JP2008050580A - Resin composition and molded product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having excellent flame retardance, light resistance and melt stability. <P>SOLUTION: The resin composition comprises an aromatic polyester component (component A) having a butylene terephthalate skeleton as a main constituent unit, a polylactic acid (component B) having ≥190°C melting point, an inorganic filler (component C), a bromine-based flame retardant (component D), an antimony-based flame retardant (component E) and a light stabilizer (component F). The contents of the components based on 100 pts.wt. of the sum total of the component A and the component B are as follows. The content of the component A is 5-95 pts.wt.; the content of the component C is 0-150 pts.wt.; the content of the component D is 5-80 pts.wt.; the content of the component E is 0-30 pts.wt. and the content of the component F is 0-5 pts.wt. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition based on a bio-based polymer polylactic acid and excellent in heat resistance, flame retardancy and light resistance and excellent in high cycle moldability. Moreover, this invention relates to the electronic component which consists of this composition, and the component for household appliances.

  PBT is a thermoplastic resin material having various excellent characteristics such as oxidation resistance and solvent resistance, and a molded product having good physical and mechanical properties can be obtained by injection molding. However, in order to use for lighting parts, PBT needs to be provided with flame retardancy to ensure product safety. However, application of flame retardant reduces the light resistance of the resin, causes yellowing defects, and melt stability. The problem is that the drawbacks are reduced. In addition, when a filler is added with the intention of imparting rigidity and heat resistance, the surface appearance of molded products deteriorates, making it difficult to apply to electronic parts and parts for home appliances that require surface appearance. Met. More recently, molding with a hot runner system and recycling of molded products have become more frequent due to the need to reduce molding waste, and higher resin melt stability has been demanded.

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, and therefore 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.

However, in the most promising polylactic acid, problems of heat resistance and chemical resistance have been pointed out, but stereocomplex polylactic acid containing D-lactic acid as a raw material (see Non-Patent Document 1) is a conventional poly L-lactic acid. It is a resin having a remarkably high melting point and a crystalline resin compared to the above, and is expected to be used for such characteristics. 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, it is possible to simultaneously decompose the ester bond part contained in the thermoplastic polyester by thermally decomposing or solvolyzing the aliphatic polyester contained in the structural material. Therefore, disposal is easy after the end of use. 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 is considered to be difficult to put into practical use as an engineering plastic because of poor thermal stability during melt molding and extremely poor moldability. It was. Therefore, studies have been made to select PBT having excellent moldability as an aromatic polyester and obtain a PBT composition that solves the problem of moldability.
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 wt% or less and molded under the condition that it does not melt to increase the heat distortion temperature of the molded product. Improvements in formability have been proposed. (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 can point out a problem that the heat resistance is lowered because the glass transition temperature is lowered.
In these proposals, poly-L-lactic acid or poly-D-lactic acid (hereinafter sometimes abbreviated as lactic acid homopolymer) that is stably produced is selectively used as polylactic acid. It was greatly reduced, and the problem of solvent resistance became clear.
However, there has not yet been proposed a composition of stereocomplex polylactic acid and PBT in which the formation of a stereocomplex phase is not necessarily stable.
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 containing a biopolymer and having a small environmental load. Another object of the present invention is to provide a resin composition excellent in flame retardancy, light resistance and melt stability. Furthermore, the objective of this invention is providing the resin composition excellent in antistatic property, heat resistance, and surface appearance. Moreover, this invention is providing the molded article which consists of this resin composition.

  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 a brominated flame retardant (component D). An antimony flame retardant (E component) and a light stabilizer (F component) are contained, and the content of the A component is 5 to 95 parts by weight per 100 parts by weight of the total of the A component and the B component. 0 to 150 parts by weight, D component content is 5 to 80 parts by weight, E component content is 0 to 30 parts by weight, and F component content is 0 to 5 parts by weight. Moreover, this invention is an electronic component, a component for household electric appliances, a lighting component, or a fluorescent lamp cap made of the resin composition.

  Since the resin composition of the present invention contains polylactic acid which is a bio-based polymer, the load on the environment is small. The resin composition of the present invention is excellent in flame retardancy, light resistance, melt stability, and high cycle moldability. Furthermore, the resin composition of the present invention is excellent in heat resistance, surface appearance, and antistatic properties.

  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.
In the present invention, the use of poly L-lactic acid or poly D-lactic acid homopolymer, and stereocomplex polylactic acid in which stereocomplex phase formation has progressed only to a low level can be used for the heat resistance of the resin composition (for example, molding products). This is not adopted in the present invention because it reduces the deflection temperature under load) and the solvent resistance.

In the resin composition of the present invention, the stereocrystallization ratio (Cr) of polylactic acid is preferably in the range of 50 to 100%, more preferably 60 to 100%, more preferably 70 to 100%. The stereocrystallinity is preferably in the range of 80 to 100%, more preferably 90 to 100%, more preferably 95 to 100%. Particularly preferred is 100%.
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 1 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 1 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 known methods. 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, hydridotrioxoline (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 (component B) has such a range of stereogenicity (S) and stereocrystallization ratio (Cr), the appearance, low warpage, dimensional stability and heat resistance of the resin composition of the present invention. Various physical properties such as the above can be made high, and further, high cycle formability can be suitably achieved.
The polylactic acid (component B) preferably contains a metal phosphate represented by the following formula (3) 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 formula (3) is Na, K, Al, Mg, or Ca. In particular, K, Na, or Al can be preferably used. The content of the compound represented by the formula (3) is preferably 10 ppm to 2% by weight, more preferably 50 ppm to 0.5% by weight, and still more preferably 100 ppm to 0.00% with respect to polylactic acid (component B). 3% by weight. 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 component) and the resin composition of this invention, thermal decomposition property, hydrolysis resistance, etc.
The block forming agent reacts with the molecular end of polylactic acid (component B) to partially connect the poly L-lactic acid unit and poly D-lactic acid unit to form blocked polylactic acid, forming a stereo complex phase It is an agent that promotes.
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 (component B) preferably contains a compound having a specific functional group as a block forming agent and a heat and humidity resistance improver, and a carbodiimide compound (component K) is suitably selected. The content of the K 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 (K 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 part by weight, the effect is hardly recognized and 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. The polylactic acid (component B) has a lactide content in such a range, thereby improving the stability of the resin composition when melted, enabling efficient molding with high cycle moldability, and improving the hydrolysis resistance of the molded product. It is because it can raise. In order to reduce the lactide content to such a range, 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 (component B), a conventionally known lactide reduction treatment or It can be achieved by performing in combination.

(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.
The aromatic polyester preferably has a carboxyl group concentration of 60 eq / ton or less.

(Inorganic filler: component C)

The inorganic filler (component C) used in the present invention contains 0 to 150 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.

(Brominated flame retardant: D component)
The resin composition of the present invention contains 5 to 80 parts by weight of brominated flame retardant (D component) and 0 to 30 antimony flame retardant auxiliary (E component) per 100 parts by weight of the total of component A and component B. It is preferable to contain by weight. The content of component D is preferably 10 to 50 parts by weight, more preferably 10 to 30 parts by weight. The content of component E is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight.
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 (D component) 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 part of its terminal glycidyl group or These are all modified products, brominated diphenyl ether flame retardant, brominated imide flame retardant, brominated polystyrene flame retardant 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.

  The brominated flame retardant (component D) is preferably a compound represented by the following formula (i) or (ii).

(Wherein X represents a bromine element and / or a chlorine element, and n represents an integer of 5 or more and 20 or less)

(Wherein X represents a bromine element and / or chlorine element, and n represents an integer of 3 to 12)

(Antimony flame retardant aid (E component)
As the antimony flame retardant aid (E) 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 _{(E), (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 (E) 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, when 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.

(Anti-dropping agent)
Furthermore, application of polytetrafluoroethylene (PTFE) is essential for exhibiting the anti-dropping property. As PTFE suitably used as the anti-dropping agent, various shapes such as a fibrous shape and a particulate shape are known, but a fibrous shape is optimal.
The content of the anti-dropping agent is preferably 0.01 to 5 parts by weight per 100 parts by weight of the total of component A and component B.

(Light stabilizer: F component)
The resin composition of the present invention has high light stability by using the above-mentioned polylactic acid (component B) and PBT (component A) together. However, in order to further enhance the light stability, the light stabilizer (F Application of the component) is preferred. The content of the photostabilizer (F component) is 0.000 per 100 parts by weight of the total of the A component and B component. -5 parts by weight, preferably 0.01-1 part by weight, more preferably 0.02-0.5 part by weight.
Specific examples of the light stabilizer suitably used in the present invention include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds, hindered amine compounds, and the like. be able to.

  Specific examples of the benzophenone compounds include benzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxybenzophenone, 2,2′4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-do Decyloxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 5-chloro-2-hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy- 4-Met Shi-2'-carboxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methylcyclohexyl acryloxy-isopropoxyphenyl) benzophenone.

  Specific examples of benzotriazole compounds include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-t-butyl-4′-methyl-2′-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-tert-butyl-2-hydroxyphenyl) benzotriazole 2- [2′-hydroxy-3 ′, 5 '-Bis (α, α-dimethylbenzyl) phenyl] benzotriazole, 2- [2'-hydroxy-3', 5'-bis (α, α-dimethylbenzyl) Eniru] -2H- benzotriazole, 2- (4'Okutokishi 2'-hydroxyphenyl) benzotriazole and the like.

Specific examples of the aromatic benzoate compounds include alkylphenyl salicylates such as pt-butylphenyl salicylate and p-octylphenyl salicylate.
Specific examples of oxalic acid anilide compounds include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, 2- And ethoxy-3′-dodecyl oxalic acid bisanilide.
Specific examples of the cyanoacrylate compound include ethyl 2-cyano-3,3′-diphenyl acrylate, 2-ethylhexyl 2-cyano-3,3′-diphenyl acrylate, and the like.

Specific examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2. , 2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy -2,2,6,6-tetramethylpiperidine, 4-octadecyloxy-2,2,6,6-tetramethylpiperidine,
4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2, 2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate,
Bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6,6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl) -4-piperidyl) sebacate, bis (2,2,6,6-tetramethylpi-4-peridyl) adipate, bis (2,2,6,6-tetramethylpi-4-peridyl) terephthalate, 1,2-bis (2 , 2,6,6-tetramethylpi-4-peridyloxy) -ethane,
α, α′-bis (2,2,6,6-tetramethylpi-4-peridyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyl) -tolylene-2,4-di Carbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1 , 3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- “2- {3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl -4 Piperidinol and β, β, β ', β'- tetramethyl-3,9 [2,4,8,10-tetra oxa spiro (5,5) Undekan'n] and the like condensates of Jimetanoru.

  In this invention, the said stabilizer may be used by 1 type and may be used in combination of 2 or more type. Moreover, it is preferable to use a hindered phenol compound and / or a benzotriazole compound as the stabilizer.

(Transesterification inhibitor: G component)
The resin composition of the present invention preferably contains 0.01 to 5 parts by weight of a transesterification inhibitor (G component) per 100 parts by weight of the total of component A and component B. The content of the G component is preferably 0.01 to 1 part by weight, more preferably 0.02 to 0.5 part by weight. By containing the G component, the resin composition has improved melt viscosity stability, can suppress decomposition during molding and molecular weight reduction, and can be suitably melt-molded.
As the transesterification inhibitor (G component), in the PBT resin composition, sodium dihydrogen phosphate, potassium acetate, trimethyl phosphate, phenylphosphonic acid, and the like are known. The catalyst deactivator can be suitably applied.

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.
The composition of the present invention, which is excellent in flame retardancy, light resistance, heat resistance and appearance of the molded product and has good melt stability of the molten resin, makes use of its characteristics. A molded article for electronic parts and a molded article for home appliances can be suitably molded.

(Antioxidant: H component)
Furthermore, it is preferable that the resin composition of this invention contains 0.01-5 weight part of antioxidant (H component) per 100 weight part of total of A component and B component. More preferably, it is 0.01-2 weight part, More preferably, it is the range of 0.02-0.5 weight part. 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′-methyl-5′- t-butyl-4′-hydroxyphenyl) -propionate, n-tetradecyl 3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediolbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], 2,2′-methylene-bis (4-methyl-t-butylphenol), triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -Propionate], tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3-t-butyl- 4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane, N, N′-bis-3- (3 ′ , 5′-di-t-butyl-4′-hydroxyphenyl) propionylhexamethylenediamine, N, N′-tetramethylene-bis [3- (3′-methyl-5′-t-butyl-4′-hydroxy) Phenyl) 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 And oxyamide.
Preferably, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate] and tetrakis [methylene-3- (3 ′, 5′-di-t-butyl- 4-hydroxyphenyl) propionate] methane and the like.

Specifically, the phosphite compound used in the present invention is preferably one in which at least one P—O bond is bonded to an aromatic group. Specifically, tris (2,6-di-t -Butylphenyl) phosphite, tetrakis (2,6-di-t-butylphenyl) 4,4'-biphenylene phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di -Phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl-di-tridecyl) phos Phyto, 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-t-butylphenyl) butane, tris (mixed mono and di-nonylphenyl) Phosphite, 4,4'-isopropylidene-bis (phenyl - dialkyl phosphite), and the like.
Also, 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 can be preferably used.

  Specific examples of thioether compounds include 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-stearylthiopro) Pionate).

(Antistatic agent: J component)
In the resin composition of the present invention, it is preferable to apply an antistatic agent to impart antistatic properties. The antistatic performance in the present invention is antistatic property that does not substantially impair everyday dust and does not impair the commercial value of the lighting component. As an evaluation standard for daily dust adhesion, a plate-shaped sample is charged until it is saturated at an electrode-sample distance of 20 mm and an applied voltage of 10 kV, and then immediately held over the cigarette ash to observe and judge the degree of ash adhesion. did. When the saturation voltage is 1.25 kV or less and the half decay time is 30 seconds or less, there is no adhesion of cigarette ash. Increase the product value of
Such antistatic properties can be achieved by blending 0.01 to 10 parts by weight of the antistatic agent (J component) with respect to 100 parts by weight of the total of the A component and the B component.
Examples of antistatic agents (component J) include anionic antistatic agents, cationic antistatic agents, nonionic antistatic agents, amphoteric antistatic agents and other low molecular antistatic agents, and polymeric antistatic agents. Can be mentioned.

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. From the viewpoint of maintaining good whiteness of molded products and maintaining light resistance, the antistatic agent (component J) may be a low molecular weight antistatic agent alone or a low molecular weight antistatic agent and a polymer. It is preferable to use a mold antistatic agent in combination.

  The antistatic agent (component J) is contained in an amount sufficient to develop the time until the saturation voltage and the charged voltage are attenuated to half. This amount is 0.1 to 10 parts by weight per 100 parts by weight of the total of component A and component B. For example, when an antistatic agent comprising a mixture of sodium dodecylbenzenesulfonate and polyethylene glycol is used, it is preferably 0. 0.5 to 7.5 parts by weight, more preferably 0.75 to 5 parts by weight. By mix | blending in this range, the melt stability at the time of shaping | molding can be maintained, providing sufficient antistatic property.

  The composition of the present invention, which is excellent in flame retardancy, light resistance, heat resistance and appearance of molded articles and has good melt stability of the molten resin, further acquires antistatic properties. A molded product for electronic parts, a molded product for home appliances, and a molded product for lighting parts can be suitably molded. In addition, by using PBT and scPLA having a high molecular weight, the toughness strength of the resin can be increased, and the pinning strength and tap strength can be increased, so that it can be suitably used for molding a molded product for a fluorescent lamp cap.

  The toughness strength in the present invention refers to 1) toughness required for fluorescent lamp base materials, 2) toughness that does not break when inserting electrode pins, 2) tap strength during assembly, and 3) resistance to ensure safety when handling fluorescent lamps. The material property corresponding to the deformability. The toughness that does not break when inserting an electrode pin in the present invention is a 1.8 mmΦ in a 1.9 mmΦ pin insertion hole at a position 10 mm or more away from the outer edge of the fluorescent lamp cap (cross section 30 mmΦ, center circumference 48 mm). A jig composed of a guide part having a length of 5 mm and a taper part having a gradient (15.0-1.8) /40.0 followed by 300 mm / min. This means that the pinning strength when inserted at a speed of 60 kgf or more. If it is less than 60 kgf, cracks occur when pins are inserted into the fluorescent lamp caps, which hinders automation by robots.

In the present invention, the tap strength means that a 4.0 mmφ tapped screw is tightened with a force of 5 kgf into a 3.0 mmφ screw hole at a position 10 mm or more away from the outer edge of the fluorescent lamp base (cross section 30 mmφ, center circumference 48 mm). The resistance to screwing cracks that are not cracked when inserted.
In the flame retardant polyester resin composition for fluorescent lamp caps of the present invention, the occurrence of cracking by this test method is 1 sample or less per 50 samples of fluorescent lamp caps. In the case where one or more samples per 50 samples are generated by this test method, cracks occur during screwing in the fluorescent lamp assembling process and cannot be used.

  The deformation resistance in the present invention refers to resistance to cracking when a fluorescent lamp cap molded article having a half-circular section divided into two is bent by 3 mm so as to be warped opposite to the center of the arc. In the flame retardant polyester resin composition for fluorescent lamp caps of the present invention, the occurrence of cracking by this test method is 1 sample or less per 50 samples of fluorescent lamp caps. If this test method causes one or more cracks per 50 samples, the breakage may occur due to the inset pressure when the fluorescent lamp is attached, or the crack may be caused by the pressing force when printing the logo mark in the manufacturing process. It does not endure practical use.

(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-naphthocyclohexanecarboxylate, organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearamide, Carboxylic acid amides such as ethylene bislauric 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 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 specifically includes 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 comprises aromatic polyester (component A), polylactic acid (component B), inorganic filler (component C), brominated flame retardant (component D), antimony based flame retardant (component E) and light. It can be produced by mixing a stabilizer (F 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 molding electronic parts, parts for home appliances, lighting parts, or fluorescent lamp caps. Therefore, this invention includes the electronic component, the component for household appliances, the lighting component, or the fluorescent lamp base which consist 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 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) 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 in the vicinity of 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
Total 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 diffraction peaks around 24.0 ° (3 ) Melt stability Melt stability is the melt viscosity retention after treatment at 260 ° C. for 10 minutes, and 80% or more was determined to be acceptable (◯). When it was 85% or more, it was judged to be excellent (（), and when it was less than 80%, it was judged to be unacceptable (x). The melt viscosity was measured at 260 ° C. in accordance with JIS K7199 using a Capillograph 10 manufactured by Toyo Seiki Seisakusho.

4). The physical properties of the molded product were measured by the following methods.
(1) Light resistance Irradiation from a distance of 20 cm with a fluorescent lamp 96W × 2 lamps at 80 ° C., ΔE was measured at 100 hr, and if ΔE ≦ 5, there was no practical problem and it was judged that the color resistance was good.
(2) Antistatic control After the test piece was conditioned for 24 hours in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, an Honest meter (Static H-0110 manufactured by Sicid Electrostatic Co., Ltd.) was used under the same conditions. Then, charging was performed at an electrode-sample distance of 20 mm and an applied voltage of 10 kV, and the time during which the charged voltage decayed to half (half decay time) was measured. When the half decay time was 30 seconds or less, it was determined to be acceptable.
As an evaluation standard for daily dust adhesion, a disk-shaped test piece was charged until it was saturated at an electrode-sample distance of 20 mm and an applied voltage of 10 kV, and immediately passed over a cigarette ash at a distance of 5 mm. When the degree of ash adhesion was observed, almost no ash adhesion was observed when the half decay time was 30 seconds or less.
(3) Surface appearance The surface appearance was measured by a 60 degree specular gloss according to JISK7105. Those with a glossiness of less than 90% were rejected, and those with 90% or more were judged acceptable. As for smoothness, it was judged that it was judged to be improved compared to the molded product (PBT / glass) by hand, and a case where no improvement was seen was judged to be rejected.
What passed in both judgments was judged to be acceptable.
(4) Flammability Evaluated by a method (UL94) defined by US Underwriters Laboratory (test piece thickness 0.8 mm).
(5) Deflection temperature under load Deflection temperature under load was measured according to ASTM-648.
(6) Flexural modulus The flexural modulus was measured according to ASTM-790.
(7) Pinning strength:
In the 1.9mmΦ pin insertion hole of the fluorescent lamp base, a jig consisting of a guide part with a length of 1.8mmΦ and a length of 5mm followed by a taper with a slope (15.0-1.8) /40.0 is 300mm / min. . It is the pinning strength when inserted at a speed of. It measured using Minebea Co., Ltd. product TCM-1 million tensile tester. When it was 60 kgf or more, it was determined to be acceptable.
(8) Tap strength:
This is resistance to cracking when a 4.0 mmφ tapped screw is tightened into a 3.0 mmφ screw hole with a force of 5 kgf. Evaluation was made based on the number of samples in which no cracking occurred per 50 fluorescent lamp caps. 50/50 was determined to be acceptable.
(9) Deformation resistance Resistance to cracking when a fluorescent lamp cap molded article having a half-circular section divided into two is bent by 3 mm so as to bend away from the center of the arc. Evaluation was made based on the number of samples in which no cracking occurred per 50 fluorescent lamp caps. 50/50 was determined to be acceptable.
(10) Chemical resistance of molded products:
The molded article was immersed in the following chemicals and held at 25 ° C. for 1 day, and then the appearance and weight change were examined (chemicals used: toluene, dichloromethane, THF, acetone, ethanol, 20% sulfuric acid, 10% NaOH). In any of the compositions of the examples, no noticeable shape change was observed, and there was a large change in weight, which was a pass level that was not a practical problem at 2-3%, but was not acceptable in the comparative example.

[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 X1: Nisshinbo Co., Ltd. Calcium silicate (crystal nucleating agent)
X2: Talc (crystal nucleating agent)

[Examples 1 to 6]
Stereocomplex polylactic acid (component B) of Production Example 5 and PBT resin ("DURANEX 2002" manufactured by Wintech Polymer Co., Ltd.) (component A) were mixed at the quantitative ratio shown in Table 3 and dried at 120 ° C for 5 hours. did. Thereafter, flame retardants, transesterification inhibitors, antioxidants and the like listed in Table 3 were blended in the quantitative ratios shown in Table 3, using a twin-screw kneader, cylinder temperature, 250 ° C., feed rate 2 Kg / hr. Was kneaded 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 good flame retardancy, light resistance and melt stability, and also has good surface properties.

[Comparative Examples 1-2]
A resin composition was obtained in the same manner as in Example 1 except that polylactic acid was changed to the types and amounts shown in Table 3. Table 3 shows the physical properties of the resin composition obtained.
The obtained resin composition was injection molded in the same manner as in Example 1 to obtain a molded product. Table 3 shows the quality of the molded product. The obtained molded product had a gloss of 90% or less, and was judged to have failed surface properties.
It is understood that the resin composition of the present invention has good flame retardancy, light resistance and melt stability, and also has good surface properties and a high molded product cycle. By adding an antistatic agent and a light stabilizer, antistatic properties and light resistance can be further enhanced.

Abbreviations in Table 3 are as follows.
C1 (inorganic filler): glass fiber (13 μm diameter, 5 mm chopped strand: manufactured by Nippon Electric Glass Co., Ltd.)
C2 (inorganic filler): calcium silicate (manufactured by Nacalai Tesque)
C3: Talc (Nihon Talc Co., Ltd. P-2)
D1 (flame retardant): manufactured by Teijin Chemicals Ltd., Fireguard 7500 degree of polymerization n = about 5
D2 (flame retardant): Dainippon Ink & Chemicals, Inc., EP100
E1 (antimony flame retardant aid): antimony trioxide (Nippon Seiko Co., Ltd .: PATOX-M)
E2 (antimony flame retardant aid): antimony pentoxide (NA1030 manufactured by Nissan Chemical Co., Ltd.)
F1 (light stabilizer): Triazole (Asahi Denka Co., Ltd.), LA-31
F2 (light stabilizer): benzoate (Sumitomo Chemical Co., Ltd.), Sumisorb 400
J1 (antistatic agent): Takemoto Yushi Co., Ltd., sodium dodecylbenzenesulfonate mixture, TPL456
J2 (antistatic agent): Takemoto Yushi Co., Ltd., tetrabutylphosphonium dodecylbenzenesulfonate / PEG mixture, TPL416
G1 (transesterification inhibitor): Tris (2,6-di-t-butylphenyl) phosphite G2 (transesterification inhibitor): tetraphenyl-4,4′-biphenylene phosphite H1 (antioxidant): n -Octadecyl 3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate H2 (antioxidant): tetrakis [methylene-3- (3', 5'-di-t-butyl) -4-hydroxyphenyl) propionate] methane titanium oxide: colorant

[Examples 7 to 12]
Stereocomplex polylactic acid (component B) of Production Example 5 and PBT resin ("Juranex 2002" manufactured by Wintech Polymer Co., Ltd.) (component A) are mixed in the quantitative ratio shown in Table 4 and dried at 120 ° C for 5 hours. Dried. Thereafter, the inorganic filler, crystal nucleating agent (C2: calcium silicate, C3: talc), bromine-based flame retardant, antimony-based flame retardant auxiliary, transesterification inhibitor, antioxidant, etc. in the quantitative ratio shown in Table 4 Blended. Furthermore, as a dripping preventing agent, fibrous PTFE is blended in an amount of 0.5 parts by weight per 100 parts by weight of the A component and the B component, and kneaded using a twin-screw kneader at a cylinder temperature of 250 ° C. and a feed rate of 2 kg / hr. A resin composition was obtained. 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 to obtain a molded product. The obtained molded product was white and had a good shape.

  The fact that the solvent resistance of the composition of the present invention is good has been described in the test items, but by applying a flame retardant and an inorganic filler, flame retardancy and light resistance can be improved, and high heat resistance, It is understood that the thermal deformation temperature is equivalent to (PBT / glass), the surface appearance is greatly improved, and the molding cycle is also high. Furthermore, it is easily understood that application of an antistatic agent and a light stabilizer can impart antistatic properties and can further enhance light resistance.

[Comparative Examples 3 to 4]
In Example 1, polylactic acid was changed to the type and amount shown in Table 4, and PBT resin ("DURANEX 2002" manufactured by Wintech Polymer Co., Ltd.) (A) was mixed at a quantitative ratio shown in Table 4 at 120 ° C. Dry and dry for 5 hours. Thereafter, an inorganic filler, bromine-based flame retardant, antimony-based flame retardant aid, transesterification inhibitor, and antioxidant are blended in the quantitative ratios shown in Table 4, and fibrous PTFE is added as component A and B as an anti-dropping agent. 0.5 parts by weight per 100 parts by weight of the total components were blended and 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 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 4 minutes (2 minutes for PBT alone) to obtain a molded product. Table 4 shows the physical properties of the obtained molded article.

Abbreviations in Table 4 are as follows.
C1 (inorganic filler): glass fiber (13 μm diameter, 5 mm chopped strand: manufactured by Nippon Electric Glass Co., Ltd.)
C2 (inorganic filler): calcium silicate (manufactured by Nacalai Tesque)
C3: Talc (Nihon Talc Co., Ltd. P-2)
D1 (flame retardant): manufactured by Teijin Chemicals Ltd., Fireguard 7500 degree of polymerization n = about 5
D2 (flame retardant): Dainippon Ink & Chemicals, Inc., EP100
E1 (antimony flame retardant aid): antimony trioxide (Nippon Seiko Co., Ltd .: PATOX-M)
E2 (antimony flame retardant aid): antimony pentoxide (NA1030 manufactured by Nissan Chemical Co., Ltd.)
F1 (light stabilizer): Triazole (Asahi Denka Co., Ltd.), LA-31
F2 (light stabilizer): benzoate (Sumitomo Chemical Co., Ltd.), Sumisorb 400
J1 (antistatic agent): Takemoto Yushi Co., Ltd., sodium dodecylbenzenesulfonate mixture, TPL456
J2 (antistatic agent): Takemoto Yushi Co., Ltd., tetrabutylphosphonium dodecylbenzenesulfonate / PEG mixture, TPL416
G1 (transesterification inhibitor): Tris (2,6-di-t-butylphenyl) phosphite G2 (transesterification inhibitor): tetraphenyl-4,4′-biphenylene phosphite H1 (antioxidant): n -Octadecyl 3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate H2 (antioxidant): tetrakis [methylene-3- (3', 5'-di-t-butyl) -4-hydroxyphenyl) propionate] methane

[Example 13]
Using the pellets obtained in Example 12, samples of fluorescent lamp caps (cross-section 30 mmφ, center circumference 48 mm) were molded with a hot runner injection molding machine at a cylinder temperature of 250 to 265 ° C., and fluorescent lamp cap characteristics were evaluated. did. The pin insertion hole is located at a position 16 mm away from the outer edge of the sample, and the screw hole is located at a position 21 mm away from the outer edge of the sample. As described above, the molded product of the present invention has good flame retardancy, light resistance, and melt stability. However, regarding the characteristics of the fluorescent lamp cap, the pinning strength is 77 kgf, and the tap strength and deformation resistance are both 50. It was a good level of / 50.

  Since the resin composition of the present invention is excellent in flame retardancy, light resistance and melt stability, it can be used for electronic parts, home appliances, lighting parts and the like.

Claims (9)

Aromatic polyester (component A) having a butylene terephthalate skeleton as the main structural unit, polylactic acid (component B) having a melting point of 190 ° C. or higher, inorganic filler (component C), brominated flame retardant (component D), antimony-based difficulty Contains a flame retardant (E component) and a light stabilizer (F component), and the content of the A component is 5 to 95 parts by weight and the content of the C component is 0 to 150 per 100 parts by weight of the total of the A component and the B component. A resin composition having a content of 5 parts by weight, a D component of 5 to 80 parts by weight, an E component of 0 to 30 parts by weight, and an F component of 0 to 5 parts by weight. The resin composition according to claim 1, wherein the pinning strength is 60 kgf or more.
(Here, the pinning strength is 1.9 mmΦ pin insertion hole of the fluorescent lamp base, 1.8 mmΦ 5 mm long guide part, and the following gradient (15.0-1.8) /40.0 taper part) This is the pinning strength when a jig made of is inserted at a speed of 300 mm / min.) The resin composition according to claim 1, wherein the brominated flame retardant (D component) is a compound represented by the following formula (i) or (ii).

(Wherein X represents a bromine element and / or a chlorine element, and n represents an integer of 5 or more and 20 or less)

(Wherein X represents a bromine element and / or chlorine element, and n represents an integer of 3 to 12) The resin composition of Claim 1 which contains 0.01-5 weight part of transesterification inhibitors (G component) per 100 weight part of total of A component and B component. The resin composition of Claim 1 which contains 0.01-5 weight part of antioxidant (H component) per 100 weight part of total of A component and B component. The resin composition of Claim 1 which contains 0.01-10 weight part of antistatic agents (J component) per 100 weight part of total of A component and B component. The resin composition according to claim 1, comprising 0.001 to 5 parts by weight of a carbodiimide compound (K component) per 100 parts by weight of polylactic acid (B component). The resin composition according to any one of claims 1 to 7, which is used for molding an electronic part, a part for home appliances, a lighting part or a fluorescent lamp cap. An electronic part, a part for household electrical appliance, a lighting part or a fluorescent lamp base made of the resin composition according to claim 8.