JP2005154479A - Resin composition and molded article composed of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition having excellent moldability, heat resistance and mechanical characteristics, and to provide a molded article composed of the resin composition. <P>SOLUTION: The resin composition is obtained by compounding a polylactic acid resin with a naturally derived organic filler having ≤1,000 ppm chlorine content, ≥200 ppm sulfur content and a larger amount of aluminum than that of calcium. The sulfur content of the naturally derived organic filler is preferably ≤2,000 ppm and the chlorine content of the same is preferably ≥150 ppm. The naturally derived organic filler is preferably edge dust. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a resin composition comprising a polylactic acid resin and a naturally-occurring organic filler satisfying specific requirements, and excellent in moldability, heat resistance, and mechanical properties, and a molded article comprising the same.

  The polylactic acid resin has a high melting point and can be melt-molded. Therefore, it is expected to be a practically excellent resin derived from plant resources. However, since the polylactic acid resin has a low crystallization speed, there is a limit to use it as a molded product after crystallization. For example, when molding a polylactic acid resin, a long molding cycle time or heat treatment after molding is required. There has been a big problem that it is still insufficient practically in terms of formability and heat resistance, such as necessary and large deformation during molding and heat treatment.

  As one of the methods for improving this problem, a method of adding a crystallization accelerator such as a crystal nucleating agent has been studied conventionally, but there has been a problem that the effect of the improvement is still not sufficient. In addition, methods using inorganic fillers such as glass fiber are also being studied, but since it is necessary to add a large amount, the specific gravity of the molded product increases, and the residue increases when incinerated or discarded. There was also a problem.

  On the other hand, from the viewpoint of protecting the global environment, many attempts have been made to use natural organic materials such as wood powder, paper powder, bamboo powder, and kenaf as resin fillers. Proposals for blending paper powder as an organic filler have been made (for example, Patent Documents 1 and 2).

  However, according to the invention described in Patent Document 1, although heat resistance is slightly improved, an appropriate filler has not been selected, and it is still insufficient for practical use, and further improvement is desired.

  Further, according to the invention described in Patent Document 2, it is described that dioxin generation during incineration can be suppressed by reducing the chlorine content of paper or pulp as much as possible. Further improvement is strongly desired, and further improvement is strongly desired.

The resin composition obtained by solving the above various problems can be used for various applications, for example, automobile parts, electrical / electronic parts, building materials, civil engineering materials, furniture members, game machine materials, Since it can be set as a useful article as various daily necessities, it is strongly desired to solve the above problems.
Japanese Patent Laid-Open No. 10-323810 (page 2-4) JP 2003-73988 A (page 2-4)

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue.

  Therefore, the present invention is a resin composition comprising a polylactic acid resin and a naturally-occurring organic filler that satisfies specific requirements, a resin composition excellent in moldability, heat resistance, and mechanical properties, and a molding comprising the same Is to provide goods.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a resin composition comprising a polylactic acid resin and a naturally-derived organic filler satisfying specific requirements is excellent in conformity with the above-mentioned purpose. The inventors have found that the present invention exhibits its characteristics, and have reached the present invention.

That is, the present invention
(1) A resin composition comprising a polylactic acid resin and a natural organic filler having a chlorine content of 1000 ppm or less, a sulfur content of 200 ppm or more, and an aluminum content greater than the calcium content,
(2) The resin composition according to (1), wherein the naturally-occurring organic filler has a sulfur content of 2000 ppm or less,
(3) The resin composition according to (1), wherein the chlorine content of the naturally-derived organic filler is 150 ppm or more,
(4) The resin composition according to (1), wherein the natural organic filler is paper powder,
(5) A molded article comprising the resin composition according to any one of (1) to (4).

  The resin composition of the present invention is a resin composition comprising a polylactic acid resin and a natural organic filler having a chlorine content of 1000 ppm or less, a sulfur content of 200 ppm or more, and an aluminum content greater than the calcium content. It has excellent moldability, heat resistance, and mechanical properties. In addition, a molded article made of this resin composition can be used for various applications such as automobile parts, electrical / electronic parts, building materials, civil engineering materials, furniture members, materials for game machines, various daily necessities, taking advantage of the above characteristics. .

  Hereinafter, the present invention will be described in detail.

  The polylactic acid resin used in the present invention is a polymer mainly composed of L-lactic acid and / or D-lactic acid, but may contain other copolymerization components other than lactic acid. Other monomer units include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentane. Glycol compounds such as erythritol, bisphenol A, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid , Isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarbohydrate Acids, dicarboxylic acids such as 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium isophthalic acid, hydroxycarboxylic acids such as glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, and caprolactone And lactones such as valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. Such a copolymerization component is not particularly limited, but from the viewpoint of moldability and heat resistance, the content is usually preferably 0 to 30 mol%, and preferably 0 to 10 mol% in all monomer components. Preferably there is.

  In the present invention, from the viewpoint of heat resistance, it is preferable to use a polylactic acid resin having a high optical purity of the lactic acid component. That is, among the total lactic acid components of the polylactic acid 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% or more It is particularly preferable that the L-form is contained at 95% or more, or the D-form is more preferably contained at 95% or more, the L-form is contained at 98% or more, or the D-form is contained at 98% or more. Further preferred. Moreover, the upper limit of the content of L-form or D-form is usually 100% or less.

  The melting point of the polylactic acid resin is not particularly limited, but is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably 160 ° C. or higher. The melting point of the polylactic acid resin is usually increased by increasing the optical purity of the lactic acid component, and the polylactic acid resin having a melting point of 120 ° C. or higher contains 90% or more of the L form or 90% or more of the D form. In addition, a polylactic acid resin having a melting point of 150 ° C. or higher can be obtained by containing 95% or more of L-form or 95% or more of D-form. In the present invention, the melting point of the polylactic acid resin is a value measured with a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min.

  The molecular weight and molecular weight distribution of the polylactic acid resin are not particularly limited as long as it can be substantially molded, but the weight average molecular weight is usually 10,000 or more, preferably 40,000 or more, and further 8 It is desirable to be 10,000 or more. Although there is no restriction | limiting in particular as an upper limit, Preferably it is 500,000 or less from a viewpoint of a moldability. The weight average molecular weight here refers to the molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography.

  A modified polylactic acid resin may be used. For example, by using a maleic anhydride-modified polylactic acid resin, an epoxy-modified polylactic acid resin, an amine-modified polylactic acid resin, etc., not only heat resistance but also mechanical properties are obtained. It tends to improve, which is preferable.

  As a method for producing the polylactic acid resin, a known polymerization method can be used, and examples thereof include a direct polymerization method from lactic acid and a ring-opening polymerization method via lactide.

  Any naturally-occurring organic filler used in the present invention can be used as long as it is derived from a natural product and satisfies the requirements defined in the present invention.

  Specific examples of naturally-occurring organic fillers include rice husks, wood chips, okara, waste paper pulverized materials, chip sized materials such as clothing pulverized materials, cotton fibers, hemp fibers, bamboo fibers, wood fibers, kenaf fibers, jute Fiber, banana fiber, plant fiber such as coconut fiber, pulp or cellulose fiber processed from these plant fibers and fiber such as animal fibers such as silk, wool, Angola, cashmere, camel, paper powder, wood flour , Bamboo powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch, etc. From the viewpoint of heat resistance, paper powder, wood powder, bamboo powder, cellulose powder , Powdered powder such as rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein powder, starch etc., paper powder, wood powder, bamboo powder, cellulose powder are more preferred , More preferably paper dust and wood flour, paper powders are particularly preferred. These natural organic fillers may be collected directly from natural products, but from the viewpoint of protecting the global environment and conserving resources, waste materials such as waste paper, waste wood and old clothes are recycled. May be used.

  Waste paper is newspaper, magazine, other recycled pulp, or paperboard such as corrugated cardboard, cardboard, paper tube, etc. Any one can be used as long as it is processed from plant fiber. From the point that the effect of improving the heat resistance and the heat resistance is likely to be high, crushed paperboard such as newspaper and corrugated cardboard, cardboard and paper tube is preferable, and among them, pulverized paperboard such as cardboard, cardboard and paper tube is more preferable. .

  Specific examples of the wood include coniferous wood such as pine, cedar, oak, and fir, and broad-leaved wood such as beech, shii, and eucalyptus, and the type is not limited.

  When the natural organic filler is paper powder, the paper powder is made from pulp and contains chemicals commonly used as papermaking raw materials. It is preferable that As the pulp, any of mechanical pulp, semi-chemical pulp, chemical pulp and the like may be used. However, mechanical pulp is likely to be easily improved in formability and heat resistance, and dioxins are less likely to be generated. Is preferred. In addition, as pulp, not only wood pulp, but also non-wood such as kenaf, bagasse, bamboo, flax, hemp, manila hemp, jute, kozo, mitsumata, ganpi, straw, cotton, etc. Either pulp or waste paper pulp may be used.

  Examples of chemicals commonly used as a raw material for papermaking include sizing agents such as rosin, alkyl ketene dimer, and alkenyl succinic anhydride, paper strength enhancers such as polyacrylamide and starch, polyethylene Yield improvers such as imines, polymer flocculants, drainage improvers, deinking agents such as nonionic surfactants, slime control agents such as organic halogens, pitch control agents such as organic or enzyme-based, Organic substances such as bleaching agents such as hydrogen oxide, ozone, oxygen, chlorine dioxide and sodium hypochlorite, cleaning agents, antifoaming agents, pigment dispersants and lubricants, aluminum sulfate used as a fixing agent for sizing agents, poly Aluminum chloride, and other sodium hydroxide, magnesium hydroxide, and sodium sulfate used as raw materials for papermaking , Sodium silicate, aluminum chloride, may comprise an inorganic material such as chlorine sodium preferred.

  When the naturally-derived organic filler is paper powder, the paper powder is not particularly limited, but the adhesive is used because it tends to increase the moldability and heat resistance improvement effect. It is preferable to include. The adhesive is not particularly limited as long as it is usually used when processing paper. Emulsion adhesives such as vinyl acetate resin emulsions and acrylic resin emulsions, polyvinyl alcohol adhesives, Examples include cellulose-based adhesives, natural rubber-based adhesives, starch paste, and hot-melt adhesives such as ethylene-vinyl acetate copolymer resin-based adhesives and polyamide-based adhesives. Emulsion-based adhesives, polyvinyl alcohol-based adhesives An adhesive and a hot melt adhesive are preferable, and an emulsion adhesive and a polyvinyl alcohol adhesive are more preferable. These adhesives are also used as binders for paper processing agents. Adhesives include clay, talc, kaolinite, montmorillonite, mica, synthetic mica, zeolite, silica, graphite, carbon black, magnesium oxide, calcium oxide, titanium oxide, calcium sulfide, magnesium carbonate, calcium carbonate, and barium carbonate. Inorganic fillers such as barium sulfate, aluminum oxide and neodymium oxide are preferably contained, and clay, talc, kaolinite, montmorillonite, synthetic mica and silica are more preferable.

  The naturally-derived organic filler used in the present invention contains various elements as a result of undergoing various treatments and the inherent components.

  The naturally-derived organic filler used in the present invention is required to have a chlorine content of 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less, still more preferably 400 ppm or less, Especially preferably, it is 300 ppm or less. If the chlorine content exceeds 1000 ppm, the moldability and heat resistance improving effects tend to be small. Furthermore, when a resin composition using a naturally-derived organic filler having a chlorine content exceeding 1000 ppm and a molded product comprising the same are incinerated and discarded, dioxins tend to be easily generated. In addition, the lower limit of the chlorine content is preferably 150 ppm or more, more preferably 170 ppm or more, and further preferably 180 ppm or more in that the moldability and heat resistance tend to be improved. For the measurement of the chlorine content, any known method can be used. In the present invention, the chlorine content is a value measured using a coulometric titration method.

  The naturally-derived organic filler of the present invention needs to have a sulfur content of 200 ppm or more, preferably 300 ppm or more, more preferably 500 ppm or more, still more preferably 700 ppm or more, and particularly preferably. Is 1000 ppm or more. If the sulfur content is less than 200 ppm, the effect of improving moldability and heat resistance tends to be reduced. Further, the upper limit of the sulfur content is preferably 2000 ppm or less, more preferably 1800 ppm or less, and even more preferably 1500 ppm or less, from the viewpoint that the moldability and heat resistance improving effects tend to increase. For the measurement of the sulfur content, any known method can be used. In the present invention, the sulfur content is a value measured using an ultraviolet fluorescence method.

  In the present invention, the ash content of the naturally derived organic filler is not particularly limited, but is preferably 1% by weight or more from the viewpoint that the effect of improving moldability and heat resistance tends to be high. % Or more, preferably 5.5% by weight or more, more preferably 7.5% by weight or more, and particularly preferably 8% by weight or more. If it is less than 1% by weight, the effect of improving moldability and heat resistance tends to be small. The upper limit is not particularly limited, but is preferably 60% by weight or less, and more preferably 30% by weight or less. Here, the ash content is the weight of the remaining ash content when the natural organic filler is baked for 8 hours at a high temperature of 450 ° C. or higher using an electric furnace or the like with respect to the weight of the natural organic filler before baking. It is a ratio.

  The naturally-occurring organic filler contains aluminum and calcium, and the amount of aluminum needs to be larger than the amount of calcium. From the viewpoint of heat resistance, it is preferable that the material further contains silicon. More preferably, the amount of each of silicon and silicon is greater than the amount of calcium.

  The abundance ratio of aluminum, silicon, and calcium may be any as long as it satisfies the requirements stipulated in the present invention. For example, when the total number of the above elements is 100, aluminum is 10 to 60%, silicon Is 10 to 90%, calcium is preferably 1 to 30%, aluminum is 20 to 50%, silicon is 15 to 80%, calcium is more preferably 1 to 25%, and aluminum is 30 to 50%. %, Silicon is 20 to 70%, and calcium is more preferably 3 to 20%. About these elemental analysis, although it can measure even if it uses either the simple substance of a natural origin organic filler, and the ash content of a natural origin organic filler, in this invention, it shall measure using ash content. . Elemental analysis is measured by using an apparatus combining X-ray fluorescence analysis, atomic absorption spectrometry, scanning electron microscope (SEM) or transmission electron microscope (TEM) and energy dispersive X-ray microanalyzer (XMA). However, in the present invention, it is a value measured using fluorescent X-ray analysis.

  Naturally-derived organic fillers having the above composition can be obtained by appropriately adjusting the type and amount of chemicals and other treatment agents used in the production process, or are commercially available Therefore, naturally-derived organic fillers having such a composition can also be selected.

  Naturally-derived organic fillers that have been surface-treated may be used, such as alkali treatment, heat treatment, acetylation treatment, cyanoethylation treatment, silane coupling treatment, and glyogisal treatment. It is preferable to use the organic filler because the moldability, heat resistance and mechanical properties tend to be improved.

  Moreover, in this invention, as long as the resin composition of this invention is obtained, the organic filler derived from a natural product can be used by 1 type (s) or 2 or more types, It should contain the paper powder which has the said preferable characteristic. Is preferred.

  In the present invention, the blending amount of the naturally derived organic filler that satisfies the requirements stipulated in the present invention is not particularly limited, but from the viewpoint of improving heat resistance and mechanical properties, it is based on 100 parts by weight of the polylactic acid resin. It is preferably 1 to 350 parts by weight, more preferably 1 to 300 parts by weight, further preferably 5 to 200 parts by weight, particularly preferably 10 to 150 parts by weight, and 15 to 100 parts by weight. Most preferred. If the blending amount of the natural-derived organic filler is less than 1 part by weight, the moldability and heat resistance improving effect tends to be small, and if it exceeds 350 parts by weight, the natural-derived organic filler is polylactic acid. It becomes difficult to disperse uniformly in the resin, and the moldability, heat resistance, mechanical properties, and surface appearance tend to deteriorate.

  In the present invention, as long as the effects of the present invention are not impaired, crystallization accelerators, thermoplastic resins other than polylactic acid resins, fillers other than organic fillers derived from nature that satisfy the requirements defined in the present invention, stabilizers , Mold release agent, carboxyl group reactive end-capping agent, foaming agent, flame retardant, antistatic agent, lubricant, sliding property improving agent (graphite, fluororesin, etc.), antibacterial agent, colorant including pigment and dye, heat One or more other components that are usually added to a resin composition such as a curable resin (for example, a phenol resin, a melamine resin, a polyester resin, and a silicone resin) can be added.

  In this invention, it is preferable to mix | blend a crystallization promoter at the point that it becomes easy to obtain the resin composition excellent in moldability and heat resistance, and a molded article. Moreover, it is easy to obtain a resin composition and a molded product having excellent bleed-out resistance against bleed-out which becomes a problem when a plasticizer is used as a crystallization accelerator.

  The crystallization accelerator used in the present invention can be selected from a wide variety of compounds, but the crystal nucleating agent that promotes the formation of crystal nuclei of the polymer, or the softening of the polymer to facilitate movement and promote crystal growth. A plasticizer can be preferably used.

  The blending amount of the crystallization accelerator used in the present invention is preferably 50 to 0.01 parts by weight, more preferably 30 to 0.05 parts by weight with respect to 100 parts by weight of the polylactic acid resin. .

  As the crystal nucleating agent used as a crystallization accelerator in the present invention, those generally used as a polymer crystal nucleating agent can be used without any particular limitation, and both inorganic crystal nucleating agents and organic crystal nucleating agents can be used. Can be used.

  Specific examples of inorganic crystal nucleating agents include talc, kaolin, montmorillonite, synthetic mica, clay, zeolite, silica, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, sulfuric acid Examples thereof include metal salts of barium, aluminum oxide, neodymium oxide and phenylphosphonate. These inorganic crystal nucleating agents are preferably modified with an organic substance in order to enhance dispersibility in the composition.

  Specific examples of organic crystal nucleating agents 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, magnesium stearate, stearic acid Barium, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum Minium dibenzoate, potassium dibenzoate, lithium dibenzoate, organic carboxylic acid metal salts such as sodium β-naphthalate, sodium cyclohexanecarboxylate, organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearamide , Ethylene bislauric acid amide, palmitic acid amide, hydroxy stearic acid amide, erucic acid amide, organic carboxylic acid amides such as trimesic acid tris (t-butylamide), low density polyethylene, high density polyethylene, polypropylene, polyisopropylene, polybutene Polymers such as poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, and high melting point polylactic acid, Sodium salt or potassium salt of a polymer having a carboxyl group such as sodium salt of tylene-acrylic acid or methacrylic acid copolymer, sodium salt of styrene-maleic anhydride copolymer (so-called ionomer), benzylidene sorbitol and its derivatives, sodium-2, Phosphorus compound metal salts such as 2'-methylenebis (4,6-di-t-butylphenyl) phosphate and 2,2-methylbis (4,6-di-t-butylphenyl) sodium can be exemplified. .

  As the crystal nucleating agent used in the present invention, among those exemplified above, at least one selected from talc, organic carboxylic acid metal salts and organic carboxylic acid amides is particularly preferable. The crystal nucleating agent used in the present invention may be used alone or in combination of two or more.

  The compounding amount of the crystal nucleating agent is preferably in the range of 0.01 to 30 parts by weight, more preferably in the range of 0.05 to 10 parts by weight, with respect to 100 parts by weight of the polylactic acid resin. A range of parts by weight is more preferred.

  As the plasticizer used in the present invention, generally well-known plasticizers can be used. For example, polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, phosphate ester plasticizers. Agents, polyalkylene glycol plasticizers and epoxy plasticizers.

  Specific examples of the polyester plasticizer include dicarboxylic 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 acids 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.

  Specific examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate, and glycerin monoacetomonomontanate.

  The polyvalent carboxylic acid ester plasticizer is an ester compound obtained by reacting a polyvalent carboxylic acid with an alcohol.

  Examples of the polyvalent carboxylic acid include phthalic acid, trimellitic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, citric acid and the like. Acid, adipic acid and citric acid are preferred.

  Examples of the alcohol include methanol, ethanol, 1-propanol, 1-butanol, 1-hexanol, 1-heptanol, 1-octanol, phenol, benzyl alcohol, ethylene glycol monomethyl ether (also known as methyl glycol), and ethylene glycol monoethyl. Ether (also known as ethyl glycol), ethylene glycol monobutyl ether (also known as butyl glycol), ethylene glycol monophenyl ether (also known as phenyl glycol), ethylene glycol monobenzyl ether (also known as benzyl glycol), diethylene glycol monomethyl ether (also known as methyl) Diglycol), diethylene glycol monoethyl ether (also known as ethyl diglycol), diethylene glycol monobutyl -Tel (also known as butyl diglycol), diethylene glycol monophenyl ether (also known as phenyl diglycol), diethylene glycol monobenzyl ether (also known as benzyl diglycol) triethylene glycol monomethyl ether (also known as methyl triglycol), triethylene glycol monoethyl Ether (also known as ethyl triglycol), triethylene glycol monobutyl ether (also known as butyl triglycol), triethylene glycol monophenyl ether (also known as phenyl triglycol), triethylene glycol monobenzyl ether (also known as benzyltriglycol), Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether Propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether , Tripropylene glycol monophenyl ether, etc. In terms of bleed-out resistance, diethylene glycol monomethyl ether (also known as methyl diglycol), diethylene glycol monoethyl ether (also known as ethyl diglycol), diethylene glycol monobutyl ether (also known as butyl) Diglycol), triethylene glycol monomethyl Ether (also known as methyl triglycol), triethylene glycol monoethyl ether (also known as ethyl triglycol), and triethylene glycol monobutyl ether (also known as butyl triglycol) are preferred, diethylene glycol monomethyl ether (also known as methyl diglycol), diethylene glycol Monoethyl ether (also known as ethyl diglycol) and diethylene glycol monobutyl ether (also known as butyl diglycol) are more preferred.

  Specific examples of polycarboxylic acid ester plasticizers obtained using the above polycarboxylic acids and alcohols include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate , Phthalates such as butylbenzyl phthalate, tributyl trimellitic acid, trioctyl trimellitic acid, trimellitic acid esters such as trihexyl trimellitic acid, methyl diglycol butyl diglycol succinate, benzyl methyl diglycol succinate and benzyl butyl Succinate such as diglycol succinate, diisodecyl adipate, n-octyl-n-decyl adipate, bis (butyldiglycol) adipate, methyl diglycol butyl Adipic acid esters such as glycol adipate, benzylmethyl diglycol adipate and benzylbutyl diglycol adipate, acetyl triethyl citrate, acetyl tributyl citrate, methoxycarbonylmethyl dibutyl citrate, ethoxycarbonylmethyl dibutyl citrate, butoxycarbonyl methyl dibutyl citrate Citric acid esters such as dimethoxycarbonylmethyl monobutyl citrate, diethoxycarbonylmethyl monobutyl citrate and dibutoxycarbonylmethyl monobutyl citrate, azelaic acid esters such as di-2-ethylhexyl azelate, dibutyl sebacate and sebacine And sebacic acid esters such as di-2-ethylhexyl acid. (Butyl diglycol) adipate, methyl diglycol butyl diglycol succinate, benzyl methyl diglycol succinate, benzyl butyl diglycol succinate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, benzyl butyl diglycol adipate, Acetyl tributyl citrate, methoxycarbonylmethyl dibutyl citrate, ethoxycarbonylmethyl dibutyl citrate, butoxycarbonylmethyl dibutyl citrate, dimethoxycarbonylmethyl monobutyl citrate, diethoxycarbonylmethyl monobutyl citrate, dibutoxycarbonylmethyl monobutyl sight Rates are preferred.

  Specific examples of the phosphate ester plasticizer include tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl-2-ethylhexyl phosphate and tricresyl phosphate. .

  Specific examples of the polyalkylene glycol plasticizer include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, bisphenols Polyalkylene glycols such as propylene oxide addition polymers, tetrahydrofuran addition polymers of bisphenols, or terminal-capped compounds such as terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds.

  The epoxy plasticizer generally refers to an epoxy triglyceride composed of an alkyl epoxy stearate and soybean oil, but there are also so-called epoxy resins mainly made of bisphenol A and epichlorohydrin. Can be used.

  Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearamide, oleic acid Examples thereof include aliphatic carboxylic acid esters such as butyl, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oils, and paraffins.

  Among the plasticizers used in the present invention, at least one selected from polyester plasticizers, polycarboxylic acid ester plasticizers, and polyalkylene glycol plasticizers is particularly preferable. Only one type of plasticizer may be used in the present invention, or two or more types may be used in combination.

  Moreover, the compounding quantity of a plasticizer has the preferable range of 0.01-50 weight part with respect to 100 weight part of polylactic acid resin, The range of 0.1-30 weight part is more preferable, 0.5-20 weight A range of parts is more preferred.

  In the present invention, each of the crystal nucleating agent and the plasticizer may be used alone, but it is preferable to use both in combination.

  In the present invention, it is preferable to add a thermoplastic resin other than the polylactic acid resin in that a material excellent in surface appearance, moldability, mechanical properties, heat resistance and toughness can be easily obtained.

  In the present invention, the thermoplastic resin other than the polylactic acid resin is not particularly limited, and any resin can be used. For example, polyacetal resin, polyester resin other than polylactic acid resin, polyolefin resin such as polyamide resin, polyethylene resin and polypropylene resin, polystyrene resin, acrylic resin, polyurethane resin, chlorinated polyethylene resin, chlorinated polypropylene resin, aromatic and fat Group polyketone resin, fluorine resin, polyphenylene sulfide resin, polyether ether ketone resin, polyimide resin, thermoplastic starch resin, AS resin, ABS resin, AES resin, ACS resin, polyvinyl chloride resin, polyvinylidene chloride resin, vinyl ester Resin, MS resin, polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene oxide resin, poly-4-methylpen 1, a thermoplastic resin other than polylactic acid resin such as polyetherimide resin, cellulose acetate resin, and polyvinyl alcohol resin, and at least selected from polyacetal resin, polyester resin other than polylactic acid resin, and polyamide resin. It is preferable to mix 1 type. In addition, the thermoplastic resin includes a so-called impact resistance improver that can greatly improve impact resistance, and includes, for example, a core layer and one or more shell layers covering the core layer. In addition, a multilayer structure polymer called a so-called core-shell rubber, in which adjacent layers are composed of different polymers, is preferably used. By blending these resins, a molded product having excellent characteristics can be obtained.

  In the present invention, the polyacetal resin is a polymer having an oxymethylene unit as a main repeating unit, and even a so-called polyacetal homopolymer obtained by a polymerization reaction using formaldehyde or trioxane as a main raw material is mainly composed of an oxymethylene unit. Which may be any so-called polyacetal copolymer containing not more than 15% by weight of oxyalkylene units having 2 to 8 adjacent carbon atoms in the main chain, and also containing other structural units, Any of a block copolymer, a terpolymer, and a crosslinked polymer may be used, and these may be used alone or in combination of two or more.

  Among them, a polyacetal copolymer is preferable, and a polyacetal copolymer containing 2% by weight or less of an oxyalkylene unit having 2 adjacent carbon atoms in the main chain or an oxyalkylene unit having 4 adjacent carbon atoms in the main chain Is more preferable, and a polyacetal copolymer containing 1.4 to 0.2% by weight of an oxyalkylene unit having 2 adjacent carbon atoms in the main chain or 4 in the main chain. Polyacetal copolymers containing 3 to 0.5% by weight of oxyalkylene units having adjacent carbon atoms are particularly preferred.

  The viscosity of the polyacetal resin of the present invention is not particularly limited as long as it can be used as a molding material, but the melt flow rate (MFR) can be measured by the ASTM D1238 method, and the MFR is 1.0 to 50 g / 10. Minute range is preferable, and 1.5 to 35 g / 10 min is particularly preferable.

  The polyacetal resin in the present invention includes 2,2′-methylenebis (4-methyl-6-tert-butylphenol), calcium ricinoleate, cyanoguanazine, hexamethylenebis (3,5-t-butyl-4-hydroxyhydrocyanate ), Melamine-formaldehyde resin, nylon 6/66, nylon 66/610/6, nylon 612/6, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocyanate)] methane, 1, 6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol [3- (3,5-di-t-butyl-5-methyl-4- Hydroxyphenyl) propionate] is preferably contained.

  In the present invention, a resin composition and a molded article excellent in surface appearance, moldability, mechanical properties, heat resistance, and toughness can be obtained by blending a polyacetal resin.

  In the present invention, the polyester resin other than the polylactic acid resin is (i) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, (b) a hydroxycarboxylic acid or an ester-forming derivative thereof, (c) It is a polymer or copolymer obtained by polycondensation of one or more selected from lactones, and is a thermoplastic polyester resin other than polylactic acid resin.

  Examples of the dicarboxylic acid or ester-forming derivative thereof include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malon Examples thereof include aliphatic dicarboxylic acids such as acid, glutaric acid and dimer acid, alicyclic dicarboxylic acid units such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

  Examples of the diol or ester-forming derivatives thereof include aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1, Aroma such as 6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol or the like, or a long chain glycol having a molecular weight of 200 to 100,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. Dioxy compounds such as 4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F, and the like And La ester forming derivatives.

  Examples of the hydroxycarboxylic acid include glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and ester formation thereof. Sex derivatives and the like. Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one.

  Specific examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polypropylene terephthalate, polypropylene (terephthalate / isophthalate), polyethylene terephthalate, polyethylene (terephthalate / isophthalate). Bisphenol A (terephthalate / isophthalate), polybutylene naphthalate, polybutylene (terephthalate / naphthalate), polypropylene naphthalate, polyethylene naphthalate, polycyclohexanedimethylene terephthalate, polycyclohexanedimethylene (terephthalate / isophthalate), poly (Cyclohexanedimethylene / ethylene) terephthalate, poly (cyclohexanedimethylene / ethylene) Aromatic polyesters such as terephthalate / isophthalate), polybutylene (terephthalate / isophthalate) / bisphenol A, polyethylene (terephthalate / isophthalate) / bisphenol A, polybutylene (terephthalate / succinate), polyethylene (terephthalate / succinate), polybutylene ( Terephthalate / adipate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sulfoisophthalate / adipate), polybutylene (terephthalate / sebate), polyethylene (terephthalate / sebate), polyether ester copolymer of polybutylene terephthalate / polyethylene glycol Polyethylene terephthalate / polyethylene glycol -Terester copolymer, polybutylene terephthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / poly (propylene oxide / ethylene oxide) ) Glycol block copolymer, polybutylene terephthalate / isophthalate / poly (propylene oxide / ethylene oxide) glycol block copolymer, polybutylene terephthalate / polybutylene adipate block copolymer, polybutylene terephthalate / poly-ε-caprolactone copolymer Copolymers such as polyether or aliphatic polyester copolymerized with aromatic polyester, polyethylene oxalate Polybutylene oxalate, polyneopentyl glycol oxalate, polyethylene succinate, polybutylene succinate, polybutylene adipate, polyethylene adipate, polybutylene (succinate / adipate), polyethylene (succinate / adipate), polyhydroxybutyric acid and β-hydroxybutyric acid And polyhydroxyalkanoates such as copolymers of β-hydroxyvaleric acid, aliphatic polyesters such as polycaprolactone, aliphatic polyester carbonates such as polybutylene succinate carbonate, p-oxybenzoic acid / polyethylene terephthalate, p-oxybenzoic acid Examples thereof include liquid crystalline polyesters such as copolyesters such as acid / 6-oxy-2-naphthoic acid.

  Among these, a polymer obtained by polycondensation of aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol or its ester-forming derivative as main components is preferable. Specifically, polybutylene terephthalate, polypropylene terephthalate , Polyethylene terephthalate, poly (cyclohexanedimethylene / ethylene) terephthalate, polybutylene naphthalate, polybutylene terephthalate / isophthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate / polyethylene glycol polyether ester copolymer, polyethylene terephthalate / polyethylene Polyether ester copolymer of glycol, polybutylene terephthalate poly (tetramethylene oxide) glycol polyether Polyester copolymer, Polyethylene terephthalate / poly (tetramethylene oxide) glycol polyether ester copolymer, Polybutylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol polyether ester copolymer, Polybutylene (terephthalate / adipate) ) And polyethylene (terephthalate / adipate). Ratio of aromatic dicarboxylic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer obtained by polycondensation of the above aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol or its ester-forming derivative as main components Is more preferably 50 mol% or more, and further preferably 60 mol% or more.

  Further, among these, a polymer obtained by polycondensation containing terephthalic acid or its ester-forming derivative and butanediol or its ester-forming derivative as main components is more preferable. Specifically, polybutylene terephthalate, polybutylene. Polyterylene terephthalate / isophthalate, Polybutylene terephthalate / polyethylene glycol polyether ester copolymer, Polybutylene terephthalate / poly (tetramethylene oxide) glycol polyether ester copolymer, Polybutylene terephthalate / isophthalate / poly (tetramethylene oxide) ) A polyether ester copolymer of glycol and polybutylene (terephthalate / adipate) can be preferably mentioned. The ratio of terephthalic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer obtained by polycondensation of terephthalic acid or its ester-forming derivative and butanediol or its ester-forming derivative as a main component is 50 mol% or more. More preferably, it is more preferably 60 mol% or more.

  Preferred examples of the polyester resin other than the polylactic acid resin used in the present invention include polyethylene succinate, polybutylene succinate, polybutylene adipate, polyethylene adipate, polybutylene (succinate / adipate), polyethylene (succinate / adipate), poly Mention may be made of butylene succinate carbonate, polyhydroxybutyric acid and copolymers of β-hydroxybutyric acid and β-hydroxyvaleric acid. These may be used alone or in combination of two or more.

  In the present invention, a resin composition and a molded product excellent in surface appearance, moldability, mechanical properties, heat resistance, and toughness can be obtained by blending polyester other than polylactic acid resin.

  In the present invention, the polyamide resin is a thermoplastic polymer having an amide bond starting from an amino acid, lactam or diamine and a dicarboxylic acid.

  Examples of amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid. Examples of lactam include ε-caprolactam and ω-laurolactam.

  Examples of the diamine include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4,4-trimethylhexamethylene diamine, 5-methylnonamethylene diamine, 2,4-dimethyloctamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3, 8-bis (aminomethyl) tricyclodecane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) ) Piperazine, Ami Such as ethyl piperazine, and the like.

  Dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5- Examples include sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and diglycolic acid.

  Preferred polyamides used in the present invention include polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon). 610), polyhexamethylene dodecamide (nylon 612), polyundecane methylene adipamide (nylon 116), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polytrimethylhexamethylene terephthalamide, polyhexa Methylene isophthalamide (nylon 6I), polyhexamethylene terephthalate / isophthalamide (nylon 6T / 6I), polybis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl-4) Aminocyclohexyl) methane dodecamide (nylon dimethyl PACM12), polymetaxylylene adipamide (nylon MXD6), polyundecamethylene terephthalamide (nylon 11T), polyundecamethylene hexahydroterephthalamide (nylon 11T (H)) and These copolyamides, mixed polyamides and the like. Among these, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 116 and their copolymerized polyamide and mixed polyamide are preferable, and nylon 6, nylon 11, and nylon 12 are particularly preferable.

  Moreover, the melting point of the polyamide resin to be used is preferably 90 to 240 ° C, more preferably 100 to 230 ° C, from the problem of the thermal stability of the polylactic acid resin and the naturally occurring organic filler.

  In the present invention, a resin composition and a molded article excellent in surface appearance, moldability, mechanical properties, heat resistance and toughness can be obtained by blending a polyamide resin.

  Moreover, in this invention, an impact resistance improving agent can also be mix | blended as thermoplastic resins other than a polylactic acid resin. By blending a polylactic acid resin, a naturally derived organic filler, and an impact resistance improver, a resin composition and a molded product excellent in impact resistance, toughness, moldability and heat resistance can be obtained.

  The impact resistance improver used in the present invention is not particularly limited as long as it can be used for improving the impact resistance of a thermoplastic resin. For example, at least one selected from the following various impact resistance improvers can be used.

  That is, specific examples of impact modifiers include ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene-1 copolymers, various acrylic rubbers, ethylene-acrylic acid copolymers. And alkali metal salts thereof (so-called ionomers), ethylene-glycidyl (meth) acrylate copolymers, ethylene-alkyl acrylate copolymers (for example, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers) ), Acid-modified ethylene-propylene copolymer, diene rubber (for example, polybutadiene, polyisoprene, polychloroprene), copolymer of diene and vinyl monomer (for example, styrene-butadiene random copolymer, styrene-butadiene block copolymer) Coalescence, styrene-butadiene Styrene block copolymer, styrene-isoprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, polybutadiene grafted with styrene, butadiene-acrylonitrile copolymer) , Polyisobutylene, a copolymer of isobutylene and butadiene or isoprene, natural rubber, thiocol rubber, polysulfide rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber and the like.

  Furthermore, it is composed of those having various degrees of cross-linking, various micro structures such as those having a cis structure, a trans structure, etc., those having a vinyl group, etc., a core layer and one or more shell layers covering it, A so-called core-shell type multi-layered polymer in which adjacent layers are made of different polymers can also be used.

  The various (co) polymers mentioned in the above specific examples may be any of random copolymers, block copolymers and graft copolymers, and can be used as the impact resistance improver of the present invention. it can.

  Furthermore, in making these (co) polymers, it is also possible to copolymerize monomers such as other olefins, dienes, aromatic vinyl compounds, acrylic acid, acrylic ester and methacrylic ester. is there.

  Among these impact modifiers, a polymer containing an acrylic unit and a polymer containing a unit having an acid anhydride group and / or a glycidyl group are preferable. Preferable examples of the acrylic unit herein include methyl methacrylate units, methyl acrylate units, ethyl acrylate units and butyl acrylate units. Preferred examples of units having an acid anhydride group or glycidyl group May include maleic anhydride units and glycidyl methacrylate units.

  The impact resistance improver is a so-called core-shell type multi-layer polymer composed of a core layer and one or more shell layers covering the core layer, and adjacent layers are composed of different polymers. It is preferable that the polymer is a multilayer structure polymer containing methyl methacrylate units or methyl acrylate units in the shell layer. Such a multilayer structure polymer preferably contains an acrylic unit, or preferably contains a unit having an acid anhydride group and / or a glycidyl group. Preferred examples of the acrylic unit include a methyl methacrylate unit, an acrylic acid A methyl unit, an ethyl acrylate unit, and a butyl acrylate unit can be mentioned, As a suitable example of a unit which has an acid anhydride group and a glycidyl group, a maleic anhydride unit and a glycidyl methacrylate unit can be mentioned. In particular, the shell layer contains at least one selected from methyl methacrylate units, methyl acrylate units, maleic anhydride units and glycidyl methacrylate units, and includes butyl acrylate units, ethyl hexyl acrylate units, styrene units and butadiene units. A multilayer structure containing at least one selected from the above in the core layer is preferably used.

  The glass transition temperature of the impact resistance improver is preferably −20 ° C. or lower, and more preferably −30 ° C. or lower.

  The blending amount of the thermoplastic resin other than the polylactic acid resin in the present invention is preferably in the range of 0.5 to 120 parts by weight, and in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the polylactic acid resin. More preferably, it is more preferable that it is the range of 3-70 weight part, and it is especially preferable that it is the range of 5-50 weight part.

  In this invention, it is preferable to mix | blend fillers other than the natural origin organic filler which satisfy | fills the requirements prescribed | regulated to this invention. By blending fillers other than naturally-derived organic fillers that satisfy the requirements stipulated in the present invention, it is possible to obtain molded articles having excellent mechanical properties, heat resistance, and low-temperature moldability.

  As fillers other than naturally-derived organic fillers that satisfy the requirements defined in the present invention, fiber-like, plate-like, granular, and powdery ones that are usually used for reinforcing thermoplastic resins can be used. Specifically, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, sepiolite, asbestos, slag fiber, zonolite, Elastadite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, and fibrous inorganic fillers such as boron fiber, fibrous organic fillers such as polyester fiber, nylon fiber, acrylic fiber, Glass flakes, non-swelling mica, graphite, metal foil, ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, finely divided silicic acid, feldspar powder, potassium titanate, shirasu balloon, carbonic acid Plate-like and granular inorganic fillers such as Lucium, Magnesium carbonate, Barium sulfate, Calcium oxide, Aluminum oxide, Titanium oxide, Aluminum silicate, Silicon oxide, Gypsum, Novacurite, Dawsonite and Clay, meet the requirements specified in the present invention There are no naturally-occurring organic fillers. Among these fillers, fibrous inorganic fillers or plate-like inorganic fillers, and naturally-occurring organic fillers that do not satisfy the requirements stipulated in the present invention are preferable, particularly glass fibers, wollastonite, boric acid. Aluminum whiskers, potassium titanate whiskers, mica and kaolin are preferred. These fillers can be used alone or in combination of two or more. The aspect ratio of the fibrous filler is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more.

  Fillers other than naturally-derived organic fillers that satisfy the requirements specified in the present invention are coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin. It may be treated with a coupling agent such as aminosilane or epoxysilane.

  In the present invention, a layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions is added as a filler other than the naturally-occurring organic filler that satisfies the requirements stipulated in the present invention. Is preferred. In the present invention, the layered silicate in which the exchangeable cation existing between the layers is exchanged with the organic onium ion is the exchange of the exchangeable cation of the layered silicate having the exchangeable cation between the layers with the organic onium ion. Inclusion compound.

  A layered silicate having an exchangeable cation between layers has a structure in which plate-like materials having a width of 0.05 to 0.5 μm and a thickness of 6 to 15 angstroms are laminated. Has a cation. The cation exchange capacity is 0.2 to 3 meq / g, and preferably the cation exchange capacity is 0.8 to 1.5 meq / g.

  Specific examples of layered silicates include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate, and titanium phosphate, Li type Examples include swellable mica such as fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, and Li-type tetrasilicon fluorine mica, and may be natural or synthesized. Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Na-type tetrasilicon fluorine mica and Li-type fluorine teniolite are preferable.

  Examples of organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred. As the ammonium ion, any of primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium may be used.

  Primary ammonium ions include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like.

  Secondary ammonium ions include methyl dodecyl ammonium and methyl octadecyl ammonium.

  Examples of tertiary ammonium ions include dimethyl dodecyl ammonium and dimethyl octadecyl ammonium.

  Quaternary ammonium ions include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium, trimethyloctylammonium, trimethyldodecylammonium, and trimethyloctadecylammonium. Alkyltrimethylammonium ions such as dimethyldioctylammonium, dimethyldidodecylammonium, dimethyldialkylammonium ions such as dimethyldioctadecylammonium, trialkylmethylammonium ions such as trioctylmethylammonium and tridodecylmethylammonium, benzene Such as benzethonium ion having two thereof.

  Besides these, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, amino at the terminal Examples also include ammonium ions derived from polyalkylene glycols having a group.

  Among these ammonium ions, preferred compounds include trioctylmethylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium and the like. These ammonium ions are generally available as a mixture, and the above compound names are representative compound names containing a small amount of analogs. These may be used alone or in combination of two or more.

  Further, those having a reactive functional group and those having high affinity are preferable, and ammonium ions derived from 12-aminododecanoic acid, polyalkylene glycol having an amino group at the terminal, and the like are also preferable.

  The layered silicate in which the exchangeable cation existing in the interlayer used in the present invention is exchanged with the organic onium ion is obtained by reacting the layered silicate having the exchangeable cation between the layer and the organic onium ion by a known method. Can be manufactured. Specifically, a method by an ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method by directly reacting a layered silicate with a liquid or melted ammonium salt may be used.

  In the present invention, the amount of organic onium ions relative to the layered silicate is determined by the cation exchange of the layered silicate in terms of the dispersibility of the layered silicate, the thermal stability during melting, the gas during molding, the suppression of odor generation, etc. Usually, the amount is in the range of 0.4 to 2.0 equivalents, preferably 0.8 to 1.2 equivalents with respect to the capacity.

  In addition to the above organic onium salts, these layered silicates are preferably pretreated with a coupling agent having a reactive functional group in order to obtain better mechanical strength. Examples of the coupling agent having a reactive functional group include isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds.

  In the present invention, the blending amount of the filler other than the naturally derived organic filler that satisfies the requirements defined in the present invention is preferably 0.1 to 300 parts by weight with respect to 100 parts by weight of the polylactic acid resin. -200 weight part is more preferable, 1-100 weight part is further more preferable, and 1-50 weight part is especially preferable.

  In the present invention, a stabilizer is preferably blended from the viewpoint that a resin composition and a molded product excellent in mechanical properties, moldability, heat resistance and durability can be easily obtained. As a stabilizer used by this invention, what is normally used for the stabilizer of a thermoplastic resin can be used. Specific examples include antioxidants and ultraviolet absorbers.

  Examples of the antioxidant used in the present invention include hindered phenol compounds, phosphite compounds, and thioether compounds.

  Examples of hindered phenol compounds include n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl- 5'-tert-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexanediol -Bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis- [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate], 2,2′-methylenebis- (4-methyl-t-butylphenol), triethylene glycol-bis- [3- (3-t-butyl-5- Til-4-hydroxyphenyl) propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane, N, N′- Bis-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionylhexamethylenediamine, N, N′-tetramethylene-bis-3- (3′-methyl-5′-t -Butyl-4'-hydroxyphenol) propionyldiamine, N, N'-bis- [3- (3,5-di-t-butyl-4-hydroxyphenol) propionyl] hydrazide N-salicyloyl-N'-salicylidenehydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N'-bis [2- {3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide and the like. Preferably, triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl- 4'-hydroxyphenyl) propionate] methane.

  As the phosphite compound, those in which at least one P—O bond is bonded to an aromatic group are preferable. Specific examples include tris (2,4-di-t-butylphenyl) phosphite, tetrakis ( 2,4-di-t-butylphenyl) 4,4′-biphenylenephosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,6-di-) t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl) -6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butyl-phenyl) Nyl) butane, tris (mixed mono and di-nonylphenyl) phosphite, tris (nonylphenyl) phosphite, 4,4′-isopropylidenebis (phenyl-dialkyl phosphite) and the like, and tris (2, 4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) Pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenephosphonite and the like can be preferably used.

  Specific examples of the thioether compound include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropioate). Nate), pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis ( 3-stearyl thiopropionate).

  Examples of the ultraviolet absorber used in the present invention include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds and hindered amine compounds.

  Specific examples of benzophenone compounds include benzophenone, 2,4-dihydrobenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2,2′-dihydroxy. -4,4'-dimethoxybenzophenone, 2,2'-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-5 Sulfobenzophenone, 5-chloro-2-hydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy -4- (2-hydroxy-3-methyl-acrylic Such as carboxymethyl isopropoxycarbonyl benzophenone and the like.

  Specific examples of the benzotriazole-based compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-5′-methyl-phenyl) benzotriazole, 2 -(3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-isoamyl-2-hydroxyphenyl) benzotriazole, (2-hydroxy- 5-tert-butylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-di Tylbenzyl) phenyl] benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis- (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy-4′- Octoxyphenyl) benzotriazole and the like.

  Specific examples of the aromatic benzoate compound include alkylphenyl salicylates such as pt-butylphenyl salicylate and p-octylphenyl salicylate.

  Specific examples of oxalic acid anilide compounds include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, 2- And ethoxy-3′-dodecyl oxalic acid bisanilide.

  Specific examples of the cyanoacrylate compound include ethyl-2-cyano-3,3'-diphenyl-acrylate, 2-ethylhexyl-2-cyano-3,3'-diphenyl-acrylate, and the like.

  Specific examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2. , 2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy -2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyl Oxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (d Rucarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6 6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) -carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -oxalate, bis (2, 2,6,6-tetramethyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (2,2,6,6-tetramethyl-4 -Piperidyl) -adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (2,2,6,6-tetramethyl) Ru-4-piperidyloxy) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl) -4-piperidyltolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6, 6-tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxy 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyl Xy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′, Examples include condensates with β ′,-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.

In the present invention, the stabilizer may be used alone or in combination of two or more. Moreover, it is preferable to use a hindered phenol compound and / or a benzotriazole compound as the stabilizer. The blending amount of the stabilizer is 0.01 to 3 parts by weight with respect to 100 parts by weight of the polylactic acid resin. Preferably, 0.03 to 2 parts by weight is more preferable.

  In the present invention, a release agent is preferably blended from the viewpoint that a resin composition and a molded product excellent in mechanical properties, moldability, heat resistance and durability can be easily obtained. As the mold release agent used in the present invention, those usually used for a thermoplastic resin mold release agent can be used. Specifically, fatty acids, fatty acid metal salts, oxy fatty acids, fatty acid esters, partially aliphatic saponified esters, paraffin, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid lower alcohol esters, fatty acid polyhydric alcohols Examples thereof include esters, fatty acid polyglycol esters, and modified silicones.

  As the fatty acid, those having 6 to 40 carbon atoms are preferable. Specifically, oleic acid, lauric acid, stearic acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, Examples include stearic acid, montanic acid, and mixtures thereof. As the fatty acid metal salt, an alkali metal salt or an alkaline earth metal salt of a fatty acid having 6 to 40 carbon atoms is preferable, and specific examples include calcium stearate, sodium montanate, and calcium montanate. Examples of the oxy fatty acid include 1,2-oxystearic acid, and examples of the fatty acid ester include stearic acid ester, oleic acid ester, linoleic acid ester, linolenic acid ester, adipic acid ester, behenic acid ester, arachidic acid ester, and montan. Examples of the acid ester, isostearic acid ester, ester of polymerized acid, and aliphatic partially saponified ester include montanic acid partially saponified ester. As the paraffin, those having 18 or more carbon atoms are preferable, and examples thereof include liquid paraffin, natural paraffin, microcrystalline wax, petrolatum, and the like, and the low molecular weight polyolefin preferably has a molecular weight of 5000 or less, specifically, polyethylene wax, Examples thereof include maleic acid-modified polyethylene wax, oxidized type polyethylene wax, chlorinated polyethylene wax, and polypropylene wax. Fatty acid amides preferably have 6 or more carbon atoms, and specifically include oleic acid amide, erucic acid amide, and behen. Examples of the alkylene bis fatty acid amide include those having 6 or more carbon atoms. Specifically, methylene bis stearamide, ethylene bis stearamide, N, N-bis (2-H Droxyethyl) stearamide and the like, examples of the aliphatic ketone include higher aliphatic ketones, and the fatty acid lower alcohol ester preferably has 6 or more carbon atoms, ethyl stearate butyl stearate, ethyl behenate, Examples of the fatty acid polyhydric alcohol ester include glycerin monostearate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol adipate stearate, dipentaerythritol adipate stearate, sorbitan monobehe Examples of fatty acid polyglycol esters include polyethylene glycol fatty acid esters and polypropylene glycol fatty acid esters. Examples of the corn include tilstyryl-modified silicone, polyether-modified silicone, higher fatty acid alkoxy-modified silicone, higher fatty acid-containing silicone, higher fatty acid ester-modified silicone, methacryl-modified silicone, and fluorine-modified silicone.

  Among the above, fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, fatty acid partial saponified ester, paraffin, low molecular weight polyolefin, aliphatic amide, alkylene bis fatty acid amide are preferred, and fatty acid partial saponified ester and / or alkylene bis fatty acid amide are preferred. More preferred.

  Of these, montanic acid ester, montanic acid partial saponified ester, polyethylene wax, oxidized polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylene bis stearic acid amide are preferable, and particularly, montanic acid partial saponified ester and ethylene bis stearic acid amide are preferable. .

  In this invention, the said mold release agent may be used by 1 type, and may be used in combination of 2 or more type.

  Moreover, 0.01-3 weight part is preferable with respect to 100 weight part of polylactic acid resin, and, as for the compounding quantity of a mold release agent, 0.03-2 weight part is more preferable.

  In the present invention, it is preferable to add a carboxyl group-reactive end-blocking agent from the viewpoint that durability such as mechanical properties, wet heat resistance and dry heat resistance is easily improved. The carboxyl group-reactive end-blocking agent used in the present invention is not particularly limited as long as it is a compound that can block the carboxyl end group of the polymer, and those used as the carboxyl-terminal blocking agent of the polymer are used. be able to. In the present invention, such a carboxyl group-reactive end-blocking agent is not only used to block the end of a polylactic acid resin, but also an acidic low-molecular compound produced by thermal decomposition or hydrolysis of a polylactic acid resin or a natural organic filler. Acidic groups can also be blocked. Further, the end-capping agent is more preferably a compound that can also block the hydroxyl end where an acidic low molecular weight compound is generated by thermal decomposition.

  As such a carboxyl group-reactive end-blocking agent, it is preferable to use at least one compound selected from an epoxy compound, an oxazoline compound, an oxazine compound, and a carbodiimide compound, and among them, an epoxy compound and / or a carbodiimide compound are preferable. .

  As an epoxy compound that can be used as a carboxyl group-reactive end-blocking agent in the present invention, a glycidyl ether compound, a glycidyl ester compound, a glycidyl amine compound, a glycidyl imide compound, and an alicyclic epoxy compound can be preferably used. By blending these, a molded product having excellent mechanical properties, moldability, heat resistance and durability can be obtained.

  Examples of glycidyl ether compounds include butyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, o-phenylphenyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, ethylene oxide phenol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol Diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane trig Bisphenols such as sidyl ether, pentaerythritol polyglycidyl ether, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone; Examples thereof include a bisphenol A diglycidyl ether type epoxy resin, a bisphenol F diglycidyl ether type epoxy resin, a bisphenol S diglycidyl ether type epoxy resin obtained from a condensation reaction with epichlorohydrin. Among these, bisphenol A diglycidyl ether type epoxy resin is preferable.

  Examples of glycidyl ester compounds include benzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, stearic acid glycidyl ester, lauric acid glycidyl ester, palmitic acid glycidyl ester, versatic acid glycidyl ester, oleic acid glycidyl ester Ester, linoleic acid glycidyl ester, linolenic acid glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, naphthalene dicarboxylic acid diglycidyl ester, bibenzoic acid diglycidyl ester, methyl terephthalic acid diglycidyl ester , Hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, Hexane dicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetra A glycidyl ester etc. can be mentioned. Among these, benzoic acid glycidyl ester and versatic acid glycidyl ester are preferable.

  Examples of glycidylamine compounds include tetraglycidylaminodiphenylmethane, triglycidyl-paraaminophenol, triglycidyl-metaaminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylenediamine, diglycidyltribromoaniline, tetraglycidylbisamino Examples include methylcyclohexane, triglycidyl cyanurate, and triglycidyl isocyanurate.

  Examples of glycidylimide compounds include N-glycidylphthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl-3-methylphthalimide, N-glycidyl-3,6- Dimethylphthalimide, N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, N-glycidyl-3,4,5,6-tetrabromophthalimide, N -Glycidyl-4-n-butyl-5-bromophthalimide, N-glycidyl succinimide, N-glycidyl hexahydrophthalimide, N-glycidyl-1,2,3,6-tetrahydrophthalimide, N-glycidyl maleimide, N- Glycidyl-α, β-dimethyl Succinimide, N-glycidyl-α-ethylsuccinimide, N-glycidyl-α-propylsuccinimide, N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, N-glycidylnaphthamide, N-glycidylsteramide, etc. be able to. Of these, N-glycidylphthalimide is preferable.

  Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, N-methyl-4, 5-epoxycyclohexane-1,2-dicarboxylic imide, N-ethyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide N-naphthyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-tolyl-3-methyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, and the like.

  Further, as other epoxy compounds, epoxy-modified fatty acid glycerides such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized whale oil, phenol novolac type epoxy resins, cresol nozolac type epoxy resins, and the like can be used.

  Examples of the oxazoline compound that can be used as a carboxyl group-reactive end-blocking agent used in the present invention include 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline, 2-propoxy-2-oxazoline, 2-butoxy 2-oxazoline, 2-pentyloxy-2-oxazoline, 2-hexyloxy-2-oxazoline, 2-heptyloxy-2-oxazoline, 2-octyloxy-2-oxazoline, 2-nonyloxy-2-oxazoline, 2 -Decyloxy-2-oxazoline, 2-cyclopentyloxy-2-oxazoline, 2-cyclohexyloxy-2-oxazoline, 2-allyloxy-2-oxazoline, 2-methallyloxy-2-oxazoline, 2-crotyloxy-2-oxazoline , 2-pheno Ci-2-oxazoline, 2-cresyl-2-oxazoline, 2-o-ethylphenoxy-2-oxazoline, 2-o-propylphenoxy-2-oxazoline, 2-o-phenylphenoxy-2-oxazoline, 2-m -Ethylphenoxy-2-oxazoline, 2-m-propylphenoxy-2-oxazoline, 2-p-phenylphenoxy-2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl- 2-oxazoline, 2-butyl-2-oxazoline, 2-pentyl-2-oxazoline, 2-hexyl-2-oxazoline, 2-heptyl-2-oxazoline, 2-octyl-2-oxazoline, 2-nonyl-2- Oxazoline, 2-decyl-2-oxazoline, 2-cyclopentyl-2-oxy Zolin, 2-cyclohexyl-2-oxazoline, 2-allyl-2-oxazoline, 2-methallyl-2-oxazoline, 2-crotyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-o-ethylphenyl-2 -Oxazoline, 2-o-propylphenyl-2-oxazoline, 2-o-phenylphenyl-2-oxazoline, 2-m-ethylphenyl-2-oxazoline, 2-m-propylphenyl-2-oxazoline, 2-p -Phenylphenyl-2-oxazoline, 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (4,4'-dimethyl- 2-oxazoline), 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4,4'-diethyl-2-oxy) Sazoline), 2,2'-bis (4-propyl-2-oxazoline), 2,2'-bis (4-butyl-2-oxazoline), 2,2'-bis (4-hexyl-2-oxazoline) 2,2'-bis (4-phenyl-2-oxazoline), 2,2'-bis (4-cyclohexyl-2-oxazoline), 2,2'-bis (4-benzyl-2-oxazoline), 2 , 2'-p-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-o-phenylenebis (2-oxazoline), 2,2'-p -Phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2) -Oxazoline), 2, 2 -M-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-ethylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2,2'- Hexamethylene bis (2-oxazoline), 2,2'-octamethylene bis (2-oxazoline), 2,2'-decamethylene bis (2-oxazoline), 2,2'-ethylenebis (4-methyl-2) -Oxazoline), 2,2'-tetramethylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-9,9'-diphenoxyethanebis (2-oxazoline), 2,2'- Examples include cyclohexylenebis (2-oxazoline), 2,2'-diphenylenebis (2-oxazoline), and the like. Furthermore, the polyoxazoline compound etc. which contain the above-mentioned compound as a monomer unit can be mentioned.

  Examples of oxazine compounds as carboxyl group-reactive endblockers that can be used in the present invention include 2-methoxy-5,6-dihydro-4H-1,3-oxazine, 2-ethoxy-5,6-dihydro. -4H-1,3-oxazine, 2-propoxy-5,6-dihydro-4H-1,3-oxazine, 2-butoxy-5,6-dihydro-4H-1,3-oxazine, 2-pentyloxy- 5,6-dihydro-4H-1,3-oxazine, 2-hexyloxy-5,6-dihydro-4H-1,3-oxazine, 2-heptyloxy-5,6-dihydro-4H-1,3- Oxazine, 2-octyloxy-5,6-dihydro-4H-1,3-oxazine, 2-nonyloxy-5,6-dihydro-4H-1,3-oxazine, 2-decyloxy-5 6-dihydro-4H-1,3-oxazine, 2-cyclopentyloxy-5,6-dihydro-4H-1,3-oxazine, 2-cyclohexyloxy-5,6-dihydro-4H-1,3-oxazine, 2-allyloxy-5,6-dihydro-4H-1,3-oxazine, 2-methallyloxy-5,6-dihydro-4H-1,3-oxazine, 2-crotyloxy-5,6-dihydro-4H- 1,3-oxazine and the like, and further, 2,2′-bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-methylenebis (5,6-dihydro-4H— 1,3-oxazine), 2,2'-ethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-propylenebis (5,6-dihydro-4H-1,3- Oxazi ), 2,2'-butylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2, 2'-p-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-m-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2, 2'-naphthylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-P, P'-diphenylene bis (5,6-dihydro-4H-1,3-oxazine), etc. Can be mentioned. Furthermore, the polyoxazine compound etc. which contain an above-described compound as a monomer unit are mentioned.

  Among the oxazoline compounds and oxazine compounds, 2,2′-m-phenylenebis (2-oxazoline) and 2,2′-p-phenylenebis (2-oxazoline) are preferable.

  The carbodiimide compound that can be used as a carboxyl group-reactive end-blocking agent in the present invention is a compound having at least one carbodiimide group represented by (—N═C═N—) in the molecule. The organic isocyanate can be heated in the presence of a simple catalyst and produced by a decarboxylation reaction.

  Examples of carbodiimide compounds include diphenylcarbodiimide, di-cyclohexylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, diisopropylcarbodiimide, dioctyldecylcarbodiimide, di-o-toluylcarbodiimide, di-p-toluylcarbodiimide, di-p- Nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2 , 5-dichlorophenylcarbodiimide, p-phenylene-bis-o-toluylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene- Su-di-p-chlorophenylcarbodiimide, 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide, hexamethylene-bis-cyclohexylcarbodiimide, ethylene-bis-diphenylcarbodiimide, ethylene-bis-dicyclohexylcarbodiimide, N , N′-di-o-triylcarbodiimide, N, N′-diphenylcarbodiimide, N, N′-dioctyldecylcarbodiimide, N, N′-di-2,6-dimethylphenylcarbodiimide, N-triyl-N ′ -Cyclohexylcarbodiimide, N, N'-di-2,6-diisopropylphenylcarbodiimide, N, N'-di-2,6-di-tert-butylphenylcarbodiimide, N-toluyl-N'-phenylcarbodiimide, N, N'-di-p-nitrophenyl Carbodiimide, N, N′-di-p-aminophenylcarbodiimide, N, N′-di-p-hydroxyphenylcarbodiimide, N, N′-di-cyclohexylcarbodiimide, N, N′-di-p-toluylcarbodiimide, N, N'-benzylcarbodiimide, N-octadecyl-N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N-octadecyl-N'-tolylcarbodiimide, N-cyclohexyl-N'-tolylcarbodiimide, N- Phenyl-N'-tolylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, N, N'-di-o-ethylphenylcarbodiimide, N, N'-di-p-ethylphenylcarbodiimide, N, N'-di -O-isopropylphenylcarbodiimide, N, N'-di p-isopropylphenylcarbodiimide, N, N'-di-o-isobutylphenylcarbodiimide, N, N'-di-p-isobutylphenylcarbodiimide, N, N'-di-2,6-diethylphenylcarbodiimide, N, N '-Di-2-ethyl-6-isopropylphenylcarbodiimide, N, N'-di-2-isobutyl-6-isopropylphenylcarbodiimide, N, N'-di-2,4,6-trimethylphenylcarbodiimide, N, Mono- or dicarbodiimide compounds such as N'-di-2,4,6-triisopropylphenylcarbodiimide, N, N'-di-2,4,6-triisobutylphenylcarbodiimide, poly (1,6-hexamethylenecarbodiimide) ), Poly (4,4'-methylenebiscyclohexylcarbodiimide), Poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide), poly (4,4'-diphenylmethanecarbodiimide), poly (3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide) , Poly (naphthylene carbodiimide), poly (p-phenylene carbodiimide), poly (m-phenylene carbodiimide), poly (tolyl carbodiimide), poly (diisopropylcarbodiimide), poly (methyl-diisopropylphenylene carbodiimide), poly (triethylphenylene carbodiimide) ) And polycarbodiimides such as poly (triisopropylphenylenecarbodiimide). Of these, N, N′-di-2,6-diisopropylphenylcarbodiimide, 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide, and polycarbodiimide are preferable.

  As the carboxyl group-reactive end-blocking agent, one or more compounds can be arbitrarily selected and used.

In the resin composition of the present invention, the carboxyl terminal and the acidic low molecular compound may be appropriately blocked according to the use to be used as a molded product, but the specific carboxyl terminal and acidic low molecular compound are blocked. From the viewpoint of hydrolysis resistance, it is preferable to adjust the addition amount so that the acid concentration in the composition is 10 equivalents / 10 ⁶ g or less, and the acid concentration in the composition is adjusted to 5 equivalents / 10 ⁶ g or less. More preferably, it is particularly preferable to adjust to 1 equivalent / 10 ⁶ g or less. The acid concentration in the polymer composition can be measured by dissolving the polymer composition in a suitable solvent and then titrating with an alkali compound solution such as sodium hydroxide having a known concentration, or by NMR.

  0.01-10 weight part is preferable with respect to 100 weight part of polylactic acid resin, and, as for the quantity of a carboxyl group reactive terminal blocker, 0.05-5 weight part is further more preferable.

  In the present invention, it is preferable to further add a reaction catalyst of a carboxyl group reactive end-blocking agent. The reaction catalyst referred to here is a compound that has an effect of promoting the reaction between the carboxyl group-reactive end-blocking agent and the polymer end or the acidic group of the acidic low-molecular compound, and has the effect of promoting the reaction with a small amount of addition. Certain compounds are preferred. Examples of such compounds include alkali metal compounds, alkaline earth metal compounds, tertiary amine compounds, imidazole compounds, quaternary ammonium salts, phosphine compounds, phosphonium salts, phosphate esters, organic acids, Lewis acids. Specific examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, stearin Sodium phosphate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, hydrogen phosphate Dipotassium, Alkali metal compounds such as dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, sodium salt of phenol, potassium salt, lithium salt, cesium salt, calcium hydroxide, water Alkaline earth such as barium oxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, magnesium stearate, strontium stearate Metal compounds, triethylamine, tributylamine, trihexylamine, triamylamine, triethanolamine, dimethylaminoethanol, triethylenediamine, dimethylphenylamine , Dimethylbenzylamine, 2- (dimethylaminomethyl) phenol, dimethylaniline, pyridine, picoline, tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7, 2-methylimidazole, 2-ethyl Imidazole, 2-isopropylimidazole, 2-ethyl-4-methylimidazole, imidazole compounds such as 4-phenyl-2-methylimidazole, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium chloride, triethylbenzyl Quaternary ammonium salts such as ammonium chloride, tripropylbenzylammonium chloride, N-methylpyridinium chloride, trimethylphosphine, Phosphine compounds such as triethylphosphine, tributylphosphine, trioctylphosphine, phosphonium salts such as tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium bromide, triphenylbenzylphosphonium bromide, trimethyl phosphate, triethyl phosphate , Tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tri (p-hydroxy) phenyl phosphate, tri (p-methoxy ) Phenyl phosphate Phosphoric acid esters, oxalic acid, p-toluenesulfonic acid, dinonylnaphthalenedisulfonic acid, organic acids such as dodecylbenzenesulfonic acid, Lewis acids such as boron trifluoride, aluminum tetrachloride, titanium tetrachloride, tin tetrachloride, etc. These may be used alone or in combination of two or more. Among these, it is preferable to use an alkali metal compound, an alkaline earth metal compound, and a phosphate ester, and particularly an alkali metal or an organic salt of an alkaline earth metal can be preferably used. Particularly preferred compounds are sodium stearate, potassium stearate, calcium stearate, magnesium stearate, sodium benzoate, sodium acetate, potassium acetate, calcium acetate and magnesium acetate. Further, an organic salt of an alkali metal or alkaline earth metal having 6 or more carbon atoms is preferable, and it is preferable to use one or more of sodium stearate, potassium stearate, calcium stearate, magnesium stearate, and sodium benzoate.

  The addition amount of the reaction catalyst is not particularly limited, but when the polylactic acid resin is 100 parts by weight, 0.001 to 1 part by weight is preferable, and 0.01 to 0.1 part by weight is more preferable. Furthermore, 0.02 to 0.1 parts by weight is most preferable.

  In this invention, it is preferable to mix | blend a foaming agent from the point that light weight, heat resistance, and a mechanical characteristic are easy to improve. As the foaming agent, a chemical foaming agent, a physical foaming agent, or the like can be used, but a chemical foaming agent is preferable in terms of easy control of the foaming ratio and bubbles.

  Chemical foaming agents include azo compounds such as azodicarbonamide, azobisisobutyronitrile, barium azodicarboxylate, hydrazide compounds such as 4,4′-oxybisbenzenesulfonyl hydrazide and p-toluenesulfonyl hydrazide, dinitrosopenta Nitroso compounds such as methylenetetramine, hydrazo compounds such as hydrazodicarbonamide, 5-phenyltetrazole, 5-aminotetrazole, azobistetrazole, bistetrazole and other tetrazole compounds, hydrazodicarboxylic acid esters, azodicarboxylic acid esters, Examples thereof include ester compounds such as citric acid esters, isocyanate compounds, sodium bicarbonate, sodium carbonate, and the like, and azodicarbonamide and azobis Preferred are azo compounds such as butyronitrile and barium azodicarboxylate, tetrazole compounds such as 5-phenyltetrazole, 5-aminotetrazole, azobistetrazole, and bistetrazole, and isocyanate compounds, and azodicarbonamide and azobisisobutyridine. Azo compounds such as nitrile and barium azodicarboxylate are more preferred, and azodicarbonamide is more preferred.

  Physical foaming agents include ethane, butane, pentane, hexane, heptane, ethylene, propylene, petroleum ether, methyl chloride, monochlorotrifluoromethane, dichlorodifluoromethane, dichlorotetrafluoroethane, water, air, carbon dioxide, nitrogen gas Butane, pentane, hexane, water, air, carbon dioxide gas, nitrogen gas are preferred, water, air, carbon dioxide gas, nitrogen gas are more preferred, water, air, Carbon dioxide gas is more preferable. In addition, it is preferable to use a substance that can be used as a supercritical fluid such as carbon dioxide gas or nitrogen gas as a foaming agent in a supercritical fluid state because a foam that does not decrease in strength can be obtained.

  The blending amount of the foaming agent is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 15 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polylactic acid resin. More preferably, it is part by weight.

  Moreover, it is preferable to mix | blend a foaming adjuvant by the point that a foaming behavior is stabilized and a foaming magnification, a foam density, and a bubble size become easy to control. Foaming aids include metal oxides such as zinc oxide, calcium oxide, aluminum oxide, and aliphatic salts such as zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, calcium montanate, magnesium montanate, and aluminum montanate. , Paraffin, alumina, talc, calcium carbonate, mica, silica, kaolin and the like.

  The blending amount of the foaming aid is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the polylactic acid resin. More preferably, it is part by weight.

  In this invention, it is preferable to mix | blend a flame retardant with the point that a flame retardance can be provided. In the present invention, the flame retardant is not particularly limited as long as it is a substance added for the purpose of imparting flame retardancy to the resin, and a known one can be used. Specific examples include brominated flame retardants, chlorine-based flame retardants, phosphorus-based flame retardants, nitrogen compound-based flame retardants, silicone-based flame retardants, and other inorganic flame retardants. It can be used by 1 type (s) or 2 or more types. The flame retardant is preferably a flame retardant having a low environmental impact. Environment-friendly flame retardants include those that are biodegradable, those that do not generate toxic gases during incineration, those that are derived from non-petroleum raw materials such as plant resources, or natural raw materials. Flame retardants, nitrogen compound flame retardants, silicone flame retardants, and other inorganic flame retardants are preferred.

  The blending amount of the flame retardant is 0.01 to 100 parts by weight, more preferably 0.5 to 90 parts by weight, and further preferably 1 to 80 parts by weight with respect to 100 parts by weight of the polylactic acid resin.

  Among the above flame retardants, it is preferable to use at least one selected from phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants, and other inorganic flame retardants. Phosphorus flame retardants, nitrogen compound flame retardants It is more preferable to use a combination of at least two selected from flame retardants, silicone flame retardants and other inorganic flame retardants.

  When using a phosphorus-based flame retardant and a nitrogen compound-based flame retardant in combination, the phosphorus-based flame retardant includes at least one of phosphoric acid ester, condensed phosphoric acid ester, polyphosphate, and red phosphorus, especially condensed phosphorus. Any one or more of acid esters and polyphosphates are preferred, and more preferably biodegradable. Further, it is more preferable to use a condensed phosphate ester and a nitrogen compound-based flame retardant together, or it is more preferable to use a polyphosphate and a nitrogen compound-based flame retardant together, and the nitrogen compound-based flame retardant is used more than the condensed phosphate ester or the polyphosphate. It is preferable to use a small amount because of its high flame retardant effect. The condensed phosphate ester is preferably an aromatic condensed phosphate ester, preferably resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, and resorcinol poly (di-2,6-xylyl) phosphate. As a commercially available example, PX-200 manufactured by Daihachi Chemicals may be mentioned. The nitrogen compound flame retardant is preferably a triazine compound, and more preferably melamine cyanurate. A silicone resin is preferable as the silicone flame retardant used in combination with the phosphorus flame retardant. Further, as the other inorganic flame retardant used in combination with the phosphorus flame retardant, zinc borate or swellable graphite is preferable.

  When a phosphorus flame retardant and a nitrogen compound flame retardant, a silicone flame retardant, or other inorganic flame retardant are used in combination, a nitrogen compound flame retardant, a silicone flame retardant, or the like with respect to 100 parts by weight of the phosphorus flame retardant It is preferable to use 1 to 100 parts by weight of the inorganic flame retardant.

  In the present invention, it is preferable to further blend an antistatic agent in terms of imparting antistatic properties. Any known antistatic agent can be used in the present invention.

  In the antistatic agent of the present invention, its ionicity is not particularly limited, and any of cationic, anionic, zwitterionic and nonionic may be used, but the thermal decomposition of the polylactic acid resin is suppressed. In terms of being able to be made, zwitterionic and nonionic systems are preferable, and nonionic systems are more preferable. Furthermore, it is preferable that the antistatic agent is biodegradable. Examples of such include Riken Master GSR-350 made by Riken Vitamin.

  0.1-10 weight part is preferable with respect to 100 weight part of polylactic acid resin, and, as for the compounding quantity of said antistatic agent, 0.5-5 weight part is further more preferable.

  In the present invention, the temperature drop crystallization temperature (Tc) derived from the polylactic acid resin in the resin composition is not particularly limited, but is preferably 80 ° C. or higher, and 85 ° C. or higher in terms of having excellent crystallization characteristics. Is more preferable, 100 ° C. or higher is further preferable, and 110 ° C. or higher is particularly preferable. The upper limit of Tc is not particularly limited, and the higher the value, the better the crystallization characteristics. Therefore, the upper limit of Tc may be less than the melting point of the polylactic acid resin. Here, Tc is the crystallization temperature at the time of temperature decrease derived from the polylactic acid resin in the resin composition measured by DSC at a temperature decrease rate of 20 ° C./min, and is the peak top temperature of the observed crystallization peak. It is. Further, the crystallization start temperature and the crystallization end temperature at the crystallization peak are not particularly limited, but from the viewpoint of moldability, the difference between the crystallization start temperature and the crystallization end temperature is preferably 50 ° C. or less, The temperature is more preferably 40 ° C. or lower, further preferably 35 ° C. or lower, and particularly preferably 30 ° C. or lower. Such a resin composition having Tc and a crystallization peak can be obtained by using a polylactic acid resin having a preferred embodiment and a naturally derived organic filler.

  In the present invention, the relationship between the melting point (Tm) derived from the polylactic acid resin in the resin composition and Tc is not particularly limited, but Tm-Tc is 30 to 120 in that it has excellent crystallization characteristics. It is preferably in the range of ° C, more preferably in the range of 35-60 ° C, and further preferably in the range of 40-50 ° C. Here, Tm is a melting point derived from the polylactic acid resin in the resin composition measured by DSC at a temperature rising rate of 20 ° C./min. The resin composition having such characteristics can be obtained by using a polylactic acid resin having a preferable aspect or a naturally-derived organic filler, and more preferably, a polylactic acid resin having a preferable aspect and a naturally-derived organic filler. It can be obtained by using an organic filler.

  In terms of heat resistance, the resin composition of the present invention preferably has a deflection temperature under load of 80 ° C. or higher measured according to ASTM method D648 under conditions of a load of 0.45 MPa and a heating rate of 120 ° C./min. . If it is less than 80 degreeC, it exists in the tendency for heat resistance to run short and the use which can be used is limited. Further, from the viewpoint of heat resistance, it is more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, particularly preferably 110 ° C. or higher, and most preferably 125 ° C. or higher. The resin composition that satisfies the above-mentioned deflection temperature under load uses a natural organic filler that satisfies the requirements stipulated in the present invention, and by applying an optimal manufacturing method or molding method, a long molding cycle time or a heat treatment after molding. Can be obtained without the need.

  The method for producing the resin composition of the present invention is not particularly limited. For example, after pre-blending a polylactic acid resin, a naturally-derived organic filler, and other additives as necessary, at a melting point or higher. A method of uniformly kneading with a single screw or twin screw extruder, a method of removing the solvent after mixing in a solution, and the like are preferably used.

  The melt kneading temperature (cylinder temperature) when producing the resin composition of the present invention is preferably 160 to 240 ° C, more preferably 170 ° C to 230 ° C, particularly preferably 175 to 220 ° C, and 180 ° C to 200 ° C. Is most preferred. If the melt kneading temperature (cylinder temperature) is less than 160 ° C, the polylactic acid resin tends to be difficult to melt, and if the melt kneading temperature (cylinder temperature) exceeds 240 ° C, burning tends to occur.

  The resin composition of the present invention can be processed into various molded products and used by a general thermoplastic resin molding method, for example, injection molding, extrusion molding, blow molding, press molding, or the like.

  In the present invention, when a mold is used at the time of molding, the mold temperature is not particularly limited, but is preferably 30 ° C to 150 ° C, more preferably 60 ° C to 130 ° C from the viewpoint of mechanical properties and productivity. Preferably, 80 ° C to 120 ° C is more preferable, 85 ° C to 110 ° C is particularly preferable, and 90 ° C to 100 ° C is most preferable. If the mold temperature is less than 20 ° C, the mold temperature tends to be difficult to control, and if the mold temperature exceeds 140 ° C, the test piece tends to be easily deformed and a good molded product tends to be difficult to obtain. .

  Examples of the molded product made of the resin composition of the present invention include injection molded products, extrusion molded products, press molded products, blow molded products, and the like, board-shaped, sheet-shaped, film-shaped, plate-shaped, rod-shaped, columnar, box It can be used in various shapes such as shapes, lumps, tubes, fibers, granules, and other complicated shapes.

  In addition, the molded product made of the resin composition of the present invention includes automobile parts (interior / exterior parts, etc.), electrical / electronic parts (various housings, gears, gears, etc.), building materials, civil engineering materials, furniture members, agricultural materials, games. It can be used for various purposes such as machine materials, tableware, sports materials, musical instruments and daily necessities.

  Specifically, automotive parts include air flow meters, air pumps, thermostat housings, engine mounts, ignition hobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, vacuum pump cases, inhibitors Switch, Rotation sensor, Acceleration sensor, 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, distributor cap, vapor Nister housing, air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes such as automotive underhood parts, torque control lever, safety belt Parts, register blade, washer lever, window regulator handle, knob of window regulator handle, passing light lever, sun visor bracket, door trim, door pocket, column cover, cowl side, footrest deck trim, front pillar, center pillar, front scuff, Rear scuff, door cuff, front outside, rear outside, seat side, roof side, striker, striker Automotive interior parts such as tire covers, air conditioner cases, cassette deck cases, various motor housings, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers, hood louvers, wheel covers, wheel caps, grill apron cover frames, lamp reflectors Various automotive connectors such as automotive exterior parts such as lamp bezels and door handles, wire harness connectors, SMJ connectors, PCB connectors, and door grommet connectors. Electrical and electronic components include notebook PC 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 PCs, handheld mobiles, recording media (CD, DVD, PD, FDD, etc.) Drive housing and internal parts, copier housing and internal parts, facsimile housing and internal parts, parabolic antenna parts, VTR parts, TV parts, irons, hair dryers, rice cooker parts, electronics Audio equipment parts such as range parts, acoustic parts, video cameras, audio / laser discs (registered trademark) / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processors -Housing, internal parts such as parts, 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 capacitor 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, Examples include a motor brush holder, a transformer member, and a coil bobbin. Building materials include 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 hanger, stairs, doors, floors Materials, ceiling materials, pillars, foundations, beams, baseboards, window frames, doors, deck materials, etc. Civil engineering materials include vegetation nets, vegetation mats, grass protection bags, grass protection nets, curing sheets, slope protection sheets, fly ash holding sheets, drain sheets, water retention sheets, sludge / sludge dewatering bags, concrete formwork, scaffolding boards , Sheet piles, and piles. Examples of the furniture member include a chest, a desk, a chair, and various shelves. Examples of the material for the gaming machine include pachinko parts such as a pachinko machine gauge board and a frame material, and parts such as a mahjong table and a billiard table. Others include fishing lines, fishing nets, seaweed aquaculture nets, fishing bait, sea bream-related materials, gears, screws, springs, bearings, levers, key stems, cams, ratchets, rollers, water supply parts, toy parts, fans, pipes, Cleaning jigs, motor parts, microscopes, binoculars, cameras, clocks and other mechanical parts, multi-films, tunnel films, bird-proof sheets, vegetation protection nonwovens, seedling pots, vegetation piles, seed string tape, germination sheets, House lining sheets, agricultural PVC film stoppers, slow-release fertilizers, root-proof sheets, horticultural nets, insect nets, young tree nets, printed laminates, fertilizer bags, sample bags, sandbags, animal damage prevention nets, incentives Agricultural materials such as strings, windproof nets, disposable diapers, sanitary wrapping materials, cotton swabs, wet towels, toilet seat wipes, etc., medical non-woven fabrics (stitching reinforcements, anti-adhesion membranes, artificial devices) Repair material), wound dressing material, wound tape bandage, sticking material base fabric, surgical suture, fracture reinforcement, artificial organ, medical film, medical supplies, tray, knife, fork, spoon, tube, plastic can, Blisters, pouches, pallets, containers, tanks, beverage bottles, cups, baskets, fruit baskets and other containers and tableware, polo shirts, T-shirts, inners, uniforms, sweaters, socks, ties, and other clothing, curtains, and chairs Ground, carpet, table cloth, cloth mat, wallpaper, interior goods such as furoshiki, various sports materials such as golf tees, golf clubs, tennis rackets, hot melt binders such as paper, leather, non-woven fabric, magnetic materials, zinc sulfide, Binders for powders such as electrode materials, hot fill containers, containers for microwave oven cooking Container, wrap, foam buffer, paper lami, shampoo bottle, candy packaging, shrink label, lid material, hand cut tape, easy peel packaging, egg pack, HDD packaging, compost bag, recording media packaging, shopping bag, musical instrument , Carrier tape, print lamination, heat sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card, IC card, optical element, conductive embossed tape, IC tray, garbage bag, Plastic bag, draining net, body towel, hand towel, tea pack, drain filter, coat agent, adhesive, bag, toothbrush, stationery, clear file, cooler box, kumade, hose reel, planter, hose nozzle, pen cap, As a gas lighter Useful.

EXAMPLES Next, although an Example demonstrates this invention further in detail, these do not limit this invention. All the parts in the examples are based on weight. Moreover, the raw material used and the code | symbol in a table | surface are shown below.
(A) Polylactic acid resin (A-1) Poly-L-lactic acid having a D-form content of 2% and a weight-average molecular weight in terms of PMMA of 170,000 (A-2) D-form content of 1%, PMMA Poly L-lactic acid with a converted weight average molecular weight of 170,000 (B) Naturally derived organic filler (B-1) Paperboard crushed paper powder a obtained by pulverizing paperboard with a thickness of 1 mm
(B-2) Paperboard pulverized paper powder b obtained by pulverizing a paperboard having a thickness of 0.5 mm
(B-3) Copy paper ground paper powder having a fiber length distribution range of 0.05 to 5 mm (B-4) Virgin pulp ground paper powder having a fiber length distribution range of 0.05 to 5 mm (B-5) Reference Paper powder (C) crystallization accelerator obtained by the method of Example 1 (C-1) Talc (LMS300 manufactured by Fuji Talc Kogyo)
(C-2) Polyoxyethylene polyoxypropylene glycol (Pluronic F68 manufactured by Asahi Denka Kogyo)
(C-3) Bis (butyldiglycol) adipate (BXA manufactured by Daihachi Chemical Industry)
(C-4) Tributyl acetylcitrate (ATBC manufactured by Jay Plus)
(D) Release agent (D-1) Partially saponified ester of montanic acid (Clariant Lycowax OP)
(E) Thermoplastic resin other than polylactic acid resin (E-1) Polybutylene (terephthalate / adipate) resin (Ecoflex made by BASF)
(E-2) Core shell rubber (Mitsubrene S2001 made by Mitsubishi Rayon)
(F) Stabilizer (F-1) Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (Irganox 1010 manufactured by Ciba Geigy)
(G) Carboxyl group-reactive endblocker (G-1) Polycarbodiimide (Nisshinbo Carbodilite HMV-8CA)
(G-2) 2,2′-m-phenylenebis (2-oxazoline) (BOX-210 made by Takemoto Yushi)
(G-3) Bisphenol A glycidyl ether (Epicoat 828 made by Japan Epoxy Resin)
(H) Reaction catalyst (H-1) Sodium stearate (manufactured by Katayama Chemical)

[Reference Example 1]
Using bleached pulp without using chlorine gas, calcium carbonate (Optama Kogyo TP121) with an ash content of 5% by weight, neutral rosin sizing agent (Japan PMC CC-167) with 0.4% by weight of pulp, liquid Paper roll made with a stock containing 2% by weight of band, 1% by weight of cationic starch (Kate 308 manufactured by Nippon MSC), and 500 ppm of colloidal silica (BMA-0 manufactured by Nissan Eka Chemicals) as a retention agent. 1% by weight of starch (MS4600 manufactured by Nippon Food Processing Co., Ltd.), 0.1% by weight of surface sizing agent (Polymaron 1343 manufactured by Arakawa Chemical Co., Ltd.) VERSA TL-YE910 made by C.) Using 1.0% by weight, high-grade printing paper is made and the resulting paper is crushed A 100 mesh pass paper powder was obtained by grinding with a machine (CS cutter made by CONDUX).

[Examples 1 to 4, Comparative Examples 1 to 6]
Polylactic acid resin and naturally-derived organic filler were mixed in the proportions shown in Table 1, and melt kneaded using a 30 mm diameter twin screw extruder under conditions of a cylinder temperature of 190 ° C. and a rotation speed of 100 rpm to obtain a resin composition A product pellet was obtained.

  The obtained resin composition was injection molded using an injection molding machine SG75H-MIV manufactured by Sumitomo Heavy Industries under the conditions shown in Table 1 with a cylinder temperature of 190 ° C. and a mold temperature of 3 mm thick ASTM test piece (tensile Test pieces and bending test pieces) were obtained.

  Regarding the moldability, when the tensile test piece was taken out, the shortest time during which a solidified molded product without deformation was obtained was measured as the molding cycle time. It can be said that the shorter the molding cycle time, the better the moldability. The upper limit of the molding cycle time was 150 seconds. Those that require more time are said to have poor heat resistance and productivity and are not practical.

  A part of the surface layer portion of the bending test piece obtained above was cut out, and the temperature-falling crystallization temperature (Tc) and melting point (Tm) derived from the polylactic acid resin were measured. The measurement was performed using a Perkin Elmer DSC7 in a 10 mg sample, under a nitrogen atmosphere, heated from 30 ° C. to 200 ° C. at a temperature rising rate of 20 ° C./min, held at 200 ° C. for 5 minutes, and then cooled by 20 ° C. The temperature was lowered from 200 ° C. to 30 ° C./min.

  Using the bending test piece obtained above, a bending test was conducted in accordance with ASTM method D790 at a deflection temperature under load (load of 0.45 MPa) in accordance with ASTM method D648.

  These results are shown in Table 1.

  Paperboard ground paper powder a (B-1), paperboard ground paper powder b (B-2), copy paper ground paper powder (B-3), virgin pulp ground paper powder (B-4) used in Examples and Comparative Examples ) And the paper powder (B-5) obtained by the method of Reference Example 1 were used to determine the chlorine content by coulometric titration and the sulfur content by ultraviolet fluorescence. The analysis results are shown in Table 2.

  Moreover, about the natural origin organic filler used in the Example and the comparative example, it processed at 450 degreeC for 12 hours with the electric furnace, and calculated | required the ash content. The results are shown in Table 3.

  Further, the paperboard crushed paper powder a (B-1), paperboard crushed paper powder b (B-2), copy paper crushed paper powder (B-3) and the method of Reference Example 1 used in Examples and Comparative Examples were obtained. The abundance ratio of aluminum, silicon and calcium was determined using an X-ray fluorescence apparatus using the ash content of the paper dust (B-5) obtained. The analysis results are shown in Table 4.

  From the results of Tables 1 to 4, the resin composition using the naturally-derived organic filler in which the chlorine content and sulfur content of the present invention are in a specific range amount and the amount of aluminum is larger than the amount of calcium is It can be seen that the moldability, heat resistance and mechanical properties are excellent.

[Examples 5 to 9, Comparative Examples 7 to 10]
Polylactic acid resin, naturally derived organic filler, crystallization accelerator and mold release agent were mixed in the proportions shown in Table 4, and using a 30 mm diameter twin screw extruder, the cylinder temperature was 190 ° C. and the rotation speed was 100 rpm. Melt kneading was performed under the conditions to obtain pellets of the resin composition.

  Further, the obtained resin composition was injection molded using an injection molding machine SG75H-MIV manufactured by Sumitomo Heavy Industries under the conditions shown in Table 4 with a cylinder temperature of 190 ° C. and a 3 mm thick ASTM test piece (tensile Test pieces and bending test pieces) were obtained.

  Regarding the moldability, when the tensile test piece was taken out, the shortest time during which a solidified molded product without deformation was obtained was measured as the molding cycle time. It can be said that the shorter the molding cycle time, the better the moldability. The upper limit of the molding cycle time was 150 seconds. Those that require more time are said to have poor heat resistance and productivity and are not practical.

  A part of the surface layer portion of the bending test piece obtained above was cut out, and the temperature-falling crystallization temperature (Tc) and melting point (Tm) derived from the polylactic acid resin were measured. The measurement was performed using a Perkin Elmer DSC7 in a 10 mg sample, under a nitrogen atmosphere, heated from 30 ° C. to 200 ° C. at a temperature rising rate of 20 ° C./min, held at 200 ° C. for 5 minutes, and then cooled by 20 ° C. The temperature was lowered from 200 ° C. to 30 ° C./min.

  Using the bending test piece obtained above, a bending test was conducted in accordance with ASTM method D790 at a deflection temperature under load (load of 0.45 MPa) in accordance with ASTM method D648.

  The tensile test piece obtained above was heat-treated at 140 ° C. for 1 hour using a hot air dryer, and the bleed-out resistance was visually observed.

  The surface appearance of the tensile test piece obtained above was evaluated by touch and visual observation.

  These results are shown in Table 5.

  From the results shown in Table 5, it can be seen that the resin composition of the present invention and the molded article comprising the resin composition are excellent in moldability, heat resistance, mechanical properties, bleed-out resistance, and surface appearance.

[Examples 10 to 12, Comparative Examples 11 to 12]
Polylactic acid resin, naturally derived organic filler, thermoplastic resin other than polylactic acid resin, crystallization accelerator and release agent are mixed in the ratio shown in Table 5, and using a 30 mm diameter twin screw extruder, Melt kneading was performed under the conditions of a cylinder temperature of 190 ° C. and a rotation speed of 100 rpm to obtain pellets of the resin composition.

  Also, the obtained resin composition was injection molded using an injection molding machine SG75H-MIV manufactured by Sumitomo Heavy Industries under the conditions of a cylinder temperature of 190 ° C. and a mold temperature shown in Table 5, and a 3 mm thick ASTM test piece (tensile Test pieces, bending test pieces and Izod impact test pieces).

  Regarding the moldability, when the tensile test piece was taken out, the shortest time during which a solidified molded product without deformation was obtained was measured as the molding cycle time. It can be said that the shorter the molding cycle time, the better the moldability. The upper limit of the molding cycle time was 150 seconds. Those that require more time are said to have poor heat resistance and productivity and are not practical.

  A part of the surface layer portion of the bending test piece obtained above was cut out, and the temperature-falling crystallization temperature (Tc) and melting point (Tm) derived from the polylactic acid resin were measured. The measurement was performed using a Perkin Elmer DSC7 in a 10 mg sample, under a nitrogen atmosphere, heated from 30 ° C. to 200 ° C. at a temperature rising rate of 20 ° C./min, held at 200 ° C. for 5 minutes, and then cooled by 20 ° C. The temperature was lowered from 200 ° C. to 30 ° C./min.

  Using the bending test piece obtained above, the deflection temperature under load (0.45 MPa) is measured according to ASTM method D648, the bending test is performed according to ASTM method D790, and the ASTM method D256 is used using an Izod impact test piece. The Izod impact test was conducted according to the above.

  The surface appearance of the tensile test piece obtained above was evaluated by touch and visual observation.

  These results are shown in Table 6.

  From the results shown in Table 6, it can be seen that the resin composition of the present invention and the molded article comprising the resin composition are excellent in moldability, heat resistance, mechanical properties, impact resistance, and surface appearance.

[Examples 13 to 16, Comparative Examples 13 to 14]
Polylactic acid resin, naturally-derived organic filler, carboxyl group reactive end-capping agent, stabilizer, crystallization accelerator and release agent are mixed in the proportions shown in Table 6 and a 30 mm diameter twin screw extruder is used. Then, melt kneading was performed under the conditions of a cylinder temperature of 190 ° C. and a rotation speed of 100 rpm to obtain pellets of a resin composition.

  Further, the obtained resin composition was injection molded using an injection molding machine SG75H-MIV manufactured by Sumitomo Heavy Industries under the conditions shown in Table 6 with a cylinder temperature of 190 ° C. and a mold temperature of 3 mm. Test pieces and bending test pieces) were obtained.

  Regarding the moldability, when the tensile test piece was taken out, the shortest time during which a solidified molded product without deformation was obtained was measured as the molding cycle time. It can be said that the shorter the molding cycle time, the better the moldability. The upper limit of the molding cycle time was 150 seconds. Those that require more time are said to have poor heat resistance and productivity and are not practical.

  A part of the surface layer portion of the bending test piece obtained above was cut out, and the temperature-falling crystallization temperature (Tc) and melting point (Tm) derived from the polylactic acid resin were measured. The measurement was performed using a Perkin Elmer DSC7 in a 10 mg sample, under a nitrogen atmosphere, heated from 30 ° C. to 200 ° C. at a temperature rising rate of 20 ° C./min, held at 200 ° C. for 5 minutes, and then cooled by 20 ° C. The temperature was lowered from 200 ° C. to 30 ° C./min.

  Using the bending test piece obtained above, the deflection temperature under load (0.45 MPa) was measured according to ASTM method D648, and the tensile test was conducted according to ASTM method D638 using a tensile test piece. Further, after the tensile test piece was treated in a constant temperature and humidity chamber at 60 ° C. and a relative humidity of 95% for 100 hours, the tensile strength was measured and the tensile strength retention rate ((tensile strength after treatment / tensile before treatment). Strength) × 100 (%)).

  The surface appearance of the tensile test piece obtained above was evaluated by touch and visual observation.

  These results are shown in Table 7.

  From the results shown in Table 7, it can be seen that the resin composition of the present invention and the molded article comprising the resin composition are excellent in moldability, heat resistance, mechanical properties, hydrolysis resistance, and surface appearance.

Claims (5)

A resin composition comprising a polylactic acid resin and a natural organic filler having a chlorine content of 1000 ppm or less, a sulfur content of 200 ppm or more, and an aluminum content greater than that of calcium. The resin composition according to claim 1, wherein the naturally-derived organic filler has a sulfur content of 2000 ppm or less. The resin composition according to claim 1, wherein the naturally-derived organic filler has a chlorine content of 150 ppm or more. The resin composition according to claim 1, wherein the naturally-derived organic filler is paper powder. A molded product comprising the resin composition according to claim 1.