rotating twin-screw extruder, melt-mixed at about 210 ° C, extruded into strands, and cooled. I cut it in a pellet shape while rejecting it. The pellet was dried again and charged into a Φ 40 πι ιη co-rotating twin-screw extruder at a set temperature of 210 ° C. Thereafter, the pellet having a thickness of 40 μm was formed in the same manner as in Example 1. An axially oriented film was produced. Table 1 shows the vertical and horizontal stretching temperatures, stretching ratios, and heat treatment temperatures. The film was taken up by a winder and the wrinkles of the film were observed at this time. As a result, a roll sample could be obtained without any particular problem. The evaluation results of the obtained film are shown in Table 1, (Comparative Example 1).
配合する粒状二酸化ケイ素 (シリカ) の平均粒径を 6 . 0 m (富士シリ シァ 化学 (株) 製、 商品名 : サイ リシァ 7 7 0 ) に変えた以外は実施例 1 と同様にし て 4 O m厚みの二軸配向フ ィルムを作製した。 フ ィ ルムはワイ ンダ一にて巻き 取られ、 このときのフィルムのしわの発生具合等を観察したところ、 しわの発生 が顕著で、 フ ィ ルムの平面性に欠け、 製品としては不十分である と判断される。 評価結果を表 2 に示す。  The same procedure as in Example 1 was repeated except that the average particle size of the granular silicon dioxide (silica) to be blended was changed to 6.0 m (trade name: Silicia 770, manufactured by Fuji Silicon Chemical Co., Ltd.). A biaxially oriented film having a thickness of m was prepared. The film is taken up by a winder. When the degree of wrinkling of the film is observed at this time, the occurrence of wrinkles is remarkable, and the film lacks the flatness and is insufficient as a product. It is determined that there is. Table 2 shows the evaluation results.
(比較例 2 )  (Comparative Example 2)
配合する粒子を平均粒径 0 . 0 5 m微粒ニ酸化チタン (富士チタン工業 (株) 製、 商品名 : T A F— 1 1 0 ) を変えた以外は実施例 1 と同様にして二軸 配向フィルムを得た。 フィルムはワイ ンダ一にて巻き取られ、 このときのフィル ムのしわの発生具合等を観察したところ、 しわの発生が顕著で、 製品と しては不 十分であると判断される。 評価結果を表 2 に示す。  A biaxially oriented film was prepared in the same manner as in Example 1 except that the particles to be blended were changed to fine particles of titanium dioxide (average particle size: 0.05 m) (trade name: TAF-110, manufactured by Fuji Titanium Co., Ltd.) I got The film is wound up by a winder. Observation of the occurrence of wrinkles on the film at this time reveals that wrinkles are remarkable and the product is judged to be insufficient. Table 2 shows the evaluation results.
(比較例 3 )  (Comparative Example 3)
平均粒径 2 . 5〃 mの粒状二酸化ケイ素 (シリカ) の配合部数を 0 . 0 0 5重 量部にした以外は実施例 1 と同様にして二軸配向フイルムを得た。 卷取りでのし わの発生が顕著で、 製品としては不十分であると判断される。 評価結果を表 2に 示す。 The number of parts of granular silicon dioxide (silica) having an average particle size of 2.5 μm was A biaxially oriented film was obtained in the same manner as in Example 1 except that the amount was changed to parts by weight. The occurrence of wrinkles in winding is remarkable, and it is judged that the product is insufficient. Table 2 shows the evaluation results.
(比較例 4 )  (Comparative Example 4)
平均粒径約 0 . 9 z mの日東粉化工業 (株) 製炭酸カルシウム (商品名 : N S # 2 5 0 0 ) の配合部数を 1 4 0重量部にした以外は実施例 3 と同様にして二軸 配向フ ィ ルムを製造しょう とした。 しかし、 製造中、 縦延伸においてフ ィルムの 穴空き、 破断が多発して安定してフイ ルムを得ることができなかった。  In the same manner as in Example 3 except that the number of parts of calcium carbonate (trade name: NS # 250000) manufactured by Nitto Powder Chemical Co., Ltd. having an average particle size of about 0.9 zm was changed to 140 parts by weight. An attempt was made to produce a biaxially oriented film. However, during production, holes were frequently formed in the film during longitudinal stretching and breakage occurred frequently, and a stable film could not be obtained.
(比較例 5、 6 )  (Comparative Examples 5, 6)
比較例 5では、 延伸温度 · 倍率を表 1 に示すとおりに変更し、 また比較例 6で は L 一乳酸成分と D —乳酸成分との割合がおおよそ 8 0 : 2 0である分子量約 1 6万のポリ乳酸に変更し、 熱処理温度を 1 0 0 °Cにした以外は実施例 1 と同様に して二軸配向フィルムを作製した。 それぞれ、 卷取りでのしわの発生が顕著で、 製品としては不十分であると判断される。 評価結果を表 2に示す。 産業上の利用可能性  In Comparative Example 5, the stretching temperature and the magnification were changed as shown in Table 1. In Comparative Example 6, the ratio between the L-lactic acid component and the D-lactic acid component was approximately 80:20, and the molecular weight was about 16 A biaxially oriented film was produced in the same manner as in Example 1 except that the polylactic acid was changed to 100,000 and the heat treatment temperature was set to 100 ° C. In each case, the occurrence of wrinkles in winding was remarkable, and it was judged that the product was insufficient. Table 2 shows the evaluation results. Industrial applicability
この発明によれば、 所定の表面粗さを有するので、 2軸配向脂肪族ポリエステ ル系フ ィ ルムは、 滑りが良く、 フ ィルムの蛇行や、 しわ発生を抑制する。  According to the present invention, since the biaxially oriented aliphatic polyester film has a predetermined surface roughness, the biaxially oriented aliphatic polyester film has good slip and suppresses the meandering and wrinkling of the film.
また、 2軸配向脂肪族ポリエステル系フィ ルムは、 所定の組成を有するので、 腰、 強度、 低熱収縮性を保持することができる。 In addition, since the biaxially oriented aliphatic polyester film has a predetermined composition, it can maintain stiffness, strength, and low heat shrinkage.
表 1 table 1
Figure imgf000015_0001
表 2
Figure imgf000015_0001
Table 2
Figure imgf000016_0001
Figure imgf000016_0001

Claims

請 求 の 範 囲 The scope of the claims
1. ポリ乳酸系重合体を主成分とする脂肪族ポリエステルからなり、 無機系粒子 が配合され、 フィルム表面の平均粗さ R aが 0. 0 1く R a≤ 0. 0 8である 2 軸配向脂肪族ポリエステル系フ ィ ルム。 1. Biaxial composed of aliphatic polyester mainly composed of polylactic acid polymer, blended with inorganic particles, and having an average roughness Ra of 0.01 and Ra≤0.08 on the film surface Oriented aliphatic polyester film.
2. 上記脂肪族ポリエステル 1 0 0重量部に対し、 平均粒子径が 0. 1 π!〜 5 mの無機系粒子を 0. 0 1 ~ 1 2 0重量部配合した請求項 1記載の 2軸配向脂 肪族ポリエステル系フイルム。  2. The average particle size is 0.1 π! 2. The biaxially oriented aliphatic polyester film according to claim 1, wherein 0.01 to 120 parts by weight of inorganic particles of from 5 to 5 m are blended.
3. 十点平均粗さ R zが 2. 0以下である請求項 1又は 2に記載の 2軸配向脂肪 族ポリエステル系フィルム。  3. The biaxially oriented aliphatic polyester film according to claim 1, wherein the ten-point average roughness R z is 2.0 or less.
4. 静摩擦係数が 0. 8以下である請求項 1乃至 3のいずれかに記載の 2軸配向 脂肪族ポリエステル系フ ィルム。  4. The biaxially oriented aliphatic polyester film according to claim 1, having a coefficient of static friction of 0.8 or less.
5. 面配向度 Δ Ρが小さ く とも 3. 0 X 1 0—3 である請求項 1乃至 4のいずれか に記載の 2軸配向脂肪族ポリエステル系フ ィルム。 Even 5. plane orientation degree delta [rho is rather small 3. 0 X 1 0- 3 a biaxially oriented aliphatic polyester off Irumu according to any one of claims 1 to 4.
6. 縦方向又は横方向の少なく とも一方の 8 0 °Cでの収縮率が 1 0 %以下である 請求項 1乃至 5のいずれかに記載の 2軸配向脂肪族ポリエステル系フィ ルム。 6. The biaxially oriented aliphatic polyester-based film according to any one of claims 1 to 5, wherein at least one of the longitudinal direction and the transverse direction has a shrinkage ratio at 80 ° C of 10% or less.
7. ポリ乳酸系重合体を構成する L一乳酸と D—乳酸の割合が 1 0 0 : 0〜 9 4 : 6の範囲内、 又は 6 : 9 4〜 0 : 1 0 0の範囲内である請求項 1乃至 6のい ずれかに記載の 2軸配向脂肪族ポリエステル系フィルム。 7. The ratio of L-lactic acid and D-lactic acid in the polylactic acid-based polymer is in the range of 100: 0: 94: 6 or 6: 94-0: 100. The biaxially oriented aliphatic polyester-based film according to any one of claims 1 to 6.
8. L—乳酸と D—乳酸の割合が 1 0 0 : 0〜 9 4 : 6の範囲内もしくは 6 : 9 4〜 0 : 1 0 0の範囲内であるポリ乳酸系重合体 1 0 0重量部に対し、 平均粒子 径が 0. 1 zm~ 5 /mの無機系粒子を 0. 0 1〜 ; L 2 0重量部配合し、 2軸方 向に延伸することによ り、 表面の平均粗さ R aが 0. 0 1 <R a≤ 0. 0 8であ る 2軸配向脂肪族ポリエステル系フィ ルムを製造する方法。  8. 100% by weight of polylactic acid-based polymer in which the ratio of L-lactic acid and D-lactic acid is in the range of 100: 0 to 94: 6 or in the range of 6:94 to 0: 100 Parts by weight of inorganic particles having an average particle diameter of 0.1 zm to 5 / m in an amount of from 0.01 to L; 20 parts by weight of L, and biaxially stretched to obtain an average surface. A method for producing a biaxially oriented aliphatic polyester film having a roughness Ra of 0.01 <Ra≤0.08.
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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003082212A (en) * 2001-09-13 2003-03-19 Unitika Ltd Biodegradable resin film
US7226655B2 (en) 2002-07-26 2007-06-05 Asahi Kasei Kabushiki Kaisha Wrap film
US20050112352A1 (en) * 2003-11-26 2005-05-26 Laney Thomas M. Polylactic-acid-based sheet material and method of making
JP4570393B2 (en) * 2004-05-17 2010-10-27 東セロ株式会社 Polylactic acid stretched film and method for producing the same
JP2005329658A (en) * 2004-05-21 2005-12-02 Mitsubishi Polyester Film Copp Biaxially oriented aliphatic polyester film
JP2006082494A (en) * 2004-09-17 2006-03-30 Nisshinbo Ind Inc Biodegradable material to be recorded
JP2006124662A (en) * 2004-09-29 2006-05-18 Toray Ind Inc Biaxially oriented polylactic acid film, molding composed of the same and substrate
JP2009052056A (en) * 2008-12-08 2009-03-12 Mitsubishi Plastics Inc Roll-like article of polylactic acid-based film
WO2013141126A1 (en) * 2012-03-19 2013-09-26 ユニチカ株式会社 Polylactic acid resin composition and polylactic acid film obtained by molding same
WO2016027587A1 (en) 2014-08-22 2016-02-25 三井化学株式会社 Polymeric piezoelectric film

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09157408A (en) * 1995-12-11 1997-06-17 Mitsubishi Plastics Ind Ltd Stretched polylactic acid film or sheet
JP2000044701A (en) * 1998-07-27 2000-02-15 Toyobo Co Ltd Lactic acid-based polymer biaxially oriented film
JP2000290400A (en) * 1999-04-05 2000-10-17 Toyobo Co Ltd Aliphatic polyester film

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3167411B2 (en) * 1991-04-26 2001-05-21 三井化学株式会社 Porous film
JPH07205278A (en) * 1994-01-11 1995-08-08 Mitsubishi Plastics Ind Ltd Production of stretched film of polylactic acid polymer
JP3472644B2 (en) * 1994-05-19 2003-12-02 三井化学株式会社 L-lactic acid polymer composition, molded product and film
JPH09235455A (en) * 1996-03-01 1997-09-09 Shin Etsu Chem Co Ltd Biodegradable film
JPH09286909A (en) * 1996-04-23 1997-11-04 Mitsui Toatsu Chem Inc Lactic acid-based polymer film for agricultural use
JP3654719B2 (en) * 1996-09-04 2005-06-02 三井化学株式会社 Resin composition
JP3490241B2 (en) * 1997-02-13 2004-01-26 三菱樹脂株式会社 Degradable films or sheets, molded articles made of these, and methods for decomposing them
JP3659388B2 (en) * 1998-07-27 2005-06-15 東洋紡績株式会社 Lactic acid polymer biaxially stretched film
JP3196895B2 (en) * 1998-07-27 2001-08-06 東洋紡績株式会社 Biaxially stretched aliphatic polyester film
JP4644885B2 (en) * 1999-02-25 2011-03-09 東洋紡績株式会社 Aliphatic polyester film
JP2000273212A (en) * 1999-03-26 2000-10-03 Toyobo Co Ltd Aliphatic polyester-based oriented film
JP2000318335A (en) * 1999-05-17 2000-11-21 Toray Ind Inc Heat-sensitive stencil printing film and heat-sensitive stencil printing master
JP2001002126A (en) * 1999-06-18 2001-01-09 Mitsubishi Plastics Ind Ltd Window pasting case

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09157408A (en) * 1995-12-11 1997-06-17 Mitsubishi Plastics Ind Ltd Stretched polylactic acid film or sheet
JP2000044701A (en) * 1998-07-27 2000-02-15 Toyobo Co Ltd Lactic acid-based polymer biaxially oriented film
JP2000290400A (en) * 1999-04-05 2000-10-17 Toyobo Co Ltd Aliphatic polyester film

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