JP2010195914A - Glass-based inorganic filler-reinforced polyester resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve the mechanical strength of a glass-based inorganic filler-reinforced polyester resin composition containing a polybutylene terephthalate resin and a polylactic acid-based resin. <P>SOLUTION: In the glass-based inorganic filler-reinforced polyester resin composition, (B) 5-100 pts.wt. polylactic acid resin, (C) 1-20 pts.wt. mechanical strength improving agent and (D) 3-200 pts.wt. glass-based inorganic filler treated with at least one of a surface treating agent selected from a silane-based or titanate-based coupling agent are blended in (A) 100 pts.wt. polybutylene terephthalate resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a glass-based inorganic filler-reinforced polyester resin composition having excellent mechanical strength.

  Polybutylene terephthalate resin has excellent mechanical properties, electrical properties, heat resistance, weather resistance, water resistance, chemical resistance, and solvent resistance, so it can be used as an engineering plastic for automotive parts, electrical / electronic parts, etc. It is widely used for applications.

  On the other hand, in recent years, as environmental and resource issues, socially demanded countermeasures to increase greenhouse gases such as carbon dioxide and the depletion of fossil resources in the future, biobased plastics such as polylactic acid resin have been studied. It is becoming active. In addition, for plastics based on fossil raw materials, studies on blending bio-based plastics are widely conducted.

  With respect to polybutylene terephthalate resin, studies on blending bio-based plastics from the same point of view are being conducted. For example, Patent Document 1 proposes a polybutylene terephthalate resin composition containing a polybutylene terephthalate resin and a polylactic acid resin, and the content of the polylactic acid resin is 5 to 50% by mass with respect to the total composition. ing. Patent Document 2 proposes a polybutylene terephthalate resin composition containing 100 parts by weight of a polybutylene terephthalate resin having a predetermined terminal carboxyl group concentration and 1 to 99 parts by weight of a polylactic acid-based resin. However, these prior examples have been insufficiently examined for improving the mechanical strength of glass-based inorganic filler-reinforced polyester containing a polybutylene terephthalate resin and a polylactic acid-based resin.

  Patent Document 3 proposes a resin composition containing an aromatic polyester having a butylene terephthalate skeleton as a main structural unit, polylactic acid having a melting point of 190 ° C. or more, and an inorganic filler. A carbodiimide compound is once mixed with lactic acid. However, in this preceding example, a carbodiimide compound is used as a block forming agent for polylactic acid, which improves the mechanical strength of a glass-based inorganic filler-reinforced polyester containing a polybutylene terephthalate resin and a polylactic acid-based resin. It is not explicitly stated that it is valid.

JP 2006-008868 A JP 2006-063199 A JP 2008-050582 A

  An object of the present invention is to improve the mechanical strength of a glass-based inorganic filler-reinforced polyester resin composition containing a polybutylene terephthalate resin and a polylactic acid-based resin.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have achieved the above objects by combining polybutylene terephthalate resin, polylactic acid resin, and specific additives and fillers. The inventors have found that a filler-reinforced polyester resin composition can be obtained, and have completed the present invention.

  That is, the present invention relates to (A) 100 parts by weight of polybutylene terephthalate resin, (B) 5 to 100 parts by weight of polylactic acid resin, (C) 1 to 20 parts by weight of mechanical strength improver, (D) silane-based Or it is a glass system inorganic filler reinforcement | strengthening polyester resin composition which mix | blends 3 to 200 weight part of glass system inorganic fillers processed with the at least 1 sort (s) of surface treatment agent chosen from the titanate coupling agent.

  The glass-based inorganic filler-reinforced polyester resin composition of the present invention is excellent in mechanical strength and toughness. The polyester resin composition of the present invention is suitable for injection molded articles related to automobile parts, electrical / electronic parts, sundries, stationery and the like.

(A) Polybutylene terephthalate resin Polybutylene terephthalate resin (PBT resin) is terephthalic acid (terephthalic acid or its ester-forming derivative), C4 alkylene glycol (1,4-butanediol) and / or its ester. It is a thermoplastic resin having a forming derivative as at least a polymerization component.

  Examples of the polybutylene terephthalate resin include a homopolyester (polybutylene terephthalate) and / or a copolyester (a butylene terephthalate copolymer, a polybutylene terephthalate copolyester, or a modified PBT resin) containing butylene terephthalate as a main component. .

  Examples of the copolymerizable monomer in the copolyester (hereinafter sometimes simply referred to as a copolymerizable monomer) include dicarboxylic acid components excluding terephthalic acid, diols excluding 1,4-butanediol, oxycarboxylic acid components, and lactones. Ingredients and the like. The copolymerizable monomers can be used alone or in combination of two or more.

  Dicarboxylic acids (or dicarboxylic acid components or dicarboxylic acids) include aliphatic dicarboxylic acids (eg, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, C4-40 dicarboxylic acid such as hexadecane dicarboxylic acid and dimer acid, preferably C4-14 dicarboxylic acid), alicyclic dicarboxylic acid component (for example, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, highmic acid, etc.) C8-12 dicarboxylic acid), aromatic dicarboxylic acid components excluding terephthalic acid (for example, naphthalenedicarboxylic acid such as phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4, 4'-Diphenoki Ether dicarboxylic acids, 4,4′-diphenyl ether dicarboxylic acids, 4,8′-diphenylmethane dicarboxylic acids, C8-16 dicarboxylic acids such as 4,4′-diphenyl ketone dicarboxylic acids), or reactive derivatives thereof (for example, lower Alkyl esters (phthalic acids such as dimethylphthalic acid and dimethylisophthalic acid or C1-4 alkyl esters of isophthalic acid), derivatives such as acid chlorides and acid anhydrides that can form esters), and the like. Furthermore, if necessary, a polyvalent carboxylic acid such as trimellitic acid or pyromellitic acid or an ester-forming derivative thereof (such as an alcohol ester) may be used in combination. When such a polyfunctional compound is used in combination, a branched polybutylene terephthalate resin can also be obtained.

  Diols (or diol components or diols) include, for example, aliphatic alkanediols other than 1,4-butanediol [for example, alkanediols (for example, ethylene glycol, trimethylene glycol, propylene glycol, neopentyl glycol, hexanediol ( 1,6-hexanediol, etc.), octanediol (1,3-octanediol, 1,8-octanediol, etc.), lower alkanediols such as decanediol, preferably linear or branched C2-12 alkanediols More preferably linear or branched C2-10 alkanediols, etc.); (poly) oxyalkylene glycols (e.g. glycols having a plurality of oxy C2-4 alkylene units, e.g. diethylene glycol, dipropylene Glycol, ditetramethylene glycol, triethylene glycol, tripropylene glycol, polytetramethylene glycol, etc.)], alicyclic diols (eg 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol) A), aromatic diols [for example, dihydroxy C6-14 arenes such as hydroquinone, resorcinol, naphthalenediol; biphenols (such as 4,4′-dihydroxybiphenyl); bisphenols; xylylene glycol, etc.], and these And reactive derivatives (for example, ester-forming derivatives such as alkyl, alkoxy or halogen-substituted products). Furthermore, if necessary, a polyol such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, or an ester-forming derivative thereof may be used in combination. When such a polyfunctional compound is used in combination, a branched polybutylene terephthalate resin can also be obtained.

  Examples of the bisphenols include bis (4-hydroxyphenyl) methane (bisphenol F), 1,1-bis (4-hydroxyphenyl) ethane (bisphenol AD), 1,1-bis (4-hydroxyphenyl) propane, , 2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2- Bis (hydroxyaryl) C1 such as bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane 6 alkanes, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-H Bis (hydroxyaryl) C4-10cycloalkane such as loxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl Examples thereof include ketones and alkylene oxide adducts thereof. Examples of the alkylene oxide adduct include C2-3 alkylene oxide adducts of bisphenols (eg, bisphenol A, bisphenol AD, bisphenol F), such as 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, Examples include diethoxylated bisphenol A, 2,2-bis [4- (2-hydroxypropoxy) phenyl] propane, and dipropoxylated bisphenol A. The added mole number of alkylene oxide (C2-3 alkylene oxide such as ethylene oxide and propylene oxide) is about 1 to 10 moles, preferably about 1 to 5 moles with respect to each hydroxy group.

  Examples of oxycarboxylic acids (or oxycarboxylic acid components or oxycarboxylic acids) include oxycarboxylic acids such as oxybenzoic acid, oxynaphthoic acid, hydroxyphenylacetic acid, glycolic acid, and oxycaproic acid, or derivatives thereof. . Lactones include C3-12 lactones such as propiolactone, butyrolactone, valerolactone, caprolactone (eg, ε-caprolactone, etc.), and the like.

  Of these copolymerizable monomers, diols [C2-6 alkylene glycol (such as linear or branched alkylene glycol such as ethylene glycol, trimethylene glycol, propylene glycol, hexanediol), preferably 2 are preferable. Polyoxy C2-4 alkylene glycol having about -4 oxyalkylene units (such as diethylene glycol), bisphenols (such as bisphenols or alkylene oxide adducts thereof)], dicarboxylic acids [C6-12 aliphatic dicarboxylic acids (adipic acid, pimelin) Acid, suberic acid, azelaic acid, sebacic acid, etc.), asymmetric aromatic dicarboxylic acids in which the carboxyl group is substituted at the asymmetric position of the arene ring, 1,4-cyclohexanedimethanol, etc.].

  Among these compounds, aromatic compounds such as alkylene oxide adducts of bisphenols (particularly bisphenol A), and asymmetric aromatic dicarboxylic acids [phthalic acid, isophthalic acid and reactive derivatives thereof (lower alkyl such as dimethylisophthalic acid) Ester) and the like.

  The polybutylene terephthalate resin is preferably a homopolyester (polybutylene terephthalate) and / or a copolymer (polybutylene terephthalate copolyester). The polybutylene terephthalate resin usually has a proportion (modification amount) of a copolymerizable monomer. It may be 0-30 mol%, preferably 0-25 mol% of a homo or copolyester (particularly a homopolyester).

  In addition, when a homopolyester (polybutylene terephthalate) and a copolymer (copolyester) are used in combination, the proportion of the homopolyester and the copolyester is such that the proportion of the copolymerizable monomer is relative to the total monomers. The range is about 0.1 to 30 mol% (preferably 1 to 25 mol%, more preferably 5 to 25 mol%). Usually, the former / the latter = 99/1 to 1/99 (weight ratio), Preferably, it can be selected from a range of about 95/5 to 5/95 (weight ratio), more preferably about 90/10 to 10/90 (weight ratio).

  The intrinsic viscosity (IV) of the polybutylene terephthalate resin is preferably 1.4 dL / g or less, and more preferably 1.2 dL / g or less. Further, polybutylene terephthalate resins having different intrinsic viscosities may be blended. The intrinsic viscosity (IV) can be measured, for example, in o-chlorophenol at a temperature of 35 ° C. When a polybutylene terephthalate resin having an intrinsic viscosity in such a range is used, it is easy to efficiently achieve sufficient toughness and a reduced melt viscosity. If the intrinsic viscosity is too large, the melt viscosity at the time of molding becomes high, and in some cases, there is a possibility of causing poor resin flow and poor filling in the molding die.

As the polybutylene terephthalate resin, a commercially available product may be used, and terephthalic acid or a reactive derivative thereof and 1,4-butanediol and a monomer that can be copolymerized if necessary are used in a conventional manner, for example, transesterification, You may use what was manufactured by copolymerization (polycondensation) by the direct esterification method etc. Further, the production may be performed in any state of a molten state, a solid phase state, and a solution state.
(B) Polylactic acid resin The polylactic acid resin used in the present invention is a polymer mainly composed of L-lactic acid and / or D-lactic acid, and a conventionally known polymerization method can be used as a production method. Examples thereof include a direct polymerization method from lactic acid and a ring-opening polymerization method via lactide.

  The polylactic acid resin used in the present invention may contain a copolymerization component other than lactic acid. Other monomer units include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentane. Glycol compounds such as erythritol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalate Acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, 4,4'-diphenyl ether dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5- Dicarboxylic acids such as trabutylphosphonium isophthalic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid and other hydroxycarboxylic acids, and caprolactone, valerolactone, propiolactone, undecalactone And lactones such as 1,5-oxepan-2-one. These copolymer components are preferably 0 to 30 mol%, particularly preferably 0 to 10 mol%, based on all monomers of the polylactic acid resin.

  The polylactic acid resin used in the present invention is a kind selected from polyglycolic acid, polycaprolactone, polybutylene succinate, polyethylene succinate, polybutylene adipate terephthalate, polybutylene succinate terephthalate and the like as a part of its components. Alternatively, a mixture of two or more resins with polylactic acid may be used.

  In addition, the intrinsic viscosity (IV) of the polylactic acid resin used for this invention is not specifically limited, It can use in a conventionally well-known range.

  As the polylactic acid resin used in the present invention, it is preferable to use a polylactic acid resin having a thermal characteristic of a differential scanning calorimetry (DSC measurement) melting point (peak temperature) of 130 to 150 ° C. and a crystal melting heat of 0 to 10 J / g. Here, the melting point and the heat of crystal fusion were measured by sealing a sample cut out from the polylactic acid resin in an aluminum pan, holding at 200 ° C. for 1 minute, cooling to −10 ° C./min to room temperature, and subsequently 10 ° C. It is a value calculated from the crystal melting peak detected when the temperature is raised at / min. Use of a polylactic acid resin in this range is preferable in that strength and toughness can be secured.

In the present invention, the proportion of (B) polylactic acid resin is 5 to 100 parts by weight, preferably 10 to 80 parts by weight, particularly preferably 20 to 70 parts by weight, based on 100 parts by weight of (A) polybutylene terephthalate resin. is there. If the amount is less than 5 parts by weight, sufficient mechanical strength may not be improved. If the amount exceeds 100 parts by weight, the properties of the polybutylene terephthalate resin may be impaired.
(C) Mechanical strength improver The mechanical strength improver of component (C) used in the present invention is a glass comprising (A) a polybutylene terephthalate resin, (B) a polylactic acid resin, and (D) a glass-based inorganic filler. It is a substance having a function of increasing the mechanical strength of the inorganic filler-reinforced polyester resin composition, and has one or more effects on tensile strength, bending strength, bending elastic modulus, Charpy impact strength, and the like.

  Specific examples of the compound include a carbodiimide compound and an epoxy compound.

  A carbodiimide compound is a compound having a carbodiimide group (—N═C═N—) in the molecule. As the carbodiimide compound, any of an aliphatic carbodiimide compound having an aliphatic main chain, an alicyclic carbodiimide compound having an alicyclic main chain, and an aromatic carbodiimide compound having an aromatic main chain can be used. A carbodiimide compound can be used individually or in combination of 2 or more types.

  The aliphatic and alicyclic carbodiimide compounds are compounds having a carbodiimide bond in the molecule (polymer main chain), and are obtained by reacting any aliphatic and alicyclic isocyanate compounds. Examples of the starting isocyanate include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, polyfunctional aliphatic isocyanate, block polyfunctional aliphatic isocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and water of aromatic isocyanate. An additive etc. are mentioned, These 1 type (s) or 2 or more types can be used preferably. Specific examples include diisopropylcarbodiimide, dioctyldecylcarbodiimide, dicyclohexylcarbodiimide, and the like.

Examples of aromatic carbodiimide compounds include diphenylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, N-triyl-N′-phenylcarbodiimide, di-p-nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, and di-p-. Hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-p-methoxyphenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2,5-dichlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, p-phenylene-bis-di-o-triylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene-bis-di-p-chlorophenylcarbodiimide, ethylene-bis-diphenyl carbonate Mono or dicarbodiimide compounds such as rubodiimide and poly (4,4′-diphenylmethanecarbodiimide), poly (3,5′-dimethyl-4,4′-biphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide), poly (m -Phenylenecarbodiimide), poly (3,5'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), poly (1,3-diisopropylphenylenecarbodiimide), poly (1-methyl-3,5 Examples include polycarbodiimide compounds such as -diisopropylphenylenecarbodiimide), poly (1,3,5-triethylphenylenecarbodiimide), and poly (triisopropylphenylenecarbodiimide), and these can be used in combination of two or more. Of these, di-2,6-dimethylphenylcarbodiimide, poly (4,4′-diphenylmethanecarbodiimide), poly (phenylenecarbodiimide), poly (triisopropylphenylenecarbodiimide) and the like are particularly preferably used.

  Examples of the epoxy compound include polyfunctional epoxy compounds such as an epoxy resin and a vinyl copolymer having a glycidyl group. An epoxy compound can be used individually or in combination of 2 or more types.

  Examples of the epoxy resin include glycidyl ether type epoxy resin, glycidyl ester type epoxy resin (diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, dimethyl glycidyl phthalate, dimethyl glycidyl hexahydrophthalate, dimer acid glycidyl ester, aroma Tic diglycidyl ester, cycloaliphatic diglycidyl ester, etc.), glycidyl amine type epoxy resin (tetraglycidyl diaminodiphenylmethane, triglycidyl-paraaminophenol, triglycidyl-metaaminophenol, diglycidyl toluidine, tetraglycidyl metaxylylenediamine, Diglycidyl tribromoaniline, tetraglycidyl bisaminomethylcyclo Xanthine), heterocyclic epoxy resins (triglycidyl isocyanurate, hydantoin type epoxy resins, etc.), cyclic aliphatic epoxy resins (vinylcyclohexene dioxide, dicyclopentadiene oxide, alicyclic diepoxy acetals, alicyclic dice) Epoxy adipate, alicyclic diepoxycarboxylate, etc.), epoxidized polybutadiene and the like.

  Examples of glycidyl ether type epoxy resins include glycidyl ethers of polyhydroxy compounds [bisphenol type epoxy resins (for example, bisphenol A type, bisphenol AD type, or bisphenol F type epoxy resins), and aromatic polyhydroxy compounds such as resorcinol type epoxy resins. Glycidyl ethers; aliphatic epoxy resins (such as glycidyl ethers of alkylene glycols and polyoxyalkylene glycols), novolak type epoxy resins (such as phenol nopolac type and cresol novolac type epoxy resins), and the like.

  A vinyl copolymer having a glycidyl group is composed of a copolymer of a polymerizable monomer having a glycidyl group (such as a vinyl monomer having a glycidyl group) and another copolymerizable monomer. The

  The polymerizable monomer having a glycidyl group has at least one polymerizable group (such as an ethylenically unsaturated bond (such as a vinyl group) or an acetylene bond) together with the glycidyl group. Examples of such monomers include glycidyl ethers such as allyl glycidyl ether, vinyl glycidyl ether, chalcone glycidyl ether, and 2-cyclohexene-1-glycidyl ether; glycidyl (meth) acrylate, glycidyl maleate, glycidyl itaconate, vinyl benzoate Acid glycidyl ester, allylbenzoic acid glycidyl ester, cinnamic acid glycidyl ester, cinnamylidene acetic acid glycidyl ester, dimer acid glycidyl ester, epoxidized stearyl alcohol and acrylic acid or methacrylic acid ester, cycloaliphatic glycidyl ester (cyclohexene-4, Glycidyl or epoxy esters (especially glycidyl esters of α, β-unsaturated carboxylic acids) such as 5-diglycidyl carboxylate) Epoxidized unsaturated linear or cyclic olefins such as epoxy hexene and limonene oxide; N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide and the like. Of these monomers, vinyl monomers having a glycidyl group, for example, glycidyl esters of α, β-unsaturated carboxylic acids are preferred. These glycidyl group-containing polymerizable monomers can be used alone or in combination of two or more.

  Examples of the other copolymerizable monomer that can be copolymerized with a polymerizable monomer having a glycidyl group include olefin monomers (such as α-olefins such as ethylene, propylene, butene, and hexene), and diene monomers. Polymers (conjugated dienes such as butadiene and isoprene), aromatic vinyl monomers (styrene monomers such as styrene, α-methylstyrene, vinyltoluene), acrylic monomers ((meth) acrylic) (Meth) acrylic acid alkyl esters such as acid and methyl methacrylate, acrylonitrile, etc.), vinyl esters (vinyl acetate, vinyl propionate, etc.), vinyl ethers and the like. The copolymerizable monomer is preferably a monomer having an α, β-unsaturated double bond. These copolymerizable monomers can be used alone or in combination of two or more. Of the copolymerizable monomers, olefin monomers and acrylic monomers (such as (meth) acrylic acid and (meth) acrylic acid ester) are preferable.

  Particularly preferred (C) mechanical strength improver is at least selected from an aliphatic carbodiimide compound, an alicyclic carbodiimide compound, an aromatic carbodiimide compound, a glycidyl ether type aromatic epoxy resin, and a vinyl copolymer having a glycidyl group. One compound is mentioned.

In the present invention, the proportion of (C) mechanical strength improver is 1 to 20 parts by weight, preferably 1.5 to 15 parts by weight, particularly preferably 2 to 100 parts by weight of (A) polybutylene terephthalate resin. 7 parts by weight. If the amount is less than 1 part by weight, sufficient mechanical strength may not be improved. If the amount exceeds 20 parts by weight, the properties of the polybutylene terephthalate resin may be impaired. Moreover, when the ratio of (C) mechanical strength improving agent is 2 to 7 parts by weight, a particularly excellent mechanical strength improving effect is exhibited.
(D) Glass-based inorganic filler (D) Glass-based inorganic filler of the present invention is a glass-based inorganic filler treated with at least one surface treatment agent selected from silane-based or titanate-based coupling agents. Is used.

  The shape of the glass-based inorganic filler can be fibrous (glass fiber), granular (glass bead), powder (milled glass fiber), plate (glass flake), or hollow (glass balloon) depending on the purpose. ) Or a mixture thereof, among which fiber glass fiber is particularly preferable.

  Examples of the silane coupling agent include vinyl alkoxy silane, epoxy alkoxy silane, amino alkoxy silane, mercapto alkoxy silane, and allyl alkoxy silane.

  Examples of the vinylalkoxysilane include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, and the like.

  Examples of the epoxyalkoxysilane include γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and the like.

  Examples of the aminoalkoxysilane include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltrimethoxy. Silane etc. are mentioned.

  Examples of mercaptoalkoxysilanes include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  Examples of allylalkoxysilane include γ-diallylaminopropyltrimethoxysilane, γ-allylaminopropyltrimethoxysilane, γ-allylthiopropyltrimethoxysilane, and the like.

  Examples of titanate-based surface treatment agents include titanium-i-propoxyoctylene glycolate, tetra-n-butoxy titanium, tetrakis (2-ethylhexoxy) titanium, and the like.

  The amount of the surface treatment agent used is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the glass-based inorganic filler.

  Moreover, in glass fiber, what uses a polymer binder, an adhesion promoter, another adjuvant, etc. as a sizing agent is used suitably. As the polymer binder, generally known materials such as organic materials such as water-dispersible / water-soluble polyvinyl acetate, polyester, epoxide, polyurethane, polyacrylate or polyolefin resin, and mixtures thereof are preferably used.

  In this invention, the compounding quantity of (D) glass-type inorganic filler is 3-200 weight part with respect to 100 weight part of (A) polybutylene terephthalate resin (A), Preferably it is 5-150 weight part. When the amount is less than 3 parts by weight or more than 200 parts by weight, the properties of the polyester resin composition may be impaired.

  The specific embodiment of the method for preparing the composition of the present invention is not particularly limited, and can be generally prepared by a known equipment and method as a method for preparing a synthetic resin composition or a molded article. That is, necessary components can be mixed and kneaded using a single or twin screw extruder or other kneading and kneading apparatus to prepare pellets for molding. A plurality of extruders or other kneading and kneading apparatuses may be used.

  Here, (A) polybutylene terephthalate resin, (B) polylactic acid resin, and (C) mechanical strength modifier component are preferably supplied by dry blending together (A), (B), and (C) components. A method of supplying to a feed extruder or other kneading and kneading apparatus, a method of supplying (B) and (C) from one or more other supply ports to (A), and (B) and (C) components Examples thereof include a method of supplying (A) after dry blending, a method of supplying (B) from another supply port after once supplying (C) to (A) (dry blending or melt mixing), and the like.

  Moreover, as a method for supplying (D) the glass-based inorganic filler, a method of supplying from another supply port after the three components (A), (B), and (C) are plasticized is preferable.

  The glass-based inorganic filler-reinforced polyester resin composition of the present invention may contain other resins (such as thermoplastic resins) and various additives / fillers as long as the effects of the present invention are not impaired. May be included. Examples of other resins include polyester resins other than polybutylene terephthalate resins and polylactic acid resins, polyolefin resins, polystyrene resins, polyamide resins, polyacetals, polyarylene oxides, polyarylene sulfides, and fluororesins. Further, copolymers such as acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, and ethylene-ethyl acrylate resin are also exemplified. These other resins may be used alone or in combination of two or more.

  As additives and fillers, inorganic fillers other than the conventionally known (D) glass-based inorganic fillers, organic fillers, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), antistatic agents Agent, flame retardant, flame retardant aid, thermoplastic elastomer, colorant (dye, pigment, etc.), lubricant, plasticizer, lubricant, mold release agent, crystal nucleating agent, anti-dripping agent during combustion (anti-dripping agent) And the like. These additives can be used alone or in combination of two or more. In addition, mixing a part of the resin component as a fine powder with other components and adding it is a preferable method for uniformly blending these components.

  The glass-based inorganic filler-reinforced polyester resin composition of the present invention is produced by a conventionally known molding method (for example, injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotational molding, gas injection molding, etc.). ), Various molded products can be molded.

  According to the glass-based inorganic filler-reinforced polyester resin composition of the present invention, it is possible to achieve a tensile strength of 150 MPa or more by evaluating according to the evaluation criteria defined in ISO527-1, 2, , Automotive parts (interior parts, electrical system parts, in-vehicle electrical / electronic parts, mechanical parts, parts in contact with metal, etc.), electrical / electronic parts (audio equipment, video equipment, chassis of OA equipment, levers, etc.), miscellaneous goods, It can be used for various purposes such as stationery.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
Examples 1-4, Comparative Example 1
Ingredients other than the glass-based inorganic filler shown in Table 1 were dry blended and supplied from a hopper port to a twin screw extruder (manufactured by Nippon Steel Works, Ltd.) having a 30 mmφ screw, and from the side port of the extruder. A glass-based inorganic filler was supplied and melt-kneaded at 250 ° C. to obtain a pellet-shaped resin composition. Then, the test piece was created and each evaluation was performed. The results are shown in Table 1.

In addition, the detail of the used component and the measuring method of physical property evaluation are as follows.
(A) Polybutylene terephthalate resin (A-1) Polybutylene terephthalate (Intrinsic viscosity IV = 0.69 dL / g, manufactured by Wintech Polymer Co., Ltd.)
(B) Polylactic acid resin (B-1) REVODE 101-B (manufactured by Zhejiang Haisheng Biomaterials Co., Ltd., melting point 144.0 ° C., crystal melting heat 3.9 J / g)
-(C) Mechanical strength improver (C-1) Carbodiimide compound ("Carbodilite LA-1" manufactured by Nisshinbo Industries, Inc.)
(D) Glass-based inorganic filler (D-1) Glass fiber (E glass, ECS03T-187 manufactured by Nippon Electric Glass Co., Ltd.)
(D-2) Glass fiber (E glass, ECS03T-127 manufactured by Nippon Electric Glass Co., Ltd.)
<Tensile strength, tensile elongation (fracture strain)>
The obtained pellets (polyester resin composition) were dried at 140 ° C. for 3 hours, and then a tensile test piece was prepared by injection molding at a molding temperature of 250 ° C. and a mold temperature of 80 ° C., as defined in ISO527-1,2. It was evaluated according to the evaluation criteria.
<Bending strength, flexural modulus>
The obtained pellet (polyester resin composition) was dried at 140 ° C. for 3 hours, then injection molded at a molding temperature of 250 ° C. and a mold temperature of 80 ° C. to produce a bending test piece, and the evaluation criteria defined in ISO178 It evaluated according to.
<Charpy impact strength>
The obtained pellet (polyester resin composition) was dried at 140 ° C. for 3 hours, then injection molded at a molding temperature of 250 ° C. and a mold temperature of 80 ° C. to produce a Charpy impact test piece, as defined in ISO 179 / 1eA. It was evaluated according to the evaluation criteria.
<Melting point, heat of crystal melting (DSC measurement)>
The sample cut out from the pellet (polylactic acid resin) was sealed in an aluminum pan, held at 200 ° C. for 1 minute using a DSC device (DSC7 manufactured by PerkinElmer), and then cooled to −10 ° C./min to room temperature. Subsequently, the melting point (peak temperature) and the heat of crystal melting were calculated from the crystal melting peak detected when the temperature was raised at 10 ° C./min.

Claims (4)

(A) 100 parts by weight of polybutylene terephthalate resin, (B) 5 to 100 parts by weight of polylactic acid resin, (C) 1 to 20 parts by weight of mechanical strength improver, (D) silane or titanate coupling A glass-based inorganic filler-reinforced polyester resin composition comprising 3 to 200 parts by weight of a glass-based inorganic filler treated with at least one surface treatment agent selected from the agents. (C) The mechanical strength improver is at least one selected from an aliphatic carbodiimide compound, an alicyclic carbodiimide compound, an aromatic carbodiimide compound, a glycidyl ether type aromatic epoxy resin, and a vinyl copolymer having a glycidyl group. The glass-based inorganic filler-reinforced polyester resin composition according to claim 1, which is a compound. (D) The glass-based inorganic filler is a glass fiber, The glass-based inorganic filler-reinforced polyester resin composition according to claim 1 or 2. The glass-based inorganic filler-reinforced polyester resin composition according to any one of claims 1 to 3, wherein the (B) polylactic acid resin is a polylactic acid resin having a melting point of 130 to 150 ° C and a heat of crystal fusion of 0 to 10 J / g. .