JP2008050584A - Resin composition and molded product - Google Patents

Abstract

An object of the present invention is to provide a resin composition based on a biopolymer and having unprecedented heat resistance, surface appearance, low warpage, dimensional stability and rigidity.
The present invention relates to an aromatic polyester (component A) having a butylene terephthalate skeleton as a main structural unit, polylactic acid (component B) having a melting point of 190 ° C. or higher, an inorganic filler (component C), and an amorphous resin. (D component) is contained, the content of the A component is 5 to 95 parts by weight, and the content of the C component is 5 to 100 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. A resin composition having a D component content of 1 to 100 parts by weight and a molded product thereof.
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Description

  The present invention relates to a resin composition based on polylactic acid as a biobase polymer and excellent in heat resistance, low warpage, hydrolysis resistance, high cycle moldability and the like.

Polybutylene terephthalate (PBT) is a thermoplastic resin that has various excellent properties including oxidation resistance and solvent resistance, and it is possible to obtain molded products having good physical and mechanical properties by injection molding. it can. However, since PBT has high crystallinity, it has a drawback that warpage is likely to occur in a molded product and dimensional stability is poor. In addition, in order to impart rigidity and heat resistance, when a filler is blended, the surface appearance of the molded product has the disadvantage that the warp further deteriorates, and the electronic component that requires surface appearance and dimensional stability, It has been difficult to apply to household appliances, especially housing applications.
On the other hand, plastic materials including PBT increase the amount of dust when discarded after use, and are difficult to be decomposed in a natural environment, so that they remain semi-permanently even after being buried. And when it is incinerated, there is a concern of increasing carbon dioxide in the atmosphere and promoting global warming. In addition, the discarded plastics are causing problems that directly adversely affect the ecosystem, such as damage to the landscape and destruction of the living environment of the ground and marine organisms.

From the viewpoint of resource conservation and environmental protection in recent years, there has been a demand for environmentally friendly plastic materials that use non-petroleum resources as raw materials, reduce volume during disposal, ease of fine granulation, and biodegradability. I came. For this reason, bio-based polymers have attracted attention, and in particular, polylactic acid is used due to the fact that L-lactic acid as a raw material has been produced in large quantities and at low cost by fermentation, and is characterized by high rigidity. Is expected.
In particular, stereocomplex polylactic acid containing D-lactic acid as a raw material is a resin having a remarkably higher melting point and crystalline resin than conventional poly-L-lactic acid, and is expected to be used for such properties (non- (See Patent Document 1). However, at present, the technology to express the stereocomplex crystals with high reproducibility has not been completed yet. Biodegradability and characteristics as a general-purpose polymer of aromatic polyesters by combining such biopolymers and aromatic polyesters such as PBT. Studies have been made on resin compositions having both of these.

For example, a structural material in which a mixture of polyethylene terephthalate and polylactic acid is mixed has been proposed (see Patent Document 1). In this document, the ester bond part contained in the thermoplastic polyester can be decomposed at the same time by thermally decomposing or solvolyzing the aliphatic polyester contained in the structural material. It is described that a simple molded product can be obtained. However, a resin composition in which an aliphatic polyester is blended with such an aromatic polyester has poor thermal stability during melt molding and extremely poor moldability, so that it is difficult to put it into practical use as an engineering plastic.
For this reason, studies have been made to obtain a resin composition that solves the problem of moldability by using PBT having excellent moldability as an aromatic polyester. For example, in a resin composition comprising polylactic acid and a high-melting point PBT, in order to improve moldability, the PBT is contained in an amount of 15% by weight or less and molded under the condition that it does not melt. It has been proposed to improve and improve formability. (See Patent Document 2).

Moreover, the method of improving a moldability by adding polyacetal in addition to polylactic acid and PBT is disclosed (refer patent document 3). However, this method has a problem that the glass transition temperature is lowered and the heat resistance is lowered.
In these proposals, since poly-L-lactic acid or poly-D-lactic acid (hereinafter sometimes abbreviated as lactic acid homopolymer) that is stably produced is used as polylactic acid, the heat resistance of the resin composition, Solvent resistance decreases.
As described above, various compositions containing polylactic acid have been proposed, but there is no proposal for a resin composition containing stereocomplex polylactic acid and PBT in which formation of a stereocomplex phase is difficult to proceed stably.
Macromolecules 1987, 20, 904-906 JP-A-8-104797 JP 2006-36818 A Japanese Patent Laid-Open No. 2003-342459

  An object of the present invention is to provide a resin composition based on a biopolymer and having unprecedented heat resistance, surface appearance, low warpage, dimensional stability and rigidity. Moreover, the objective of this invention is providing the resin composition excellent in the flame retardance. Furthermore, the object of the present invention is to provide a molded article comprising the resin composition.

  That is, the present invention relates to an aromatic polyester (component A) having a butylene terephthalate skeleton as a main structural unit, polylactic acid (component B) having a melting point of 190 ° C. or higher, an inorganic filler (component C), and an amorphous resin (component D). ), The A component content is 5 to 95 parts by weight, the C component content is 5 to 100 parts by weight, and the D component It is a resin composition whose content is 1 to 100 parts by weight. Moreover, this invention is the molded article for housings which consists of this resin composition.

  Since the resin composition of the present invention uses polylactic acid as a bio-based polymer, the load on the environment is small. The resin composition and molded product of the present invention are excellent in heat resistance, surface appearance, low warpage, dimensional stability, and rigidity. In addition to these physical properties, the resin composition and molded article of the present invention are excellent in flame retardancy.

  Hereinafter, the present invention will be described in detail.

(Polylactic acid: B component)
The resin composition of the present invention contains polylactic acid (B component). The content of component B is preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight, and even more preferably 20 to 80 parts by weight per 100 parts by weight of the total of component A and component B. By making content of B component into this range, it becomes a resin composition excellent in heat resistance and hydrolysis resistance.
Polylactic acid is polylactic acid having a melting point of 190 ° C. or higher. The polylactic acid is preferably so-called stereocomplex polylactic acid containing a stereocomplex. Stereocomplex polylactic acid is formed from poly L-lactic acid and poly D-lactic acid. Poly L-lactic acid mainly contains L-lactic acid units represented by the following formula. Poly D-lactic acid mainly contains D-lactic acid units represented by the following formula.

The poly L-lactic acid is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and 99 to 100 mol% for realizing a high melting point. More preferably, it is composed of mol% L-lactic acid units. Examples of other units include D-lactic acid units and copolymer component units other than lactic acid. The other unit is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, still more preferably 0 to 2 mol%.
The poly-D-lactic acid is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and 99 to 100 mol% for realizing a high melting point. More preferably, it is composed of mol% L-lactic acid units. Examples of other units include L-lactic acid units and copolymer components other than lactic acid. The other component is 0 to 10 mol%, preferably 0 to 5 mol%, more preferably 0 to 2 mol%.

  As copolymerization components, units derived from dicarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones and the like having functional groups capable of forming two or more ester bonds, and various polyesters, various polyethers, various types of these various constituent components Examples are units derived from polycarbonate and the like.

Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid. Examples of polyhydric alcohols include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol. Or aromatic polyhydric alcohols, such as what added ethylene oxide to bisphenol, etc. are mentioned. Examples of the hydroxycarboxylic acid include glycolic acid and hydroxybutyric acid. Examples of the lactone include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, δ-valerolactone, and the like.
Stereocomplex polylactic acid is a mixture of poly L-lactic acid and poly D-lactic acid. Both poly L-lactic acid and poly D-lactic acid have a weight average molecular weight of preferably 100,000 to 500,000, more preferably 150,000 to 350,000.

  Poly L-lactic acid and poly D-lactic acid can be produced by a known method. For example, L- or D-lactide can be produced by heating and ring-opening polymerization in the presence of a metal catalyst. Moreover, after crystallizing a low molecular weight polylactic acid containing a metal catalyst, it can be produced by solid phase polymerization by heating under reduced pressure or in an inert gas stream. Further, it can be produced by a direct polymerization method in which lactic acid is subjected to dehydration condensation in the presence / absence of an organic solvent. The polymerization reaction can be carried out in a conventionally known reaction vessel. For example, a vertical reactor or a horizontal reactor equipped with a stirring blade for high viscosity, such as a helical ribbon blade, can be used alone or in parallel. Moreover, any of a batch type, a continuous type, a semibatch type may be sufficient, and these may be combined.

Alcohol may be used as a polymerization initiator. Such alcohol is preferably non-volatile without inhibiting the polymerization of polylactic acid. For example, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol and the like can be suitably used.
In the solid phase polymerization method, a relatively low molecular weight lactic acid polyester obtained by the above-described ring-opening polymerization method or lactic acid direct polymerization method is used as a prepolymer. It can be said that the prepolymer is preferably crystallized in advance in the temperature range of the glass transition temperature (Tg) or higher and lower than the melting point (Tm) from the viewpoint of preventing fusion. The crystallized prepolymer is filled in a fixed vertical or horizontal reaction vessel, or a reaction vessel (rotary kiln, etc.) where the vessel itself rotates like a tumbler or kiln, and the prepolymer glass transition temperature (Tg) or higher. And heated to a temperature range below the melting point (Tm). There is no problem even if the polymerization temperature is raised stepwise as the polymerization proceeds. In addition, for the purpose of efficiently removing water generated during solid phase polymerization, a method of reducing the pressure inside the reaction vessels or circulating a heated inert gas stream is also preferably used.

The metal catalyst used during the polymerization of polylactic acid is preferably deactivated with a deactivator. Examples of such deactivators include organic ligands consisting of a group of chelate ligands having an imino group and capable of coordinating to a metal catalyst, low oxidation number phosphoric acid having an acid value of 5 or less, metaphosphoric acid compounds, and the like. Examples include acidic acid salts, monovalent and polyhydric alcohols, partial esters of polyalkylene glycols, fully ether, phosphono-substituted lower aliphatic carboxylic acid derivatives, and the like.
Examples of the low oxidation number phosphoric acid having an acid number of 5 or less include dihydridooxoline (I) acid, dihydridotetraoxodiphosphoric acid (II, II) acid, hydridotrioxophosphoric acid (III) acid, dihydridopentaoxodiphosphoric acid (III ) Acid, hydridopentaoxodi (II, IV) acid, dodecaoxohexaphosphorus (III) III, hydridooctaoxotriphosphate (III, IV, IV) acid, octaoxotriphosphate (IV, III, IV) acid, hydridohexa Examples thereof include oxodiphosphoric acid (III, V), hexaoxodiphosphoric acid (IV), decaoxotetraphosphoric acid (IV), hendecaoxotetraphosphoric acid (IV), and eneoxooxotriphosphoric acid (V, IV, IV).

As a metaphosphate compound, the formula xH ₂ O.I. Polyphosphoric acid represented by yP ₂ O ₅ , x / y = 3 orthophosphoric acid, 2> x / y> 1, and referred to as diphosphoric acid, triphosphoric acid, tetraphosphoric acid, pentaphosphoric acid or the like based on the degree of condensation Acid and a mixture thereof, metaphosphoric acid represented by x / y = 1, in particular, trimetaphosphoric acid, tetrametaphosphoric acid, 1> x / y> 0, and a network having part of the phosphorus pentoxide structure Examples include ultraphosphoric acid having a structure. Metaphosphoric acid compounds include cyclic metaphosphoric acid in which about 3 to 200 phosphoric acid units are condensed, ultra-regional metaphosphoric acid having a three-dimensional network structure, or their (alkal metal salt, alkaline earth metal salt, onium salt). To do. Of these, cyclic sodium metaphosphate, ultra-region sodium metaphosphate, phosphono-substituted lower aliphatic carboxylic acid derivative dihexylphosphonoethyl acetate (hereinafter sometimes abbreviated as DHPA) and the like are preferably used.

The weight ratio of poly L-lactic acid to poly D-lactic acid in stereocomplex polylactic acid is 90:10 to 10:90. It is preferably 75:25 to 25:75, more preferably 60:40 to 40:60, and preferably as close to 50:50 as possible.
The stereocomplex polylactic acid has a weight average molecular weight of 100,000 to 500,000. More preferably, it is 100,000 to 300,000. The weight average molecular weight is a standard polystyrene equivalent weight average molecular weight value measured by gel permeation chromatography (GPC) using chloroform as an eluent.
Stereocomplex polylactic acid can be produced by coexisting and mixing poly L-lactic acid and poly D-lactic acid in a predetermined weight ratio.

Mixing can be performed in the presence of a solvent. The solvent is not particularly limited as long as it dissolves poly L-lactic acid and poly D-lactic acid. For example, chloroform, methylene chloride, dichloroethane, tetrachloroethane, phenol, tetrahydrofuran, N-methylpyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol or the like alone or in combination of two or more are preferred.
The mixing can be performed in the absence of a solvent. That is, a method of melt kneading after mixing a predetermined amount of poly L-lactic acid and poly D-lactic acid, or a method of adding and kneading one of them after melting one of them can be employed.

  Alternatively, stereoblock polylactic acid in which a poly L-lactic acid segment and a poly D-lactic acid segment are bonded can also be suitably used. Stereoblock polylactic acid is a block polymer in which a poly L-lactic acid segment and a poly D-lactic acid segment are bonded in the molecule. Such block polymers include, for example, a method of producing by sequential ring-opening polymerization, a method of polymerizing poly (L-lactic acid) and poly (D-lactic acid), and then binding them with a chain exchange reaction or a chain extender. A method of polymerizing L-lactic acid and poly-D-lactic acid and then blending and then solid-phase polymerizing to chain-extend, a method of producing from racemic lactide using a stereoselective ring-opening polymerization catalyst, etc. Any block copolymer can be used regardless of the production method. However, it is more preferable from the viewpoint of ease of production to use a high-melting stereoblock polymer obtained by sequential ring-opening polymerization and a polymer obtained by a solid phase polymerization method.

The degree of stereoification (S) of polylactic acid (component B) is represented by the following formula (2) defined from the crystal melting peak in DSC measurement. The degree of stereoification (S) of polylactic acid (component B) is preferably 80 to 100%, more preferably 90 to 100%, and still more preferably 95 to 100%. That is, the polylactic acid (component B) preferably has a highly formed stereocomplex phase. The degree of stereogenicity (S) is a parameter indicating the proportion of stereocomplex polylactic acid crystals that are finally produced in the heat treatment process.
S (%) = [(ΔHms / ΔHms ⁰ ) / (ΔHmh / ΔHmh ⁰ + ΔHms / ΔHms ⁰ )] (2)
However, ΔHms ⁰ = 203.4 J / g, ΔHmh ⁰ = 142 J / g, ΔHms = the melting enthalpy of melting point of the stereocomplex, and ΔHmh = the melting enthalpy of homocrystal.

The carboxy group concentration of polylactic acid (component B) is 15 eq / ton or less. Preferably it is 10 eq / ton or less, More preferably, it is 2 eq / ton or less. When the carboxy group concentration is within this range, a resin composition having good melt stability and wet heat durability can be obtained. The carboxy group concentration can be adjusted with a terminal blocking agent or an amidating agent. Examples of the end capping agent include monocarbodiimides, dicarbodiimides, polycarbodiimides, oxazolines, and epoxy compounds. Examples of the amidating agent include alcohol and amine.
Polylactic acid (component B) has crystallinity, and the stereo crystallization ratio (Cr) is preferably 50 to 100%, more preferably 60 to 100%, still more preferably 70 to 100 as measured by XRD. %. The stereo crystallization ratio (Cr) is represented by the following formula (1) defined by the intensity ratio of diffraction peaks in XRD measurement.
Cr (%) = ΣI _SCi / (ΣI _SCi + I _HM ) × 100 (1)
Here, ΣI _SCi = I _SC1 + I _SC2 + I _SC3 is the sum of the integrated intensities of the diffraction peaks derived from the stereocomplex crystal, and I _SCi (i = 1 to 3) is 2θ = 12.0 °, 20. The integrated intensity of each diffraction peak near 7 ° and 24.0 °, and I _HM represents the integrated intensity of the diffraction peak derived from the homocrystal.

The melting point of polylactic acid (component B) is preferably 195 to 250 ° C, more preferably 200 to 220 ° C. The melting enthalpy is 20 J / g or more, preferably 30 J / g or more.
When the polylactic acid (B) has such a range of stereogenicity (S) and stereocrystallization ratio (Cr), the appearance, low warpage, dimensional stability, heat resistance, etc. of the resin composition of the present invention The various physical properties can be made high, and high cycle moldability can be suitably achieved.
The polylactic acid (component B) preferably contains a metal phosphate represented by the following formula in order to promote the formation of a stereocomplex phase stably and highly.

In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₂ and R ₃ may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. M ₁ represents an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom, n represents 0 when M ₁ is an alkali metal atom, an alkaline earth metal atom or a zinc atom, and M ₁ When is an aluminum atom, it represents 1 or 2.
M ₁ of the metal phosphate represented by the above formula is Na, K, Al, Mg, or Ca. In particular, K, Na, or Al can be suitably used. The content of the compound is preferably 10 ppm to 2% by weight, more preferably 50 ppm to 0.5% by weight, and still more preferably 100 ppm to 0.3% by weight with respect to polylactic acid (component B). When the amount is too small, the effect of improving the degree of stereoization is small, and when too large, the resin itself is deteriorated, which is not preferable.

Furthermore, it is preferable to use a so-called crystal nucleating agent in combination to enhance the action of the metal phosphate. As such a crystal nucleating agent, various agents described below in the item of crystal nucleating agent are used, and among them, calcium silicate, talc, kaolinite, and montmorillonite are preferably selected. The amount of the crystal nucleating agent for enhancing the action of the metal phosphate is 0.05 to 5 parts by weight, more preferably 0.06 to 2 parts by weight, more preferably 0.06 to 1 part by weight per 100 parts by weight of polylactic acid. A range of parts is selected.
Polylactic acid (component B) is a group selected from the group consisting of an epoxy group, an oxazoline group, an oxazine group, an isocyanate group, a ketene group and a carbodiimide group (hereinafter sometimes abbreviated as a specific functional group) as a block forming agent. It is preferable to contain the compound which has at least 1 in a molecule | numerator.

As the block forming agent, a known agent can be suitably applied as a carboxy group blocking agent described below. Especially, the agent and carbodiimide compound which have a carbodiimide group as a specific functional group are suitably selected from the color tone of a polylactic acid (B) and the resin composition of this invention, thermal decomposability, hydrolysis resistance, etc.
The block forming agent reacts with the molecular terminal of polylactic acid (B), partially connects the poly L-lactic acid unit and poly D-lactic acid unit to form blocked polylactic acid, stereocomplex phase formation It is a promoting agent.
The amount of the block forming agent used is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight per 100 parts by weight of polylactic acid. If it is applied in a large amount exceeding this range, there is a concern that the resin hue deteriorates or plasticization occurs, which is not preferable. If the amount is less than 0.001 part by weight, the effect is hardly recognized and industrial significance is small. The metal phosphate and the block forming agent may be used in combination.

In the present invention, the carboxy group concentration of polylactic acid is 10 eq / ton or less. Preferably it is 2 eq / ton or less, More preferably, it is 1 eq / ton. When the carboxy group concentration is within this range, a resin composition having good melt stability and hydrolysis resistance of the resin composition can be obtained, especially when a flame retardant and a flame retardant aid are applied. In addition to preventing the deterioration of the melt stability and hydrolysis resistance of the resin, it also has a great effect of suppressing troubles such as suppressing the degradation and degradation of flame retardants, flame retardant aids and resins, and suppressing mold corrosion during molding. In order to reduce the carboxy group concentration to 10 eq / ton or less, a known method for reducing the carboxyl end group concentration in the polyester can be suitably applied. Specifically, addition of a heat-and-moisture resistance improver or end-capping is possible. It is also possible to esterify or amidate with an alcohol or amine without adding a stopper.
As the wet heat resistance improver, the above-described carboxy group sealing agent having a specific functional group can be suitably applied. Among them, a carbodiimide compound whose specific functional group is a carbodiimide group can effectively seal a carboxy group, and from the viewpoint of promoting the formation of polylactic acid and the hue and stereocomplex phase of the resin composition of the present invention, and hydrolysis resistance. Preferably selected.

  In the present invention, the polylactic acid (B) preferably contains a compound having a specific functional group as a block forming agent and a heat-and-moisture resistance improver, and a carbodiimide compound (J component) is suitably selected. The content of the J component is in the range of 0.001 to 5 parts by weight per 100 parts by weight of the B component. When the amount is less than 0.001 part by weight, it is unsatisfactory to exhibit its function as a block forming agent or a carboxy group sealing agent. Further, if it is applied in a large amount exceeding this range, the concern of deterioration of the resin hue or plasticization is unfavorable.

  Examples of the carbodiimide compound (J component) include the following compounds. For example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, octyldecylcarbodiimide, di-t-butylcarbodiimide, dibenzylcarbodiimide, diphenylcarbodiimide, N-octadecyl-N'-phenylcarbodiimide, N-benzyl-N'- Phenylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, di-o-toluylcarbodiimide, di-p-toluylcarbodiimide, bis (p-aminophenyl) carbodiimide, bis (p-chlorophenyl) carbodiimide, bis (o-chlorophenyl) Carbodiimide, bis (o-ethylphenyl) carbodiimide, bis (p-ethylphenyl) carbodiimide bis (o-isopropyl) Enyl) carbodiimide, bis (p-isopropylphenyl) carbodiimide, bis (o-isobutylphenyl) carbodiimide, bis (p-isobutylphenyl) carbodiimide, bis (2,5-dichlorophenyl) carbodiimide, bis (2,6-dimethylphenyl) Carbodiimide, bis (2,6-diethylphenyl) carbodiimide, bis (2-ethyl-6-isopropylphenyl) carbodiimide, bis (2-butyl-6-isopropylphenyl) carbodiimide, bis (2,6-diisopropylphenyl) carbodiimide, Bis (2,6-di-t-butylphenyl) carbodiimide, bis (2,4,6-trimethylphenyl) carbodiimide, bis (2,4,6-triisopropylphenyl) carbodiimide, bis (2,4,4) -Tributylphenyl) carbodiimide, di-β-naphthylcarbosiimide, N-tolyl-N′-cyclohexylcarbosiimide, N-tolyl-N′-phenylcarbosiimide, p-phenylenebis (o-toluylcarbodiimide), p- Phenylenebis (cyclohexylcarbodiimide, p-phenylenenebis (p-chlorophenylcarbodiimide), 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide, hexamethylenebis (cyclohexylcarbodiimide), ethylenebis (phenylcarbodiimide), ethylenebis Examples thereof include mono- or polycarbodiimide compounds such as (cyclohexylcarbodiimide).

Of these, bis (2,6-diisopropylphenyl) carbodiimide and 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide are preferred from the viewpoints of reactivity and stability.
Of these, industrially available dicyclohexylcarbodiimide, bis (2,6-diisopropylphenyl) carbodiimide, and the like can be suitably used. Furthermore, a commercially available polycarbodiimide compound as the polycarbodiimide compound can be suitably used without the need for synthesis. Examples of such commercially available polycarbodiimide compounds include Carbodilite LA-1 and HMV-8CA sold under the trade name of Carbodilite sold by Nisshinbo Co., Ltd.

  As the epoxy compound that can be used in the present invention, a glycidyl ether compound, a glycidyl ester compound, a glycidyl amine compound, a glycidyl imide compound, a glycidyl amide compound, and an alicyclic epoxy compound can be preferably used. By blending such an agent, a polylactic acid resin composition and a molded product excellent in mechanical properties, moldability, heat resistance, and durability can be obtained.

  Examples of glycidyl ether compounds include, for example, stearyl glycidyl ether, phenyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylene glycol diglycidyl ether, Bisphenol A obtained by condensation reaction of epichlorohydrin with polytetramethylene glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and other bisphenols such as bis (4-hydroxyphenyl) methane Diglycidyl ether type epoxy resin Etc. can be mentioned. Of these, bisphenol A diglycidyl ether type epoxy resins are preferred.

  Examples of glycidyl ester compounds include benzoic acid glycidyl ester, stearic acid glycidyl ester, versatic acid glycidyl ester, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid Examples include acid diglycidyl ester, dodecanedioic acid diglycidyl ester, and pyromellitic acid tetraglycidyl ester. Of these, glycidyl benzoate and glycidyl versatate are preferred.

  Examples of the glycidylamine compound include tetraglycidylamine diphenylmethane, triglycidyl-p-aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylenediamine, and triglycidyl isocyanurate.

Examples of glycidylimide and glycidylamide compounds include N-glycidylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl-3,6-dimethylphthalimide, N-glycidylsuccinimide, N-glycidyl-1,2, Examples include 3,4-tetrahydrophthalimide, N-glycidyl maleimide, N-glycidyl benzamide, N-glycidyl stearyl amide, and the like.
Of these, N-glycidylphthalimide is preferable.

Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexyl-3,4-cyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, N-methyl-4, Examples include 5-epoxycyclohexane-1,2-dicarboxylic imide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, and the like.
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 novolac type epoxy resins, and the like can be used.

  Examples of the oxazoline compound that can be used as a carboxy group blocking agent used in the present invention include 2-methoxy-2-oxazoline, 2-butoxy-2-oxazoline, 2-stearyloxy-2-oxazoline, 2-cyclohexyloxy- 2-oxazoline, 2-allyloxy-2-oxazoline, 2-benzyloxy-2-oxazoline, 2-p-phenylphenoxy-2-oxazoline, 2-methyl-2-oxazoline, 2-cyclohexyl-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-p-phenylphenyl -2-oxazoline, 2,2'-bis ( -Oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (4-butyl-2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline) 2,2′-p-phenylenebis (4-methyl-2-oxazoline), 2,2′-p-phenylenebis (4,4′-methyl-2-oxazoline), 2,2′-ethylenebis ( 2-oxazoline), 2,2′-tetramethylenebis (2-oxazoline), 2,2′-hexamethylenebis (2-oxazoline), 2,2′-ethylenebis (4-methyl-2-oxazoline), 2,2'-tetramethylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-cyclohexylenebis (2-oxazoline), 2,2'-diphenylenebis (4-methyl-2- Oki Gelsolin), and the like. Furthermore, the polyoxazoline compound etc. which contain the said compound as a monomer unit are mentioned.

  Examples of oxazine compounds that can be used in the present invention include 2-methoxy-5,6-dihydro-4H-1,3-oxazine, 2-hexyloxy-5,6-dihydro-4H-1,3-oxazine, 2- Decyloxy-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-crotyloxy-5,6-dihydro-4H-1,3-oxazine and the like. 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′-hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-p-phenylene Bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-P, P′-diphenylenebis (5,6-dihydro-4H-1,3-oxazine) and the like can be mentioned. Furthermore, the polyoxazine compound etc. which contain the above-mentioned 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 preferably selected.
Examples of isocyanate compounds that can be used in the present invention include aromatic, aliphatic, and alicyclic isocyanate compounds, and mixtures thereof.
Examples of the monoisocyanate compound include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate.

  As the diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate Isocyanate, (2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate) mixture, cyclohexane-4,4′-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, methylcyclohexane Examples include diisocyanate, tetramethylxylylene diisocyanate, and 2,6-diisopropylphenyl-1,4-diisocyanate. Of these isocyanate compounds, aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate and phenyl isocyanate are preferred.

As the ketene compound that can be used in the present invention, aromatic, aliphatic, and alicyclic ketene compounds and mixtures thereof can be used.
Specific examples include diphenyl ketene, bis (2,6-di-t-butylphenyl) ketene, bis (2,6-di-isopropylphenyl) ketene, dicyclohexyl ketene, and the like. Among these ketene compounds, aromatic ketenes such as diphenyl ketene, bis (2,6-di-t-butylphenyl) ketene, and bis (2,6-di-isopropylphenyl) ketene are preferable.
As the block forming agent and the heat-and-moisture resistance improver, one or more compounds can be appropriately selected and used. Selection of a carbodiimide compound as a moist heat resistance improver to promote the formation of a block structure and also to seal a carboxy group end or a part of an acidic low molecular weight compound can be shown as a kind of preferred embodiment.

The amount of the heat-and-moisture resistance improver used is preferably 0.001 to 5 parts by weight, more preferably 0.005 to 3 parts by weight per 100 parts by weight of polylactic acid (component B). When applied in a large amount exceeding this range, the effect of improving the hydrolysis resistance which lowers the carboxy group concentration is great, but the concern of causing plasticization and hue deterioration of the resin composition and the molded article of the composition is undesirably increased.
If the amount is less than 0.001%, the effect is hardly recognized and the industrial significance is small.

The lactide content of polylactic acid (component B) is selected in the range of 0 to 700 ppm by weight.
More preferably, a range of 0 to 500 ppm by weight, more preferably 0 to 200 ppm by weight, particularly preferably 0 to 100 ppm by weight is selected. With polylactic acid (B) having a lactide content in such a range, the stability of the resin composition at the time of melting can be improved, and the molded product can be efficiently molded with high cycle moldability and the hydrolysis resistance of the molded product is improved. Because it can. In order to reduce the lactide content to such a range, a conventionally known lactide mitigation treatment or a combination thereof can be used at any stage from the polymerization of poly L-lactic acid and poly D-lactic acid to the end of the production of polylactic acid (B). It is possible to achieve this by implementing it.

(Aromatic polyester: Component A)
The resin composition of the present invention contains an aromatic polyester (component A). The content of component A is preferably 5 to 95 parts by weight, more preferably 10 to 80 parts by weight, still more preferably 20 to 70 parts by weight, particularly preferably 100 parts by weight of the total of component A and component B. 20 to 50 parts by weight.

  The aromatic polyester (component A) has a butylene terephthalate skeleton as a main structural unit. The butylene terephthalate skeleton is represented by the following formula.

Here, “mainly” means that the butylene terephthalate skeleton occupies a mole fraction of 50 mol% or more in the aromatic polyester. The butylene terephthalate skeleton is preferably contained in a molar fraction of 70% or more, more preferably 85% or more, and even more preferably 95% or more from the viewpoint of improving moldability.
The aromatic polyester may contain a copolymer component in addition to the butylene terephthalate skeleton. Examples of the copolymer component include hydroxycarboxylic acid, dicarboxylic acid, and diol.

For example, as the hydroxycarboxylic acid, glycolic acid, D-lactic acid, L-lactic acid, 3-hydroxypropionic acid, 4-hydroxybutanoic acid, 3-hydroxybutanoic acid, 6-hydroxycaproic acid, hydroxybenzoic acid, hydroxynaphthalenecarboxylic acid An acid etc. are mentioned.
Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as isophthalic acid, naphthalene dicarboxylic acid, diphenoxyethane carboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfonic dicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid and the like. Aliphatic dicarboxylic acids such as aliphatic dicarboxylic acids, succinic acid, adipic acid, sebacic acid, azelaic acid and the like, oxyacids such as p-β-hydroxyethoxybenzoic acid, ε-oxybenzoic acid and the like Bifunctional carboxylic acid etc. are mentioned.

Examples of the diol include trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, diethylene glycol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-bis (4 ′ -Β-hydroxyphenyl) propane, bis (4′-β-hydroxyethoxyphenyl) sulfonic acid and the like.
The intrinsic viscosity of the aromatic polyester (component A) is preferably 0.5 to 2.0, more preferably 0.7 to 1.8, and still more preferably 0.8 to 1.5. The aromatic polyester (component A) preferably has a carboxy group concentration of 60 eq / ton or less. The carboxy group concentration can be adjusted by applying a heat-and-moisture resistance improver, solid phase polymerization or the like.

(Inorganic filler: component C)
The inorganic filler (component C) used in the present invention contains 5 to 100 parts by weight, preferably 10 to 90 parts by weight, and more preferably 20 to 80 parts by weight per 100 parts by weight of the total of component A and component B. . By blending an inorganic filler, the heat resistance and rigidity of the resin composition as well as the appearance, low warpage, and dimensional stability can be suitably expressed.
Examples of the inorganic filler include fibrous, powdery, plate-like and spherical fillers. A filler having a small anisotropy and a high isotropic property is excellent in reducing the warping amount of the molded product.
Examples of powdery and plate-like fillers include glass flakes, metal flakes, mica, talc, and kaolin. Among these, glass flakes, metal flakes, mica and talc are preferable, and glass flakes, mica and talc are further exemplified.
Examples of the spherical filler include glass beads, metal beads, silica beads, alumina beads, zirconia beads, silica alumina beads, true spherical silica, true spherical alumina, true spherical zirconia, true spherical silica alumina, and the like. The spherical filler preferably has an average particle size of 10 to 1000 μm.
Examples of the fibrous filler include glass fiber, glass milled fiber, wollastonite, carbon fiber, metallic conductive fiber, whisker such as potassium titanate whisker and aluminum borate whisker. Of these, glass fiber, wollastonite, carbon fiber, and metal-based conductive fiber are preferable, and glass fiber, wollastonite, and carbon fiber are most preferable.

The resin composition containing glass fiber is excellent in appearance. Glass fibers used in the present invention, A glass, C glass, not limited in particular glass composition such as E glass, optionally _{TiO 2, Zr 2 O, BeO} , CeO 2, SO 3, P 2 O 5 And the like. However, more preferably, E glass (non-alkali glass) is preferable in that it does not adversely affect the resin. The same is true for the glass milled fiber shown below. The glass fiber is obtained by quenching molten glass while drawing it by various methods to obtain a predetermined fiber shape. The rapid cooling and stretching conditions in this case are not particularly limited. In addition to a general perfect circular shape, the cross-sectional shape may be various irregular cross-sectional shapes typified by superimposing circular fibers in parallel. Furthermore, the glass fiber which mixed the perfect circular shape and the unusual cross-sectional shape may be sufficient. Such glass fibers have an average fiber diameter of 1 to 25 μm, preferably 5 to 17 μm. If glass fibers having an average fiber diameter of less than 1 μm are used, molding processability is impaired, and if glass fibers having an average fiber diameter of more than 25 μm are used, the appearance is impaired and the reinforcing effect is not sufficient. These fibers can be focused by various compounds such as epoxy, urethane, and acrylic that are currently known, and those that have been surface-treated with a silane coupling agent or the like described later are preferable. Moreover, the average fiber length in the molded product of these fibers is about 0.01-50 mm.

The glass milled fiber used in the present invention has L / D ≦ 10, and is obtained by crushing a glass fiber roving or chopped strand to a predetermined length by cutting or ball milling, It can be preferably used for improving the appearance of a molded product obtained from the composition of the present invention. L is the length of the milled fiber in the fiber axis direction, and D is the fiber diameter in the cross-sectional direction. As the glass fiber, the same glass fiber as described above can be used. These powders are preferably those which have been surface-treated with a silane coupling agent or the like, like glass fibers. The glass milled fiber preferably has an average fiber diameter of 6 to 23 μm and an average fiber length of 0.02 to 0.1 mm. In order to impart conductivity to the glass fiber, a metal coat is applied to the fiber surface. obtain. As for the diameter of this metal coat glass fiber, 6-20 micrometers is especially preferable. The metal-coated glass fiber is obtained by coating glass fiber with a metal such as nickel, copper, cobalt, silver, aluminum, iron, or an alloy thereof by a known plating method or vapor deposition method.
The metal is preferably one or more metals selected from nickel, copper and cobalt from the viewpoints of conductivity, corrosion resistance, productivity, and economy. These fibers can be focused by various compounds such as epoxy, urethane, and acrylic that are currently known, and those that have been surface-treated with a silane coupling agent or the like described later are preferable. The average fiber length in the molded product of these fibers is about 0.02 to 400 μm.

The carbon fiber used in the present invention is not particularly limited, and is a carbonaceous fiber or graphite fiber produced using various known carbon fibers such as polyacrylonitrile, pitch, rayon, lignin, hydrocarbon gas, etc. A polyacrylonitrile-based carbon fiber excellent in fiber strength is preferred. Carbon fiber can be oxidized by a currently known method represented by ozone, plasma, nitric acid, electrolysis, etc., and the carbon fiber is preferably used in order to increase the adhesion with the resin component. Carbon fibers are usually in the form of chopped strands, roving strands, milled fibers, and the like.
In order to impart conductivity or the like to the carbon fiber, a metal coat can be applied to the fiber surface. The diameter of the metal-coated carbon fiber is particularly preferably 6 to 20 μm. The metal-coated carbon fiber is obtained by coating a carbon fiber with a metal such as nickel, copper, cobalt, silver, aluminum, iron, or an alloy thereof by a known plating method or vapor deposition method. Such metal is preferably one or more metals selected from nickel, copper and cobalt from the viewpoints of conductivity, corrosion resistance, productivity, and economy, and particularly preferably nickel-coated carbon fiber.
In addition, as these carbon fibers, those bundled with various sizing agents such as an epoxy resin, a urethane resin, and an acrylic resin can be suitably used, and an epoxy resin and / or a urethane resin are preferable.

The metal-based conductive fiber used in the present invention is not particularly limited, and refers to a metal fiber or a metal-coated fiber, such as a metal fiber such as a stainless fiber, an aluminum fiber, a copper fiber, or a brass fiber. Two or more of these may be used in combination. The diameter of the metal fiber is preferably 4 to 80 μm, particularly preferably 6 to 60 μm. Such conductive fibers may be surface-treated with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like. Further, it may be converged with an olefin resin, a styrene resin, a polyester resin, an epoxy resin, a urethane resin, or the like. These fibrous fillers may be used alone or in combination of two or more.
Such a fibrous filler is preferably subjected to a surface treatment with a silane coupling agent or the like. By this surface treatment, the decomposition of the aromatic polycarbonate resin is suppressed, and the adhesiveness is further improved, so that the wet heat fatigue property and the surface impact property which are the objects of the present invention can be improved.
In the present invention, the silane coupling agent refers to a silane compound represented by the following formula.

Here, Y is a group having reactivity or affinity with a resin matrix such as amino group, epoxy group, carboxylic acid group, vinyl group, mercapto group, halogen atom, etc., and Z ¹ , Z ² , Z ³ and Z ⁴ are respectively It represents a single bond or an alkylene group having 1 to 7 carbon atoms, and an amide bond, an ester bond, an ether bond or an imino bond may be interposed in the alkylene molecular chain, and X ¹ , X ² and X ³ are each alkoxy A group, preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom.

  Specific examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ -Glycidoxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxy Examples include silane and γ-chloropropyltrimethoxysilane.

As glass flakes and metal flakes used in the present invention, those having an average particle diameter of 10 to 1000 μm are preferable, and when the average particle diameter is (a) and the thickness is (c), (a) / ( c) The ratio is preferably 5 to 500, more preferably 6 to 450, and even more preferably 7 to 400.
If the average particle size is less than 10 μm or the (a) / (c) ratio is less than 5, the rigidity is insufficient, and if the average particle size exceeds 1000 μm or the (a) / (c) ratio exceeds 500, molding is performed. The appearance of the product and the weld strength deteriorate, which is not preferable. The average particle size of the glass flake and the metal flake here is calculated as the median diameter of the weight distribution of the particle size obtained by the standard sieving method. Of these glass flakes and metal flakes, glass flakes are particularly preferred.
These glass flakes and metal flakes can be focused by various compounds such as epoxy, urethane, and acrylic that are currently known, and those that have been surface-treated with a silane coupling agent or the like described later are preferable.

  Moreover, a metal coat glass flake can also be used as a glass flake used by this invention. The metal coated on the glass flakes may be any metal that can be coated on glass, and examples thereof include gold, silver, nickel, and aluminum. Moreover, there is no restriction | limiting in particular in the method of coating, Arbitrary methods are employ | adopted. For example, a method by electroless plating is preferable, and the film thickness of the coating is usually 0.00001 to 10 μm, and the glass flakes are evenly coated on the smooth surface, preferably the end surface. The glass flake coated with such a metal can be used as it is, but the surface thereof may be further coated with a treatment agent for an antioxidant or the like. A powdery one having a diameter of 1 to 80 μm is preferable.

  Mica is a pulverized product of silicate mineral containing aluminum, potassium, magnesium, sodium, iron and the like. Mica includes muscovite, phlogopite, biotite, artificial mica, etc., and any mica can be used as the mica of the present invention, but phlogopite and biotite are themselves more flexible than muscovite, In addition, since phlogopite and biotite contain more Fe in the main component than muscovite, the hue of the phlogopite itself becomes darker. Although it is expensive, it itself is expensive and impractical. Preference is given to muscovite. In addition, as a pulverization method in the production of mica, a dry pulverization method in which mica rough is pulverized with a dry pulverizer, and mica rough is roughly pulverized in a dry pulverizer, then water is added and a wet pulverizer in a slurry state. There is a wet pulverization method in which the pulverization is followed by dehydration and drying, and the dry pulverization method is generally lower in cost, but it is difficult to pulverize mica thinly and finely in the present invention. It is preferable to use mica produced by

As the average particle diameter of mica, those having an average particle diameter of 10 to 100 μm measured by a microtrack laser diffraction method can be used. The average particle size is preferably 20 to 50 μm. If the average particle diameter of mica is less than 10 μm, the effect of improving the rigidity is not sufficient, and if it exceeds 100 μm, the rigidity is not sufficiently improved and the weld strength is not sufficient.
As the thickness of mica, one having a thickness measured by observation with an electron microscope of 0.01 to 1 μm can be used. The thickness is preferably 0.03 to 0.3 μm. When the thickness of mica is less than 0.01 μm, the mica is easily cracked at the melt processing stage, so that no further improvement in rigidity is observed. If it exceeds 1 μm, the effect of improving the rigidity is not sufficient. Further, such mica may be surface-treated with a silane coupling agent or the like, and further granulated with a binder to be granulated. Specific examples of mica include Yamaguchi Mica Industry Co., Ltd. Mica powder (mica powder) A-41, etc., which are readily available on the market.

  Moreover, a metal coat mica can also be used as a mica used by this invention. The metal to be coated on mica may be any metal that can be coated on mica, and examples thereof include gold, silver, nickel, and aluminum. Moreover, there is no restriction | limiting in particular in the method of coating, Arbitrary methods are employ | adopted. For example, a method by electroless plating is preferable, and the film thickness of the coating is usually 0.00001 to 10 μm, and the smooth surface of mica is coated evenly on the end surface. The mica coated with such a metal can be used as it is, but the surface thereof may be further coated with a treatment agent for an antioxidant or the like.

The talc in the present invention is a hydrous magnesium silicate having a layered structure, and is represented by the chemical formula 4SiO ₂ .3MgO.2H ₂ O. Usually, SiO _{2 is} about 63 wt%, MgO is about 32%, and H ₂ O is about 5 wt. %, Fe ₂ O ₃ , Al ₂ O _{3 and the} like, and the specific gravity is about 2.7. In the present invention, a powdery one having an average particle diameter of 0.01 to 20 μm is preferable from the viewpoint of securing rigidity. The average particle diameter of talc here is a value measured by a laser diffraction method. In the case of talc, if the average particle size is smaller than this range, the rigidity becomes insufficient, and if it exceeds this range, the appearance of the molded product is deteriorated, which is not preferable.

The kaolin in the present invention is a hydrous aluminum silicate having a layered structure and is represented by the chemical formula Al ₂ Si ₂ O ₅ (OH) ₄ . Usually, kaolinite calculated in nature has three types, kaolinite, dickite, and nacrite, and any of them can be used. In the present invention, a powdery one having an average particle diameter of 0.01 to 20 μm is preferable from the viewpoint of securing rigidity. The average particle diameter of kaolin here means a value measured by a laser diffraction method. In the case of kaolin, if the average particle size is smaller than this range, the rigidity becomes insufficient, and if it exceeds this range, the appearance of the molded product is deteriorated, which is not preferable.
Such a plate-like filler is preferably subjected to a surface treatment with a silane coupling agent or the like. By this surface treatment, the decomposition of the aromatic polycarbonate resin is suppressed and the adhesiveness is further improved, whereby the wet heat fatigue and the weld strength, which are the objects of the present invention, can be improved.

The wollastonite as used in the present invention is a natural white mineral having a needle-like crystal as a fibrous inorganic filler mainly composed of calcium silicate, which is substantially represented by the chemical formula CaSiO ₃ , and usually SiO ₂ is approximately about It contains 50% by weight, CaO about 47% by weight, Fe ₂ O ₃ , Al ₂ O _{3 and the} like, and the specific gravity is about 2.9. The wollastonite used in the present invention is preferably one having a particle size distribution of 3 μm or more of 75% or more, 10 μm or more of 5% or less, and an aspect ratio L / D of 3 or more, particularly L / D of 8 or more. . When 3 μm or more is 75% or more in the particle size distribution, the reinforcing effect is sufficient and the rigidity tends to be higher. Moreover, when 10 micrometers or more are 5% or less, while having favorable impact strength, the surface appearance of the molded product obtained tends to become better. Particularly when the aspect ratio is 8 or more, the reinforcing effect is sufficient and higher rigidity can be obtained. However, in consideration of the working environment, it is more preferable that the aspect ratio is 50 or less. Further, such wollastonite may be subjected to surface treatment with a usual surface treatment agent, for example, a coupling agent such as a silane coupling agent or a titanate coupling agent described later.

  Moreover, metal-coated glass flakes and metal-coated mica can also be used as the glass flakes and mica used in the present invention. The metal coated on glass flakes and mica may be any metal that can be coated on glass, and examples thereof include gold, silver, nickel, and aluminum. Moreover, there is no restriction | limiting in particular in the method of coating, Arbitrary methods are employ | adopted. For example, a method by electroless plating is preferable, and the film thickness of the coating is usually 0.00001 to 10 μm, and the glass flakes are evenly coated on the smooth surface, preferably the end surface. The glass flake coated with such a metal can be used as it is, but the surface thereof may be further coated with a treatment agent for an antioxidant or the like. A powdery one having a diameter of 1 to 80 μm is preferable.

  Moreover, a metal coat mica can also be used as a mica used by this invention. The metal to be coated on mica may be any metal that can be coated on mica, and examples thereof include gold, silver, nickel, and aluminum. Moreover, there is no restriction | limiting in particular in the method of coating, Arbitrary methods are employ | adopted. For example, a method by electroless plating is preferable, and the film thickness of the coating is usually 0.00001 to 10 μm, and the smooth surface of mica is coated evenly on the end surface. The mica coated with such a metal can be used as it is, but the surface thereof may be further coated with a treatment agent for an antioxidant or the like.

(Amorphous resin: D component)
It is preferable that the resin composition of this invention contains 0-100 weight of amorphous resin (D component) per 100 weight part of total of A component and B component. Content of D component becomes like this. Preferably it is 2-80 weight part, More preferably, it is 5-70 weight part, More preferably, it is 10-60 weight part. By containing the D component, low warpage and surface appearance can be improved.

  Amorphous resins (component D) include polyester resins other than polylactic acid, polyamide resins, polyacetal resins, polyolefin resins such as polyethylene resins and polypropylene resins, polystyrene resins, acrylic resins, polyurethane resins, chlorinated polyethylene resins, chlorine Polypropylene resin, aromatic and aliphatic polyketone resin, fluorine resin, polyphenylene sulfide resin, polyether 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 Methylpentene-1, polyetherimide resin, cellulose acetate resin, and thermoplastic resins such as polyvinyl alcohol resins. Among these, it is preferable to contain at least one selected from polyacetal resins, polyester resins other than polylactic acid, ABS, and polycarbonate resins. By containing these components, a resin composition and a molded product excellent in surface properties, mechanical properties, and toughness can be obtained.

(Brominated flame retardant: E component)
The resin composition of the present invention contains 5 to 80 parts by weight of a brominated flame retardant (E component) and 0 to 30 antimony flame retardant auxiliary (F component) per 100 parts by weight of the total of A component and B component. It is preferable to contain by weight. The content of component E is preferably 10 to 50 parts by weight, more preferably 10 to 30 parts by weight. Content of F component becomes like this. Preferably it is 1-30 weight part, More preferably, it is 2-20 weight part.
The flame retardancy of molded products for electric and electronic products is determined by the flame retardancy test using five test pieces (thickness: 1/32 inch) according to the method of Subject 94 (UL-94) of Underwriters Laboratories. It is preferable to achieve V0.

The brominated flame retardant (E) used in the present invention is, for example, a brominated bisphenol A type polycarbonate flame retardant having a bromine content of 20% by weight or more, a brominated bisphenol A type epoxy resin and / or a part or all of the terminal glycidyl group. Modified products, brominated diphenyl ether flame retardants, brominated imide flame retardants, brominated polystyrene flame retardants and the like.
Specific examples include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis (2,4,6-tribromophenoxy) ethane, ethylene bistetrabromophthalimide, Hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabromobisphenol S, tris (2,3-dibromopropyl-1) Isocyanurate, tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobisphenol A, tetrabromobisphenol Abromide A derivatives, tetrabromobisphenol A-epoxy oligomer or polymer, tetrabromobisphenol A-carbonate oligomer or polymer, brominated epoxy resins such as brominated phenol novolac epoxy, tetrabromobisphenol A-bis (2-hydroxydiethyl ether) , Tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, tris (tribromoneopentyl) phosphate, poly ( Pentabromobenzyl polyacrylate), octabromotrimethylphenylindane, dibromoneopentyl glycol, pentabromobenzyl polyacrylate Over DOO, dibromo cresyl glycidyl ether, N, N'ethylene - bis - such as tetrabromo phthalic imide. Of these, tetrabromobisphenol A-epoxy oligomer, tetrabromobisphenol A-carbonate oligomer, and brominated epoxy resin are preferable. These flame retardants are added in the range of 0 to 4% by weight, preferably 2 to 4% by weight in the total composition.

(Antimony flame retardant aid (F component)
As the antimony flame retardant aid (F) used in the present invention, antimony trioxide, antimony tetroxide, and (NaO) _p · (Sb ₂ O ₅ ) · qH ₂ O (p = 0 to 1, q = 0) It is possible to use antimony pentoxide represented by ~ 4) or sodium antimonate partially Na-chlorinated. These antimony-based flame retardant auxiliary _{(F), (NaO) p} · (Sb 2 O 5) · qH 2 O (p = 0~1, q = 0~4) antimony pentoxide or a represented by When sodium antimonate whose part is Na-chlorinated is used, metal corrosivity becomes more preferable. In particular, it is more preferable to use a solution having a pH of 6 to 9 when an ethanol solution of sodium antimonate is used, since the resin composition is less decomposed. The antimony flame retardant aid (F) preferably has a particle size of 0.02 to 5 μm. Moreover, you may surface-treat with an epoxy compound, a silane compound, an isocyanate compound, a titanate compound etc. as needed. The addition amount of the flame retardant aid is 0 to 25% by weight, preferably 1 to 15% by weight, based on the total composition.

  In the resin composition of the present invention, since the carboxy group concentration of the resin composition is 30 eq / ton or less, the decomposition of the resin, the flame retardant, and the flame retardant aid is suppressed. Corrosion and contamination can be suppressed, and the dimensional accuracy and processing efficiency of the molded product can be deteriorated, and when using the molded product, it is possible to suppress the difficulty in which the metal in contact or nearby is corroded or contaminated to impair the function of the part.

(Transesterification inhibitor: G component)
It is preferable that the resin composition of this invention contains 0.01-5 weight part of transesterification inhibitors (G component) per 100 weight part of total of A component and B component. The content of the G component is more preferably 0.01 to 1 part by weight, and more preferably 0.02 to 0.5 part by weight. By containing the G component, the melt viscosity stability of the resin composition can be increased, decomposition during resin molding and molecular weight reduction can be suppressed, the resin moldability can be increased, and melt molding can be suitably performed.
Examples of the transesterification inhibitor (G component) include sodium dihydrogen phosphate, potassium acetate, trimethyl phosphate, and phenylphosphonic acid. Moreover, the catalyst deactivator of a polylactic acid production catalyst can be applied suitably as G component.

From the catalyst deactivation ability, the formula xH ₂ O. Polyphosphoric acid represented by yP ₂ O ₅ , x / y = 3 orthophosphoric acid, 2> x / y> 1, and referred to as diphosphoric acid, triphosphoric acid, tetraphosphoric acid, pentaphosphoric acid or the like based on the degree of condensation Acid and a mixture thereof, metaphosphoric acid represented by x / y = 1, in particular, trimetaphosphoric acid, tetrametaphosphoric acid, 1> x / y> 0, and a network having part of the phosphorus pentoxide structure Ultraphosphoric acid having a structure (sometimes collectively referred to as metaphosphoric acid compounds), and acid salts of these acids, monovalent and polyhydric alcohols, or partial ester phosphorus of polyalkylene glycols Oxo acids or acidic esters thereof and the above-mentioned metaphosphoric acid compounds and phosphono-substituted aliphatic carboxylic acid derivatives are preferably used. Of these, cyclic sodium metaphosphate, ultra-region sodium metaphosphate, DHPA, and the like are preferably used.
Applying these agents, the composition of the present invention, which is excellent in high cycle moldability, appearance, dimensional stability, hydrolysis resistance, flame retardancy, and good melt stability of the molten resin, takes advantage of its properties, For example, molded products for electric and electronic parts and molded products for home appliances can be suitably molded.

(Antioxidant: H component)
The resin composition of the present invention is preferably 0.01 to 5 parts by weight, more preferably 0.01 to 2 parts by weight, and more preferably 0.01 to 2 parts by weight, per 100 parts by weight of the total of component A and component B. Preferably, 0.02 to 0.5 parts by weight are contained. By containing H component, the oxidation stability of the resin composition can be improved, and coloring and deterioration during melt molding and oxidation deterioration of the molded product can be suppressed.
Examples of the antioxidant (H component) include hindered phenol compounds, hindered amine compounds, phosphite compounds, and thioether compounds.

Examples of hindered phenol compounds include n-octadecyl 3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl 3- (3′-methyl-5′-t). -Butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl 3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6-xandiolbis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediolbis [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate] 2,2′-methylene-bis (4-methyl-t-butylphenol), triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propyl Lopionate], 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′-hydroxyphenyl) ) Propionyl] diamine, N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionyl] hydrazine, 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, etc. Is mentioned.
Preferably, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4) -Hydroxyphenyl) propionate] methane and the like.

  As the phosphite compound, one in which at least one P—O bond is bonded to an aromatic group is preferable. Specifically, tris (2,6-di-t-butylphenyl) phosphite, tetrakis (2,6-di-t-butylphenyl) 4,4′-biphenylene phosphite, bis (2,6-diphenyl) -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-ditridecylphosphite-5-tert-butylphenyl) butane, tris (mixed mono and Di-nonylphenyl) phosphite, 4,4′-isopropylidenebis (phenyl-dialkyl phosphite) and the like. Tris (2,6-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, tetraphenyl-4,4'-biphenylene phosphite and the like are preferred.

  As thioether compounds, dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate), pentaerythritol Tetrakis (3-dodecylthiopropionate), pentaerythritol tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol tetrakis (3-stearylthiopropionate), etc. Is mentioned. These may be used alone or in combination of two or more.

(Other additives)
The resin composition of the present invention can be used as it is, but various known additives such as a crystal nucleating agent, a mold release agent, a surface smoothing agent, a flame retardant, and the like can be used without departing from the spirit of the present invention. An additive selected from the group consisting of a filler, a UV absorber, a plasticizer, an antistatic agent, an elastomer, a rubber-reinforced styrene resin, polyethylene terephthalate, and a polycarbonate can be contained.
A conventionally known agent can be used as the crystal nucleating agent, and any of an inorganic crystal nucleating agent and an organic crystal nucleating agent can be used.

  Specific examples of the inorganic crystal nucleating agent include calcium silicate, talc, kaolinite, montmorillonite, synthetic mica, calcium sulfide, boron nitride, barium sulfate, aluminum oxide, neodymium oxide, and metal salts of 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 Organic carboxylic acid metal salts such as minium dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphtho sodium cyclohexanecarboxylate, organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearamide, Carboxylic acid amides such as ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide), benzylidene sorbitol and its derivatives, sodium-2,2′-methylenebis (4 Phosphorus compound metal salts such as 6-di-t-butylphenyl) phosphate and 2,2-methylbis (4,6-di-t-butylphenyl) sodium.

From the viewpoint of stability at the time of melting of a resin containing these agents, application of a nucleating agent of an inorganic nucleating agent tartrate is preferable to an organic nucleating agent, and the particle diameter is preferably lower. For example, when the average primary particle size is in the range of 0.2 to 0.05 μm, the resin composition is appropriately dispersed, so that the heat resistance of the resin composition is good.
Of inorganic nucleating agents, it is preferable to add calcium silicate. As calcium silicate, for example, one containing hexagonal crystals can be used, and the addition amount is preferably in the range of 0.01 to 1% by weight based on the resin composition, and more preferably 0. It is in the range of 05 to 0.5% by weight. If the amount is too large, the appearance tends to deteriorate, and if the amount is too small, no particular effect is exhibited, which is not preferable.

  In this invention, it is preferable to mix | blend a mold release agent. As the mold release agent used in the present invention, those used for ordinary thermoplastic resins can be used. For example, fatty acid, fatty acid metal salt, oxy fatty acid, paraffin low molecular weight polyolefin, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid partial saponified ester, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid higher alcohol ester, fatty acid polyhydric ester Examples thereof include partial alcohol partial esters, fatty acid polyglycol esters, and modified silicones. By blending these, a polylactic acid resin composition and a molded product excellent in mechanical properties, moldability, and heat resistance can be obtained.

  Fatty acids having 6 to 40 carbon atoms are preferred. Specifically, oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, montan Examples thereof include acids and mixtures thereof. The fatty acid metal salt is preferably an antari (earth) metal salt of a fatty acid having 6 to 40 carbon atoms, and specific examples include calcium stearate, sodium montanate, calcium montanate, and the like. Examples of the oxy fatty acid include 1,2-oxysteric acid. 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, arachidonic acid ester, montanic acid ester, and isostearic acid ester. Examples of the fatty acid partial saponified ester include a montanic acid partial saponified ester.

  As paraffin, those having 18 or more carbon atoms are preferable, and liquid paraffin, natural paraffin, microcrystalline wax, petrolactam and the like can be mentioned. As the low molecular weight polyolefin, for example, those having a molecular weight of 5000 or less are preferable. Examples include polyethylene wax, maleic acid-modified polyethylene wax, oxidation type polyethylene wax, chlorinated polyethylene wax, and polypropylene wax.

  Fatty acid amides having 6 or more carbon atoms are preferred, and specific examples include array acid amides, erucic acid amides, behenic acid amides, and the like. The alkylene bis fatty acid amide is preferably one having 6 or more carbon atoms, and specific examples include methylene bis stearic acid amide, ethylene bis stearic acid amide, N, N-bis (2-hydroxyethyl) stearic acid amide and the like. As the aliphatic ketone, those having 6 or more carbon atoms are preferable, and examples thereof include higher aliphatic ketones. The fatty acid ester preferably has 6 or more carbon atoms, and examples thereof include ethyl stearate, butyl stearate, ethyl behenate, stearyl stearate, stearyl oleate, and rice wax.

  Fatty acid polyhydric alcohol esters include glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol dimyristate, pentaerythritol And monostearate, pentaerythritol adipate stearate, sorbitan monobehenate, and the like. Examples of fatty acid polyglycol esters include polyethylene glycol fatty acid esters and polypropylene glycol fatty acid esters. Examples of the modified silicone include 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.

In addition, plant waxes such as carnauba wax and rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as montan wax and partially saponified ester wax of montanic acid, petroleum waxes such as paraffin wax and polyethylene wax And oil-based waxes such as castor oil and derivatives thereof, and fatty acids and derivatives thereof.
Of these, fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, fatty acid partial saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, and alkylene bis fatty acid amide are preferred, and fatty acid partial saponified ester and alkylene bis fatty acid amide are more preferred. Of these, montanic acid esters, montanic acid partially saponified ester waxes, polyethylene waxes, acid value polyethylene waxes, sorbitan fatty acid esters, erucic acid amides, and ethylene bisstearic acid amides are particularly preferably used for improving the high cycle performance. Excellent.

Particularly preferred are montanic acid partially saponified ester wax and ethylenebisstearic acid amide. In the present invention, the release agent may be used alone or in combination of two or more. The compounding amount of the release agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, based on 100 parts by weight of the polylactic acid resin (A).
Any known surface smoothing agent can be used, and examples thereof include silicone compounds, fluorine surfactants, and organic surfactants.
As the flame retardant, the following known agents other than the brominated flame retardant described above can be used as desired. Specifically, chlorine-based flame retardant, phosphorus-based flame retardant, nitrogen compound-based flame retardant, silicone-based flame retardant A flame retardant, other inorganic flame retardants, etc. can be mentioned.
Specific examples of the chlorinated flame retardant include chlorinated paraffin, chlorinated polyethylene, perchlorocyclopentadecane, and tetrachlorophthalic anhydride.
Examples of phosphorus flame retardants include organic phosphorus compounds such as phosphate esters, condensed phosphate esters, and polyphosphates, and red phosphorus.

Any known stabilizer can be used, but lithium stearate, magnesium stearate, calcium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc laurate , Various metal soap stabilizers such as zinc ricinoleate and zinc stearate,
Laurate, malate and mercapto-based organotin stabilizers, various lead-based stabilizers such as lead stearate and tribasic lead sulfate, epoxy compounds such as epoxidized vegetable oil, alkylallyl phosphite, trialkyl phosphite, etc. Phosphite compounds containing compounds exemplified in the above-mentioned transesterification inhibitor (G), β-diketone compounds such as dibenzoylmethane and dehydroacetic acid, polyols such as sorbitol, mannitol and pentaerythritol, hydrotalcites and zeolites Benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, oxalic anilide ultraviolet absorbers, hindered amine light stabilizers, and the like.

As the plasticizer, any known ones can be used. Polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, phosphate ester plasticizers, polyalkylene glycol plasticizers and An epoxy plasticizer can be used.
As the polyester plasticizer, dicarboxylic acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, propylene glycol, 1,3-butanediol, 1,4-butanediol, Examples thereof include polyesters composed of diol components such as 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone.
Specific examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin diacetomonooleate, and glycerin monoacetomonomontanate.

  Specific examples of polycarboxylic acid ester plasticizers include phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, and diheptyl phthalate, tributyl trimellitic acid, trioctyl trimellitic acid, Trimellitic acid esters such as trihexyl melitrate, adipic acid esters such as diisodecyl adipate, citrate esters such as tributyl acetylcitrate, azelaic acid esters such as di-2-ethylhexyl azelate, and di-2-ethylhexyl sebacate In addition to sebacic acid esters such as bis (methyldiglycol) succinate, methyldiglycolbutyldiglycolsuccinate, propyldiglycolbutyldiglycolsuccinate, methyldiglycol Til diglycol succinate, benzyl methyl diglycol succinate, benzyl butyl diglycol succinate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, benzyl butyl diglycol adipate, methoxycarbonylmethyl dibutyl citrate, ethoxycarbonylmethyl Examples thereof include dibutyl citrate, butoxycarbonylmethyl dibutyl citrate, dimethoxycarbonylmethyl monobutyl citrate, diethoxycarbonylmethyl monobutyl citrate, and dibutoxycarbonylmethyl monobutyl citrate.

Examples of the phosphate plasticizer include tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl-2-ethylhexyl phosphate, and tricresyl phosphate.
Polyalkylene glycol plasticizers include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, propylene oxide of bisphenols Examples thereof include polyalkylene glycols such as addition polymers and tetrahydrofuran addition polymers of bisphenols, or end-capped compounds such as terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds.
Epoxy plasticizers include epoxy triglycerides composed of alkyl epoxy stearate and soybean oil. In addition, it is also possible to use epoxy resins mainly made of bisphenol A and epichlorohydrin. it can.

  In addition, benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, and triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearic acid amide, and aliphatic carboxylic acid esters such as butyl oleate And oxy acid esters such as methyl acetyl ricinoleate and butyl acetyl ricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oils, and paraffins.

Any known antistatic agent can be used, but low molecular weight antistatic agents such as anionic antistatic agents, cationic antistatic agents, nonionic antistatic agents, and amphoteric antistatic agents. And polymeric antistatic agents.
Suitable anionic antistatic agents include sodium alkyl sulfonate, sodium alkyl benzene sulfonate and alkyl phosphate. As the alkyl group, a linear alkyl group having 4 to 20 carbon atoms is preferably used.
Suitable cationic antistatic agents include phosphonium alkyl sulfonates, phosphonium alkylbenzene sulfonates and quaternary ammonium salt compounds. As the alkyl group, a linear alkyl group having 4 to 20 carbon atoms is preferably used.

Suitable nonionic antistatic agents include polyoxyethylene derivatives, polyhydric alcohol derivatives, and alkylethanolamines. As the polyoxyethylene derivative, for example, polyethylene glycol having a number average molecular weight of 500 to 100,000 is preferably used.
Suitable amphoteric antistatic agents include alkylbetaines and sulfobetaine derivatives.
Suitable polymeric antistatic agents include polyethylene glycol methacrylate copolymers, polyether amides, polyether ester amides, polyether amide imides, polyalkylene oxide copolymers, polyethylene oxide-epichlorohydrin copolymers and polyether esters. Can be mentioned. These antistatic agents may be used in combination.

  Any known elastomer can be used as the elastomer, but polyester elastomer, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene-1 copolymer, various acrylic rubbers, Ethylene-acrylic acid copolymer and alkali metal salt thereof (so-called ionomer), ethylene-glycidyl (meth) acrylate copolymer, ethylene-acrylic acid alkyl ester copolymer (for example, ethylene-ethyl acrylate copolymer, ethylene -Butyl acrylate copolymer), acid-modified ethylene-propylene copolymer, diene rubber (eg, polybutadiene, polyisoprene, polychloroprene), copolymer of diene and vinyl monomer (eg, styrene-butadiene random copolymer) , Styrene-pig Enblock copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, and graft copolymerization of styrene with polybutadiene. And butadiene-acrylonitrile copolymer), polyisobutylene, copolymers of isobutylene and butadiene or isoprene, natural rubber, thiocol rubber, polysulfide rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber and the like.

Any known rubber-reinforced styrene-based resin can be used. For example, impact-resistant polystyrene, ABS resin, AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), and AES resin (acrylonitrile-ethylene). Propylene rubber-styrene copolymer).
These additives can be used alone or in combination of two or more kinds depending on the properties to be imparted, and for example, a stabilizer, a release agent and a filler can be added in combination.

(Physical properties of resin composition)
The stereo crystallization ratio (Cr) of the resin composition of the present invention is preferably 50 or more, more preferably 60 to 100%, and still more preferably 65 to 100%. The stereo crystallization ratio (Cr) is represented by the following formula (1) defined by the intensity ratio of diffraction peaks in XRD measurement.
Cr (%) = ΣI _SCi / (ΣI _SCi + I _HM ) × 100 (1)
Here, ΣI _SCi = I _SC1 + I _SC2 + I _SC3 is the sum of the integrated intensities of the diffraction peaks derived from the stereocomplex crystal, and I _SCi (i = 1 to 3) is 2θ = 12.0 °, 20. The integrated intensity of each diffraction peak near 7 ° and 24.0 °, and I _HM represents the integrated intensity of the diffraction peak derived from the homocrystal.

The stereogenicity (S) of the resin composition of the present invention is preferably 80% or more, more preferably 90 to 100%. The degree of stereogenicity (S) is defined by the crystal melting peak in DSC measurement and is represented by the following formula (2). The degree of stereogenicity (S) is a parameter indicating the proportion of stereocomplex polylactic acid crystals that are finally produced in the heat treatment process.
S (%) = [(ΔHms / ΔHms ⁰ ) / (ΔHmh / ΔHmh ⁰ + ΔHms / ΔHms ⁰ )] (2)
However, ΔHms ⁰ = 203.4 J / g, ΔHmh ⁰ = 142 J / g, ΔHms = the melting enthalpy of melting point of the stereocomplex, and ΔHmh = the melting enthalpy of homocrystal.
Therefore, the resin composition of the present invention preferably has a stereo crystallization ratio (Cr) of 50% or more and a stereogenicity (S) of 80% or more.

  The carboxy group concentration of the resin composition of the present invention is preferably 30 eq / ton or less, more preferably 20 eq / ton or less, and still more preferably 10 eq / ton or less. When the carboxy group concentration is within this range, a resin composition having good melt stability and wet heat durability can be obtained. The carboxy group concentration can be adjusted with a terminal blocking agent or an amidating agent. Examples of the end capping agent include monocarbodiimides, dicarbodiimides, polycarbodiimides, oxazolines, and epoxy compounds. Examples of the amidating agent include alcohol and amine.

(Manufacture of resin composition)
The resin composition of the present invention can be produced by mixing an aromatic polyester (A component), polylactic acid (B component), an inorganic filler (C component) and an amorphous resin (D component). For mixing, melt blending, solution blending, and the like can be performed by any method as long as uniform mixing is possible. In particular, it is preferable to knead in a molten state in a kneader, a single-screw kneader, a twin-screw kneader, a melt reactor, or the like.
The kneading temperature may be a temperature at which both resins melt, but taking into account the stability of the resin, the range of 230 to 280 ° C is preferable, and the range of 230 to 260 ° C is more preferable. In kneading, it is more preferable to use a compatibilizing agent because the uniformity of the resin is improved and the kneading temperature is lowered.

Examples of the compatibilizer include an inorganic filler, a polymer compound obtained by grafting or copolymerizing a glycidyl compound or an acid anhydride, a graft polymer having an aromatic polycarbonate chain, and an organometallic compound. May be used.
Further, the blending amount of the compatibilizer is preferably 15% by weight to 1% by weight, more preferably 10% by weight to 1% by weight, based on the resin composition, and less than 1% by weight as the compatibilizer. The effect is small, and if it exceeds 15% by weight, the mechanical properties deteriorate, which is not preferable

(Molding)
The resin composition of the present invention is suitable for housing molding. Therefore, this invention includes the molded article for housings which consists of this resin composition.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention does not receive any limitation by this.

1. As a resin aromatic polyester (component A), “DURANEX 2002” manufactured by Wintec Polymer Co., Ltd. was used.

2. The physical properties of polylactic acid were measured by the following methods.
(1) Melting point (Tm), glass transition temperature (Tg)
In the present invention, the melting point (Tm) and the glass transition temperature (Tg) are DSC (TA-2920 manufactured by TA Instrument Co., Ltd.), melting peak when heated at 20 ° C./min, inflection point of heat capacity. Was measured.
(2) Weight average molecular weight (Mw)
The weight average molecular weight (Mw) was used by attaching a Shodex column GPC-804L to a Waters GPC apparatus Allience, dissolving 50 mg of the sample in 5 ml of a mixed solvent of chloroform and HFIP, and developing with chloroform at 40 ° C. It was measured. The weight average molecular weight (Mw) was calculated as a polystyrene equivalent value.
(3) Lactide content Lactide content was measured by using a GPC device Allience manufactured by Waters with a Shodex column GPC-804L attached, and dissolving 50 mg of the sample in 5 ml of a mixed solvent of chloroform and HFIP. The percentage was calculated as the ratio of the area of the lactide component to the sum of the area of the polymer component and the area of the lactide component in the obtained chromatogram.
(4) Carboxy group concentration The sample was dissolved in purified o-cresol, dissolved in a nitrogen stream, and titrated with an ethanol solution of 0.05 N potassium hydroxide using bromocresol blue as an indicator.
(5) Stereoization degree (S)
The degree of stereogenicity (S) was determined by measuring melting enthalpy using DSC (TA-2920 manufactured by TA Instrument Co.), and obtaining the enthalpy according to the following formula (2).
S (%) = [(ΔHms / ΔHms ⁰ ) / (ΔHmh / ΔHmh ⁰ + ΔHms / ΔHms ⁰ )] (2)
(However, ΔHms ⁰ = 203.4 J / g, ΔHmh ⁰ = 142 J / g, ΔHms = Stereocomplex melting enthalpy, ΔHmh = Homocrystal melting enthalpy)
(6) Stereo crystallization ratio (Cr)
The stereocomplex crystallization ratio (Cr) was determined by obtaining a diffraction intensity profile in the equator direction with a ROTA FLEX RU200B type X-ray diffractometer manufactured by RIKEN ELECTRIC CO., LTD. 2θ = 12.0 °, 20.7 °, 24.0 ° The total integrated intensity ΣI _{SCi of} each diffraction peak derived from the stereocomplex crystal appearing in the vicinity and the integrated intensity I _HM of the diffraction peak derived from the homocrystal appearing near 2θ = 16.5 ° were determined according to the following formula (1). .
Measurement conditions X-ray source Cu-Kα ray (confocal mirror)
Output 45kV x 70mA
Slit 1mmΦ-0.8mmΦ
Camera length 120mm
Integration time 10 minutes Cr (%) = ΣI _SCi / (ΣI _SCi + I _HM ) × 100 (1)
(Where ΣI _SCi = I _SC1 + I _SC2 + I _SC3 and I _SCi (i = 1 to 3) are the integrated intensities of diffraction peaks around 2θ = 12.0 °, 20.7 °, and 24.0 °, respectively. is there.)

3. The physical properties of the resin composition and the molded product were measured by the following methods.
(1) Degree of stereo (S)
The degree of stereogenicity (S) was determined by measuring melting enthalpy using DSC (TA-2920 manufactured by TA Instrument Co.), and obtaining the enthalpy according to the following formula (2).
S = [(ΔHms / ΔHms ⁰ ) / (ΔHmh / ΔHmh ⁰ + ΔHms / ΔHms ⁰ )] (2)
(However, ΔHms ⁰ = 203.4 J / g, ΔHmh ⁰ = 142 J / g, ΔHms = Stereocomplex melting enthalpy, ΔHmh = Homocrystal melting enthalpy)
(2) Stereo crystallization ratio (Cr)
Using a ROTA FLEX RU200B type X-ray diffractometer manufactured by RIKEN, the diffraction intensity profile in the equator direction was obtained, and each of the stereocomplex crystals derived from 2θ = 12.0 °, 20.7 °, and 24.0 ° The stereo complex crystallization ratio (Cr ratio) was determined from the total intensity ΣI _SCi of the integrated intensity of diffraction peaks and the integrated intensity IHM of diffraction peaks derived from homocrystals appearing around 2θ = 16.5 ° according to the following formula (1).
Measurement conditions X-ray source Cu-Kα ray (confocal mirror)
Output 45kV x 70mA
Slit 1mmΦ-0.8mmΦ
Camera length 120mm
Integration time 10 minutes Cr (%) = [ΣI _SCi / (ΣI _SCi + I _HM )] × 100 (1)
Here, ΣI _SCi = I _SC1 + I _SC2 + I _SC3 and I _SCi (i = 1 to 3) are 2θ = 12.0 °, 20.7 °, integrated intensity of each diffraction peak around 24.0 ° (3 ) Flexural modulus The flexural modulus was measured according to ASTM-790.
(4) Load deflection temperature The load deflection temperature was measured according to ASTM-648.
(5) The amount of warping The amount of warping was confirmed by measuring the box warp using a molded product having a box shape of 200 mm in length, 130 mm in width, and 50 mm in height and 3 mm in thickness.
(6) Glossiness The glossiness of the molded product was determined according to JISK7105 based on the 60-degree specular glossiness, and the smoothness was determined based on the touch feeling. A glossiness of 90% or more was determined to be acceptable.
(7) Flame retardancy It evaluated by the method (UL94) which a US underwriter laboratory company established (test piece thickness 0.8mm).

[Production Examples 1 and 2] (Production of poly L-lactic acid)
To 100 parts by weight of L-lactide (manufactured by Musashino Chemical Laboratory, Inc., 100% optical purity), 0.005 part by weight of octyltinate was added, and the reaction was carried out at 180 ° C. in a reactor equipped with a stirring blade in a nitrogen atmosphere. Reacted for 2 hours. Thereafter, the remaining lactide at 13.3 kPa was removed and chipped to obtain poly L-lactic acid. The physical properties of the obtained poly L-lactic acid (PLLA1, 2) are shown in Table 1.

[Production Examples 3 and 4] (Production of poly-D-lactic acid)
To 100 parts by weight of D-lactide (manufactured by Musashino Chemical Laboratory, Inc., 100% optical purity), 0.005 part by weight of tin octylate was added, and the reactor was stirred at 180 ° C. with a stirring blade in a nitrogen atmosphere. Reacted for 2 hours. Thereafter, the remaining lactide at 13.3 kPa was removed, and chips were obtained to obtain poly-D-lactic acid. Table 1 shows the physical properties of the obtained poly-D-lactic acid (PDLA1, 2).

[Production Examples 5-1 to 5-4]
The poly L-lactic acid obtained in Production Examples 1 and 2, the poly D-lactic acid obtained in Production Examples 3 and 4, the metal phosphate, carbodiimide, and the crystal nucleating agent were mixed at a cylinder temperature of 230 ° C. with a twin-screw kneader. The melt was extruded to take a strand in a water tank, and it was made into a chip by a chip cutter to obtain a stereocomplex resin. Table 2 shows the physical properties of the obtained stereocomplex resin (scPLA).

Abbreviations in Table 2 are as follows.
NA-11: Phosphate metal salt (ADEKA (former: Asahi Denka Kogyo Co., Ltd.) ADK STAB NA-71: Phosphate metal salt (ADEKA (former: Asahi Denka Kogyo Co., Ltd.) ADK STAB LA-1: Carbodilite K1: Nisshinbo Co., Ltd. Calcium silicate (crystal nucleating agent)
K2: Talc (crystal nucleating agent)

[Examples 1 to 8]
The stereocomplex polylactic acid (B) obtained in Production Example 5 and PBT resin ("DURANEX 2002" manufactured by Wintech Polymer Co., Ltd.) (A) were mixed at the quantitative ratio shown in Table 3, and 120 ° C for 5 hours. Dry dry. Thereafter, the amorphous resin, inorganic filler, transesterification inhibitor and antioxidant shown in Table 3 were blended in the quantitative ratios shown in the table, using a twin-screw kneader, cylinder temperature 250 ° C., feed rate 2 kg. Kneaded at / hr to obtain a resin composition. Table 3 shows the physical properties of the resin composition obtained.
The obtained resin composition was injection molded at a mold temperature of 110 ° C. and a mold clamping time of 2 minutes to obtain a molded product. The obtained molded product was white and had a good shape. Table 3 shows the quality of the molded product.
It can be seen that the molded article of the present invention has a high deflection temperature under load, a small amount of warpage and excellent dimensional stability.
The resin composition of the present invention is a molded article having good surface properties, dimensional stability, and heat resistance. Therefore, the resin composition of the present invention is suitable for molding molded products for housings, for example, in-vehicle component cases such as ECU boxes and connector boxes, in-vehicle electrical components such as electronic component cases such as capacitor boxes, and metal insert components.

[Comparative Examples 1-2]
The same operation as Example 1 was performed except having changed each component into the kind and quantity of Table 3, and the resin composition was obtained. Table 3 shows the physical properties of the resin composition obtained. The obtained resin composition was injection molded under the same conditions as in Example 1 to obtain a molded product. Table 3 shows the quality of the obtained molded product.

Abbreviations in Table 3 are as follows.
D1: Polycarbonate L1225 manufactured by Teijin Chemicals Ltd.
D2: Mitsui Chemicals Co., Ltd. styrene-butadiene-acrylonitrile copolymer; Santac UT-61
C1: Glass fiber (13 μm diameter, 5 mm chopped strand: manufactured by Nippon Electric Glass Co., Ltd.)
C2: Calcium silicate (manufactured by Nacalai Tesque), C3: talc (P-2, manufactured by Nippon Talc Co., Ltd.)
G1: Acidic sodium metaphosphate G2: DHPA manufactured by Rasa Soei Co., Ltd.
H1: n-octadecyl 3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate H2: tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4) -Hydroxyphenyl) propionate] methane

[Examples 9 to 13, Comparative Examples 3 to 5]
The stereocomplex polylactic acid (B) of Production Examples 5-1 and 5-2 and PBT resin (“Juranex 2002” manufactured by Wintech Polymer Co., Ltd.) (A) were mixed at a quantitative ratio shown in Table 4 and 120 ° C. Dry for 5 hours. Thereafter, the types and amounts of amorphous resins, inorganic fillers, flame retardants, transesterification inhibitors and antioxidants listed in Table 4 were blended. Further, 1 part by weight of fibrous PTFE was added as a dripping inhibitor per 100 parts by weight of the total of the A component and the B component. Then, it knead | mixed with the cylinder temperature of 250 degreeC and the feed rate of 2 Kg / hr using the biaxial kneader, and obtained the resin composition. Table 4 shows the physical properties of the resin composition obtained.
The obtained resin composition was injection-molded at a mold temperature of 110 ° C. and a mold clamping time of 2 minutes (in the comparative example, 2 minutes for PBT alone and 4 minutes for others) to obtain a molded product. The obtained molded product was white and had a good shape. Table 4 shows the quality of the molded product.
The molded product is excellent in flame retardancy, surface appearance (glossiness), heat resistance (heat distortion temperature), and dimensional stability (low warpage).

Abbreviations in Table 4 are as follows.
C1: Glass fiber (13 μm diameter, 5 mm chopped strand: manufactured by Nippon Electric Glass Co., Ltd.)
C2: Calcium silicate (manufactured by Nacalai Tesque)
C3: Talc (Nihon Talc Co., Ltd. P-2)
D1: Polycarbonate L1225 manufactured by Teijin Chemicals Ltd.
D2: Mitsui Chemicals Co., Ltd. styrene-butadiene-acrylonitrile copolymer; Santac UT-61
E1: (Fire guard 7500 manufactured by Teijin Chemicals Ltd., polymerization degree n = about 5
F1: Antimony trioxide (PATOX-M: manufactured by Nippon Seiko Co., Ltd.)
G1: Acidic sodium metaphosphate G2: DHPA manufactured by Rasa Soei Co., Ltd.
H1: n-octadecyl 3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate H2: tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4) -Hydroxyphenyl) propionate] methane

[Examples 14 to 16, Comparative Examples 6 to 8]
The stereocomplex polylactic acid (B) of Production Example 5 and PBT resin ("Juranex 2002" manufactured by Wintech Polymer Co., Ltd.) (A) were mixed at the quantitative ratio shown in Table 5 and dried at 120 ° C for 5 hours. did. Thereafter, the amounts of amorphous resins, inorganic fillers, brominated flame retardants, antimony flame retardant aids, transesterification inhibitors, and antioxidants listed in Table 5 in the quantitative ratios shown in Table 5 The mixture was kneaded using a twin-screw kneader at a cylinder temperature of 250 ° C. and a feed rate of 2 kg / hr to obtain a resin composition. Table 5 shows the physical properties of the obtained resin composition.
The obtained resin composition was injection molded at a mold temperature of 110 ° C. and a mold clamping time of 2 minutes to obtain a molded product. The obtained molded product was white and had a good shape. In the comparative example, injection molding was performed at a mold temperature of 110 ° C. and a mold clamping time of 4 minutes (however, 2 minutes when using PBT alone). Table 5 shows the quality of the molded product. It can be seen that the molded article of the present invention is excellent in flame retardancy, surface appearance (glossiness), heat resistance (thermal deformation temperature), and dimensional stability (low warpage).

Abbreviations in Table 5 are as follows.
C1: Glass fiber (13 μm diameter, 5 mm chopped strand: manufactured by Nippon Electric Glass Co., Ltd.)
C2: calcium silicate (manufactured by Nacalai Tesque Co., Ltd.), C3: talc (manufactured by Nippon Talc Co., Ltd., D1: Teijin Chemicals Ltd. polycarbonate L1225)
D2: Mitsui Chemicals Co., Ltd. styrene-butadiene-acrylonitrile copolymer; Santac E1: Teijin Chemicals Co., Ltd. Fireguard 7500, polymerization degree n = about 5
F1: Antimony trioxide (PATOX-M: manufactured by Nippon Seiko Co., Ltd.)
G1: Lhasa Soei Co., Ltd., sodium acid metaphosphate G2: DHPA
H1: n-octadecyl 3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate H2: tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4) -Hydroxyphenyl) propionate] methane

  The resin composition of the present invention can be used for molding molded articles for housing, on-vehicle electrical components, and metal insert parts.

Claims (9)

An aromatic polyester (component A) having a butylene terephthalate skeleton as a main structural unit, a polylactic acid (component B) having a melting point of 190 ° C. or higher, an inorganic filler (component C), and an amorphous resin (component D); The content of the A component is 5 to 95 parts by weight, the content of the C component is 5 to 100 parts by weight, and the content of the D component is 1 to 100 parts by weight of the total of the A component and the B component. The resin composition which is 100 weight part. Claims containing 5 to 80 parts by weight of brominated flame retardant (E component) and 0 to 30 parts by weight of antimony flame retardant auxiliary (F component) with respect to 100 parts by weight of the total of A component and B component Item 2. The resin composition according to Item 1. The resin composition according to claim 1, further comprising 0.01 to 5 parts by weight of a transesterification inhibitor (G component) with respect to 100 parts by weight of the total of the A component and the B component. The resin composition according to claim 1, further comprising 0.01 to 5 parts by weight of an antioxidant (H component) with respect to 100 parts by weight of the total of the A component and the B component. The resin composition of Claim 1 which contains 0.001-5 weight part of carbodiimide compounds (J component) with respect to 100 weight part of B components. The resin composition according to claim 1, wherein the stereo crystallization ratio (Cr) is 50% or more and the degree of stereocrystallization (S) is 80% or more.
However, the stereo crystallization ratio (Cr) is a value defined by the following formula (1).
Cr (%) = ΣI _SCi / (ΣI _SCi + I _HM ) × 100 (1)
(Where ΣI _SCi = I _SC1 + I _SC2 + I _SC3 is the total integrated intensity of each diffraction peak derived from the stereocomplex crystal, and I _SCi (i = 1 to 3) is 2θ = 12.0 °, 20.7 respectively. (°, integrated intensity of each diffraction peak near 24.0 °, I _HM represents the integrated intensity of a diffraction peak derived from a homocrystal)
Further, the degree of stereogenicity (S) is a value defined by the following formula (2).
S (%) = [(ΔHms / ΔHms ⁰ ) / (ΔHmh / ΔHmh ⁰ + ΔHms / ΔHms ⁰ )] (2)
(Here, ΔHms ⁰ = 203.4 J / g, ΔHmh ⁰ = 142 J / g, ΔHms = the melting enthalpy of melting point of the stereo complex, and ΔHmh = the melting enthalpy of homocrystal) The resin composition according to claim 1, wherein the carboxy group concentration is 30 eq / ton or less. The resin composition for housing molding according to any one of claims 1 to 7. A molded article for a housing comprising the resin composition according to claim 8.