WO2013141126A1 - Composition de résine d'acide polylactique et film d'acide polylactique obtenu par moulage de celle-ci - Google Patents

Composition de résine d'acide polylactique et film d'acide polylactique obtenu par moulage de celle-ci Download PDF

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WO2013141126A1
WO2013141126A1 PCT/JP2013/057125 JP2013057125W WO2013141126A1 WO 2013141126 A1 WO2013141126 A1 WO 2013141126A1 JP 2013057125 W JP2013057125 W JP 2013057125W WO 2013141126 A1 WO2013141126 A1 WO 2013141126A1
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polylactic acid
inorganic particles
resin composition
lactide
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PCT/JP2013/057125
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English (en)
Japanese (ja)
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貴史 岡部
成明 石井
西村　弘
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ユニチカ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/16—Biodegradable polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a polylactic acid film excellent in dimensional stability, transparency, slip property, and operability, and a polylactic acid resin composition that can be molded.
  • polyester resins have attracted attention from the viewpoint of environmental conservation.
  • resins such as polylactic acid, polyethylene succinate, and polybutylene succinate are low in cost and highly useful because they can be mass-produced.
  • polylactic acid resin is already industrially available from plants such as corn and sweet potato, and even if incinerated after use, carbon dioxide absorbed during the growth of these plants is taken into account. Because of its neutral balance, it is considered to be a resin with a low impact on the global environment.
  • the polylactic acid-based film is excellent in rigidity, but has low dimensional stability, and when the molding process or the product itself is handled, since the slip property is not good, the operability is lowered or the product value is lowered. It is known that trouble occurs.
  • fine particles are blended in the resin to impart appropriate irregularities to the surface of the molded product, thereby improving the slip property.
  • fine particles silica, titanium dioxide, calcium carbonate, alumina are proposed.
  • Inorganic particles such as talc and kaolinite are used.
  • Patent Document 1 describes that the properties of hardness, strength, and temperature resistance are changed by adding inorganic particles such as silica and kaolinite to a polylactic acid resin.
  • inorganic particles such as silica and kaolinite
  • the obtained film was not sufficiently improved in slip property, and the films were blocked and the operability was low.
  • the inorganic particles are not easily dispersed in the resin because the particle surface is hydrophilic and the particle shape and particle size are not uniform, and the inorganic particles are not dispersed well in the resin. Even if it mix
  • Patent Document 2 discloses a resin composition obtained by blending inorganic particles surface-treated with a glycerin ester compound into a polylactic acid resin or the like.
  • this resin composition is formed into a film, the film is whitened during stretching, and a film having excellent transparency cannot be obtained. Moreover, the film obtained was inferior in operability due to poor slip properties.
  • this resin composition is disadvantageous in terms of cost because it requires a compounding process for treating the surface of the inorganic particles and preparing a master batch.
  • An object of the present invention is to provide a polylactic acid resin composition capable of solving the above-mentioned problems and molding a polylactic acid film excellent in dimensional stability, transparency, slip properties, and operability.
  • the present inventors polymerized a polylactic acid resin using a lactide having a specific D-form content, and present a specific amount of inorganic particles in the polymerization stage. As a result, the present inventors have found that the above problems can be solved, and have reached the present invention.
  • the gist of the present invention is as follows.
  • a polylactic acid resin composition containing a polylactic acid resin and inorganic particles, The D-form content of the polylactic acid-based resin is 2.0 mol% or less, or 98.0 mol% or more, The content of inorganic particles in the resin composition is 0.001 to 10% by mass,
  • a polylactic acid film excellent in dimensional stability, transparency, slip property, and operability can be produced. Since the polylactic acid-based resin composition of the present invention has good dispersibility of inorganic particles, a film obtained using the polylactic acid-based resin composition has foams, aggregates and voids due to poor dispersion of inorganic particles, which has been a problem in the past. , Problems such as particle dropout are solved, and transparency is excellent. Moreover, the blocking resistance between films improves, it is excellent in slip property, and it is excellent also in operativity, without a film tearing at the time of extending
  • the polylactic acid-based resin composition of the present invention since the polylactic acid-based resin has a specific D-form content, a film obtained using this has heat resistance and is excellent in dimensional stability.
  • the polylactic acid-based resin composition of the present invention can be manufactured by omitting the dispersing agent mixing and compounding steps in the blender, which has been necessary so far, and is advantageous in terms of cost.
  • the polylactic acid resin composition of the present invention contains a polylactic acid resin and inorganic particles.
  • the polylactic acid resin in the present invention is a polymer of D-lactic acid and / or L-lactic acid, and can be polymerized using lactide which is a dimer of D-lactic acid or L-lactic acid as a raw material.
  • the D-form content of the polylactic acid resin used in the present invention is required to be 2.0 mol% or less, or 98.0 mol% or more.
  • the D-form content is preferably 1.0 mol% or less, or preferably 99.0 mol% or more, and is 0.6 mol% or less, or 99 More preferably 4 mol% or more.
  • the D-form content is 0 mol% or more preferably 100 mol%, but it is very difficult to produce a polylactic acid resin having such D-form content, It is also expensive.
  • the D-form content of the polylactic acid-based resin is a ratio (mol%) occupied by D-lactic acid units in the total lactic acid units constituting the polylactic acid-based resin.
  • the weight average molecular weight of the polylactic acid-based resin in the present invention is preferably 70,000 to 500,000, and more preferably 100,000 to 300,000, from the viewpoint of both moldability and physical properties of the molded product.
  • the weight average molecular weight of the polylactic acid-based resin is less than 70,000, the obtained molded product may have low mechanical strength and toughness. Further, when the weight average molecular weight of the polylactic acid-based resin exceeds 500,000, the melt viscosity is high, and melt molding may be difficult.
  • the polylactic acid resin composition of the present invention contains inorganic particles together with the polylactic acid resin.
  • the kind of the inorganic particles used in the present invention is not particularly limited, and examples thereof include silica, zeolite, talc, alumina and the like. Among these, in terms of transparency and slip properties of the obtained film, silica is used. Is preferred.
  • the shape of the inorganic particles is not particularly limited, but is preferably spherical.
  • the term “spherical” means that the aspect ratio (minor axis / major axis) measured by observation with an electron microscope or the like is 0.5 to 1.
  • the content of inorganic particles in the polylactic acid-based resin composition needs to be 0.001 to 10% by mass, more preferably 0.003 to 7% by mass, and 0.005 to 5% by mass. More preferably it is.
  • the content of the inorganic particles is less than 0.001% by mass, the effect of adding the inorganic particles is not sufficiently exhibited, and at the time of film formation, the adhesion of the molten film to the processing roll and the blocking of the films can be sufficiently suppressed. Can not.
  • the content of the inorganic particles exceeds 10% by mass, the dispersibility of the inorganic particles becomes low, and at the time of film forming, the filter attached to the tip of the extruder is clogged, causing an increase in the resin pressure in the extruder.
  • Productivity may be significantly reduced.
  • the polylactic acid-based resin composition is reduced in transparency and moldability.
  • the proportion of inorganic particles having a particle size of 1 ⁇ m or less needs to be 50% or more, and preferably 60% or more.
  • the proportion of the inorganic particles having a particle diameter of 1 ⁇ m or less is less than 50%, the inorganic particles are inferior in dispersibility, and the thin film such as a film obtained has high haze.
  • the production of the polylactic acid-based resin composition is performed by polymerizing lactide in the presence of the inorganic particles. The method of doing it.
  • the viscosity of the reaction system is low at the lactide polymerization stage, so that the inorganic particles are efficiently dispersed by stirring performed during the polymerization.
  • the obtained polylactic acid-based resin composition as described above, it can be dispersed until the proportion of inorganic particles having a particle size of 1 ⁇ m or less is 50% or more.
  • the average particle size of the inorganic particles contained in the polylactic acid resin composition of the present invention is preferably 0.03 to 1 ⁇ m, more preferably 0.1 to 1 ⁇ m, and more preferably 0.5 to 1 ⁇ m. More preferably.
  • the average particle size of the inorganic particles is less than 0.03 ⁇ m, the particles aggregate and do not exhibit the anti-blocking effect, and the resulting film has insufficient running properties and wear resistance, and may have poor operability. is there.
  • the average particle diameter exceeds 1 ⁇ m the surface roughness of the film becomes too large, the transparency is lowered, and the appearance of the film becomes poor due to the generation of fish eyes.
  • the polylactic acid-based polymer composition of the present invention is added with a crystal nucleating agent, a heat stabilizer, an antioxidant, a plasticizer, a lubricant, a flame retardant, a release agent, an impact resistance agent, an end-blocking agent, etc.
  • An agent may be contained.
  • the crystal nucleating agent include organic amide compounds, organic hydrazide compounds, carboxylic acid ester compounds, organic sulfonates, phthalocyanine compounds, melamine compounds, and organic phosphonates.
  • an organic amide compound is preferable from the viewpoint of transparency.
  • heat stabilizers and antioxidants include hindered phenols, hindered amines, sulfur compounds, copper compounds, and alkali metal halides.
  • plasticizer examples include aliphatic ester derivatives and aliphatic polyether derivatives, and specific compounds include glycerin diacetomonocaprate and glycerin diacetomonolaurate.
  • lubricant examples include carboxylic acid compounds, among which a fatty acid metal salt is preferable, and specific compounds include magnesium stearate and calcium stearate.
  • flame retardant examples include bromine-based flame retardant, phosphorus-based flame retardant, intomesent flame retardant, nitrogen-based flame retardant, silicone-based flame retardant, and inorganic flame retardant.
  • the mold release agent examples include carboxylic acid compounds.
  • the impact resistance agent is not particularly limited, and examples thereof include (meth) acrylic acid ester impact resistance agents having a core-shell structure, and commercially available products include “Metablene” series manufactured by Mitsubishi Rayon Co., Ltd.
  • the terminal blocking agent is not particularly limited, and examples thereof include carbodiimide, epoxy, isocyanate, oxazoline and the like.
  • the polylactic acid resin composition of the present invention contains a polylactic acid resin and inorganic particles, and can be produced by polymerizing lactide in the presence of inorganic particles.
  • Lactide which is a polymerization raw material for polylactic acid-based resins, includes L-lactide, which is a cyclic dimer of L-lactic acid, D-lactide, which is a cyclic dimer of D-lactic acid, D-lactic acid, and L-lactic acid.
  • L-lactide which is a cyclic dimer of L-lactic acid
  • D-lactide which is a cyclic dimer of D-lactic acid, D-lactic acid, and L-lactic acid.
  • meso-lactide and DL-lactide which is a mixture of D-lactide and L-lactide, and one or more of these are used as a raw material for polylactic acid resin polymerization.
  • the D-form content is 2.0 mol% or less.
  • lactide that is 98.0 mol% or more as a raw material
  • the D-form content of lactide is 1.0 mol% or less, or 99.0 mol% or more. Preferably, it is 0.6 mol% or less, more preferably 99.4 mol% or more, more preferably 0 mol%, or even more preferably 100 mol%.
  • the D-form content of the lactide used as a raw material is the total lactic acid unit in the raw lactide composed of one or more selected from L-lactide, D-lactide, meso-lactide and DL-lactide. This is the ratio (mol%) occupied by lactic acid units.
  • the amount of free acid contained in the raw material lactide is preferably 30 meq / kg or less, more preferably 20 meq / kg or less, and 10 meq / kg or less. More preferably, it is most preferably 5 meq / kg or less.
  • the free acid contained in the raw material lactide exceeds 30 meq / kg, a high molecular weight polylactic acid resin may not be obtained due to decomposition of the catalyst or polymer during polymerization. Further, the durability of the obtained polylactic acid resin may be lowered.
  • the amount of inorganic particles present when lactide is polymerized needs to be such that the content in the resulting resin composition is 0.001 to 10% by mass.
  • the average particle diameter of the inorganic particles used as a raw material in the present invention is not particularly limited, but is preferably 1 ⁇ m or more. Inorganic particles with an average particle diameter of 1 ⁇ m or less have a high moisture content, so that when such moisture particles are used, the water content in the polymerization system increases, so that the polylactic acid resin is decomposed during the polymerization. May be adversely affected.
  • the water content of the reaction system in which lactide is polymerized in the presence of inorganic particles is preferably 120 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less.
  • the inorganic particles present in the reaction system are inferior in dispersibility, and the proportion of inorganic particles having a particle diameter of 1 ⁇ m or less is 50% in the resulting polylactic acid resin composition. It may not be more.
  • polylactic acid-based resin does not easily decompose to a predetermined molecular weight during polymerization and may adversely affect processability. Also, by coloring by decomposition, the resulting molded product has a poor appearance, etc.
  • the moisture content of lactide used as a raw material in the present invention is preferably as low as possible, preferably 20 ppm, more preferably 15 ppm, further preferably 10 ppm or less, and most preferably 5 ppm or less. Further, the moisture content of the inorganic particles is preferably as low as possible, preferably 10,000 ppm or less, more preferably 5000 ppm or less, further preferably 3000 ppm or less, and most preferably 1000 ppm or less.
  • the polylactic acid-based resin in the present invention may be produced by carrying out normal lactide polymerization in the presence of inorganic particles, and other production conditions apply the conditions of known polylactic acid-based resin production methods. Can do. That is, lactide is heated and melt-opened in the presence of a polymerization catalyst, or after low molecular weight polylactic acid polymer containing the catalyst is crystallized, under reduced pressure or under an inert gas stream.
  • a polylactic acid resin can be produced by applying the conditions of heating and solid-phase polymerization.
  • the type of the polymerization catalyst is not particularly limited, and conventionally used alkali metal, alkaline earth metal, rare earth, transition metals, fatty acid salts such as aluminum, germanium, tin, antimony, carbonate, sulfate, Phosphate, oxide, hydroxide, halide, alcoholate and the like can be used as a catalyst.
  • fatty acid salts such as aluminum, germanium, tin, antimony, carbonate, sulfate, Phosphate, oxide, hydroxide, halide, alcoholate and the like
  • stannous chloride such as tin stearate, tetraphenyltin, tin methoxide, tin ethoxide, tin propoxide, tin butoxide, dinonyloxytin, and aluminum acetylacetonate, aluminum isopropoxide, aluminum butoxide, aluminum-imine complexes, etc.
  • Aluminum-containing compounds are preferred.
  • More preferable compounds include stannous chloride, tin myristate, tin octylate, tin stearate, tin methoxide, tin ethoxide, tin propoxide, tin butoxide, dinonyloxytin, aluminum acetylacetonate, aluminum isopropoxide and the like. Illustrated. Among these, preferred examples are II-valent tin compounds, particularly II-valent tin alkoxides having 4 to 22 carbon atoms and fatty acid salts. Among these, tin (II) octylate is exemplified as the most preferable from the viewpoint of safety and catalytic activity.
  • the addition amount of the polymerization catalyst is preferably 0.001 to 1 part by mass, more preferably 0.003 to 0.1 part by mass, with respect to 100 parts by mass in total of lactide and inorganic particles. More preferably, the amount is 0.003 to 0.02 parts by mass.
  • the addition amount of the polymerization catalyst is less than 0.001 part by mass, the polymerization rate may be slow, and the polymerization may take too long.
  • the addition amount of the polymerization catalyst exceeds 1 part by mass, the polymerization rate is fast, but the coloration due to the decomposition of the polymer also increases, and the durability of the obtained polylactic acid-based resin increases due to the increase in the carboxylic acid terminal due to the decomposition. May decrease.
  • the polymerization reaction vessel for example, a vertical reactor or a horizontal reactor equipped with a stirring blade for high viscosity such as a helical ribbon blade or an anchor blade can be used alone or in parallel. Further, the polymerization may be carried out by a batch system, a continuous system or a semi-batch system, or a combination thereof. In the case of a continuous type, a stirring blade may not be necessary.
  • the polymerization temperature of melt polymerization is preferably 170 to 230 ° C, more preferably 170 to 210 ° C, and further preferably 180 to 200 ° C. Since the polymerization rate depends on the polymerization temperature, if the polymerization temperature is less than 170 ° C., the polymerization takes a long time, and if the melting point becomes high due to the improvement of the molecular weight, stirring may not be possible. When the polymerization temperature exceeds 230 ° C., the inorganic particles present in the reaction system are inferior in dispersibility, and in the obtained polylactic acid resin composition, the proportion of inorganic particles having a particle size of 1 ⁇ m or less is 50% or more. It may not be. Further, since the content of the monomer contained in the polylactic acid resin is increased, it is disadvantageous in terms of cost, the decomposition rate is increased, the coloring is increased, and the optical purity may be lowered during the polymerization.
  • a polylactic acid resin having a relatively low molecular weight obtained by the ring-opening polymerization method described above is used as a prepolymer.
  • the prepolymer is preferably crystallized in advance in the temperature range of the glass transition temperature (Tg) or higher and lower than the melting point (Tm) from the viewpoint of preventing fusion.
  • the crystallized prepolymer is filled in a fixed vertical or horizontal reaction vessel, or a reaction vessel in which the vessel itself rotates, such as a tumbler or rotary kiln, and has a melting point (not less than the glass transition temperature (Tg) of the prepolymer. Heated to a temperature range below Tm).
  • the polymerization temperature may be raised stepwise as the polymerization proceeds.
  • a method of reducing the pressure inside the reaction vessels or circulating a heated inert gas stream is also preferably used.
  • water or alcohol can be used as the polymerization initiator.
  • the alcohol is preferably non-volatile without inhibiting the polymerization of the polylactic acid-based resin.
  • polyhydric alcohols such as decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, etc.
  • Aromatic polyhydric alcohols such as aliphatic polyhydric alcohols or those obtained by adding ethylene oxide to bisphenol can be suitably used. .
  • the addition amount of the polymerization initiator is preferably 0.05 to 0.5 parts by mass, more preferably 0.07 to 0.3 parts by mass, with respect to 100 parts by mass of lactide, More preferred is 0.25 parts by mass.
  • the addition amount of the polymerization initiator is less than 0.05 parts by mass, the molecular weight of the obtained polylactic acid-based resin becomes too high, and melt extrusion may be difficult.
  • the resin composition obtained may be inferior to a mechanical characteristic.
  • the melt-opening polymerized polylactic acid-based resin usually contains 1% by mass or more of lactide, but the lactide in the polylactic acid-based resin is obtained by a known lactide weight loss method, for example, vacuum in a single-screw or multi-screw extruder. The amount can be reduced by a devolatilization method or a high vacuum treatment method in a polymerization apparatus.
  • Polylactic acid-based resins have improved melt stability and wet heat stability as the lactide content decreases, but the melt viscosity also increases. Therefore, it is reasonable and economical to adjust the content to meet the desired purpose. is there.
  • the lactide content of the polylactic acid based resin composition of the present invention is preferably 0 to 5000 ppm, more preferably 0 to 3000 ppm, further preferably 0 to 2000 ppm, and 0 to 1000 ppm. Is particularly preferred. When the lactide content exceeds 5000 ppm, not only the smoke is generated during the molding process and the operability is lowered, but the durability of the obtained molded product may be lowered.
  • a step of diluting inorganic particles by mixing a separately polymerized polylactic acid resin may be included.
  • the separately polymerized polylactic acid-based resin is mixed to dilute the inorganic particles, so that the content of the inorganic particles is preferably lower, and is substantially free of inorganic particles. More preferably.
  • the weight-average molecular weight of a separately polymerized polylactic acid-based resin (hereinafter also referred to as a polylactic acid-based resin for dilution) is preferably 100,000 to 500,000 from the viewpoint of compatibility between moldability and molded article physical properties. More preferably, it is 10,000 to 300,000.
  • the D-form content of the polylactic acid resin for dilution is 2.0 mol% or less or 98.0 mol% or more in the resin composition after mixing.
  • the mixing amount of the polylactic acid resin for dilution may be such that the content of inorganic particles in the mixed resin composition is 0.001 to 10% by mass.
  • a known mixing method can be applied, and for example, a ribbon blender method, an extrusion melt blend method, a Banbury blend method, or the like can be applied.
  • the polylactic acid-based resin composition of the present invention is produced by the above-described method, and is usually granulated into a shape such as a pellet or a rod.
  • the polylactic acid-based resin composition can be used for molding as it is.
  • the polylactic acid resin composition of the present invention is not particularly limited, but can be diluted to about 10 to 100 times and used for molding.
  • the polylactic acid polymer composition of the present invention is excellent in dispersibility of inorganic particles, it is suitable for use in applications where the appearance is important and for thin films such as films and sheets. In particular, when used in a film or sheet, it has a remarkable effect that haze is reduced.
  • the polylactic acid-based film of the present invention is formed by molding a polylactic acid-based resin composition having excellent dispersibility of inorganic particles as described above, it has excellent transparency, and its haze is 4% or less. It is preferable that it is 3% or less practically. When the haze exceeds 4%, the appearance of transparency is low, and the commercial value tends to decrease in applications such as packaging materials.
  • the thickness of the polylactic acid film of the present invention is preferably 10 to 50 ⁇ m. When the thickness is less than 10 ⁇ m, there is no stiffness when used as a packaging bag, and when the thickness is greater than 50 ⁇ m, the cost may be disadvantageous.
  • the melting point of the polylactic acid film of the present invention is preferably 150 ° C. or higher, and more preferably 160 ° C. or higher. If the melting point is less than 150 ° C, the heat resistance may be inferior.
  • the molding method of the polylactic acid film of the present invention is not particularly limited, and a known molding method can be applied.
  • a T-die method, an inflation method, a calendar method, etc. can be exemplified, and among these, the T-die method is preferable.
  • an unstretched sheet having a thickness of 100 to 600 ⁇ m is obtained by supplying the polylactic acid-based polymer composition of the present invention to an extruder hopper, melt-kneading and extruding, and cooling with a cast roll.
  • the cylinder temperature is preferably 160 to 250 ° C.
  • the T die temperature is 200 to 250 ° C.
  • the cast roll is preferably 30 to 60 ° C.
  • the monomer of the polylactic acid resin may adhere to the cast roll and become a sheet stain.
  • the cast roll temperature exceeds 60 ° C., the temperature becomes equal to or higher than the glass transition temperature of the polylactic acid-based resin, so that cooling becomes insufficient and a stable form sheet may not be obtained.
  • the obtained unstretched sheet can be stretched as necessary to obtain a stretched film.
  • the stretching direction may be uniaxial or biaxial, but it is preferable to stretch in the biaxial direction.
  • Examples of the stretching method include a roll method and a tenter method, and either a sequential biaxial stretching method or a simultaneous biaxial stretching method may be employed.
  • the surface magnification in biaxial stretching is preferably 6 to 16 times. If the surface magnification is less than 6 times, the mechanical properties of the resulting film, particularly the tensile strength, is low and may not be practically used. On the other hand, if the surface magnification exceeds 16 times, the film may not withstand the stretching stress during stretching and may break.
  • the stretching temperature is preferably 50 to 90 ° C, more preferably 60 to 80 ° C.
  • the stretching temperature is less than 50 ° C.
  • the film may be broken at the initial stage of stretching due to insufficient heat for stretching.
  • the stretching temperature exceeds 90 ° C., heat is excessively applied to the film, and draw stretching tends to occur, resulting in frequent occurrence of stretch spots.
  • a coating agent may be coated on the unstretched sheet before the stretching process.
  • the coating method is not particularly limited, and examples include gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, and dip coating.
  • a thermal relaxation treatment may be performed after stretching.
  • the thermal relaxation treatment method include a method of blowing hot air, a method of irradiating infrared rays, a method of irradiating microwaves, a method of contacting on a heat roll, and the like. The method is preferred.
  • the thermal relaxation treatment is preferably carried out in the range of 80 to 160 ° C. for 1 second or longer and under a relaxation rate of 2 to 8%.
  • the polylactic acid resin composition is preliminarily crosslinked with a crosslinking agent such as an organic peroxide and a crosslinking aid as necessary. May be.
  • the polylactic acid film of the present invention is a single layer, a good package can be obtained, but other layers may be laminated so that it can be applied to the contents, storage method, and bag making method. Good.
  • the lamination method include coating, dry lamination, extrusion lamination, and the like, and can be selected as appropriate.
  • Raw material (1) Lactide / L-lactide: manufactured by Tokyo Chemical Industry Co., Ltd., D-form content 0.06%, free acid amount 3 meq / kg, moisture content 5 ppm DL-lactide: manufactured by Tokyo Chemical Industry Co., Ltd., D-form content: 50%, free acid amount: 3 meq / kg, moisture content: 5 ppm
  • Inorganic particles / SO-C5 Silica manufactured by Admatech, average particle size of 1.5 ⁇ m, proportion of particles having a particle size of 1 ⁇ m or less, 15%, moisture content of 500 ppm -HPS-1000: Silica manufactured by Toagosei Co., Ltd., average particle size 2 ⁇ m, proportion of particles having a particle size of 1 ⁇ m or less, 5%, moisture content 1900 ppm SY-310P: silica manufactured by Fuji Silysia Chemical Ltd., average particle size of 3 ⁇ m, proportion of particles having
  • talc average particle size of 2.5 ⁇ m, proportion of particles with a particle size of 1 ⁇ m or less, 7%, moisture content of 5000 ppm (3)
  • Polylactic acid resin for dilution S-6 manufactured by Toyota Motor Corporation, D-form content 0.1 mol%, lactide content 1000 ppm, Moisture content 100ppm, weight average molecular weight 170,000, melting point 176 ° C 4032D: manufactured by Nature Works, D-form content: 1.4 mol%, lactide content: 2200 ppm, moisture content: 100 ppm, weight average molecular weight: 180,000, melting point: 166 ° C.
  • Crystal nucleating agent T-530SF N, N'-ethylenebis-12-hydroxystearylamide, manufactured by Ito Oil Co., Ltd.
  • Lactide content in polylactic acid resin The polylactic acid resin composition was weighed so that the content of the polylactic acid resin was 0.1 g, and 9 mL of methylene chloride and 1 mL of internal standard solution ( 2,6-dimethyl- ⁇ -pyrone (5000 ppm solution) was added to dissolve the polylactic acid resin. To this solution, 40 mL of cyclohexane was added to precipitate a polylactic acid resin. The inorganic particles and the precipitated polylactic acid-based resin were separated by filtration with an HPLC disk filter (pore size: 0.45 ⁇ m), and the filtrate was subjected to GC measurement with Agilent Technologies 7890A GC System to calculate the lactide content.
  • Haze (transparency) According to JIS-K7105, a film having a thickness of 25 ⁇ m or 50 ⁇ m was used as a sample, and haze was measured using a haze meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. In the present invention, 4% or less was evaluated as acceptable.
  • Example 1 Polymerization of lactide in the presence of inorganic particles
  • a glass tube was charged with 95 parts by mass of L-lactide and 5 parts by mass of silica (SO—C5) as inorganic particles, and the system was purged with nitrogen.
  • 0.01 parts by mass of tin octylate was added as a polymerization catalyst, and then the temperature was raised to 150 ° C. in a nitrogen atmosphere.
  • stirring was started, the internal temperature was further raised to 190 ° C. and a polymerization reaction was performed for 2 hours, and then the polymerization reaction product was taken out.
  • the obtained polymerization reaction product was vacuum-dried at 130 ° C. for 30 hours to remove the lactide remaining in the polymerization reaction product, thereby obtaining a polylactic acid resin composition.
  • Example 2 (Inorganic particle dilution after lactide polymerization)
  • the polylactic acid resin composition obtained in Example 1 was mixed with the diluting polylactic acid resin (S-6) in an amount such that the dilution rate of the inorganic particles was 100 times, and the screw diameter was 25 mm ⁇ and the temperature was 230 ° C. It was supplied to a single screw extruder and melt extruded to obtain a polylactic acid resin composition in which inorganic particles were diluted.
  • the polylactic acid resin composition diluted with inorganic particles is melt-extruded at a T-die temperature of 230 ° C., closely adhered to a cast roll whose temperature is controlled at 35 ° C., and has a thickness of 250 ⁇ m.
  • An unstretched sheet was obtained.
  • the end of the unstretched film is gripped with a clip of a simultaneous biaxial stretching machine, preheated at 70 ° C., and then stretched at 70 ° C. to 3.0 times MD and 3.3 times TD.
  • simultaneous biaxial stretching was performed. Then, after a heat treatment for 4 seconds at a temperature of 140 ° C.
  • Example 3 Polymerization of lactide was carried out in the same manner as in Example 1, except that the types of raw material lactide and inorganic particles, mixing / polymerization conditions, the type of dilution resin and the dilution ratio were changed as shown in Tables 1 to 3. In addition, dilution and film forming were performed in the same manner as in Example 2.
  • silica SY-310P
  • Comparative Example 2 the raw material inorganic particles were silica. (SO-C5) was dried and the moisture content was 80 ppm.
  • a crystal nucleating agent was added during the polymerization of lactide.
  • Comparative Example 1 A film was formed in the same manner as in Example 2 using the dilute polylactic acid resin (S-6) alone.
  • Comparative Example 5 After dry blending 95 parts by weight of polylactic acid resin (S-6) for dilution and 5 parts by weight of silica (SO-C5), PCM-30 type twin screw extruder (screw diameter 30 mm ⁇ , average groove) Using a depth of 2.5 mm), a resin composition was obtained by melt kneading under the conditions of 190 ° C., screw rotation speed of 200 rpm, residence time of 1.6 minutes, and discharge of 250 g / min. The obtained resin composition was diluted and film-formed in the same manner as in Example 2.
  • Tables 1 to 3 show the properties after polymerization and the properties after dilution of the polylactic acid resin compositions obtained in Examples and Comparative Examples, and the properties of the obtained polylactic acid films.
  • the polylactic acid-based resin composition obtained by polymerizing lactide in the presence of inorganic particles obtained in Examples 1 to 20 has good dispersibility of the inorganic particles. Even if inorganic particles are diluted with a polylactic acid-based resin for dilution and then formed into a film, it has excellent operability during extrusion film formation and stretching. The resulting polylactic acid-based film is transparent and slippery. It was excellent in dimensional stability.
  • a film formed from a polylactic acid-based resin to which inorganic particles are not added is inferior in slip property, and when the film is wound, the films are likely to block each other, Was seen.
  • Comparative Example 2 since the content of inorganic particles present when polymerizing lactide was too large, inorganic particles aggregated during the polymerization, and the resulting resin composition had an inorganic particle size of 1 ⁇ m or less. The proportion of particles was less than 50%. Even if the resin composition is diluted with a polylactic acid-based resin for dilution, the aggregated inorganic particles are clogged in the filter during film formation, or the film is cut during stretching because of low dispersibility. It was inferior to. Moreover, the obtained film was inferior in transparency, and since the inorganic particles were not uniformly dispersed, the slip property was also inferior.
  • the resin compositions obtained in Comparative Examples 3 to 4 also had the same problems as Comparative Example 2 because the proportion of inorganic particles having a particle diameter of 1 ⁇ m or less was less than 50%.
  • the resin composition of Comparative Example 5 was obtained by mixing and melting and kneading inorganic particles with a prepolymerized polylactic acid resin, the dispersibility of the inorganic particles was inferior and the particle diameter was 1 ⁇ m or less. The proportion of inorganic particles was less than 50%. Although this resin composition was excellent in extrusion operability and stretching operability, the obtained film was inferior in transparency and slip property.
  • the resin composition of Comparative Example 6 had a low melting point and poor heat resistance because the D-form content of the polylactic acid resin deviated from the range specified in the present invention. Therefore, curl was observed when the stretched film was wound, and the obtained film was inferior in dimensional stability.

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Abstract

Une composition de résine d'acide polylactique qui contient une résine d'acide polylactique et des particules inorganiques. Cette composition de résine d'acide polylactique est caractérisée en ce que la teneur en forme D dans la résine d'acide polylactique n'est pas supérieure à 2,0% en mole ou inférieure à 98,0% en mole, la teneur en particules inorganiques dans la composition de résine est de 0,001 à 10% en masse et le rapport de particules inorganiques ayant un diamètre de particule de 1 µm ou moins parmi les particules inorganiques dans la composition de résine est de 50 % ou plus.
PCT/JP2013/057125 2012-03-19 2013-03-14 Composition de résine d'acide polylactique et film d'acide polylactique obtenu par moulage de celle-ci WO2013141126A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018012583A1 (fr) * 2016-07-14 2018-01-18 株式会社カネカ Procédé de production de composition de résine de polyester aliphatique
CN116060090A (zh) * 2021-10-31 2023-05-05 中国石油化工股份有限公司 一种乳酸制丙交酯的催化剂及其合成方法和应用

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JPH08193124A (ja) * 1995-01-13 1996-07-30 Kanebo Ltd ポリ乳酸の製造方法
JP2001059029A (ja) * 1999-08-23 2001-03-06 Mitsubishi Plastics Ind Ltd 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
JP2002220541A (ja) * 2001-01-29 2002-08-09 Toyo Ink Mfg Co Ltd 樹脂組成物、及び該樹脂組成物を用いて成る成形物
JP2003025427A (ja) * 2001-07-19 2003-01-29 Unitika Ltd ポリ乳酸系二軸延伸フィルム
JP2005054002A (ja) * 2003-08-08 2005-03-03 Toray Ind Inc 脂肪族ポリエステル組成物およびそれからなるフイルム
JP2006008972A (ja) * 2004-05-26 2006-01-12 Kri Inc 樹脂組成物、樹脂成型体、及び樹脂成型体の製造方法
JP2008019338A (ja) * 2006-07-12 2008-01-31 Asahi Kasei Chemicals Corp 防汚性艶消しフィルムまたはシート
WO2010131678A1 (fr) * 2009-05-12 2010-11-18 日産化学工業株式会社 Procédé pour la production de fines particules de sel métallique de l'acide phosphonique

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08193124A (ja) * 1995-01-13 1996-07-30 Kanebo Ltd ポリ乳酸の製造方法
JP2001059029A (ja) * 1999-08-23 2001-03-06 Mitsubishi Plastics Ind Ltd 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
JP2002220541A (ja) * 2001-01-29 2002-08-09 Toyo Ink Mfg Co Ltd 樹脂組成物、及び該樹脂組成物を用いて成る成形物
JP2003025427A (ja) * 2001-07-19 2003-01-29 Unitika Ltd ポリ乳酸系二軸延伸フィルム
JP2005054002A (ja) * 2003-08-08 2005-03-03 Toray Ind Inc 脂肪族ポリエステル組成物およびそれからなるフイルム
JP2006008972A (ja) * 2004-05-26 2006-01-12 Kri Inc 樹脂組成物、樹脂成型体、及び樹脂成型体の製造方法
JP2008019338A (ja) * 2006-07-12 2008-01-31 Asahi Kasei Chemicals Corp 防汚性艶消しフィルムまたはシート
WO2010131678A1 (fr) * 2009-05-12 2010-11-18 日産化学工業株式会社 Procédé pour la production de fines particules de sel métallique de l'acide phosphonique

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018012583A1 (fr) * 2016-07-14 2018-01-18 株式会社カネカ Procédé de production de composition de résine de polyester aliphatique
CN116060090A (zh) * 2021-10-31 2023-05-05 中国石油化工股份有限公司 一种乳酸制丙交酯的催化剂及其合成方法和应用
CN116060090B (zh) * 2021-10-31 2024-05-07 中国石油化工股份有限公司 一种乳酸制丙交酯的催化剂及其合成方法和应用

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