JP2009221438A - Polyphenylene ether resin composition and molded item - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyphenylene ether resin composition which excels in flowability and gives a molded item excellent in stiffness, impact resistance, and appearance. <P>SOLUTION: The polyphenylene ether resin composition comprises 10 to 45 parts by weight of a polyphenylene ether resin, 10 to 85 parts by weight of a styrene-based resin, and 5 to 45 parts by weight of a polylactic acid resin, wherein the sum total of them is 100 parts by weight. In addition, the polyphenylene ether resin composition-molded item made by molding the composition is disclosed. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a modified polyphenylene ether resin composition that gives a molded article having excellent fluidity and excellent rigidity, impact resistance, and appearance.

Polyphenylene ether resins are used in various members including electric / electronic devices and OA / information devices as resins having excellent rigidity, impact resistance, heat resistance, dimensional stability, electric characteristics and the like. However, polyphenylene ether resins are rarely used alone and are mainly used in alloys with other resins for the purpose of improving fluidity (molding processability). However, rigidity and impact resistance are improved by alloying. It is important to improve fluidity without loss.

As a method for improving the fluidity of a polyphenylene ether resin, it has long been known that the polyphenylene ether resin is a polymer alloy with polystyrene. Polyphenylene ether resin and polystyrene are compatible with each other at an arbitrary ratio, but the produced polymer alloy exhibits physical properties according to its composition. Therefore, in order to improve the fluidity of the polyphenylene ether resin while maintaining the excellent characteristics, there is a limit only by alloying with polystyrene.

Patent Document 1 describes a resin composition comprising a polyphenylene ether resin and a resin having an aliphatic polyester structure composed of 1,4-butanediol and succinic acid, and the resin having an aliphatic polyester structure is polyphenylene. It is described as being effective in improving the biodegradability and fluidity of ether resins. In the examples, the ratio of polyphenylene ether resin to the total of both is in the range of 50 to 90%. When the ratio of polyphenylene ether resin decreases, the melt flow rate (MFR) increases, but at the same time the biodegradability decreases. Has been shown to do.

Patent Document 2 discloses a composition in which a polybutylene terephthalate resin, an aliphatic polyester resin, a polyphenylene ether resin, and a resin composition in which a polystyrene resin is added to the resin composition, a compatibilizer, a phosphate ester, and the like are added. It is described that it retains biodegradability, is excellent in mechanical properties, molding processability (fluidity), and hydrolysis resistance, and has high flame retardancy.

However, in all the examples, the total of polybutylene terephthalate resin and aliphatic polyester resin is 80 parts by weight, whereas 20 parts by weight of polyphenylene ether resin or 16 parts by weight of polyphenylene ether resin and 4 parts by weight of polystyrene resin. Part. Therefore, in Patent Document 2, polyphenylene ether resin or polyphenylene ether resin and polystyrene resin, and a compatibilizing agent or phosphate ester are added to a polyester resin composition comprising a polybutylene terephthalate resin and an aliphatic polyester resin. Is an improvement.

JP 2005-60637 A JP 2007-169402 A

An object of the present invention is to provide a polyphenylene ether resin composition that provides a molded product having excellent fluidity and less appearance defects such as peeling during molding without impairing mechanical properties such as excellent rigidity and impact resistance of the polyphenylene ether resin. Is to provide.

The present inventors have found that when polylactic acid is blended with a composition comprising a polyphenylene ether resin and a styrene resin, the fluidity is surprisingly improved and the appearance of the molded product is improved. The present invention has been completed.

That is, the gist of the present invention is that the polyphenylene ether resin (component A) is 10 to 45 parts by weight, the styrene resin (component B) is 10 to 85 parts by weight, and the polylactic acid resin (component C) is 5 to 45 parts by weight (provided that A The total of the component C is 100 parts by weight) and the polyphenylene ether resin composition.

The polyphenylene ether resin composition of the present invention gives a molded article excellent in rigidity and impact resistance, excellent fluidity, and having a good appearance with extremely little occurrence of peeling, rough skin, and the like.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

The polyphenylene ether resin in the present invention is a polymer having an aromatic polyether structure, preferably the following formula (1)

（式中、Ｒ₁は置換されていても良い炭素数１〜３の低級アルキル基、Ｒ₂およびＲ_３はそれぞれ、水素原子または置換されていてもよい炭素数１〜３の低級アルキル基を示す。）
で表される構造単位を主鎖に持つ重合体であって、ホモポリマーであってもコポリマーであってもよい。Ｒ₁としては、メチル基、エチル基が好ましい。 Ｒ₂およびＲ₃が炭素数１〜３の低級アルキル基である場合、メチル基、エチル基が好ましい。

Wherein R ₁ is an optionally substituted lower alkyl group having 1 to 3 carbon atoms, R ₂ and R ₃ are each a hydrogen atom or an optionally substituted lower alkyl group having 1 to 3 carbon atoms. Show.)
A polymer having a structural unit represented by the following formula in its main chain, which may be a homopolymer or a copolymer. R ₁ is preferably a methyl group or an ethyl group. When R ₂ and R ₃ are lower alkyl groups having 1 to ₃ carbon atoms, a methyl group and an ethyl group are preferable.

Examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1, Homopolymers such as 4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, Mention may be made of copolymers derived from dialkylphenols and 2,3,6-trialkylphenols. Among them, preferred are poly (2,6-dimethyl-1,4-phenylene) ether derived from 2,6-dimethylphenol and 2,6-dimethylphenol and 2,3,6-trimethylphenol. Copolymer.

Polyphenylene ether resins include polyphenylene ether resins and unsaturated carboxylic acids or derivatives thereof (for example, maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, etc., and acid anhydrides, esters, amides, imides thereof). Etc., and acrylic acid, methacrylic acid, etc. Maleic acid is preferred among them), styrene or a derivative thereof in the presence or absence of a radical generator, in a molten state, a solution state or a slurry. In the state, a known modified polyphenylene ether resin obtained by reacting at a temperature of 80 to 350 ° C. can also be used. Furthermore, a mixture of the above-described polyphenylene ether resin and any ratio of these modified polyphenylene ether resins can be used.

The polyphenylene ether resin used in the present invention has an intrinsic viscosity at 30 ° C. measured in chloroform of 0.2 to 0.8 dl / g. If the intrinsic viscosity is less than 0.2 dl / g, the mechanical strength of the resin composition tends to be reduced. Conversely, if the intrinsic viscosity exceeds 0.8 dl / g, the fluidity of the resin composition is lowered and the molding process is difficult. Tend to be. The preferred intrinsic viscosity of the polyphenylene ether resin is 0.3 to 0.6 dl / g, particularly 0.3 to 0.5 dl / g.

Examples of the styrene resin used in the present invention include a styrene monomer polymer, a copolymer of a styrene monomer and another copolymerizable monomer, and a styrene graft copolymer. Is mentioned.

Examples of the styrene monomer include styrene, α-methyl styrene, p-methyl styrene, and preferably styrene. Examples of the monomer copolymerizable with the styrenic monomer include vinyl cyanide such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, and ethyl methacrylate. (Meth) acrylic acid alkyl ester, maleimide, N-phenylmaleimide and the like can be mentioned, preferably vinyl cyanide and (meth) acrylic acid alkyl ester.

As a copolymer of a styrene monomer and another copolymerizable monomer, a styrene / acrylonitrile resin (AS resin) is preferable. Examples of styrene-based graft copolymers include impact-resistant polystyrene (HI-PS resin), acrylonitrile / butadiene / styrene resin (ABS resin), AES resin in which butadiene of ABS resin is replaced with ethylene-propyne rubber, acrylonitrile / Examples include acrylate / styrene resin (AAS resin). Examples of the method for producing the styrene-based copolymer include known methods such as an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, and a bulk polymerization method.

As the styrene-based resin, polystyrene (GP-PS) and impact-resistant polystyrene (HI-PS) are preferable from the viewpoint of compatibility with polyphenylene ether. In particular, when a resin composition excellent in impact resistance is required, it is preferable to use impact resistant polystyrene. As these styrene resins, commercially available ones may be used.

The polylactic acid used in the present invention may be, for example, either a lactic acid homopolymer composed only of D-lactic acid or L-lactic acid, or a lactic acid copolymer composed of D-lactic acid and L-lactic acid. In the case of a copolymer, the melting point changes depending on the ratio between the two. Therefore, when a polymer having a high melting point is desired, the ratio of D- or L-lactic acid is 75 mol% or more, particularly 90 mol% or more. Is preferred. The copolymer may be a block copolymer or a random copolymer, and by using these, the heat resistance may be improved by making a stereocomplex. It is also possible to use a mixture of poly D-lactic acid and poly L-lactic acid.

The weight average molecular weight (Mw) of polylactic acid is a polystyrene conversion value by gel permeation chromatographic analysis, and is usually 50,000 to 500,000, preferably 100,000 to 250,000. If the weight average molecular weight is less than 50,000, it is difficult to obtain practically required physical properties. On the other hand, if the weight average molecular weight exceeds 500,000, the moldability tends to deteriorate.

As polylactic acid, a lactic acid monomer or lactide, and a copolymer with other components copolymerizable therewith can also be used. The proportion of lactic acid units in the copolymer is preferably 50% by weight or more. Examples of the copolymer component include dicarboxylic acid having two or more ester bond-forming functional groups, polyhydric alcohol, hydroxycarboxylic acid, lactone, and the like, and various polyesters, polyethers, polycarbonates, and the like having these as constituent components. It is done.

Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid.

Polyhydric alcohols include aromatic polyhydric alcohols such as those obtained by addition reaction of ethylene oxide with bisphenol, ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, glycerin, sorbitan, trimethylolpropane, neopentyl glycol And aliphatic glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol.

Examples of the hydroxycarboxylic acid include glycolic acid, hydroxybutylcarboxylic acid, and hydroxycarboxylic acid described in JP-A-6-184417.

Examples of the lactone include glycolide, ε-caprolactone, ε-propiolactone, δ-butyrolactone, β-butyrolactone, γ-butyrolactone, pivalolactone, δ-valerolactone, and the like.

The polylactic acid used in the present invention can be synthesized by a conventionally known method. For example, JP-A-7-33861, JP-A-59-96123, Polymer Proceedings Proceedings Vol. 44, 3198. It can be synthesized by direct dehydration condensation from a lactic acid monomer described in page 3199 or the like, or by ring-opening polymerization of a lactic acid cyclic dimer lactide.

When direct dehydration condensation is performed, any lactic acid of L-lactic acid, D-lactic acid, DL-lactic acid, and a mixture thereof may be used. When ring-opening polymerization is performed, any one of L-lactide, D-lactide, DL-lactide, meso-lactide, and a mixture thereof may be used.

Synthesis, purification and polymerization operations of lactide used in ring-opening polymerization are described in, for example, US Pat. No. 4,057,537, European Patent Application No. 261572, Polymer Bulletin, 14, 491-495 (1985), and Macromol. Chem. 187, 1611-1628 (1986).

The catalyst used in the polymerization reaction for obtaining the polylactic acid is not particularly limited, but a known catalyst for lactic acid polymerization can be used. Examples of the catalyst include tin lactate, tin tartrate, dicaprylate, dilaurate, dipalmitate, distearate, dioleate, alpha-naphthoate, beta-naphthoate, and octylate. Tin compounds such as powder tin, tin oxide, zinc dust, zinc halide, zinc oxide, organic zinc compounds, titanium compounds such as tetrapropyl titanate, zirconium compounds such as zirconium isopropoxide, antimony trioxide, etc. Examples thereof include antimony compounds, bismuth compounds such as bismuth (III) oxide, and aluminum compounds such as aluminum oxide and aluminum isopropoxide.

Among these, a catalyst made of tin or a tin compound is particularly preferable from the viewpoint of activity. The amount of the catalyst used is, for example, about 0.001 to 5% by weight with respect to lactide when ring-opening polymerization is performed.

The polymerization reaction can be usually performed at 100 to 220 ° C. in the presence of the catalyst, although it varies depending on the type of the catalyst. It is also preferable to carry out the two-stage polymerization described in, for example, JP-A-7-247345.

The polyphenylene ether resin composition of the present invention is characterized by containing three components of polyphenylene ether resin (component A), styrene resin (component B), and polylactic acid resin (component C) as essential components, and component A. When the total of the B component and the C component is 100 parts by weight, the proportion of the A component is 10 to 45 parts by weight, the proportion of the B component is 10 to 85 parts by weight, and the proportion of the C component is 5 to 45 parts by weight. It is characterized by that.

Conventionally used modified polyphenylene ether resins composed of a polyphenylene ether resin and a styrenic resin are not yet satisfactory in terms of fluidity. Even if the polyphenylene ether resin is modified with polylactic acid, the effect of improving the fluidity is small, peeling is observed in the molded product, and the surface smoothness is also poor. This is considered due to the extremely low compatibility between the polyphenylene ether resin and polylactic acid.

On the other hand, a resin composition containing a polyphenylene ether resin, a styrene resin and polylactic acid in the above ratio gives a molded article having good fluidity and good appearance. This is probably because the styrene resin improves the compatibility between the polyphenylene ether resin and polylactic acid.

A preferred ratio of the components A to C constituting the resin composition is 15 to 45 parts by weight of polyphenylene ether resin, particularly 20 to 45 parts by weight, 15 to 75 parts by weight of styrenic resin, particularly 25 to 25 parts by weight, with the total being 100 parts by weight. 70 parts by weight, 10 to 40 parts by weight of polylactic acid, especially 15 to 35 parts by weight, whereby a resin composition having both excellent properties and good fluidity of the polyphenylene ether resin is obtained.

In addition, since polylactic acid imparts biodegradability to the resin composition, it is preferable that the ratio of polylactic acid is 25% by weight or more when a product having high biodegradability is desired. Moreover, it is preferable that a styrene resin is the same amount or more as a polyphenylene ether resin from a viewpoint of ensuring the uniformity of a resin composition.

In order to improve impact strength, the polyphenylene ether resin composition of the present invention may further contain a styrene elastomer. The styrenic elastomer preferably blended in the present invention is a block copolymer in which the hard segment is composed of a styrene polymer and the soft segment is composed of polybutadiene, polyisoprene and hydrogenated products thereof, specifically, SBS. (Styrene / butadiene / styrene block copolymer), SIS (styrene / isoprene / styrene block copolymer), SEBS (styrene / ethylene / butylene / styrene block copolymer: hydrogenated product of SBS), SEPS (styrene / ethylene / propylene / styrene block copolymer) Copolymer: a hydrogenated product of SIS), preferably SEBS.

The composition ratio of the hard segment and the soft segment of the styrenic elastomer can be appropriately selected within the range of 10:90 to 90:10 (molar ratio), preferably 10:90 to 50:50. The combination form of the soft segment blocks may be a diblock type or a triblock type.

The number average molecular weight of the styrenic elastomer is preferably 20000 to 18000, more preferably 30000 to 160000, and still more preferably 35000 to 140000. By setting the number average molecular weight to 20000 or more, the impact resistance and dimensional stability of the finally obtained resin composition are excellent, and further, the appearance of a molded product obtained from the resin composition can be improved. . Moreover, it is preferable to set the number average molecular weight to 180,000 or less because the fluidity of the finally obtained resin composition is improved and the molding process becomes easy.

The blending amount of the styrene-based elastomer is usually 1 to 25 parts by weight with respect to 100 parts by weight of the polyphenylene ether resin composition composed of components A to C, but 3 to 20 parts by weight, particularly 5 to 15 parts by weight. When the blending amount of the styrene elastomer is less than 1 part by weight, the effect of improving the impact strength is small, and when the blending amount of the styrene elastomer exceeds 25 parts by weight, the rigidity and load deflection temperature of the resin composition are lowered.

Furthermore, the polyphenylene ether resin composition of the present invention may contain other resin components without departing from the spirit of the present invention. The blending amount in this case is usually 50% by weight or less of the polyphenylene ether resin composition composed of components A to C.

In addition to the above components, the polyphenylene-ether resin composition of the present invention, if necessary, a colorant such as a pigment or a dye, a release agent, a stabilizer, a phosphate ester, a flame retardant such as a condensed phosphate ester, Hindered amine, benzotriazole, benzophenone, epoxy and other UV absorbers, antioxidants, lubricants, plasticizers, antistatic agents, slidability improvers, additives such as compatibilizers, difluoroethylene polymers, Tetrafluoroethylene polymer, tetrafluoroethylene-hexafluoropropylene copolymer, copolymer of tetrafluoroethylene and an ethylene monomer that does not contain fluorine, etc., and fluorine resin, glass fiber that has a drip-preventing action during resin combustion Reinforcing fillers such as glass flakes, carbon fibers, metal fibers other than stainless microfibers, or titanium Potassium, aluminum borate, whiskers and calcium silicate can be blended mica, talc, an inorganic filler clay. The blending method of these additives can be appropriately carried out by a conventionally known method that makes use of these characteristics.

Examples of the colorant include dyes, inorganic pigments, and organic pigments generally used for thermoplastic resins. Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, indigo dyes, diphenylmethane dyes, acridine dyes, cyanine dyes, nitro dyes, and nigrosine. Inorganic pigments include oxide pigments such as titanium oxide, red pepper and cobalt blue, hydroxide pigments such as alumina white, sulfide pigments such as zinc sulfide and cadmium yellow, silicate pigments such as white carbon and talc, and carbon black. Etc.

Examples of organic pigments include nitro pigments, azo pigments, phthalocyanine pigments, and condensed polycyclic pigments. Among these, an inorganic pigment is preferable because it is difficult to bleed out to the surface of the molded product. The colorant may also be used as a masterbatch with a thermoplastic resin such as polyphenylene ether resin, polystyrene resin, polycarbonate resin, or acrylic resin for the purpose of improving handling at the time of extrusion.

The blending amount of the colorant is preferably 0.01 to 20 parts by weight and more preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the polyphenylene ether resin composition composed of components A to C. In addition, inorganic pigments such as titanium oxide may be used for purposes other than coloring (for example, imparting light-shielding properties), and the blending amount in that case is usually 5 to 20 wt. Parts, preferably 5 to 15 parts by weight. Two or more of these colorants may be used in combination.

Examples of the stabilizer include hindered phenol compounds, phosphorus compounds, and zinc oxide. Specific examples of the hindered phenol compound include n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl- 4-methylphenol, 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8, 10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-tert-butyl-5-methyl) 4-hydroxyphenyl) propionate], 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-) -Tert-butyl-4-hydroxybenzyl) benzene, 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris- (3,5-di -Tert-butyl-4-hydroxybenzyl) -isocyanurate, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) and the like. Among these, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-tert-butyl-4 -Hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol, 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-) 5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane is preferred.

As the phosphorus compound, for example, a phosphonite compound or a phosphite compound is preferably used. Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,5-di-tert-butylphenyl) -4,4′-. Biphenylene diphosphonite, tetrakis (2,3,4-trimethylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,3-dimethyl-5-ethylphenyl) -4,4'-biphenylene diphosphonite Tetrakis (2,6-di-tert-butyl-5-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,3,4-tributylphenyl) -4,4'-biphenylenediphosphonite Tetrakis (2,4,6-tri-tert-butylphenyl) -4,4′-biphenylenediphosphonite and the like. I can get lost.

Among these, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene diphosphonite is preferable. Examples of the phosphite compound include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6-diphenyl). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, 4,4'-butylidenebis (3-methyl-6- tert-butylphenylditridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-tert-butyl-phenyl) butane, tris (nonylphenyl) phosphite, 4,4 '-Isopropylidenebis (phenyldialkylphosphite) and the like 2,4-di-tert-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,6-di-tert-butyl-4-methyl) Phenyl) pentaerythritol diphosphite is preferred.

As zinc oxide, for example, those having an average particle diameter of 0.02 to 1 μm are preferable, and those having an average particle diameter of 0.08 to 0.8 μm are more preferable. Among these stabilizers, zinc oxide is preferable because it does not easily generate mold deposits and hardly changes color.

The blending amount of the stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the polyphenylene ether resin composition composed of components A to C. If the blending amount is less than 0.01 parts by weight, the effect as a stabilizer cannot be sufficiently exhibited. On the other hand, when the amount exceeds 5 parts by weight, the mechanical strength is reduced and mold deposits are generated during molding. Two or more of these stabilizers may be used in combination.

Examples of the mold release agent include aliphatic carboxylic acid, aliphatic carboxylic acid ester, polyolefin wax, silicone oil and the like. Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid.

Of these, preferred aliphatic carboxylic acids are mono- or dicarboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferred. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melicic acid, tetratriacontanoic acid. , Montanic acid, glutaric acid, adipic acid, azelaic acid and the like.

As the aliphatic carboxylic acid component constituting the aliphatic carboxylic acid ester, the same aliphatic carboxylic acid as that described above can be used. On the other hand, examples of the alcohol component constituting the aliphatic carboxylic acid ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols.

These alcohols may have a substituent such as a fluorine atom or an aryl group. Of these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the aliphatic alcohol also includes an alicyclic alcohol.

Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. Is mentioned. These aliphatic carboxylic acid esters may contain an aliphatic carboxylic acid and / or alcohol as impurities, and may be a mixture of a plurality of compounds.

Specific examples of the aliphatic carboxylic acid ester include beeswax (mixture based on myristyl palmitate), stearyl stearate, behenyl behenate, octyldodecyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin diester Examples thereof include stearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monosterate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

Examples of polyolefin waxes include olefin homopolymers and copolymers. Examples of the olefin homopolymer include polyethylene wax, polypropylene wax and the like, partial oxides thereof, and mixtures thereof. Examples of the olefin copolymer include ethylene, propylene, 1-butene, 1-hexene, 1-decene, 2-methylbutene-1, 3-methylbutene-1,3-methylpentene-1, 4-methylpentene-1, and the like. Copolymers such as α-olefins, monomers copolymerizable with these olefins, for example, unsaturated carboxylic acids or their anhydrides [maleic anhydride, (meth) acrylic acid, etc.], (meth) acrylic acid esters And a copolymer with a polymerizable monomer such as [methyl (meth) acrylate, alkyl ester having 1 to 6 carbon atoms of (meth) acrylic acid such as ethyl (meth) acrylate], and the like. In addition, these copolymers include random copolymers, block copolymers, or graft copolymers. The olefin copolymer is usually a copolymer of ethylene and at least one monomer selected from other olefins and polymerizable monomers. Of these polyolefin waxes, polyethylene wax is most preferred. The polyolefin wax may have a linear or branched structure.

Examples of silicone oils include those composed of polydimethylsiloxane, and some or all of the methyl groups of polydimethylsiloxane are substituted with phenyl groups, hydrogen atoms, alkyl groups having 2 or more carbon atoms, halogenated phenyl groups, and fluoroester groups. Silicone oil, epoxy-modified silicone oil having an epoxy group, amino-modified silicone oil having an amino group, alcohol-modified silicone oil having an alcoholic hydroxyl group, polyether-modified silicone oil having a polyether structure, and the like. May be used in combination.

The compounding amount of the release agent is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 6 parts by weight, with respect to 100 parts by weight of the polyphenylene ether resin composition composed of components A to C. More preferably, 3 parts by weight. If the blending amount is less than 0.01 parts by weight, the release effect is hardly exhibited. On the other hand, when the amount exceeds 10 parts by weight, problems such as a decrease in heat resistance, mold contamination, and poor plasticization occur.

To prepare the polyphenylene ether resin composition of the present invention, for example, using the kneaders such as uniaxial and multiaxial kneaders, Banbury mixer, roll, Brabender plastogram, kneader, etc. (2) A method in which the above components and a part of the additive added as necessary are kneaded in advance and further kneaded together with other components (master batch (3) The additive added as necessary is dissolved in a suitable solvent, for example, hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and derivatives thereof, or suspended. And a solution mixing method of mixing with a resin component. From the viewpoint of cost, a method using a single or twin screw extruder is particularly preferable.

In order to produce a resin molding from the polyphenylene ether resin composition of the present invention, a method generally employed for thermoplastic resins can be used, but an injection molding method is often used because of good productivity. . In addition to general injection molding methods, injection molding methods include ultra-high-speed injection molding methods, injection compression molding methods, two-color molding methods, hollow molding methods such as gas assist, molding methods using heat insulating molds, and rapid heating. Any method such as a molding method using a mold, foam molding (including a supercritical fluid), insert molding, or IMC (in-mold coating molding) molding method can be used. Furthermore, an extrusion molding method, a sheet molding method, a thermoforming method, a rotational molding method, a lamination molding method, a press molding method, and the like can be employed. A molding method using a hot runner method can also be adopted.

In addition, in the present invention, from the viewpoint of reducing environmental burden such as waste reduction and cost reduction, when manufacturing a resin molded body from a resin composition, such as non-conforming product, sprue, runner, used product, etc. Recycled raw materials can be used by mixing with virgin materials (so-called material recycling). At this time, it is preferable to use the recycled raw material because it can be used after being pulverized, since it is possible to reduce inconvenience when the molded product is manufactured. The content ratio of the recycled material is usually 70% by weight or less, preferably 50% by weight or less, and more preferably 30% by weight or less with respect to the total amount of the recycled material and the virgin material.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples, unless the summary is exceeded. “Part” means “part by weight”. The raw materials used are shown in Table 1.

Table 1

<Manufacture of resin composition pellets>
Each component described in Table 1 was blended in the ratio (weight ratio) described in Table 2, mixed for 20 minutes with a tumbler, and then an extruder manufactured by Ikekai Co., Ltd. (PCM30, screw diameter 30 mm, L / L). D = 42), the mixture was kneaded under the conditions of a screw rotation speed of 200 rpm and a cylinder temperature of 270 ° C., and the molten resin extruded into a strand was rapidly cooled in a water tank and pelletized using a pelletizer.

<Physical property evaluation>
Using a Capillograph 1-C (nozzle: 1 mmφ × 30 mmL) manufactured by Fluid Toyo Seiki Co., Ltd., the melt viscosity of the resin composition pellets at 250 ° C., γ = 91.2 sec ¹ and γ = 6080 sec ¹ was measured. The melt viscosity is indicated by Pa · s, and this value indicates that the lower the value, the better the fluidity.

Flexural modulus and Charpy impact strength After drying the resin composition pellets at 80 ° C for 5 hours, using a SG125 type injection molding machine manufactured by Sumitomo Heavy Industries, at a mold temperature of 80 ° C and a cylinder set temperature of 250 ° C, the flexural modulus and notch A Charpy impact strength test piece was molded and each test was performed. The flexural modulus test was conducted according to ISO178, and the Charpy impact strength test was conducted according to ISO179.

<Appearance>
After drying the resin composition pellets at 80 ° C. for 5 hours, 10 molded ISO dumbbell pieces were visually evaluated with an SG125 type injection molding machine manufactured by Sumitomo Heavy Industries at a mold temperature of 80 ° C. and a cylinder set temperature of 250 ° C.
Peeling is hardly recognized: ○
Peeling is observed: ×
Peeling was observed and the surface smoothness was poor: XX
The evaluation results are shown in Table 3.

Table 2

表中、「−」は未測定を示す。 Table 3

In the table, “-” indicates unmeasured.

Claims (5)

  10 to 45 parts by weight of polyphenylene ether resin (component A), 10 to 85 parts by weight of styrene resin (component B), 5 to 45 parts by weight of polylactic acid resin (component C) (the total of components A to C is 100 parts by weight) A polyphenylene ether resin composition characterized by comprising:   15 to 45 parts by weight of polyphenylene ether resin (component A), 15 to 75 parts by weight of styrene resin (component B), 10 to 40 parts by weight of polylactic acid resin (component C) (the total of the components A to C is 100 parts by weight) A polyphenylene ether resin composition characterized by comprising: The polyphenylene ether resin composition according to claim 1 or 2, wherein the polyphenylene ether resin is a polymer having a structural unit represented by the following formula (1) in the main chain.

(In the formula, R ₁ represents a lower alkyl group having 1 to 3 carbon atoms, and R ₂ and R ₃ each represents a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms.)   The polyphenylene ether resin composition according to any one of claims 1 to 3, wherein the styrene resin is a polystyrene resin (GP-PS) or an impact-resistant polystyrene resin (HI-PS).   A polyphenylene ether resin composition molded article obtained by melt-molding the polyphenylene ether resin composition according to any one of claims 1 to 4.