WO2015020120A1 - Composition de résine contenant de l'acide polylactique - Google Patents

Composition de résine contenant de l'acide polylactique Download PDF

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WO2015020120A1
WO2015020120A1 PCT/JP2014/070805 JP2014070805W WO2015020120A1 WO 2015020120 A1 WO2015020120 A1 WO 2015020120A1 JP 2014070805 W JP2014070805 W JP 2014070805W WO 2015020120 A1 WO2015020120 A1 WO 2015020120A1
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polylactic acid
acid resin
resin composition
metal salt
parts
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PCT/JP2014/070805
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English (en)
Japanese (ja)
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洋平 椛島
淳一 三井
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ユニチカ株式会社
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Priority to JP2015530938A priority Critical patent/JPWO2015020120A1/ja
Publication of WO2015020120A1 publication Critical patent/WO2015020120A1/fr

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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable

Definitions

  • the present invention relates to a polylactic acid resin composition capable of producing a molded article having a high crystallization speed and excellent heat resistance in a short time.
  • biodegradable polylactic acid resin has attracted attention from the viewpoint of environmental conservation.
  • Polylactic acid is a crystalline polymer, has a higher melting point and higher heat resistance than other biodegradable polyester resins.
  • Polylactic acid can be mass-produced, so the cost is low and its usefulness is high.
  • polylactic acid can be produced using plants such as corn and sweet potato as raw materials, and can contribute to saving of depleted resources such as oil.
  • the polylactic acid resin has a problem that the crystallization speed is extremely slow and the molding cycle becomes long in order to obtain a molded body that is sufficiently crystallized practically. Therefore, in order to improve the crystallization rate, it has been studied to add various crystal nucleating agents to the polylactic acid resin.
  • Patent Document 1 proposes an aromatic sulfonate having an average particle diameter adjusted to a range of 0.1 to 10 ⁇ m as a crystal nucleating agent for polylactic acid resin, and polylactic acid resin to which the crystal nucleating agent is added.
  • the composition is shown.
  • the crystal nucleating agent is uniformly dispersed in the resin.
  • the surface area becomes larger as the particle size becomes smaller and the effect is more easily achieved, it is preferable to use a crystal nucleating agent having a smaller particle size.
  • a crystal nucleating agent having a small particle size is likely to aggregate when added and kneaded in the resin, making it difficult to uniformly disperse in the resin.
  • Patent Document 1 describes that it is substantially preferable to use a crystal nucleating agent having an average particle size of 0.5 ⁇ m or more.
  • a crystal nucleating agent having such a particle size is simply referred to as polylactic acid resin. It is described that the resin composition was obtained by mixing. In such a polylactic acid resin composition described in Patent Document 1, there is a high possibility that the crystal nucleating agent is aggregated, and a resin composition in which the crystal nucleating agent having a sufficiently small average particle diameter is uniformly dispersed is obtained. It wasn't. For this reason, the polylactic acid resin composition described in the cited document 1 is not sufficient in improving the crystal performance.
  • the present invention solves the above problems, and is a resin composition in which a crystal nucleating agent having a sufficiently small particle size is uniformly dispersed in a polylactic acid resin, and the crystal performance of the polylactic acid resin It is a technical problem to provide a polylactic acid resin composition capable of obtaining a molded article that is sufficiently improved, has a high crystallization rate, and is excellent in heat resistance in a short time.
  • the gist of the present invention is as follows.
  • the number of dimethyl metal salts of 5-sulfoisophthalic acid (B) having a particle diameter of less than 0.1 ⁇ m, counted when observed with the above, is 5 or more in any of 10 fields of ultrathin sections.
  • a polylactic acid resin composition is injection-molded, and an ISO-compliant test specimen for measuring general physical properties (size: length ⁇ width ⁇ thickness: 80 mm ⁇ 10 mm ⁇ 4 mm) is molded.
  • a test piece A (size: length ⁇ width ⁇ thickness: 1 mm ⁇ 0.5 mm ⁇ 0.5 mm) is cut out from the test piece.
  • Five ultrathin sections (0.5 mm ⁇ 0.5 mm ⁇ 0.1 ⁇ m) having a thickness of 0.1 ⁇ m are cut out in a direction perpendicular to the length direction of the test piece A.
  • [4] A method for producing the polylactic acid resin composition according to [1] above, Pulverizing 5-sulfoisophthalic acid dimethyl metal salt (B) with a dry pulverizer in which the inner surface of the pulverizing cylinder and the material of the pulverizing medium are steel and / or ceramic, for 1 hour or more;
  • the pulverized product of 5-sulfoisophthalic acid dimethyl metal salt (B) obtained by the above process, together with the polylactic acid resin (A), has a screw L / D ratio of 20 to 60 and a screw rotation speed of 100 to A process for melt-kneading with a twin-screw extruder at 300 rpm, and a method for producing a polylactic acid resin composition.
  • the dimethyl metal salt of 5-sulfoisophthalic acid (B) having a sufficiently small particle size is uniformly dispersed in the polylactic acid resin (A).
  • the crystal performance of (A) is sufficiently improved, the crystallization speed is fast, and a molded article excellent in heat resistance can be obtained in a short time.
  • polylactic acid resin (A) when the D-form content is within a specific range, the steric regularity of polylactic acid resin is improved, so that the crystal performance is further improved, and the crystallization speed is faster.
  • the heat resistance of the obtained molded body is also superior.
  • the dispersibility of the 5-sulfoisophthalic acid dimethyl metal salt (B) can be further improved, so that the crystal performance of the resin composition can be further improved. it can.
  • the polylactic acid resin composition of the present invention is particularly suitable for injection molding applications, and it is possible to obtain injection molded articles such as electrical and electronic equipment parts and miscellaneous goods with high productivity, and these molded articles are heat resistant. Therefore, it can be used in a high temperature environment. And since the polylactic acid resin composition of this invention has a resin derived from a natural product as a main component, it can contribute to the saving of exhaustion resources, such as petroleum, and its industrial utility value is very high.
  • polylactic acid resin (A) constituting the polylactic acid resin composition of the present invention will be described.
  • polylactic acid resin (A) in the present invention poly (L-lactic acid), poly (D-lactic acid), and a mixture or copolymer thereof can be used.
  • the polylactic acid resin (A) is preferably mainly composed of poly (L-lactic acid), and the D-form content is preferably 1.0 mol% or less.
  • the polylactic acid resin (A) may be mainly composed of poly (D-lactic acid), and the D-form content is preferably 99.0 mol% or more. Furthermore, it is preferable that the D-form content is 0 to 0.6 mol% or 99.4 to 100 mol%.
  • the polylactic acid resin (A) has excellent crystal performance when the D-form content is within this range. Specifically, since the polylactic acid resin composition has a short molding cycle, the polylactic acid resin composition is excellent in moldability, and the resulting molded body has improved heat resistance. When the polylactic acid resin has a D-form content outside this range, the crystal performance is not sufficiently improved, and the polylactic acid resin composition does not improve moldability and improves the heat resistance of the resulting molded article. May be less effective.
  • the D-form content of the polylactic acid resin (A) is a ratio (mol%) of the D-lactic acid unit in the total lactic acid units constituting the polylactic acid resin (A). Therefore, for example, in the case of a polylactic acid resin (A) having a D-form content of 1.0 mol%, this polylactic acid resin (A) has a ratio of D-lactic acid units of 1.0 mol%, and L -The proportion of lactic acid units is 99.0 mol%.
  • the D-form content of the polylactic acid resin (A) is such that all of L-lactic acid and D-lactic acid obtained by decomposing the polylactic acid resin (A) are methyl esters, as will be described later in Examples. And calculated by a method of analyzing the methyl ester of L-lactic acid and the methyl ester of D-lactic acid with a gas chromatography analyzer.
  • polylactic acid resin (A) used in the present invention various commercially available polylactic acid resins can be used, and those having a D-form content in the above range are preferably used.
  • a polymer obtained by polymerizing a cyclic dimer of lactic acid can also be used.
  • lactides L-lactide having a sufficiently low D-form content or D-lactide having a sufficiently low L-form content is used as a raw material. It is preferable to use a product prepared by a known melt polymerization method or further using a solid phase polymerization method in combination.
  • polylactic acid resin (A) of the present invention polyglycolic acid, polycaprolactone, polybutylene succinate, polyethylene succinate, polybutylene adipate are used as subcomponents as long as the effects of the present invention are not impaired.
  • One or two or more resins selected from terephthalate, polybutylene succinate terephthalate, and the like may be contained.
  • the polylactic acid resin composition of the present invention contains 5-sulfoisophthalic acid dimethyl metal salt (B).
  • the polylactic acid resin (A) has improved crystal performance, and the polylactic acid resin composition has a shorter molding cycle when obtaining a molded body, It becomes possible to obtain a molded body excellent in heat resistance.
  • the content of 5-sulfoisophthalic acid dimethyl metal salt (B) is required to be 0.01 to 10 parts by mass with respect to 100 parts by mass of the polylactic acid resin (A). Part by mass is preferable, and 0.1 to 5 parts by mass is more preferable.
  • the content of 5-sulfoisophthalic acid dimethyl metal salt (B) is less than 0.01 parts by mass, the effect of promoting crystallization is poor.
  • the amount exceeds 10 parts by mass the crystallization promoting effect is saturated, which is not only economically disadvantageous, but also may adversely affect the physical properties such as lowering the strength of the obtained molded product.
  • the finely divided dimethyl 5-sulfoisophthalic acid metal salt (B) is uniformly dispersed in the polylactic acid resin (A).
  • the number of 5-sulfoisophthalic acid dimethyl metal salts (B) having a particle size of less than 0.1 ⁇ m, counted when observed under the following condition (1) is an ultrathin slice. In any of the 10 fields of view, it is necessary that the number is 5 or more, preferably 8 or more, and more preferably 10 or more.
  • Condition (1) is that a polylactic acid resin composition is injection-molded, a test piece for measuring general physical properties (size; length ⁇ width ⁇ thickness: 80 mm ⁇ 10 mm ⁇ 4 mm) in conformity with ISO is tested from the test piece A piece A (size; length ⁇ width ⁇ thickness: 1 mm ⁇ 0.5 mm ⁇ 0.5 mm) was cut out, and an ultrathin section (0 ⁇ m thick) in a direction perpendicular to the length direction of the test piece A (0 ⁇ m) .5 mm ⁇ 0.5 mm ⁇ 0.1 ⁇ m), the conditions for preparing ultrathin sections, and each of the five sections, using a transmission electron microscope (TEM), with a magnification of 30,000 times, 5 ⁇ m It consists of the condition of observing two fields of view of a 5 ⁇ m field arbitrarily and observing a total of 10 fields.
  • TEM transmission electron microscope
  • the polylactic acid resin composition when injection-molded, it is preferably injection-molded using a FANUC injection molding machine ( ⁇ -100iA) under the conditions of a cylinder temperature of 190 ° C. and a mold temperature of 95 ° C.
  • the particle diameter in dimethyl metal 5-sulfoisophthalate (B) refers to the major axis diameter.
  • Such a polylactic acid resin composition in which the dimethyl metal salt of 5-sulfoisophthalic acid (B) finely dispersed in the polylactic acid resin (A) is uniformly dispersed employs the method described in detail below. It is preferable to manufacture. That is, the polylactic acid resin composition was obtained in a step of pulverizing 5-sulfoisophthalic acid dimethyl metal salt (B) under specific conditions using a dry pulverizer (pulverization step), and then in this step.
  • a pulverized product of 5-sulfoisophthalic acid dimethyl metal salt (B) and a polylactic acid resin (A) can be produced by a method including two steps of a melt kneading step (melt kneading step) under specific conditions. preferable.
  • a method for pulverizing 5-sulfoisophthalic acid dimethyl metal salt (B) using a dry pulverizer in a pulverization step an apparatus in which a material to be pulverized and a pulverization medium are rolled in a pulverization container is used.
  • dry pulverizers such as batch or continuous stirring mills, planetary mills, rotary ball mills, and vibration mills.
  • dimethyl 5-sulfoisophthalic acid metal salt (B) is pulverized into fine particles (pulverized product). At the same time, the obtained pulverized product has cracks.
  • the dry pulverizer is subjected to various forces such as impact, friction, compression, and shear. From the viewpoint of being able to act on an object in a composite manner, a vibration mill having a mechanism for vibrating a pulverizing cylinder and moving a pulverizing medium therein to pulverize is preferable.
  • the material of the inner surface of the grinding cylinder needs to be steel and / or ceramic for reasons of grinding efficiency.
  • the inner surface of the pulverizing cylinder may be coated with fluorine resin, silicon resin, urethane resin, or the like.
  • the shape of the grinding medium is preferably a ball, and the material needs to be steel and / or ceramic for reasons of grinding efficiency.
  • steel materials include carbon steel, chrome steel, and stainless steel, and ceramic materials include alumina, zirconia, and high-purity silica. Both materials are preferably carbon steel.
  • the filling rate of the grinding medium and the material to be ground is preferably 60 to 90% by volume, particularly 75 to 85% by volume of the volume of the grinding cylinder.
  • the filling rate is less than 60% by volume, it takes time to grind and the productivity tends to decrease.
  • the amount exceeds 90% by volume, the pulverization ability may decrease.
  • the pulverization time must be 1 hour or more, and preferably 2 to 6 hours. If the pulverization time is less than 1 hour, it is likely to be difficult to pulverize to a fine particle size or to provide cracks. On the other hand, even if pulverization is performed for more than 6 hours, it is difficult to further reduce the particle size, and productivity tends to decrease.
  • additives such as a grinding aid may be used in combination for the purpose of improving the grinding efficiency.
  • the grinding aid include alcohols such as methanol, ethanol and propanol, glycols such as propylene glycol and ethylene glycol, amines such as triethanolamine, higher fatty acids such as palmitic acid, stearic acid and oleic acid or the like.
  • metal materials such as carbon black, carbon black, graphite and the like, and these may be used alone or in combination of two or more.
  • dimethyl 5-sulfoisophthalate metal salt (B) is preferably pulverized to an average particle size of 1.0 ⁇ m or less, and more preferably pulverized to an average particle size of 0.8 ⁇ m or less, more preferably 0.5 ⁇ m or less. It is preferable.
  • the average particle diameter means a 50% volume diameter (median diameter) obtained by measurement by a laser diffraction / scattering method.
  • the pulverized product of finely divided dimethyl metal 5-sulfoisophthalate (B) obtained by the pulverization step has cracks due to impact during pulverization. Therefore, by the melt-kneading process described later, it is melt-kneaded with the polylactic acid resin (A) under specific conditions, so that it is pulverized to a finer particle size and finely divided into 5-sulfoisophthalic acid dimethyl metal salt (B ) Can be uniformly dispersed in the polylactic acid resin (A).
  • a polylactic acid resin (A) and a pulverized product of 5-sulfoisophthalic acid dimethyl metal salt (B) obtained by the pulverization step are melt-kneaded under specific conditions using a twin-screw extruder. It is. At this time, it is necessary to apply a sufficient shearing force with two screws. Therefore, it is necessary to set the L / D ratio, which is the ratio of the screw length (L) and the inner diameter (D), of the twin-screw extruder to 20 to 60 and the screw rotation speed to 100 to 300 rpm. .
  • the L / D ratio is preferably 30 to 60, and the screw rotation speed is preferably 150 to 280 rpm.
  • the pulverized product of 5-sulfoisophthalic acid dimethyl metal salt (B) which has been finely divided by the pulverization process and has cracks, is applied with an appropriate shear force. As a result, it is further pulverized mainly with the crack as a trigger.
  • the dimethyl metal salt of 5-sulfoisophthalic acid (B) after further microparticulation in this way is uniformly dispersed in the resin composition without agglomeration again when melt-kneaded under the above conditions. Is done.
  • the L / D ratio is less than 20 or the screw rotation speed is less than 100 rpm, even if the pulverized product of 5-sulfoisophthalic acid dimethyl metal salt (B) has cracks, It becomes difficult to further pulverize.
  • the L / D ratio exceeds 60 or the screw rotation speed exceeds 300 rpm, heat is excessively applied during melt-kneading, and thermal degradation of the polylactic acid resin (A) is promoted.
  • the polylactic acid resin composition of the present invention in which the dimethyl metal salt of 5-sulfoisophthalic acid (B) finely divided in the polylactic acid resin (A) is uniformly dispersed is obtained.
  • the polylactic acid resin composition of the present invention is obtained by uniformly dispersing a 5-sulfoisophthalic acid dimethyl metal salt (B) finely divided to a particle size of less than 0.1 ⁇ m in the resin without aggregation. As a result, it has excellent crystal performance.
  • the 5-sulfoisophthalic acid dimethyl metal salt (B) having a small average particle diameter is simply melted and kneaded with the polylactic acid resin, the 5-sulfoisophthalic acid dimethyl metal salt (B) will be contained in the polylactic acid resin. Since it aggregates, the polylactic acid resin composition of this invention cannot be obtained.
  • the polylactic acid resin composition of the present invention preferably contains a lubricant (C).
  • Lubricant (C) is generally called a lubricant, and is, for example, an external lubricant that is coated on the surface of the pellet, or an internal lubricant that is dispersed inside the pellet by being melt-kneaded. It is.
  • lubricants include hydrocarbon-based lubricants such as liquid paraffin, natural paraffin, and low molecular weight polyethylene, fatty acid-based lubricants such as higher fatty acids and oxyfatty acids, fatty acid amide-based lubricants such as fatty acid amide, alkylene bis fatty acid amide, As ester lubricants, lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids, etc., aliphatic alcohols, polyhydric alcohols, polyglycols, polyglycerols, etc. as alcohol lubricants, Examples include metal soap lubricants. Among these, from the viewpoint of dispersibility and moldability, hydrocarbon-based lubricants are preferable, and liquid paraffin is more preferable.
  • liquid paraffin commercially available products include Diana Process Oil PW-380 and PW-150 manufactured by Idemitsu Kosan Co., Ltd., and Moresco White P-80 and P-100 manufactured by MORESCO.
  • the lubricant (C) it is preferable to coat the surface of the polylactic acid resin (A). That is, by coating the surface of the polylactic acid resin (A) before melt-kneading and then adding 5-sulfoisophthalic acid dimethyl metal salt (B) to the melt-kneading step, 5-sulfoisophthalic acid is obtained. Dispersion of the dimethyl metal salt (B) can be suppressed, and the dispersibility of the dimethyl metal salt of 5-sulfoisophthalic acid (B) in the polylactic acid resin (A) after melt-kneading has also been improved. As a result, it becomes easy to uniformly disperse, and as a result, the crystal performance of the polylactic acid resin composition is also improved.
  • the content of the lubricant (C) is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, with respect to 100 parts by mass of the polylactic acid resin (A). If it is less than 0.05 parts by mass, the effect of preventing scattering and improving dispersibility of the dimethyl metal salt of 5-sulfoisophthalic acid (B) becomes poor. On the other hand, if it exceeds 3 parts by mass, the dimethyl metal salt of 5-sulfoisophthalic acid (B) may be aggregated, which is not preferable.
  • the resin composition of this invention may contain other resin components other than polylactic acid resin (A) in the range which does not impair the effect of this invention.
  • the resin composition of this invention and another resin component can also be mix
  • Such other resin components include polyamide, polyethylene, polypropylene, polybutadiene, polystyrene, acrylonitrile / styrene copolymer resin, acrylonitrile / butadiene / styrene copolymer resin, poly (acrylic acid), poly (acrylic ester), poly Non-aliphatic polyester resins such as (methacrylic acid), poly (methacrylic acid ester), polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and copolymers thereof.
  • the polylactic acid resin composition of the present invention includes pigments, heat stabilizers, antioxidants, inorganic fillers, plant fibers, reinforcing fibers, weathering agents, release agents, charging agents, as long as the properties are not impaired. Additives such as inhibitors, impact resistance improvers, plasticizers, and reactive compounds can be added.
  • pigment examples include titanium and carbon black.
  • heat stabilizers and antioxidants include hindered phenols, hindered amines, sulfur compounds, copper compounds, alkali metal halides, and the like.
  • Examples of the inorganic filler include talc, mica, calcium carbonate, zinc carbonate, wollastonite, alumina, magnesia, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon black, Examples include zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fiber, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite, carbon fiber, and layered silicate.
  • blending talc the heat resistance of a polylactic acid resin composition and a molding cycle can be improved, improving mechanical characteristics, such as a bending elastic modulus.
  • the content of talc is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the polylactic acid resin (A).
  • the gas barrier property of a polylactic acid resin composition can be improved by mix
  • Examples of plant fibers include kenaf fibers, bamboo fibers, jute fibers, and other cellulosic fibers.
  • Examples of reinforcing fibers include organic reinforcing fibers such as aramid fibers, polyarylate fibers, and liquid crystal polymer fibers.
  • Examples of weathering agents include benzotriazole and benzoxazinone.
  • As the mold release agent various carboxylic acid compounds, particularly, various fatty acid esters, various fatty acid amides, and the like are preferably used.
  • the impact resistance improver is not particularly limited, and various types such as a (meth) acrylic ester impact resistance agent having a core-shell structure can be used.
  • plasticizer examples include glycerin diacetomonolaurate, glycerin diacetomonocaprate, polyglycerin acetate, polyglycerin fatty acid ester, medium chain fatty acid triceride, dimethyl adipate, dibutyl adipate, triethylene glycol diacetate, methyl acetylricinoleate Acetyltributylcitric acid, polyethylene glycol, dibutyldiglycol succinate, bis (butyldiglycol) adipate, bis (methyldiglycol) adipate, adipic acid ester and the like.
  • the content of the plasticizer is preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the polylactic acid resin (A) from the viewpoints of heat resistance, flame retardancy, and flexibility.
  • a carbodiimide compound is preferable.
  • the heat-and-moisture resistance is improved, the compatibility by melt kneading is further improved, and the mechanical properties are also improved.
  • Various compounds can be used as the carbodiimide compound, and there are no particular limitations as long as it has one or more carbodiimide groups in the molecule.
  • the carbodiimide compound include aliphatic monocarbodiimide, aliphatic polycarbodiimide, alicyclic monocarbodiimide, alicyclic polycarbodiimide, aromatic monocarbodiimide, aromatic polycarbodiimide, and the like.
  • the addition amount of the carbodiimide compound is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polylactic acid resin (A). If the addition amount is less than 0.1 parts by mass, the desired moist heat resistance may not be obtained, and if the addition amount exceeds 10 parts by mass, the heat resistance is lowered and is not economically preferable. The color tone may be greatly impaired.
  • the polylactic acid resin composition of the present invention has improved crystal performance as described above, but in order to exhibit the excellent performance of such a resin composition of the present invention, it is necessary to obtain a molded product. It is preferable to employ a method for sufficiently promoting crystallization. That is, it is preferable to obtain a molded body by increasing the heat treatment temperature, the mold temperature, etc. during molding to a high temperature (about 80 to 110 ° C.) to actively promote crystallization.
  • the polylactic acid resin composition of the present invention can be formed into various molded products by injection molding, blow molding, extrusion molding, inflation molding, and molding methods such as vacuum molding, pressure molding, and vacuum / pressure molding after sheet processing. .
  • it is suitable for the injection molding method, and can be used for gas injection molding, injection press molding, etc. in addition to general injection molding.
  • the cylinder temperature is preferably 180 to 260 ° C, more preferably 190 to 250 ° C.
  • the mold temperature is preferably 70 ° C. or higher, and more preferably 80 to 110 ° C.
  • molded body obtained from the polylactic acid resin composition of the present invention include personal computer casing parts and casings, cellular phone casing parts and casings, and other appliances such as OA equipment casing parts and connectors.
  • Resin parts Automotive resin parts such as bumpers, instrument panels, console boxes, garnishes, door trims, ceilings, floors, and panels around engines; agricultural materials such as containers and cultivation containers; and resin parts for agricultural machinery; Resin parts for marine products such as food containers; dishes and food containers such as dishes, cups, spoons; medical resin parts such as syringes and infusion containers; houses, civil engineering, and drainage materials, fences, storage boxes, construction switchboards, etc.
  • polylactic acid resin (A) 0.3 g of polylactic acid resin (A) was weighed and added to 6 ml of 1N potassium hydroxide / methanol solution and sufficiently stirred at 65 ° C. Next, 450 ⁇ l of sulfuric acid was added and stirred at 65 ° C., the polylactic acid resin was decomposed and methyl esterified, and 5 ml was measured as a sample. To this sample, 3 ml of pure water and 13 ml of methylene chloride were mixed and shaken.
  • Heat resistance heat distortion temperature
  • the deflection temperature under load was measured according to ISO 75-1 at a load of 0.45 MPa.
  • the heat distortion temperature is preferably 100 ° C. or higher.
  • Bending strength and bending elastic modulus were measured in accordance with ISO178 using a test piece prepared in the same manner as in (2) above.
  • the bending strength is preferably 90 MPa or more, and more preferably 100 MPa or more.
  • the flexural modulus is preferably 4.0 GPa or more, and more preferably 8 GPa or more.
  • A2: Toyota Motor Corporation S-12 D body content 0.1 mol%
  • A-1 D body content 0.6 mol%
  • the median diameter of dimethyl metal 5-sulfoisophthalate (B) was measured as follows.
  • a dispersion obtained by mixing 0.02 g of dimethyl metal salt of 5-sulfoisophthalic acid with 30 mL of isopropyl alcohol (IPA) was prepared in a beaker, and an ultrasonic homogenizer (QUICK HOMO MIXER LR-1, manufactured by Mizuho Kogyo Co., Ltd.) The dispersion process was performed for 10 minutes at an output of 220 W).
  • a laser diffraction / scattering particle size distribution measuring apparatus LA-920, manufactured by Horiba, Ltd.
  • the particle size distribution was measured while diluting the dispersion in IPA so as to obtain a concentration suitable for the measurement.
  • the particle size distribution was obtained on a volume basis, and the median diameter was calculated.
  • the refractive index of IPA was 1.38
  • the refractive index of 5-sulfoisophthalic acid dimethyl metal salt was 1.60
  • the relative refractive index of 5-sulfoisophthalic acid dimethyl metal salt in IPA was 1.16.
  • Lubricant (C) -Liquid paraffin P-80 manufactured by MORESCO (4) Grinding aid / higher fatty acid metal salt: Magnesium stearate manufactured by Taihei Chemical Industry Co., Ltd. (5) Inorganic filler / talc: MW-HST manufactured by Hayashi Kasei Co., Ltd. (6) Reactive compound / carbodiimide compound: EN-160 manufactured by Matsumoto Yushi Seiyaku Co., Ltd.
  • Example 1 (Crushing process) As a dry pulverizer, a dry vibration mill pulverizer (FV-20, the inner surface of the pulverizing cylinder and the material of the pulverizing medium is carbon steel) manufactured by Chuo Kakoki Co., Ltd. is used.
  • the dimethyl metal salt B1 was ground (grinding condition 10) to obtain a ground product B10 of dimethyl metal 5-sulfoisophthalate having a median diameter of 0.4 ⁇ m.
  • A1 was used as the polylactic acid resin (A), and B10 was used as a pulverized product of the dimethyl metal salt of 5-sulfoisophthalic acid (B).
  • Examples 2-7, Comparative Examples 1-2 A polylactic acid resin composition was obtained in the same manner as in Example 1 except that the ratios of the polylactic acid resin A1 and the pulverized product B10 were changed to those shown in Tables 1 and 2.
  • Example 8 (Crushing process) The mixture was pulverized under the same conditions as in pulverization condition 10 (pulverization condition 11) except that 20 parts by mass of magnesium stearate was added to 100 parts by mass of dimethyl metal 5-sulfoisophthalate (B1). The obtained pulverized product B11 had a median diameter of 0.3 ⁇ m. (Melting and kneading process) A polylactic acid resin composition was obtained in the same manner as in Example 1 except that B11 was used as a pulverized product of dimethyl 5-sulfoisophthalate metal salt (B).
  • Examples 9-12, Comparative Example 3 (Crushing process) As shown in Tables 1 and 2, pulverization was performed under the same conditions as the pulverization condition 10 (pulverization conditions 12 to 16) except that the pulverization time was 0.5, 1, 5, 6, and 7 hours.
  • the obtained pulverized product B12 had a median diameter of 2.0 ⁇ m, B13 of 1.0 ⁇ m, and B14 to B16 of 0.3 ⁇ m.
  • B12 to B16 were used as pulverized products of dimethyl 5-sulfoisophthalate metal salt (B).
  • Example 13 (Crushing process) As a dry pulverizer, a dry vibration mill pulverizer (FM-20, the material of the inner surface of the pulverizing cylinder is alumina and the material of the pulverizing medium is zirconia) manufactured by Chuo Kakoki Co., Ltd. is used. -Dimethyl sulfoisophthalate metal salt B1 was pulverized (grinding condition 17) to obtain pulverized product B17 of dimethyl metal 5-sulfoisophthalate metal salt having a median diameter of 0.4 ⁇ m. (Melting and kneading process) A polylactic acid resin composition was obtained in the same manner as in Example 1 except that B17 was used as a pulverized product of 5-sulfoisophthalic acid dimethyl metal salt (B).
  • FM-20 dry vibration mill pulverizer
  • the material of the inner surface of the pulverizing cylinder is alumina and the material of the pulverizing medium is zirconia
  • Example 14 (Crushing process) The pulverization medium was pulverized under the same conditions as the pulverization condition 10 except that the material was alumina (pulverization condition 18). The obtained pulverized product B18 had a median diameter of 1.0 ⁇ m. (Melting and kneading process) A polylactic acid resin composition was obtained in the same manner as in Example 1 except that B18 was used as a pulverized product of dimethyl 5-sulfoisophthalate metal salt (B).
  • Melting and kneading condition 31 L / D ratio 20 and screw rotation speed 150 rpm
  • Melt-kneading condition 32 L / D ratio of 30, screw rotation speed 150 rpm
  • Melting and kneading condition 33 L / D ratio 60
  • Melt-kneading condition 34 L / D ratio 49
  • Melting and kneading condition 35 L / D ratio 40, screw rotation speed 250 rpm
  • Example 20 (Crushing process) The pulverized product B14 was obtained under the pulverization condition 14. (Melting and kneading process) A polylactic acid resin composition was obtained in the same manner as in Example 10 except that the melt-kneading was performed under the melt-kneading conditions 35.
  • Example 21 A pulverized product of 5-sulfoisophthalic acid dimethyl metal salt having a median diameter of 0.4 ⁇ m and pulverized under the same conditions as pulverizing condition 10 except that 5-sulfoisophthalic acid dimethyl metal salt B2 was used. B20 was obtained. (Melting and kneading process) A polylactic acid resin composition was obtained in the same manner as in Example 1 except that B20 was used as a pulverized product of 5-sulfoisophthalic acid dimethyl metal salt (B).
  • Examples 22 to 28 A polylactic acid resin composition was obtained in the same manner as in Example 1 except that the polylactic acid resin (A), the type and ratio of the pulverized product, and the melt-kneading conditions were changed to those shown in Table 1.
  • melt-kneading condition 36 is an L / D ratio 49 and a screw rotation speed 280 rpm
  • melt-kneading condition 37 is an L / D ratio 49 and a screw rotation speed 300 rpm.
  • Comparative Examples 4-9 (Crushing process) In Comparative Examples 4 to 9, the dimethyl metal salt of 5-sulfoisophthalic acid (B) was used as it was in the melt-kneading step without being pulverized.
  • Example 1 except that polylactic acid resin (A), 5-sulfoisophthalic acid dimethyl metal salt (B), lubricant (C) and additive amount, and melt kneading conditions were changed to those shown in Table 2. In the same manner as above, a polylactic acid resin composition was obtained.
  • melt-kneading condition 39 is an L / D ratio of 10 and a screw rotation speed of 150 rpm
  • melt-kneading condition 40 is an L / D ratio of 70 and a screw rotation speed of 150 rpm
  • melt-kneading condition 41 is an L / D ratio of 49 and screw rotation.
  • melt-kneading conditions 42 are L / D ratio 49, screw rotation speed 400rpm.
  • compositions and properties of the polylactic acid resin compositions obtained in Examples 1 to 28 are shown in Table 1, and the compositions and properties of the polylactic acid resin compositions obtained in Examples 29 to 41 and Comparative Examples 1 to 20 are shown in Table 2. Shown in
  • the polylactic acid resin compositions obtained in Examples 1 to 41 had a particle size in any of 10 fields of ultrathin sections when observed under condition (1). Since the number of 5-sulfoisophthalic acid dimethyl metal salts (B) of less than 0.1 ⁇ m is counted five or more, the crystal performance is excellent, and any of the molding cycle, half-crystallization time, and heat distortion temperature It was also excellent.
  • the polylactic acid resin compositions obtained in Examples 29 to 31, 36, and 38 to 41 contained the lubricant (C), the dispersion of dimethyl metal salt of 5-sulfoisophthalic acid (B) As a result, the crystal performance (molding cycle, semi-crystallization time, heat distortion temperature) was improved.
  • the polylactic acid resin compositions obtained in Examples 37 to 41 contained talc, the bending strength and the flexural modulus were improved, and the crystal performance (molding cycle, heat distortion temperature) was also improved.
  • the polylactic acid resin compositions obtained in Examples 32-36 and 38-41 contained a carbodiimide compound, they were excellent in heat and humidity resistance.
  • the polylactic acid resin composition obtained in Comparative Example 1 contained too little dimethyl 5-sulfoisophthalate metal salt (B), so that when viewed under condition (1), the field of view of the ultrathin section was The number of dimethyl metal salts of 5-sulfoisophthalic acid (B) having a particle size of less than 0.1 ⁇ m may be less than 5, and crystal performance (molding cycle, semi-crystallization time, heat distortion temperature) It was inferior to.
  • the polylactic acid resin composition obtained in Comparative Example 2 has too much content of 5-sulfoisophthalic acid dimethyl metal salt (B), so that the crystallization promoting effect is saturated, and the bending strength and the bending elastic modulus are low. It became.
  • the number of 5-sulfoisophthalic acid dimethyl metal salts (B) having a particle diameter of less than 0.1 ⁇ m counted in (1) may be less than 5, and the crystal performance is inferior.
  • the polylactic acid resin composition of Comparative Example 14 using a screw having an L / D ratio that is too high and Comparative Example 19 having a screw rotation speed that is too high are excessively heated during melt kneading.
  • the thermal degradation of the lactic acid resin (A) was promoted, and the heat and humidity resistance was reduced as compared with Examples 17 and 35, respectively.

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  • 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)

Abstract

　La présente invention se rapporte à une composition de résine contenant de 0,01 à 10 parties en masse d'un sel métallique (B) diméthyle d'acide 5-sulfo-isophtalatique pour 100 parties en masse d'une résine d'acide polylactique (A); cinq ou plus de cinq particules du sel métallique (B) diméthyle d'acide 5-sulfo-isophtalatique ayant une granulométrie inférieure à 0,1 µm étant présentes dans n'importe quel champ de vision de 10 degrés d'une lamelle ultra-mince.
PCT/JP2014/070805 2013-08-07 2014-08-07 Composition de résine contenant de l'acide polylactique WO2015020120A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10662327B2 (en) * 2016-10-28 2020-05-26 GranBio Intellectual Property Holdings, LLC Nanocellulose nucleating agents for crystallization of polylactides and other polymers

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0673245A (ja) * 1992-05-19 1994-03-15 Chisso Corp 難燃性ポリプロピレン樹脂組成物及び製造方法
JP2001046474A (ja) * 1999-08-10 2001-02-20 Showa Denko Kk 輸液用容器
WO2009004769A1 (fr) * 2007-06-29 2009-01-08 Unitika Ltd. Composition de résine d'acide polylactique cristallin et corps moulé fait en cette résine
JP2010150365A (ja) * 2008-12-25 2010-07-08 Takemoto Oil & Fat Co Ltd ポリ乳酸樹脂用結晶核剤及びポリ乳酸樹脂組成物
JP2010248448A (ja) * 2009-04-20 2010-11-04 Toyota Motor Corp 脂肪族ポリエステル樹脂組成物及び脂肪族ポリエステル樹脂成形体
WO2011096299A1 (fr) * 2010-02-02 2011-08-11 花王株式会社 Procédé de fabrication d'une composition de résine d'acide polylactique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0673245A (ja) * 1992-05-19 1994-03-15 Chisso Corp 難燃性ポリプロピレン樹脂組成物及び製造方法
JP2001046474A (ja) * 1999-08-10 2001-02-20 Showa Denko Kk 輸液用容器
WO2009004769A1 (fr) * 2007-06-29 2009-01-08 Unitika Ltd. Composition de résine d'acide polylactique cristallin et corps moulé fait en cette résine
JP2010150365A (ja) * 2008-12-25 2010-07-08 Takemoto Oil & Fat Co Ltd ポリ乳酸樹脂用結晶核剤及びポリ乳酸樹脂組成物
JP2010248448A (ja) * 2009-04-20 2010-11-04 Toyota Motor Corp 脂肪族ポリエステル樹脂組成物及び脂肪族ポリエステル樹脂成形体
WO2011096299A1 (fr) * 2010-02-02 2011-08-11 花王株式会社 Procédé de fabrication d'une composition de résine d'acide polylactique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10662327B2 (en) * 2016-10-28 2020-05-26 GranBio Intellectual Property Holdings, LLC Nanocellulose nucleating agents for crystallization of polylactides and other polymers

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