JP2012136561A - Resin composition and molded article comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in characteristics such as moldability, impact resistance and heat resistance.SOLUTION: The resin composition comprises: 100 pts.wt. of a polylactic acid-based resin (A), 0.1 to 50 pts.wt. of a crystal-nucleating agent (B), and a polyglycerol fatty acid ester (C) in an amount of 0.1 to 300 pts.wt. per 100 pts.wt. of the crystal-nucleating agent (B), wherein, in the photograph of a transmission electron microscope, the average L/D [a value obtained by dividing a major axis direction length (L) by a minor axis direction length (D)] of (B) the crystal-nucleating agent in the resin composition is 10 or more, and the major axis direction length (L) of (B) the crystal-nucleating agent is 30 μm or less.

Description

  In the present invention, (A) 0.1 to 50 parts by weight of the crystal nucleating agent with respect to 100 parts by weight of the polylactic acid-based resin, and (C) polyglycerol with respect to 100 parts by weight of the crystal nucleating agent. The present invention relates to a resin composition comprising 0.1 to 300 parts by weight of a fatty acid ester and excellent in properties such as moldability, impact resistance and heat resistance, and a molded product comprising the same.

  In recent years, biodegradable polymers that are decomposed in the natural environment by the action of microorganisms existing in soil or water have attracted attention from the viewpoint of global environmental conservation, and various biodegradable polymers have been developed. Among these, biodegradable polymers that can be melt-formed include, for example, polyhydroxybutyrate, polycaprolactone, aliphatic dicarboxylic acid components such as succinic acid and adipic acid, and glycol components such as ethylene glycol and butanediol. Aliphatic polyesters and polylactic acid are well known. Among these, polylactic acid resin can be produced at low cost by fermentation using microorganisms, using lactic acid as a raw material for lactic acid as a raw material, and has a high melting point of about 170 ° C. It is expected as a possible biopolymer. However, since polylactic acid resin has a low crystallization rate, there is a limit to use it as a molded product after crystallization. For example, when polylactic acid resin is injection-molded, a long molding cycle time or heat treatment after molding is required. In addition to the need for a large amount of deformation, there is a large problem in practical use, such as large deformation during molding and heat treatment.

  As a method for improving this problem, a method of adding a crystal nucleating agent, a dispersing agent, and a crystallization accelerator has been conventionally studied.

  Patent Document 1 discloses a resin composition and an injection-molded product that contain a thermoplastic resin, a plasticizer, and a crystal nucleating agent and are excellent in moldability, heat resistance, and impact resistance. However, although it has some improvement effect on properties such as heat resistance and impact resistance, the moldability is still insufficient, and there is no disclosure about the dispersion of the crystal nucleating agent, and the moldability, impact resistance, heat resistance There is no suggestion of a solution for obtaining a resin composition that is excellent in both properties such as properties.

  Patent Document 2 discloses a resin composition that contains a polylactic acid resin, a plasticizer, and a crystal nucleating agent and is excellent in molding processability, impact resistance, heat resistance, and the like. However, there is no specific disclosure regarding properties such as moldability, impact resistance, and heat resistance, and a solution for obtaining a resin composition that is excellent in all of the characteristics such as moldability, impact resistance, and heat resistance. There is no suggestion about.

  Patent Document 3 discloses a sheet and a product containing a thermoplastic polymer, a nucleating agent, a dispersing agent, and a plasticizer and having excellent moldability and the like. However, there is no disclosure about properties such as injection moldability, impact resistance, and heat resistance, and there is no solution for obtaining a resin composition that is excellent in all of the characteristics such as moldability, impact resistance, and heat resistance. There is no suggestion.

  Patent Document 4 discloses a polylactic acid composition containing polylactic acid, polyglycerol fatty acid ester or polyglycerol condensed hydroxy fatty acid ester and having excellent thermal characteristics and flexibility. However, although it has some improvement effect on characteristics such as heat resistance, there is no disclosure about characteristics such as moldability and impact resistance, and it is excellent in all characteristics such as moldability, impact resistance and heat resistance. There is no suggestion of a solution for obtaining the resin composition.

  As described above, it is very difficult to obtain a resin composition that has excellent properties such as moldability, impact resistance, and heat resistance by using any method, but it can be used practically without problems. There are many requests for materials that can be made, and further improvements have been demanded.

JP 2009-91453 A (page 1-3, Examples) JP 2006-193561 A (page 1-9) JP 2003-523432 A (page 1-2, Examples) JP 2008-69299 A (page 1-2, Examples)

  This invention makes it a subject to provide the resin composition excellent in characteristics, such as a moldability, impact resistance, and heat resistance which were difficult in the prior art mentioned above, and a molded article consisting thereof.

  The present invention employs the following means in order to solve such problems.

That is, the present invention
(1) (B) 0.1 to 50 parts by weight of the crystal nucleating agent with respect to 100 parts by weight of the (A) polylactic acid resin, and (C) polyglycerol fatty acid with respect to 100 parts by weight of the (B) crystal nucleating agent. It is a resin composition formed by blending 0.1 to 300 parts by weight of an ester, and the average L / D (length in the major axis direction) of the (B) crystal nucleating agent in the resin composition in a transmission electron micrograph. (Value obtained by dividing (L) by the length in the short axis direction (D)) is 10 or more, (B) the resin composition in which the length (L) in the long axis direction of the crystal nucleating agent is 30 μm or less,
(2) The resin composition according to (1), wherein the (C) polyglycerol fatty acid ester is a polyglycerol fatty acid ester which is a fatty acid ester with polyglycerol and a fatty acid having 12 or more carbon atoms,
(3) The (C) polyglycerin fatty acid ester is a polyglycerin fatty acid ester which is a fatty acid ester of polyglycerin having an average degree of polymerization of 1.5 to 3 and stearic acid. Resin composition,
(4) The resin composition according to any one of (1) to (3), wherein the (B) crystal nucleating agent is talc.
(5) The resin composition according to any one of (1) to (4), wherein (B) a crystal nucleating agent and (C) a crystallization accelerator different from polyglycerin fatty acid ester are blended. object,
(6) A molded article comprising the resin composition according to any one of (1) to (5).

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition excellent in characteristics, such as a moldability, impact resistance, and heat resistance, and a molded article consisting thereof can be provided.

[(A) Polylactic acid resin]
In the present invention, the (A) polylactic acid-based resin is a polymer mainly composed of L-lactic acid and / or D-lactic acid, but may contain other copolymerization components other than lactic acid. Examples of such other copolymer component units include polyvalent carboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones, and the like. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid , Azelaic acid, sebacic acid, dodecanedioic acid, fumaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutyl Polycarboxylic acids such as phosphonium sulfoisophthalic acid, ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentylglyco Glycerin, pentaerythritol, bisphenol A, aromatic polyhydric alcohol obtained by addition reaction of bisphenol with ethylene oxide, polyhydric alcohols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycolic acid, Hydroxycarboxylic acids such as 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid, hydroxybenzoic acid, and glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ -Units generated from lactones such as butyrolactone, β- or γ-butyrolactone, pivalolactone, and δ-valerolactone. Such a copolymerized unit usually preferably has a content of 0 to 30 mol%, preferably 0 to 10 mol%, when the total monomer units are 100 mol%.

  In the present invention, it is preferable to use a polylactic acid resin having a high optical purity of the lactic acid component in terms of moldability and heat resistance. That is, among the total lactic acid components of the polylactic acid-based resin, it is preferable that the L isomer is contained at 80% or more, or the D isomer is contained at 80% or more, the L isomer is contained at 90% or more, or the D isomer is 90%. More preferably, the L-form is contained at 95% or more, or the D-form is contained at 95% or more, the L-form is contained at 98% or more, or the D-form is contained at 98% or more. Is most preferred. Moreover, the upper limit of the content of L-form or D-form is usually 100% or less.

  In the present invention, as the polylactic acid-based resin, it is preferable to use a polylactic acid stereocomplex in terms of moldability and heat resistance. As a method for forming a polylactic acid stereocomplex, for example, L-form is 90% or more, and in terms of heat resistance, preferably 95%, more preferably 98% or more poly-L-lactic acid, and D-form is 90%. From the viewpoint of heat resistance, preferably, 95%, more preferably 98% or more of poly-D-lactic acid can be mixed using a method such as melt kneading, solid phase kneading, or solution mixing. In addition, as another method, a method of forming a block copolymer composed of a poly-L-lactic acid segment and a poly-D-lactic acid segment can also be mentioned, and a polylactic acid stereocomplex can be easily formed. A method of preparing a block copolymer comprising a poly-L-lactic acid segment and a poly-D-lactic acid segment is preferred. In addition, the polylactic acid stereocomplex may be used alone, but the polylactic acid stereocomplex and poly-L-lactic acid or poly-D-lactic acid may be used in combination.

  In the present invention, as a method for producing a polylactic acid-based resin, a known polymerization method can be used, and a direct polymerization method from lactic acid, a ring-opening polymerization method via lactide, or the like can be used.

  In the present invention, the molecular weight and molecular weight distribution of the polylactic acid-based resin are not particularly limited as long as it can be substantially molded, but it is easy to control the phase structure and the impact resistance is improved. In this respect, the weight average molecular weight is preferably 10,000 or more, more preferably 50,000 or more, further preferably 100,000 or more, and particularly preferably 200,000 or more. The upper limit is not particularly limited, but is preferably 800,000 or less, more preferably 600,000 or less, and more preferably 400,000 or less. The weight average molecular weight herein is a weight average molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  In the present invention, the melting point of the polylactic acid resin is not particularly limited, but is preferably 120 ° C. or higher, and more preferably 150 ° C. or higher.

[(B) Crystal nucleating agent]
In the present invention, the (B) crystal nucleating agent is an inorganic crystal nucleating agent among inorganic crystal nucleating agents and organic crystal nucleating agents, and the organic crystal nucleating agent is described later (D). Included in crystallization accelerators.

  In the present invention, specific examples of the inorganic crystal nucleating agent include talc, kaolinite, montmorillonite, mica, synthetic mica, clay, zeolite, silica, graphite, carbon black, zinc oxide, magnesium oxide, calcium oxide, titanium oxide, Examples include calcium sulfide, boron nitride, magnesium carbonate, calcium carbonate, barium sulfate, aluminum oxide, neodymium oxide, and metal salts of phenylphosphonate, and talc, kaolinite, montmorillonite, Mica and synthetic mica are preferable, and talc is more preferable in terms of moldability. These may be used alone or in combination of two or more. These inorganic crystal nucleating agents are preferably modified with an organic substance in order to improve dispersibility in the resin composition.

  In the present invention, the D50 average particle size of the crystal nucleating agent (B) used as a raw material is preferably 0.001 to 20 μm, more preferably 0.01 to 10 μm, and preferably 0.1 to 1 μm. More preferably it is.

  In the present invention, it is preferable to improve the dispersibility of the (B) crystal nucleating agent in the resin composition in terms of moldability, impact resistance and heat resistance. The smaller the D50 average particle size, the better the dispersibility of the (B) crystal nucleating agent in the resin composition, which is more preferable in terms of moldability, impact resistance and heat resistance.

  In the present invention, (B) crystal nucleating agent and (C) polyglycerin fatty acid ester are added in combination, so that (B) in the resin composition is compared with the case where (C) polyglycerin fatty acid ester is not added. The dispersibility of the crystal nucleating agent can be further improved. The dispersibility of the (B) crystal nucleating agent in the resin composition here can be quantified by the average L / D of the (B) crystal nucleating agent described later.

  In this invention, 0.01-100 weight part is preferable with respect to 100 weight part of (A) polylactic acid resin, and, as for the compounding quantity of (B) crystal nucleating agent, 0.1-50 weight part is more preferable.

[(C) Polyglycerol fatty acid ester]
In the present invention, the (C) polyglycerol fatty acid ester is an ester obtained by an esterification reaction of polyglycerol and a fatty acid.

  In the present invention, (C) polyglycerol which is a constituent component of polyglycerol fatty acid ester is specifically shown, for example, diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, octaglycerol, nonaglycerol. Diglycerin, which is a polyglycerin having an average degree of polymerization of 1.5 to 5, diglycerin, triglycerin, tetraglycerin and pentaglycerin are preferred, and diglycerin which is a polyglycerin having an average degree of polymerization of 1.5 to 3. Triglycerin is more preferable, and diglycerin having an average degree of polymerization of 2 is particularly preferable.

  In the present invention, a fatty acid having 12 or more carbon atoms is used as the fatty acid which is the other component of the (C) polyglycerol fatty acid ester. Specifically, for example, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, nonadecanoic acid, arachidic acid, gadoleic acid, eicosadienoic acid, arachidonic acid, behenic acid , Erucic acid, docosadienoic acid, lignoceric acid, isostearic acid, ricinoleic acid, 12-hydroxystearic acid, 9-hydroxystearic acid, 10-hydroxystearic acid, hydrogenated castor oil fatty acid (small amount in addition to 12-hydroxystearic acid) Fatty acids containing stearic acid and palmitic acid), preferably palmitic acid, stearic acid, and oleic acid, which may be one or a mixture of two or more thereof.

  In the present invention, preferred specific examples of polyglycerin fatty acid ester obtained from polyglycerin and fatty acid ester include diglycerin palmitic acid ester, diglycerin stearic acid ester, diglycerin oleic acid ester, decaglycerin palmitic acid ester, decaglycerin stearin. Examples include acid esters and decaglycerin oleic acid esters, diglycerin stearic acid esters and diglycerin palmitic acid esters are preferred, and diglycerin stearic acid esters are more preferred.

  In the present invention, the method for producing (C) polyglycerol fatty acid ester is not particularly limited, but esterification reaction between polyglycerol and fatty acid, transesterification reaction between polyglycerol and fatty acid ester, polyglycerol and fat and oil For example, a polyglycerin fatty acid ester can be obtained by addition polymerization reaction of glycidol to a fatty acid without using polyglycerin, but the polyglycerin fatty acid ester used in the present invention is any However, an esterification reaction of polyglycerin and a fatty acid is preferable in terms of moldability, impact resistance and heat resistance.

  In the present invention, the esterification reaction of polyglycerin and fatty acid is performed at 100 ° C. to 300 ° C. in the presence of an alkali catalyst, an acid catalyst, or a non-catalyst under normal pressure, reduced pressure, or the presence of an inert gas using the above raw materials. It is preferable to carry out the reaction while heating in the range of ° C. In particular, the reaction is performed in the presence of an inert gas in the presence of an alkali catalyst or an acid catalyst in the range of 120 ° C to 260 ° C while removing the generated water from the system. It is preferable to do so. Further, it may be carried out in an azeotropic solvent such as toluene or xylene. At this time, the fatty acid esterification rate of the polyglycerol fatty acid ester is preferably 50% or more, and more preferably 60% or more.

  In the present invention, the (C) polyglycerol fatty acid ester may be purified as necessary. The purification method may be any known method and is not particularly limited. For example, purification by adsorption with activated carbon or activated clay, treatment under reduced pressure using water vapor or nitrogen as a carrier gas, washing with acid or alkali, or molecular distillation Alternatively, unreacted polyglycerin and the like may be separated and removed using liquid-liquid distribution, adsorbent, resin, molecular sieve, loose reverse osmosis membrane, ultrafiltration membrane, or the like.

  In this invention, the compounding quantity of (C) polyglycerol fatty acid ester is 0.1-300 weight part with respect to 100 weight part of (B) crystal nucleating agents, 10-150 weight part is more preferable, 30-100 Part by weight is more preferred.

[(B) Average L / D of crystal nucleating agent]
In the present invention, the average L / D of the (B) crystal nucleating agent is a quantification of the dispersibility of the (B) crystal nucleating agent in the resin composition, and using a transmission electron microscope (TEM). The resin composition was observed at a magnification of 2,000 times, and the shape of about 10 arbitrary (B) crystal nucleating agents was observed and measured. The longest length (L), which is the longest length, was It is the average value of the values divided by the short axis direction length (D), which is a short length, and (B) the average L / D of the crystal nucleating agent is preferably 10 or more. In the present invention, the length (L) in the major axis direction of the (B) crystal nucleating agent in the resin composition is preferably 30 μm or less, more preferably 10 μm or less, and further preferably 1 μm. preferable.

[(D) Crystallization accelerator]
In the present invention, it is preferable to use (D) a crystallization accelerator different from (B) crystal nucleating agent and (C) polyglycerin fatty acid ester.

  In the present invention, examples of the (D) crystallization accelerator include organic crystal nucleating agents and plasticizers.

  In the present invention, specific examples of the organic crystal nucleating agent include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate. , Calcium oxalate, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, stearic acid Magnesium, barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, Organic carboxylic acid metal salts such as zinc tyrate, aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, and organic sulfonates such as sodium p-toluenesulfonate and sodium sulfoisophthalate , Carboxylic acid amides such as stearic acid amide, ethylene bislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide), sodium salt of ethylene-acrylic acid or methacrylic acid copolymer, Sodium salt or potassium salt of polymer having carboxyl group such as sodium salt of styrene-maleic anhydride copolymer (so-called ionomer), benzylidene sol Bitol and its derivatives, phosphorus compound metal salts such as sodium-2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate and 2,2-methylbis (4,6-di-t-butylphenyl) ) Sodium and the like are mentioned, and from the viewpoint that the effect of improving heat resistance is great, organic carboxylic acid metal salts and carboxylic acid amides are preferred. These may be used alone or in combination of two or more.

  In the present invention, as the plasticizer, any of the commonly known plasticizers can be used without limitation. For example, polyester plasticizer, glycerin plasticizer, polyvalent carboxylic ester plasticizer, polyalkylene Examples thereof include glycol plasticizers, epoxy plasticizers, and castor oil plasticizers.

  In the present invention, as the polyester plasticizer, acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, propylene glycol, 1,3-butanediol, 1,4- Examples thereof include polyesters composed of diol components such as butanediol, 1,6-hexanediol, ethylene glycol, and diethylene glycol, and polyesters composed of hydroxycarboxylic acid such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or monofunctional alcohol, or may be end-capped with an epoxy compound or the like.

  In the present invention, specific examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate, glycerin monoacetomonomontanate, or glycerin triacetate. Examples thereof include those having an alkylene oxide unit such as ethylene oxide or propylene oxide added thereto, such as polyoxyethylene glycerol triacetate. In the present invention, the glycerin plasticizer does not contain a polyglycerin fatty acid ester.

  In the present invention, the polyvalent carboxylic acid plasticizer includes dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate or butyl benzyl phthalate, trimellit Trimellitic acid esters such as tributyl acid, trioctyl trimellitic acid or trihexyl trimellitic acid, succinic acid esters such as isodecyl succinate, triethylene glycol monomethyl ether succinate or benzyl methyl diglycol succinate, diisodecyl adipate, adipine Acid n-octyl-n-decyl ester, adipic acid diethylene glycol monomethyl ether ester, adipic acid methyl diglycol butyl diglycol ester, adipic acid Adipic acid ester such as benzyl methyl diglycol ester, adipic acid or benzylbutyl diglycol adipic acid ester, azelaic acid ester such as di-2-ethylhexyl azelate, sebacine such as dibutyl sebacate or di-2-ethylhexyl sebacate An acid ester etc. can be mentioned.

  In the present invention, the polyalkylene glycol plasticizer includes polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, and bisphenols. Polyalkylene glycols such as propylene oxide addition polymers, and bisphenol tetrahydrofuran addition polymers, and end-capping compounds such as terminal epoxy-modified compounds or terminal ether-modified compounds, and the like. Glycols, polypropylene glycols, poly (ethylene oxide / propylene oxide) blocks and / or random copolymers are preferred.

  In the present invention, the epoxy plasticizer generally refers to an epoxy triglyceride composed of an epoxy alkyl stearate and soybean oil, etc. In addition, mainly using bisphenol A and epichlorohydrin as raw materials, So-called epoxy resins can also be used.

  In the present invention, the castor oil plasticizer may be any castor oil and derivatives thereof, such as castor oil, dehydrated castor oil, castor hydrogenated oil, castor oil fatty acid, dehydrated castor oil fatty acid, ricinoleic acid, Ricinoleic acid, 12-hydroxystearic acid, sebacic acid, undecylenic acid, heptylic acid, castor oil fatty acid condensate, castor oil fatty acid ester, methyl ricinolate, ethyl ricinolate, isopropyl ricinolate, butyl ricinolate, ethylene glycol monolysylate , Propylene glycol monolysylate, trimethylolpropane monolysylate, sorbitan monolysylate, castor oil fatty acid polyethylene glycol ester, castor oil ethylene oxide adduct, castor oil-based polyol, castor oil-based toluol or Masi oil-based diols can be mentioned, and in terms of transparency, castor oil fatty acid ester, methyl ricinolate, ethyl ricinolate, isopropyl ricinolate, butyl ricinolate, ethylene glycol monolysylate, propylene glycol monolysylate, Trimethylolpropane monolysylate, sorbitan monolysylate, castor oil fatty acid polyethylene glycol ester, castor oil ethylene oxide adduct, castor oil-based polyol, castor oil-based toluol or castor oil-based diol are preferred.

  Other plasticizers include neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethyl butyrate, polyoxyethylene diacetate, polyoxyethylene di (2-ethylhexanoate), poly Polyol esters such as oxypropylene monolaurate, polyoxypropylene monostearate, polyoxyethylene dibenzoate, polyoxypropylene dibenzoate, aliphatic carboxylic acid esters such as butyl oleate, triethyl acetylcitrate, tributyl acetylcitrate, Oxyacid esters such as ethoxycarbonylmethyldibutyl citrate, di-2-ethylhexyl citrate, methyl acetylricinoleate or butyl acetylricinoleate, soybeans , Soybean oil fatty acid, soybean oil fatty acid ester, epoxidized soybean oil, rapeseed oil, rapeseed oil fatty acid, rapeseed oil fatty acid ester, epoxidized rapeseed oil, linseed oil, linseed oil fatty acid, linseed oil fatty acid ester, epoxidized linseed oil, coconut oil or coconut oil Examples include vegetable oil-based compounds such as fatty acids, pentaerythritol, sorbitol, polyacrylic acid esters, silicone oils, and paraffins.

  In the present invention, the plasticizer may be one kind, or two or more kinds may be used in combination, but in terms of moldability and heat resistance, it is preferably one containing two or more, and at least one is a polyalkylene glycol. More preferred is a plasticizer. Two or more polyalkylene glycol plasticizers can be used in combination.

  In the present invention, the blending amount of (D) crystallization accelerator is preferably in the range of 1 to 20 parts by weight with respect to 100 parts by weight of (A) polylactic acid resin in terms of moldability, impact resistance and heat resistance. The range of 2 to 10 parts by weight is more preferable, and the range of 2 to 7 parts by weight is more preferable.

[Other additives]
In the present invention, fillers (glass fibers, carbon fibers, metal fibers, natural fibers, organic fibers, glass flakes, glass, etc.) that are different from ordinary additives such as inorganic crystal nucleating agents, as long as the object of the present invention is not impaired. Beads, ceramic fibers, ceramic beads, asbestos, wollastonite, sericite, bentonite, dolomite, fine silicate, feldspar powder, potassium titanate, shirasu balloon, aluminum silicate, silicon oxide, gypsum, novaculite, dosonite or clay) Catalyst deactivators (hindered phenol compounds, thioether compounds, vitamin compounds, triazole compounds, polyamine compounds, hydrazine derivative compounds, phosphorus compounds, etc.), UV absorbers (resorcinol, salicylate, benzo) Triazole, Ben Phenones), heat stabilizers (such as hindered phenols, hydroquinones, phosphites and their substitutes), lubricants, mold release agents (montanic acid and salts thereof, esters thereof, half esters thereof, stearyl alcohol, stearamide and polyethylene) Waxes, etc.), coloring agents including dyes (eg nigrosine) and pigments (eg cadmium sulfide, phthalocyanine), anti-coloring agents (eg phosphites, hypophosphites), flame retardants (red phosphorus, phosphate esters, bromine) Polystyrene, brominated polyphenylene ether, brominated polycarbonate, magnesium hydroxide, melamine and cyanuric acid or salts thereof, silicon compounds, etc.), conductive agent or colorant (carbon black, etc.), slidability improver (graphite, fluororesin) Etc.), antistatic agents, etc. It can be added alone or in combination.

[Production method]
The method for producing the resin composition of the present invention is not particularly limited as long as the requirements specified in the present invention are satisfied. For example, (A) a polylactic acid-based resin, (B) a crystal nucleating agent, and (C) After mixing polyglycerin fatty acid ester, if necessary, (D) crystallization accelerator, and other additives uniformly in a solution using a single screw or twin screw extruder, etc. A method of volatilizing and removing the solvent is preferably used.

  In the present invention, as a method of melt kneading using a single screw or twin screw extruder, for example, in order to obtain a resin composition having a preferred phase structure, for example, (A) polylactic acid resin, (B) crystal nucleus And (C) polyglycerin fatty acid ester, (D) crystallization accelerator and other additives, if necessary, from the raw material supply port and melt-kneading, (A) polylactic acid resin from the main feeder (B) Crystal nucleating agent and (C) Polyglycerin fatty acid ester, (D) Crystallization accelerator is supplied as required, and other additives are added from the side feeder installed in the middle of the extruder as necessary. The method of supply etc. are mentioned.

  In the present invention, the melt-kneading temperature when producing the resin composition is preferably 170 to 250 ° C, more preferably 175 to 240 ° C, and particularly preferably 180 to 230 ° C.

[Molded products and applications]
The resin composition of the present invention can be formed into a molded product by various known molding methods. As the molding method, injection molding, extrusion molding, press molding, blow molding and the like are preferable, and particularly useful by processing into various molded products such as injection molded products, extrusion molded products, press molded products and blow molded products. It can also be used as a sheet, film, fiber, or the like.

  In the present invention, when injection molding is selected as the molding method, the mold temperature is preferably 30 to 120 ° C, more preferably 50 to 100 ° C, from the viewpoint of moldability, impact resistance and heat resistance. 70-99 degreeC is further more preferable.

  Molded articles made of the resin composition of the present invention are used in various applications such as automobile parts (interior / exterior parts, etc.), electrical / electronic parts (various housings, gears, gears, etc.), building members, civil engineering members, agricultural materials, and daily necessities. Can be used. Specifically, air flow meter, air pump, thermostat housing, engine mount, ignition hobbin, ignition case, clutch bobbin, sensor housing, idle speed control valve, vacuum switching valve, ECU housing, vacuum pump case, inhibitor switch, rotation sensor, Accelerometer, Distributor cap, Coil base, Actuator case for ABS, Top and bottom of radiator tank, Cooling fan, Fan shroud, Engine cover, Cylinder head cover, Oil cap, Oil pan, Oil filter, Fuel cap, Fuel strainer, Distribution Turcap, vapor canister housing Air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, automotive underhood parts, torque control levers, safety belt parts, register blades , Washer lever, window regulator handle, window regulator handle knob, passing light lever, sun visor bracket, various motor housings, spare tire covers, door trims and other automotive interior parts, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers , Hood louver, wheel cover, wheel cap, grill apron cover frame, lamp reflector, lamp bezel Automotive exterior parts such as door handles, mention may be made of wire harness connector, SMJ connector, PCB connector, the auto parts typified by various connector for automobiles such as door grommet connector. Also, notebook computer housings and internal parts, CRT display housings and internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile personal computers and handheld mobiles, recording media (CD, DVD, PD, FDD) Etc.) Electrical and electronic parts represented by drive housings and internal parts, copier housings and internal parts, facsimile housings and internal parts, parabolic antennas and the like. Furthermore, audio equipment parts such as VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video cameras, audio / laser discs (registered trademark) / compact discs, lighting parts, refrigerator parts, Examples include home and office electrical product parts such as air conditioner parts, typewriter parts, and word processor parts. Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, motor cases, switches, capacitors, variable capacitors Case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor Electric and electronic parts such as brush holders, transformer members, coil bobbins, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels , Heat insulation walls, adjusters, plastic bundles, ceiling fishing gear, stairs, doors, floors and other building materials, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other fishery related parts, vegetation nets, vegetation mats, grass bags, Weed prevention net, curing sheet, slope protection sheet, fly ash holding sheet, drain sheet, water retention sheet, sludge / sludge dehydration bag, concrete formwork and other civil engineering related members, gears, screws, springs, bearings, levers, key stems, Cams, ratchets, rollers, water supply parts, toy parts, fans, tegs, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, clocks, and other mechanical parts, multi-films, tunnel films, bird seats, vegetation Nonwoven fabric for protection, pot for seedling, vegetation pile, seed string tape, germination sheet, house lining sheet, agricultural PVC film stopper, slow-release fertilizer, root prevention , Garden net, insect net, infant tree net, print laminate, fertilizer bag, sample bag, sandbag, animal damage prevention net, inducement string, wind net, etc., paper diaper, sanitary wrapping material, cotton swab, towel , Hygiene items such as toilet seat wipes, medical non-woven fabrics (stitching reinforcements, anti-adhesion membranes, prosthetic repair materials), wound dressings, wound tape bandages, sticker base fabrics, surgical sutures, fracture reinforcements, medical Medical supplies such as film, calendar, stationery, clothing, food packaging film, trays, blisters, knives, forks, spoons, tubes, plastic cans, pouches, containers, tanks, baskets and other containers and tableware, hot Fill containers, microwave cooking containers, cosmetic containers, wraps, foam buffers, paper laminates, shampoo bottles, beverage bottles, cups, candy packaging, paper Containers and packaging for wrapping films such as urlink labels, lid materials, envelopes with windows, fruit baskets, hand cut tape, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, electrical and electronic parts , Natural fiber composites, polo shirts, T-shirts, innerwear, uniforms, sweaters, socks, ties and other clothing, curtains, chairs, carpets, tablecloths, futons, wallpaper, furoshiki and other interior goods, carrier tape, prints Laminate, heat sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather, non-woven fabric hot melt binder, magnetic material, zinc sulfide, electrode material Such as powder binder, optical element , Conductive embossed tape, IC tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, draining net, body towel, hand towel, tea pack, drainage filter, clear file, coating agent, adhesive, It is useful as a bag, chair, table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter, etc.

  The following examples illustrate the invention.

  In Examples and Comparative Examples, the following materials were used in the formulations shown in the table, but these do not limit the present invention.

(A) Polylactic acid based resin (A-1) Poly L lactic acid resin (D-form 1.2%, weight average molecular weight (PMMA conversion) 160,000, melting point 170 ° C.)
(A-2) Poly L lactic acid resin (D-form 0.5%, weight average molecular weight 150,000 (PMMA conversion), melting point 180 ° C.)
(A-3) Polylactic acid stereocomplex (weight average molecular weight 150,000 (PMMA conversion), melting point 210 ° C.)

(B) Crystal nucleating agent (B-1) Talc (D50 average particle size 4 μm, P-6 made by Nippon Talc)
(B-2) Talc (D50 average particle diameter 0.9 μm, Specialty Minerals Ultra Talc 609)

(C) Polyglycerin fatty acid ester (C-1) Diglycerin stearic acid ester (polyglycerin average polymerization degree 2, fatty acid carbon number 18, fatty acid esterification rate 63%) [Reference Example 2]
(C-2) Diglycerin palmitic acid ester (polyglycerin average polymerization degree 2, fatty acid carbon number 16, fatty acid esterification rate 69%) [Reference Example 3]

(D) Crystallization accelerator (D-1) Polyalkylene glycol plasticizer (D-1-1) Polyethylene glycol / polypropylene glycol copolymer (Adeka Pluronic F68)
(D-1-2) Polyethylene glycol (PEG6000S manufactured by Sanyo Chemical Industries)
(D-2) Polyvalent carboxylic acid plasticizer (D-2-1) Adipic acid benzylmethyl diglycol ester (Daifatty-101 manufactured by Daihachi Chemical Industry)

(E) Other additives (E-1) Monoglycerol stearic acid ester (polyglycerol average polymerization degree 1, fatty acid carbon number 18, fatty acid esterification rate 65%) [Reference Example 4].

[Reference Example 1]
A blend of poly-L-lactic acid having a weight average molecular weight of 150,000 (PMMA conversion) and 50 parts by weight of poly-D-lactic acid having a weight average molecular weight of 150,000 (PMMA conversion), biaxial with 30 mm diameter and L / D = 45 Using an extruder (TEX-30α manufactured by Nippon Steel Works), melt kneading was performed under conditions of a cylinder temperature of 200 ° C. and a rotation speed of 150 rpm to obtain (A-3) a polylactic acid stereocomplex.

[Reference Example 2]
In a 500 ml four-necked flask, 100 parts by weight of diglycerin, 50 parts by weight of stearic acid and 0.1 part by weight of tripotassium phosphate are reacted at 250 ° C. while removing generated water under a nitrogen stream. Then, 0.3 part by weight of phosphoric acid was added to obtain (C-1) diglycerin stearate.

[Reference Example 3]
In the same process as in Reference Example 2, palmitic acid was added instead of stearic acid to obtain (C-2) diglycerin palmitic acid ester.

[Reference Example 4]
In the same step as in Reference Example 2, monoglycerin was added instead of diglycerin to obtain (E-1) monoglycerin stearate.

  The measurement method and determination method used in the present invention are shown below.

(1) (A) Weight average molecular weight (Mw) of polylactic acid resin
It is a value of weight average molecular weight in terms of standard PMMA measured by gel permeation chromatography (GPC). Hexafluoroisopropanol was used as a solvent, the flow rate was 0.5 mL / min, and 0.1 mL of a solution having a sample concentration of 1 mg / mL was injected and measured.

(2) Formability (molding cycle time)
Using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.), injection molding is performed at a cylinder temperature of 210 ° C and a mold temperature of 90 ° C. At the time of taking out, the shortest time for obtaining a solidified molded product without deformation was measured as the molding cycle time. It can be said that the shorter the molding cycle time, the better the moldability.

(3) Impact resistance (Izod impact strength)
According to ASTM D256, the Izod impact strength of a 3 mm thick notched strip-shaped product was measured.

(4) Heat resistance (DTUL)
According to ASTM D648, the deflection temperature under load (load 0.45 MPa) of a molded article of 12.7 mm × 127 mm × 3 mm was measured.

(5) (B) Average L / D of crystal nucleating agent
A sample was cut from the central part of a molded article of 12.7 mm × 127 mm × 3 mm, the resin composition was observed at a magnification of 2,000 using a transmission electron microscope (TEM), and the observed part was photographed. In the photograph, (A) the polylactic acid-based resin is identified as white, and (B) the crystal nucleating agent is identified as black. About 10 arbitrary (B) crystal nucleating agents in the resin composition, the shape is observed and measured, and the longest length (L), which is the longest length, is the shortest length, which is the shortest length. The average value divided by (D) is the average L / D of the (B) crystal nucleating agent, and is preferably a value of 10 or more. Moreover, it is preferable that the length (L) of the (B) crystal nucleating agent in the resin composition is 30 μm or less.

[Examples 1 to 10, Comparative Examples 1 to 8]
As shown in Tables 1 and 2, the raw materials were blended and melted under the conditions of a cylinder temperature of 210 ° C. and a rotation speed of 150 rpm using a 30 mm diameter, L / D = 45 twin screw extruder (TEX-30α manufactured by Nippon Steel). Kneading was performed to obtain a resin composition. The obtained resin composition was subjected to injection molding at a cylinder temperature of 210 ° C. and a mold temperature of 90 ° C. using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.) to obtain a molded product. Tables 1 and 2 show the results of various evaluations using the obtained molded product.

  From the results of Tables 1 and 2, in Examples 1 to 10 where (B) crystal nucleating agent average L / D is 10 or more, (B) Crystal nucleating agent average L / D is molded from Comparative Examples 1 to 8 having 10 or less. It can be seen that it is excellent in heat resistance, impact resistance and heat resistance.

Claims (6)

(A) 0.1 to 50 parts by weight of the crystal nucleating agent with respect to 100 parts by weight of the polylactic acid-based resin, and (C) the polyglycerol fatty acid ester with respect to 100 parts by weight of the (B) crystal nucleating agent. 1 to 300 parts by weight of a resin composition, which is an average L / D (long axis direction length (L) of (B) crystal nucleating agent in the resin composition in a transmission electron micrograph (The value obtained by dividing the length by the short axis length (D)) is 10 or more, and (B) the long axis direction length (L) of the crystal nucleating agent is 30 μm or less. The resin composition according to claim 1, wherein the (C) polyglycerol fatty acid ester is a polyglycerol fatty acid ester which is a fatty acid ester of polyglycerol and a fatty acid having 12 or more carbon atoms. The resin composition according to any one of claims 1 to 2, wherein the (C) polyglycerol fatty acid ester is a polyglycerol fatty acid ester which is a fatty acid ester of polyglycerol having an average degree of polymerization of 1.5 to 3 and stearic acid. object. The resin composition according to any one of claims 1 to 3, wherein the (B) crystal nucleating agent is talc. The resin composition according to any one of claims 1 to 4, wherein (B) a crystal nucleating agent and (C) a crystallization accelerator different from (C) a polyglycerol fatty acid ester are blended. A molded article comprising the resin composition according to any one of claims 1 to 5.