Mechanical property enhancers, mechanical property enhancer compositions, thermoplastic resin compositions, and molded articles

Abstract

The present invention provides a mechanical properties enhancer capable of improving the mechanical properties of a thermoplastic resin composition containing fibrous fillers, a mechanical properties enhancer composition containing the same, a thermoplastic resin composition containing the same and fibrous fillers, and a molded article thereof. [Solution] This is a mechanical property enhancer for a thermoplastic resin composition containing fibrous fillers, comprising one or more polymer compounds (E) obtained by reacting a polyester (a) obtained by reacting a diol (a1) and a dicarboxylic acid (a2), a compound (b) having hydroxyl groups at both ends, and an epoxy compound (D) having two or more epoxy groups.

Description

Technical Field

[0001] The present invention relates to a mechanical property improver, a mechanical property improver composition, a thermoplastic resin composition (hereinafter, also simply referred to as "resin composition"), and a molded article. Specifically, it relates to a mechanical property improver capable of improving the mechanical properties of a thermoplastic resin composition containing a fibrous filler, a mechanical property improver composition containing the same, a thermoplastic resin composition containing these and a fibrous cleaning filler, and a molded article thereof.

Background Art

[0002] Thermoplastic resins are not only lightweight and easy to process, but also have excellent properties such as being able to design the base material according to the application, and thus are important materials that are indispensable in modern times. In particular, since thermoplastic resins can be melt-molded, the production of molded products is widely carried out, and the molded products are used in various applications.

[0003] Especially in recent years, in the fields of automobiles, office equipment, electrical products, etc., attempts have been made to replace some of their parts, especially some sheet metals, with thermoplastic resin products for the purpose of weight reduction, energy saving, and cost reduction. However, the mechanical properties (tensile strength, flexural strength, flexural modulus, Charpy impact strength, heat distortion temperature, etc.) of a thermoplastic resin alone are not satisfactory. Therefore, fibrous fillers such as glass fibers are blended with thermoplastic resins to improve the mechanical properties. For example, in Patent Document 1, an ABS resin composition has been proposed which can be processed in a short time and can obtain a molded product excellent in mechanical strength such as the flexural strength and Izod impact strength of a molded product of the ABS resin composition and heat resistance such as the heat distortion temperature. In Patent Document 2, a glass fiber reinforced thermoplastic resin composition excellent in weather resistance and having a toned color has been proposed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

[0005] However, even when fibrous fillers were incorporated into thermoplastic resins, the improvement in their mechanical properties was not satisfactory. In particular, further improvements were needed in mechanical properties such as flexural strength, flexural modulus, Charpy impact strength, and thermal distortion temperature.

[0006] Therefore, the object of the present invention is to provide a mechanical properties enhancer that can improve the mechanical properties of a thermoplastic resin composition containing fibrous fillers, a mechanical properties enhancer composition containing the same, a thermoplastic resin composition containing the same and fibrous fillers, and a molded article thereof. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the present inventors have found that a polymer compound having a predetermined structure can improve the mechanical properties of a thermoplastic resin containing fibrous fillers, and that by using this, the above problems can be solved, thus completing the present invention.

[0008] In other words, the mechanical property enhancer of the present invention contains one or more polymer compounds (E) obtained by reacting a polyester (a) obtained by reacting a diol (a1) and a dicarboxylic acid (a2), a compound (b) having hydroxyl groups at both ends, and an epoxy compound (D) having two or more epoxy groups, and is characterized in that it is for use in thermoplastic resin compositions containing fibrous fillers.

[0009] In the mechanical properties enhancer of the present invention, the polymer compound (E) comprises a polyester block (A) composed of the polyester (a) and a polyether block (B) composed of the compound (b). Preferably, the structure is formed by the polyester block (A), the polyether block (B), and the epoxy compound (D) being linked together via ester bonds or ether bonds.

[0010] Furthermore, in the mechanical property enhancer of the present invention, it is preferable that the polymer compound (E) has a structure in which a block polymer (C) having carboxyl groups at both ends is formed by repeatedly and alternately bonding a block of polyester (A) and a block of polyether (B) via ester bonds, and the epoxy compound (D) is bonded via ester bonds.

[0011] The mechanical properties improving agent composition of the present invention is characterized by containing one or more selected from the group consisting of alkali metal salts (F) and ionic liquids (G), and the mechanical properties improving agent of the present invention.

[0012] The thermoplastic resin composition of the present invention is characterized by containing a thermoplastic resin, a fibrous filler, and the mechanical property enhancer of the present invention.

[0013] Another thermoplastic resin composition of the present invention is characterized by containing a thermoplastic resin, a fibrous filler, and the mechanical property improving agent composition of the present invention.

[0014] The molded article of the present invention is characterized by being obtained from the thermoplastic resin composition of the present invention.

[0015] Other molded articles of the present invention are characterized by being obtained from other thermoplastic resin compositions of the present invention. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide a mechanical property enhancer that can improve the mechanical properties of a thermoplastic resin composition containing fibrous fillers, such as flexural strength, flexural modulus, Charpy impact strength, and heat distortion temperature. Furthermore, it is possible to provide a mechanical property enhancer composition containing this, a thermoplastic resin composition containing this and fibrous fillers, and a molded article having excellent mechanical properties. [Modes for carrying out the invention]

[0017] Embodiments of the present invention will be described in detail below. [Mechanical property enhancer for thermoplastic resin compositions containing fibrous fillers] First, the mechanical properties enhancer of the present invention will be described. The mechanical properties enhancer of the present invention is for use in thermoplastic resin compositions containing fibrous fillers, and can improve the mechanical properties of thermoplastic resins containing fibrous fillers.

[0018] The mechanical properties enhancer of the present invention contains one or more polymer compounds (E) obtained by reacting a polyester (a) obtained by reacting a diol (a1) and a dicarboxylic acid (a2), a compound (b) having hydroxyl groups at both ends, and an epoxy compound (D) having two or more epoxy groups.

[0019] The polymer compound (E) has a polyester block (A) composed of polyester (a) and a polyether block (B) composed of compound (b), and it is preferable from the viewpoint of improving mechanical properties that the polyester block (A), the polyether block (B), and the epoxy compound (D) are bonded together via ester bonds or ether bonds.

[0020] The polymer compound (E) has a polyester block (A) composed of a polyester (a) and a polyether block (B) composed of a compound (b) having hydroxyl groups at both ends, and is formed by the reaction of the hydroxyl group or carboxyl group at the end of the polyester (a) with the hydroxyl group at the end of the compound (b) and the reaction of the hydroxyl group formed by the reaction of the epoxy group or epoxy groups of the epoxy compound (D). It is preferable from the viewpoint of improving mechanical properties to have a structure bonded via an ester bond or an ether bond.

[0021] The polyester block (A) is composed of a polyester (a) obtained by reacting a diol (a1) and a dicarboxylic acid (a2). The polyester (a) can be obtained by subjecting the diol (a1) and the dicarboxylic acid (a2) to an esterification reaction.

[0022] Examples of the diol (a1) used in the polymer compound (E) according to the present invention include aliphatic diols and aromatic group-containing diols. The diol (a1) may be a mixture of two or more kinds.

[0023] Examples of the aliphatic diol include 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 1,2-, 1,3- or 1,4-cyclohexanediol, cyclododecanediol, dimer diol, hydrogenated dimer diol, diethylene glycol, dipropylene glycol, triethylene glycol, and the like. Here, the aliphatic diol preferably has hydrophobicity from the viewpoint of improving mechanical properties. More specifically, the aliphatic diol is preferably other than polyethylene glycol.

[0024] Examples of the diol containing an aromatic group include mononuclear dihydric phenol compounds such as bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, 1,4-benzenedimethanol, an ethylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A, 1,4-bis(2-hydroxyethoxy)benzene, resorcinol, pyrocatechol, and polyhydroxyethyl adducts thereof.

[0025] Among these diols, 1,4-cyclohexanedimethanol, 1,4-butanediol, and ethylene glycol are preferable, and 1,4-butanediol and 1,4-cyclohexanedimethanol are more preferable from the viewpoint of improving mechanical properties.

[0026] Examples of dicarboxylic acid (a2) used in the polymer compound (E) according to the present invention include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. Dicarboxylic acid (a2) may also be a mixture of two or more types.

[0027] The aliphatic dicarboxylic acid used in polymer compound (E) according to the present invention may be a derivative of the aliphatic dicarboxylic acid (for example, an acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.). The aliphatic dicarboxylic acid and its derivatives may also be a mixture of two or more types.

[0028] Examples of aliphatic dicarboxylic acids include those having 2 to 20 carbon atoms, such as oxalic acid, malonic acid, succinic acid, glutaric acid, methylsuccinic acid, dimethylmalonic acid, 3-methylglutaric acid, ethylsuccinic acid, isopropylmalonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid (1,10-decanedicarboxylic acid), tridecanediic acid, tetradecanediic acid, Examples include hexadecanedioic acid, octadecanediic acid, eicosanedioic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid, 1,1-cyclohexanediacetic acid, dimer acid, maleic acid, fumaric acid, etc. Among these aliphatic dicarboxylic acids, succinic acid or adipic acid is preferred from the viewpoint of improving mechanical properties.

[0029] The aromatic dicarboxylic acid used in polymer compound (E) according to the present invention may be a derivative of the aromatic dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.). Furthermore, the aromatic dicarboxylic acid and its derivatives may be a mixture of two or more types.

[0030] Examples of aromatic dicarboxylic acids include aromatic dicarboxylic acids having 8 to 20 carbon atoms, such as terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate, and potassium 3-sulfoisophthalate. Among these aromatic dicarboxylic acids, terephthalic acid, isophthalic acid, and phthalic acid (including phthalic anhydride) are preferred from the viewpoint of improving mechanical properties, and phthalic acid (including phthalic anhydride) is more preferred.

[0031] In the polymer compound (E) according to the present invention, it is also preferable to use both aliphatic dicarboxylic acid and aromatic dicarboxylic acid in combination as the dicarboxylic acid (a2).

[0032] For dicarboxylic acid (a2), adipic acid, succinic acid, and phthalic acid (including phthalic anhydride) are preferred from the viewpoint of improving mechanical properties, and combinations thereof are also preferred.

[0033] Next, we will describe the compound (b) having hydroxyl groups at both ends and the polyether (B) block. The polyether (B) block is composed of the compound (b) having hydroxyl groups at both ends.

[0034] Compound (b) is preferably a compound having hydroxyl groups at both ends and one or more ethyleneoxy groups represented by the following general formula (1), from the viewpoint of improving mechanical properties.

[0035] Compound (b) is preferably a hydrophilic compound, more preferably a polyether having an ethyleneoxy group represented by general formula (1), even more preferably polyethylene glycol from the viewpoint of improving mechanical properties, and particularly preferably polyethylene glycol represented by the following general formula (2).

[0036] In general formula (2) of TIFF2026122604000002.tif18155, m represents an integer from 5 to 250. From the viewpoint of improving mechanical properties, m is preferably from 20 to 200, and more preferably from 40 to 180.

[0037] Compound (b) includes polyethylene glycol obtained by the addition reaction of ethylene oxide, as well as polyethers obtained by the addition reaction of ethylene oxide with one or more other alkylene oxides (e.g., propylene oxide, 1,2-, 1,4-, 2,3-, or 1,3-butylene oxide), and this polyether may be random or blocked.

[0038] Furthermore, compound (b) may also contain polyethylene glycol and polytetramethylene glycol in combination, from the viewpoint of improving mechanical properties. When used in combination, the proportion of polytetramethylene glycol is preferably 10 to 80 mol%, more preferably 15 to 70 mol%, and even more preferably 20 to 50 mol%, relative to the total number of moles of polyethylene glycol and polytetramethylene glycol, from the viewpoint of improving mechanical properties.

[0039] Further examples of compound (b) include compounds in which ethylene oxide is added to an active hydrogen atom-containing compound, and compounds in which ethylene oxide and one or more other alkylene oxides (e.g., propylene oxide, 1,2-, 1,4-, 2,3-, or 1,3-butylene oxide) are added. These can be either random addition or block addition.

[0040] Examples of active hydrogen atom-containing compounds include glycols, divalent phenols, primary monoamines, secondary diamines, and dicarboxylic acids.

[0041] Examples of glycols that can be used include aliphatic glycols with 2 to 20 carbon atoms, alicyclic glycols with 5 to 12 carbon atoms, and aromatic glycols with 8 to 26 carbon atoms.

[0042] Examples of aliphatic glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-hexanediol, 1,4-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 1,18-octadecanediol, 1,20-eicosanediol, diethylene glycol, triethylene glycol, and thiodiethylene glycol.

[0043] Examples of alicyclic glycols include 1-hydroxymethyl-1-cyclobutanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1-methyl-3,4-cyclohexanediol, 2-hydroxymethylcyclohexanol, 4-hydroxymethylcyclohexanol, 1,4-cyclohexanedimethanol, and 1,1'-dihydroxy-1,1'-dicyclohexyl.

[0044] Examples of aromatic glycols include dihydroxymethylbenzene, 1,4-bis(β-hydroxyethoxy)benzene, 2-phenyl-1,3-propanediol, 2-phenyl-1,4-butanediol, 2-benzyl-1,3-propanediol, triphenylethylene glycol, tetraphenylethylene glycol, and benzopinacol.

[0045] As divalent phenols, phenols having 6 to 30 carbon atoms can be used, such as catechol, resorcinol, 1,4-dihydroxybenzene, hydroquinone, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, dihydroxydiphenyl thioether, binaphthol, and their alkyl (1 to 10 carbon atoms) or halogen-substituted derivatives.

[0046] Examples of primary monoamines include aliphatic primary monoamines having 1 to 20 carbon atoms, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, s-butylamine, isobutylamine, n-amylamine, isoamylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-octadecylamine, and n-icosylamine.

[0047] Examples of secondary diamines that can be used include aliphatic secondary diamines with 4 to 18 carbon atoms, heterocyclic secondary diamines with 4 to 13 carbon atoms, alicyclic secondary diamines with 6 to 14 carbon atoms, aromatic secondary diamines with 8 to 14 carbon atoms, and secondary alkanol diamines with 3 to 22 carbon atoms.

[0048] Examples of aliphatic secondary diamines include N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N'-dibutylethylenediamine, N,N'-dimethylpropylenediamine, N,N'-diethylpropylenediamine, N,N'-dibutylpropylenediamine, N,N'-dimethyltetramethylenediamine, N,N'-diethyltetramethylenediamine, N,N'-dibutyltetramethylenediamine, N,N'-dimethylhexamethylenediamine, N,N'-diethylhexamethylenediamine, N,N'-dibutylhexamethylenediamine, N,N'-dimethyldecamethylenediamine, N,N'-diethyldecamethylenediamine, and N,N'-dibutyldecamethylenediamine.

[0049] Examples of heterocyclic secondary diamines include piperazine and 1-aminopiperidine.

[0050] Examples of alicyclic secondary diamines include N,N'-dimethyl-1,2-cyclobutanediamine, N,N'-diethyl-1,2-cyclobutanediamine, N,N'-dibutyl-1,2-cyclobutanediamine, N,N'-dimethyl-1,4-cyclohexanediamine, N,N'-diethyl-1,4-cyclohexanediamine, N,N'-dibutyl-1,4-cyclohexanediamine, N,N'-dimethyl-1,3-cyclohexanediamine, N,N'-diethyl-1,3-cyclohexanediamine, and N,N'-dibutyl-1,3-cyclohexanediamine.

[0051] Examples of aromatic secondary diamines include N,N'-dimethylphenylenediamine, N,N'-dimethylxylylenediamine, N,N'-dimethyldiphenylmethanediamine, N,N'-dimethyldiphenyletherdiamine, N,N'-dimethylbenzidine, and N,N'-dimethyl-1,4-naphthalenediamine.

[0052] Examples of secondary alkanoldiamines include N-methyldiethanolamine, N-octyldiethanolamine, N-stearyldiethanolamine, and N-methyldipropanolamine.

[0053] Dicarboxylic acids can be those having 2 to 20 carbon atoms, such as aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids.

[0054] Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, methylsuccinic acid, dimethylmalonic acid, β-methylglutaric acid, ethylsuccinic acid, isopropylmalonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, hexadecanedic acid, octadecanediic acid, and eicosanedic acid.

[0055] Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate, and potassium 3-sulfoisophthalate.

[0056] Examples of alicyclic dicarboxylic acids include 1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid, and dicyclohexyl-4,4'-dicarboxylic acid.

[0057] These active hydrogen atom-containing compounds can be used individually or as a mixture of two or more.

[0058] Next, we will describe epoxy compounds (D) that have two or more epoxy groups constituting a polymer compound (E). The epoxy compound (D) used in the present invention is not particularly limited as long as it has two or more epoxy groups, and includes, for example, polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis(orthocresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis(orthocresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resol Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as synnovolac and terpenephenol; polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct, and dicyclopentadiene dimethanol; homopolymers or copolymers of glycidyl esters and glycidyl methacrylates of aliphatic, aromatic, or alicyclic polybasic acids such as maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and endomethylenetetrahydrophthalic acid;Examples include epoxy compounds having a glycidylamino group such as N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, and diglycidyl orthotoluidine; epoxides of cyclic olefin compounds such as vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymers; heterocyclic compounds such as triglycidyl isocyanurate; and epoxidized soybean oil. Furthermore, these epoxy compounds may be internally crosslinked by terminal isocyanate prepolymers, or their molecular weight may be increased using polyvalent active hydrogen compounds (polyvalent phenols, polyamines, carbonyl group-containing compounds, polyphosphate esters, etc.). Two or more epoxy compounds (D) may be used.

[0059] From the viewpoint of improving mechanical properties, the epoxy compound (D) is preferably bisphenol F diglycidyl ether, dicyclopentadiene dimethanol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hexanediol diglycidyl ether, or polypropylene glycol diglycidyl ether, with bisphenol F diglycidyl ether and polypropylene glycol diglycidyl ether being more preferred.

[0060] From the viewpoint of improving mechanical properties, polypropylene glycol diglycidyl ether represented by the following general formula (4) is preferred.

[0061] In general formula (4) of TIFF2026122604000003.tif33155, n represents an integer from 1 to 30. From the viewpoint of improving mechanical properties, n is preferably from 2 to 25, and more preferably from 3 to 15.

[0062] The number-average molecular weight of polypropylene glycol diglycidyl ether is preferably 200 to 2000, more preferably 250 to 1500, and even more preferably 300 to 1000, from the viewpoint of improving mechanical properties.

[0063] The number-average molecular weight of polypropylene glycol diglycidyl ether can be calculated from its epoxy equivalent. The epoxy equivalent is measured in accordance with JIS K7236.

[0064] Polypropylene glycol diglycidyl ether may be a commercially available product, such as ADEKA ED-506 (registered trademark) manufactured by ADEKA Corporation, and Denacol EX-920 and Denacol EX-931 (registered trademark) manufactured by Nagase ChemteX Corporation.

[0065] The epoxy equivalent of epoxy compound (D) is preferably 70 to 2,000, more preferably 100 to 1,000, and even more preferably 150 to 600, from the viewpoint of improving the appearance and mechanical properties.

[0066] The epoxy equivalent of epoxy compounds is measured in accordance with JIS K7236.

[0067] The polymer compound (E) according to the present invention is obtained by reacting a polyester (a) obtained by the reaction of a diol (a1) and a dicarboxylic acid (a2), a compound (b) having hydroxyl groups at both ends, and an epoxy compound (D) having two or more epoxy groups, and comprises a polyester block (A) composed of polyester (a) and a polyether block (B) composed of compound (b), and is preferably having a structure in which the hydroxyl or carboxyl groups at the ends of polyester (a), the hydroxyl groups at the ends of compound (b), and the epoxy groups of the epoxy compound having two or more epoxy groups, or hydroxyl groups formed by the reaction of these epoxy groups, are linked via ester bonds or ether bonds, which are preferable from the viewpoint of improving mechanical properties.

[0068] Furthermore, from the viewpoint of improving mechanical properties, the polymer compound (E) is preferably a structure in which a block polymer (C) having carboxyl groups at both ends is formed by repeatedly and alternately bonding polyester blocks (A) composed of polyester (a) and polyether blocks (B) composed of compound (b) via ester bonds, and an epoxy compound (D) is bonded to it via ester bonds formed by the reaction of the carboxyl groups of the block polymer (C) and the epoxy groups of the epoxy compound (D). It is also preferable that the polymer compound (E) has a structure in which it is bonded via ester bonds formed by the reaction of carboxyl groups to hydroxyl groups formed by ring-opening of epoxy groups in reaction with carboxyl groups.

[0069] The polyester (a) constituting the polyester (A) block according to the present invention may consist of a diol (a1) and a dicarboxylic acid (a2), and preferably, from the viewpoint of improving mechanical properties, it has a structure in which a residue of the diol (a1) with the hydroxyl group removed and a residue of the dicarboxylic acid (a2) with the carboxyl group removed are linked via an ester bond.

[0070] Furthermore, polyester (a) is preferably a structure having carboxyl groups at both ends, from the viewpoint of improving mechanical properties. Moreover, the degree of polymerization of polyester (a) is preferably in the range of 2 to 50, from the viewpoint of improving mechanical properties.

[0071] A polyester (a) having carboxyl groups at both ends can be obtained by esterifying a diol (a1) with a dicarboxylic acid (a2).

[0072] The dicarboxylic acid (a2) may be a derivative thereof (for example, an acid anhydride, an ester such as an alkyl ester, an alkali metal salt, an acid halide, etc.), and if polyester (a) is obtained using a derivative, both ends may be treated to form carboxyl groups at the end, or the reaction may proceed in that state to obtain the next reaction for obtaining a block polymer (C) having a structure with carboxyl groups at both ends.

[0073] The reaction ratio of dicarboxylic acid (a2) to diol (a1) is preferably such that dicarboxylic acid (a2) is used in excess so that both ends become carboxyl groups, and preferably in excess of 1 molar equivalent or more relative to diol (a1). A catalyst to promote the esterification reaction may be used in the esterification reaction, and conventionally known catalysts such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate can be used.

[0074] Furthermore, if derivatives such as esters, alkali metal salts, or acid halides are used instead of dicarboxylic acids, the reaction between these derivatives and the diol may be followed by treatment of both ends to obtain a dicarboxylic acid, and the reaction may proceed in that state to obtain the next block polymer (C) having a structure with carboxyl groups at both ends.

[0075] A preferred polyester (a) consisting of a diol (a1) and a dicarboxylic acid (a2), having carboxyl groups at both ends, is preferably one that reacts with compound (b) to form an ester bond and create the structure of a block polymer (C). The carboxyl groups at both ends may be protected, modified, or in precursor form. Furthermore, an antioxidant such as a phenolic antioxidant may be added to the reaction system to suppress oxidation of the product during the reaction.

[0076] Compound (b), having hydroxyl groups at both ends, preferably reacts with polyester (a) to form an ester bond or ether bond, preferably an ester bond, to form the structure of block polymer (C), wherein the hydroxyl groups at both ends may be protected, modified, or in precursor form.

[0077] The block polymer (C) having a structure with carboxyl groups at both ends according to the present invention comprises a block (A) composed of the polyester (a) and a block (B) composed of the compound (b), and these blocks are repeatedly and alternately bonded together via ester bonds formed by carboxyl groups and hydroxyl groups. An example of such a block polymer (C) is one having a structure represented by the following general formula (3).

[0078] In general formula (3), (A) represents a block composed of polyester (a) having carboxyl groups at both ends, (B) represents a block composed of compound (b) having hydroxyl groups at both ends, and t is the number of repeats in the repeating unit, preferably an integer from 1 to 10 from the viewpoint of improving mechanical properties. More preferably t is a number from 1 to 7, and most preferably a number from 1 to 5.

[0079] A block polymer (C) having a structure with carboxyl groups at both ends can be obtained by polycondensation reaction of a polyester (a) having carboxyl groups at both ends and a compound (b) having hydroxyl groups at both ends. However, it is not necessarily required to synthesize the polymer from the polyester (a) and compound (b) if the polyester (a) and compound (b) have a structure equivalent to one in which they are repeatedly and alternately bonded via ester bonds formed by carboxyl groups and hydroxyl groups.

[0080] The reaction ratio of the polyester (a) and the compound (b) can be adjusted so that the amount of polyester (a) is 1.05X to 1.15X moles relative to the amount of compound (b), thereby preferably obtaining a block polymer (C) having carboxyl groups at both ends.

[0081] During the reaction, after the synthesis reaction of polyester (a) is completed, the compound (b) may be added to the reaction system without isolating polyester (a) and the reaction may proceed as is.

[0082] A catalyst that promotes the esterification reaction may be used in the polycondensation reaction. Conventionally known catalysts such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate can be used. In addition, antioxidants such as phenolic antioxidants may be added to the reaction system to suppress oxidation of the product during the reaction.

[0083] The polymer compound (E) according to the present invention preferably has a structure in which a block polymer (C) having a structure with carboxyl groups at both ends and an epoxy compound (D) having two or more epoxy groups are linked via ester bonds, from the viewpoint of improving mechanical properties. The ester bonds may be ester bonds formed by the reaction between the terminal carboxyl groups of the block polymer (C) and the epoxy groups of the epoxy compound (D), or ester bonds formed by the reaction between the hydroxyl groups formed by this reaction (reaction between carboxyl groups and epoxy groups) and the carboxyl groups, and the presence of both types of ester bonds is preferable from the viewpoint of improving mechanical properties.

[0084] Furthermore, such polymer compound (E) may also contain ester bonds formed by the carboxyl group of the polyester (a) and the epoxy group of the epoxy compound (D).

[0085] Furthermore, such polymer compound (E) may contain ester bonds formed by the reaction of a carboxyl group of polyester (a) with a hydroxyl group formed by the reaction of an epoxy group of epoxy compound (D).

[0086] Furthermore, such polymer compound (E) may also contain ether bonds formed by a hydroxyl group of the polyester (a) or a hydroxyl group of compound (b) and an epoxy group of the epoxy compound (D).

[0087] One method for obtaining a polymer compound (E) having a structure in which the block polymer (C) and the epoxy compound (D) are bonded via ester bonds is to react the block polymer (C) and the epoxy compound (D). That is, the carboxyl groups of the block polymer (C) can be reacted with the epoxy groups of the epoxy compound (D). More preferably, the hydroxyl groups formed from the reacted epoxy groups can be reacted with the carboxyl groups.

[0088] The reaction ratio between the block polymer (C) and the epoxy compound (D) is preferably adjusted so that the number of epoxy groups in the epoxy compound (D) is 0.5 to 5 equivalents of the number of carboxyl groups in the block polymer (C) being reacted, and more preferably 0.5 to 1.5 equivalents. Furthermore, the above reaction may be carried out in various solvents or in a molten state.

[0089] During the reaction, after the synthesis reaction of the block polymer (C) is completed, the epoxy compound (D) may be added to the reaction system without isolating the block polymer (C) and the reaction may proceed as is. In this case, the carboxyl groups of the unreacted polyester (a) used in excess when synthesizing the block polymer (C) may react with some of the epoxy groups of the epoxy compound (D) to form ester bonds.

[0090] The preferred polymer compound (E) according to the present invention does not necessarily have to be synthesized from the block polymer (C) and the epoxy compound (D), as long as it has a structure equivalent to that of a block polymer (C) having a structure with carboxyl groups at both ends and an epoxy compound (D) having two or more epoxy groups, linked via ester bonds formed by the respective carboxyl groups and epoxy groups. The ester bonds formed by carboxyl groups and epoxy groups referred to here also include ester bonds formed by a carboxyl group and a hydroxyl group formed from the epoxy group by reaction with the carboxyl group.

[0091] Furthermore, the polymer compound (E) according to the present invention may be reacted with compound (b) and / or epoxy compound (D) without isolating polyester (a) after obtaining polyester (a) from diol (a1) and dicarboxylic acid (a2).

[0092] In the present invention, the number-average molecular weight of compound (b) in polymer compound (E) is calculated from the measured hydroxyl value and is preferably 400 to 10,000, more preferably 1,000 to 8,000, and even more preferably 2,000 to 8,000, from the viewpoint of improving mechanical properties. The method for measuring the hydroxyl value and the method for calculating the number-average molecular weight from the hydroxyl value are described below.

[0093] <Method for calculating the number-average molecular weight from the hydroxyl value> The hydroxyl value was measured using the hydroxyl value measurement method described below, and the number-average molecular weight (hereinafter also referred to as "Mn") was determined using the following formula. Number-average molecular weight = (56110 × 2) / hydroxyl value

[0094] <Hydroxyl Value Measurement Method> • Reagent A (acetylating agent) (1) Triethyl phosphate 1560 mL (2) Acetic anhydride 193 mL (3) Perchloric acid (60%) 16g Mix the above reagents in the order of (1) → (2) → (3). Reagent B Mix pyridine and pure water in a volume ratio of 3:1. Reagent C Add 2-3 drops of phenolphthalein solution to 500 mL of isopropyl alcohol, and neutralize with 1N-KOH aqueous solution.

[0095] First, weigh 2 g of the sample into a 200 mL Erlenmeyer flask, add 10 mL of triethyl phosphate, and heat to dissolve. Add 15 mL of reagent A, stopper the flask, and shake vigorously. Add 20 mL of reagent B, stopper the flask, and shake vigorously. Add 50 mL of reagent C. Titrate with 1 N KOH aqueous solution and calculate using the following formula. Hydroxyl value [mgKOH / g] = 56.11 × f × (TB) / S f: Factor of 1N-KOH aqueous solution B: Blank titration volume [mL] T: Titration volume for this test [mL] S: Sample volume [g]

[0096] Furthermore, in the present invention, the number-average molecular weight of polyester (a) in polymer compound (E) is preferably 1,000 to 10,000, more preferably 1,500 to 8,000, and even more preferably 2,500 to 7,500, in terms of polystyrene equivalent, from the viewpoint of improving mechanical properties. If the number-average molecular weight is 1,000 or more, it has excellent storage stability, and if it is 10,000 or less, the reaction to obtain polymer compound (E) does not take long, making it economical, and there is no risk of the obtained polymer compound (E) becoming discolored due to a long reaction time.

[0097] The method for measuring the number-average molecular weight in terms of polystyrene is gel permeation chromatography (GPC). The measurement method is described below.

[0098] <Method for measuring the number-average molecular weight based on polystyrene equivalent> The number-average molecular weight (hereinafter also referred to as "Mn") was measured by gel permeation chromatography (GPC). The measurement conditions for Mn were as follows: Equipment: GPC instrument manufactured by JASCO Corporation Solvent: Chloroform Reference material: Polystyrene Detector: Differential refractometer (RI detector) Column stationary phase: Shodex LF-804 manufactured by Showa Denko Corporation Column temperature: 40℃ Sample concentration: 1 mg / 1 mL Flow rate: 0.8mL / min. Injection volume: 100μL

[0099] Furthermore, the number-average molecular weight of the block polymer (C) having a structure with carboxyl groups at both ends is preferably 5,000 to 50,000, more preferably 10,000 to 45,000, and even more preferably 15,000 to 40,000, in terms of polystyrene, from the viewpoint of improving mechanical properties. If the number-average molecular weight is 5,000 or more, it has excellent storage stability, and if it is 50,000 or less, the reaction to obtain the polymer compound (E) does not take long, making it economical, and there is no risk of the obtained polymer compound (E) becoming discolored due to a long reaction time.

[0100] The method for measuring the number-average molecular weight in terms of polystyrene is gel permeation chromatography (GPC). The measurement method is as described above.

[0101] Component (E) according to the present invention may be a single type or a mixture of two or more types.

[0102] The mechanical property enhancer of the present invention is used to improve the mechanical properties of a thermoplastic resin composition containing fibrous fillers.

[0103] The thermoplastic resin composition according to the present invention contains a fibrous filler.

[0104] Examples of fibrous fillers include glass fibers, carbon fibers, graphite fibers, stainless steel fibers, metal fibers such as aluminum and brass fibers, slag fibers, gypsum fibers, ceramic fibers, zirconia fibers, alumina fibers, silica fibers, silica-alumina fibers, titanium oxide fibers, boron nitride fibers, silicon nitride fibers, silicon carbide fibers, boron fibers, cellulose fibers, cellulose nanofibers, and rock wool. Among these, glass fibers are preferred in terms of improving mechanical properties.

[0105] Glass fibers may be treated with a surface treatment agent. Examples of such surface treatment agents include silane-based, titanate-based, aluminum-based, chromium-based, zirconium-based, and borane-based coupling agents. Among these, silane-based and titanate-based coupling agents are preferred, and silane-based coupling agents are particularly preferred. Examples of such silane-based coupling agents include triethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-chloropropyltrimethoxysilane.

[0106] Furthermore, a consolidating agent may be used to bind the glass fibers together. Examples of consolidating agents include polypropylene resin, polyurethane resin, polyester resin, acrylic resin, epoxy resin, starch, and vegetable oil. Chopped strands, which are single fibers bound together, can also be used as glass fibers.

[0107] The thermoplastic resin in the thermoplastic resin composition according to the present invention will be described.

[0108] Examples of thermoplastic resins include polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, cross-linked polyethylene, ultra-high molecular weight polyethylene, α-olefin polymers such as polybutene-1, poly-3-methylpentene, poly-4-methylpentene, or polyolefin resins and copolymers thereof such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-propylene copolymer; polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid copolymer, vinyl chloride-maleic acid copolymer, vinyl chloride-cyclohexylmaleimide copolymer, and other halogen-containing resins; petroleum resins, coumarone resins, polystyrene, polyvinyl acetate, acrylic resins, styrene and / or α-methylstyrene and other monomers (e.g., maleic anhydride, phenylmaleimide, me) Copolymers with methyl tacrylate, butadiene, acrylonitrile, etc. (e.g., acrylonitrile-styrene copolymer (AS) resin, ABS resin, acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS) resin, styrene-butadiene-styrene block copolymer (SBS) resin, methyl methacrylate-butadiene-styrene copolymer (MBS) resin, heat-resistant ABS resin, etc.); polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; polyethylene terephthalate, polybutylene Aromatic polyesters such as polyalkylene terephthalates like polychlorohexanedimethylene terephthalate, polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate, and linear polyesters such as polytetramethylene terephthalate; biodegradable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid (PLA resin), polymalic acid, polyglycolic acid, polydioxane, and poly(2-oxetanone);Examples include polyamides such as polyphenylene oxide, polycaprolactam, and polyhexamethylene adipamide; polycarbonate (PC); polycarbonate / ABS resin; branched polycarbonate; polyacetal; polyphenylene sulfide; polyurethane; crystalline resins; polyimide resins; polysulfone; polyphenylene ether; polyether ketone; polyether ether ketone; liquid crystal polymers; thermoplastic resins; and blends thereof.

[0109] Furthermore, the thermoplastic resin may be an elastomer such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber, olefin-based elastomer, styrene-based elastomer, polyester-based elastomer, nitrile-based elastomer, nylon-based elastomer, vinyl chloride-based elastomer, polyamide-based elastomer, or polyurethane-based elastomer. Examples of thermoplastic resins that can be used in the present invention include fluororesins and silicone resins. In the resin composition of the present invention, these thermoplastic resins may be used individually or in combination of two or more. The thermoplastic resin may also be alloyed.

[0110] These thermoplastic resins can be used regardless of molecular weight, degree of polymerization, density, softening point, proportion of insoluble matter in the solvent, degree of stereoregularity, presence or absence of catalyst residue, type and blending ratio of raw material monomers, type of polymerization catalyst (e.g., Ziegler catalyst, metallocene catalyst, etc.), polymerization method (e.g., bulk polymerization, suspension polymerization, etc.).

[0111] Among these thermoplastic resins, polyamide resins, polyester resins, polypropylene resins, and polycarbonate resins are preferred from the viewpoint of improving mechanical properties, with polyamide resins being more preferred.

[0112] Polyamide resins are polymers containing amide bonds, primarily made from amino acids, lactams, or diamines and dicarboxylic acids.

[0113] Examples of raw materials for polyamide resins include amino acids such as 6-aminocaproic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and para-aminomethylbenzoic acid; lactams such as γ-butyrolactam, δ-valerolactam, ε-caprolactam, and ω-laurolactam; ethylenediamine, 1,3-diaminopropane, tetramethylenediamine (1,4-diaminobutane), pentamethylenediamine (1,5-diaminopentane), hexamethylenediamine (1,6-diaminohexane), and heptamine. Methylenediamine (1,7-diaminoheptane), octamethylenediamine (1,8-diaminooctane), nonamethylenediamine (1,9-diaminononane), decamethylenediamine (1,10-diaminodecane), 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane Aliphatic diamines such as 1,20-diaminoeicosane, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclo Alicyclic diamines such as hexyl)propane, bis(aminopropyl)piperazine, aminoethylpiperazine, aromatic diamines such as metaxylylenediamine, paraxylylenediamine, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanediic acid, 1,3-cyclohexanedicarboxylic acid, 1,Examples include alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfisoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid, among other aromatic dicarboxylic acids. The polyamide resin may be a polyamide homopolymer derived from one of the above raw materials, or a copolymer derived from two or more of the above raw materials.

[0114] Specific examples of polyamide resins include polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polypentamethylene adipamide (polyamide 56), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebaamide (polyamide 610), polypentamethylene sebaamide (polyamide 510), polytetramethylene pimeraamide (nylon 47), polytetramethylene sveramide (polyamide 48), polytetramethylene azeramide (polyamide 49), and polytetramethylene sebaamide (poly Polyamide 410), Polytetramethylene undecamide (Polyamide 411), Polytetramethylene dodecamide (Polyamide 412), Polytetramethylene tridecanamide (Polyamide 413), Polytetramethylene tetradecanamide (Polyamide 414), Polytetramethylene pentadecanamide (Polyamide 415), Polytetramethylene hexadecanamide (Polyamide 416), Polytetramethylene heptadecanamide (Polyamide 417), Polytetramethylene octadecanamide (Polyamide 418), Polyhexamethylene dodeca Polyamide 612, Polyundecaneamide (Polyamide 11), Polydodecaneamide (Polyamide 12), Polycaproamide / Polyhexamethylene adipamide copolymer (Polyamide 6 / 66), Polycaproamide / Polyhexamethylene terephthalamide copolymer (Polyamide 6 / 6T), Polyhexamethylene adipamide / Polyhexamethylene terephthalamide copolymer (Polyamide 66 / 6T), Polyhexamethylene adipamide / Polyhexamethylene isophthalamide copolymer (Polyamide 66 / 6I), Polyhexamethylene Dipamide / Polyhexamethylene isophthalamide / Polycaproamide copolymer (Polyamide 66 / 6I / 6), Polyhexamethylene terephthalamide / Polyhexamethylene isophthalamide copolymer (Polyamide 6T / 6I), Polyhexamethylene terephthalamide / Polydecaneamide copolymer (Polyamide 6T / 12), Polyhexamethylene adipamide / Polyhexamethylene terephthalamide / Polyhexamethylene isophthalamide copolymer (Polyamide 66 / 6T / 6I), Polymetaxylylene adipamide (Polyamide MXD6),Polymeta-xylylene sebamid (polyamide MXD10), polypara-xylylene adipamide (polyamide PXD6), polypara-xylylene sebamid (polyamide PXD10), polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer (polyamide 6T / M5T), polyhexamethylene terephthalamide / polypentamethylene terephthalamide copolymer (polyamide 6T / 5T), polypentamethylene terephthalamide / polypentamethylene adipamide copolymer (5T / 56), polynonameethylene terephthalamide Examples include polyamide (polyamide 9T), polynonameethylene terephthalamide / poly2-methyl-1,8-octamethylene terephthalamide copolymer (polyamide 9T / M8T), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene terephthalamide / polyhexamethylene adipamide copolymer (polyamide 10T / 66), polydecamethylene terephthalamide / polyhexamethylene dodecamide copolymer (polyamide 10T / 612), polydodecamethylene terephthalamide (polyamide 12T), and copolymers thereof. Here, " / " indicates a copolymer, and the same applies hereafter. One of these polyamide resins may be used alone, or two or more may be used in combination.

[0115] In the present invention, in a thermoplastic resin composition containing a fibrous filler into which a mechanical properties enhancer is blended, the content of the fibrous filler relative to the thermoplastic resin is preferably 1 to 80 parts by mass, more preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, even more preferably 15 to 55 parts by mass, and even more preferably 20 to 50 parts by mass, per 100 parts by mass of the total of the thermoplastic resin and the fibrous filler.

[0116] In the present invention, when component (E), which is a mechanical property improver, is blended into a thermoplastic resin composition containing fibrous filler, the amount blended is preferably 0.01 to 20 parts by mass, more preferably 0.02 to 10 parts by mass, even more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total of the fibrous filler and thermoplastic resin.

[0117] [Mechanical property enhancer composition for fibrous filler-containing thermoplastic resin compositions] The mechanical properties improving agent of the present invention is preferably used in combination with one or more selected from the group consisting of alkali metal salts (F) and ionic liquids (G) as a mechanical properties improving agent composition for fibrous filler-containing thermoplastic resin compositions, and is more preferably used in combination with one or more selected from the group consisting of alkali metal salts (F).

[0118] Below, we will first explain alkali metal salts (F). Alkali metal salts (F) include salts of organic or inorganic acids. Examples of alkali metals include lithium, sodium, potassium, cesium, and rubidium. Examples of organic acids include aliphatic monocarboxylic acids with 1 to 18 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, and lactic acid; aliphatic dicarboxylic acids with 1 to 12 carbon atoms, such as oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, and adipic acid; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; and sulfonic acids with 1 to 20 carbon atoms, such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethanesulfonic acid. Examples of inorganic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphate, nitric acid, and perchloric acid. In particular, salts of lithium, sodium, and potassium are preferred from the standpoint of improving mechanical properties and safety for living organisms and the environment, with sodium being more preferred. Furthermore, from the standpoint of improving mechanical properties, salts of acetate, perchloric acid, p-toluenesulfonic acid, and dodecylbenzenesulfonic acid are preferred, with dodecylbenzenesulfonic acid being more preferred. Two or more alkali metal salts may be used.

[0119] Specific examples of alkali metal salts (F) include lithium acetate, sodium acetate, potassium acetate, lithium chloride, sodium chloride, potassium chloride, lithium phosphate, sodium phosphate, potassium phosphate, lithium sulfate, sodium sulfate, lithium perchlorate, sodium perchlorate, potassium perchlorate, lithium p-toluenesulfonate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, etc. Among these, lithium p-toluenesulfonate, sodium p-toluenesulfonate, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, etc. are preferred in terms of improved mechanical properties and safety for living organisms and the environment, with sodium dodecylbenzenesulfonate being the most preferred.

[0120] The alkali metal salt (F) may be incorporated into the mechanical properties enhancer of the present invention, or it may be used in combination with the mechanical properties enhancer of the present invention in a thermoplastic resin. From the viewpoint of improving mechanical properties, the amount of alkali metal salt (F) to be incorporated is preferably 0.01 to 25 parts by mass, more preferably 0.1 to 25 parts by mass, even more preferably 3.0 to 20 parts by mass, and even more preferably 5.0 to 18 parts by mass, per 100 parts by mass of the mechanical properties enhancer of the present invention.

[0121] Next, we will explain ionic liquids (G). Examples of ionic liquids (G) include room-temperature molten salts having a melting point of 100°C or less, in which at least one of the cations or anions constituting the ionic liquid is an organic ion, and an initial conductivity of 1 to 200 ms / cm, preferably 10 to 200 ms / cm, such as the room-temperature molten salt described in International Publication No. 95 / 15572.

[0122] Examples of cations constituting the ionic liquid (G) include cations selected from the group consisting of amidinium, pyridinium, pyrazolium, and guanidinium cations.

[0123] Among these, the following are examples of amidinium cations. (1) Imidazolinium cation Examples include those with 5 to 15 carbon atoms, such as 1,2,3,4-tetramethylimidazolinium, 1,3-dimethylimidazolinium, and 1-ethyl-3-methylimidazolinium; (2) Imidazolium cation Examples include those with 5 to 15 carbon atoms, such as 1,3-dimethylimidazolium and 1-ethyl-3-methylimidazolium. (3) Tetrahydropyrimidinium cation Examples include those with 6 to 15 carbon atoms, such as 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium and 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium; (4) Dihydropyrimidinium cation Examples include those with 6 to 20 carbon atoms, such as 1,3-dimethyl-1,4-dihydropyrimidinium, 1,3-dimethyl-1,6-dihydropyrimidinium, 8-methyl-1,8-diazabicyclo[5,4,0]-7,9-undecadienium, and 8-methyl-1,8-diazabicyclo[5,4,0]-7,10-undecadienium.

[0124] Examples of pyridinium cations include those with 6 to 20 carbon atoms, such as 3-methyl-1-propylpyridinium and 1-butyl-3,4-dimethylpyridinium.

[0125] Examples of pyrazolium cations include those with 5 to 15 carbon atoms, such as 1,2-dimethylpyrazolium and 1-n-butyl-2-methylpyrazolium.

[0126] Examples of guanidinium cations include the following: (1) Guanidinium cation having an imidazolinium skeleton Examples include those with 8 to 15 carbon atoms, such as 2-dimethylamino-1,3,4-trimethylimidazolinium and 2-diethylamino-1,3,4-trimethylimidazolinium; (2) Guanidinium cation having an imidazolium skeleton Examples include those with 8 to 15 carbon atoms, such as 2-dimethylamino-1,3,4-trimethylimidazolium and 2-diethylamino-1,3,4-trimethylimidazolium; (3) Guanidinium cation having a tetrahydropyrimidinium skeleton Examples include those with 10 to 20 carbon atoms, such as 2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium and 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium; (4) Guanidinium cation having a dihydropyrimidinium skeleton Examples include those with 10 to 20 carbon atoms, such as 2-dimethylamino-1,3,4-trimethyl-1,4-dihydropyrimidinium, 2-dimethylamino-1,3,4-trimethyl-1,6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4-dihydropyrimidinium, and 2-diethylamino-1,3-dimethyl-4-ethyl-1,6-dihydropyrimidinium.

[0127] The cation may be used alone or in combination of two or more types. Of these, amidinium cation is preferred, more preferably imidazolium cation, and particularly preferably 1-ethyl-3-methylimidazolium cation, from the viewpoint of improving mechanical properties.

[0128] In the ionic liquid (G), the following are examples of organic or inorganic acids that constitute the anion. Examples of organic acids include carboxylic acids, sulfuric acid esters, sulfonic acids, and phosphate esters; examples of inorganic acids include superacids (e.g., borofluoric acid, tetraboric acid, perchloric acid, hexafluorinated phosphoric acid, hexafluorinated antimonylic acid, and hexafluorinated arsenic acid), phosphoric acid, and boric acid. The above organic and inorganic acids may be used individually or in combination of two or more.

[0129] Among organic and inorganic acids, those preferred from the viewpoint of improving the mechanical properties of the ionic liquid (G) are superacids, acids that form anions other than conjugate bases of superacids, and mixtures thereof, whose Hamett acidity function (-H0) of the anions constituting the ionic liquid is 12 to 100.

[0130] Examples of anions other than conjugate bases of superacids include halogen (e.g., fluorine, chlorine, and bromine) ions, alkyl (1 to 12 carbon atoms) benzenesulfonic acid (e.g., p-toluenesulfonic acid and dodecylbenzenesulfonic acid) ions, and poly(n=1 to 25) fluoroalkanesulfonic acid (e.g., undecafluoropentanesulfonic acid) ions.

[0131] Furthermore, superacids include protonic acids, those derived from combinations of protonic acids and Lewis acids, and mixtures thereof. Examples of protonic acids as superacids include bis(trifluoromethylsulfonyl)imide acid, bis(pentafluoroethylsulfonyl)imide acid, tris(trifluoromethylsulfonyl)methane, perchloric acid, fluorosulfonic acid, alkane (1 to 30 carbon atoms) sulfonic acid (e.g., methanesulfonic acid, dodecanesulfonic acid, etc.), poly(n=1 to 30)fluoroalkane (1 to 30 carbon atoms) sulfonic acid (e.g., trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, and tridecafluorohexanesulfonic acid), borofluoric acid, and tetrafluoroboric acid. Of these, borofluoric acid, trifluoromethanesulfonic acid, bis(trifluoromethanesulfonyl)imide acid, and bis(pentafluoroethylsulfonyl)imide acid are preferred from the viewpoint of ease of synthesis.

[0132] Examples of protic acids used in combination with Lewis acids include hydrogen halides (e.g., hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid, and mixtures thereof. Of these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of the ionic liquid.

[0133] Examples of Lewis acids include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and mixtures thereof. Of these, boron trifluoride and phosphorus pentafluoride are preferred from the viewpoint of the initial conductivity of the ionic liquid.

[0134] The combination of protonic acid and Lewis acid is arbitrary, but examples of superacids consisting of these combinations include tetrafluoroboric acid, hexafluorophosphate, tantalumic acid hexafluoride, antimonymic acid hexafluoride, tantalumsulfonic acid hexafluoride, boric acid tetrafluoride, phosphoric acid hexafluoride, triborate chloride, arsenic acid hexafluoride, and mixtures thereof.

[0135] Of these anions, the most preferred from the viewpoint of improving the mechanical properties of the ionic liquid (G) is the conjugate base of a superacid (a superacid consisting of a protonic acid and a superacid consisting of a combination of a protonic acid and a Lewis acid), and even more preferred are the superacid consisting of a protonic acid and the conjugate base of a superacid consisting of a protonic acid and boron trifluoride and / or phosphorus pentafluoride.

[0136] Among the ionic liquids (G), those preferred from the viewpoint of improving mechanical properties are ionic liquids having amidinium cations, more preferred are ionic liquids having 1-ethyl-3-methylimidazolium cations, and particularly preferred are 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide.

[0137] The ionic liquid (G) may be blended into the mechanical properties enhancer of the present invention, or it may be used blended with the mechanical properties enhancer of the present invention in a thermoplastic resin. From the viewpoint of improving mechanical properties, the amount of ionic liquid (G) blended is preferably 0.01 to 25 parts by mass, more preferably 0.1 to 25 parts by mass, even more preferably 3.0 to 20 parts by mass, and even more preferably 5.0 to 18 parts by mass, per 100 parts by mass of the mechanical properties enhancer of the present invention.

[0138] In the mechanical properties improving agent composition of the present invention, an alkali metal salt (F) and an ionic liquid (G) may be used in combination.

[0139] To obtain the mechanical properties improving agent composition of the present invention, one or more components selected from the group consisting of alkali metal salts (F) and ionic liquids (G) may be mixed with the mechanical properties improving agent of the present invention, and other optional components as needed. Various mixers can be used for mixing. Heating may be used during mixing. Examples of mixers that can be used include tumbler mixers, Henschel mixers, ribbon blenders, V-type mixers, W-type mixers, super mixers, Nauter mixers, etc. Alternatively, one or more components selected from the group consisting of alkali metal salts (F) and ionic liquids (G) may be added to the reaction system during the synthesis reaction of a polymer compound (E).

[0140] Furthermore, the mechanical properties enhancer of the present invention may be used as a mechanical properties enhancer composition having mechanical properties enhancement properties by incorporating a salt of a Group 2 element, to the extent that it does not impair the effects of the present invention. Examples of Group 2 element salts include salts of organic acids or inorganic acids, and examples of Group 2 elements include beryllium, magnesium, calcium, strontium, and barium. Examples of organic acids include aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, and lactic acid; aliphatic dicarboxylic acids having 1 to 12 carbon atoms such as oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, and adipic acid; aromatic carboxylic acids having benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; and sulfonic acids having 1 to 20 carbon atoms such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethanesulfonic acid. Examples of inorganic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphate, nitric acid, and perchloric acid.

[0141] Salts of Group 2 elements may be incorporated into the mechanical properties enhancer of the present invention, or they may be used in combination with the mechanical properties enhancer of the present invention in a thermoplastic resin. The amount of Group 2 element salt incorporated is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and most preferably 3.0 to 12 parts by mass, per 100 parts by mass of the mechanical properties enhancer of the present invention.

[0142] Furthermore, the mechanical properties improving agent of the present invention may be used as a mechanical properties improving agent composition having mechanical properties by incorporating a surfactant, to the extent that it does not impair the effects of the present invention. As the surfactant, nonionic, anionic, cationic, or amphoteric surfactants can be used. Examples of nonionic surfactants include polyethylene glycol-type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; polyhydric alcohol-type nonionic surfactants such as fatty acid esters of polyethylene oxide and glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol or sorbitan, alkyl ethers of polyhydric alcohols, and aliphatic amides of alkanolamines. Examples of anionic surfactants include carboxylates such as alkali metal salts of higher fatty acids; sulfate esters such as higher alcohol sulfates and higher alkyl ether sulfates; sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates; and phosphate esters such as higher alcohol phosphates. Examples of cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethyl betaine and higher alkyldihydroxyethyl betaine. These can be used alone or in combination of two or more. In the mechanical properties improving agent composition of the present invention, anionic surfactants are preferred among the above surfactants, and sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates are particularly preferred.

[0143] The surfactant may be incorporated into the mechanical properties enhancer of the present invention, or it may be used in combination with the mechanical properties enhancer of the present invention in a thermoplastic resin. The amount of surfactant to be incorporated is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and most preferably 1 to 10 parts by mass, per 100 parts by mass of the mechanical properties enhancer of the present invention.

[0144] Furthermore, the mechanical properties improving agent of the present invention may be combined with a compatibilizer to the extent that it does not impair the effects of the present invention, thereby forming a mechanical properties improving agent composition having mechanical properties improving properties. By combining with a compatibilizer, the compatibility between the mechanical properties improving agent of the present invention and fibrous fillers and thermoplastic resins can be improved. Examples of such compatibilizers include modified vinyl polymers having at least one functional group (polar group) selected from the group consisting of carboxyl groups, epoxy groups, amino groups, hydroxyl groups, and polyoxyalkylene groups, for example, polymers described in Japanese Patent Application Publication No. 3-258850, modified vinyl polymers having sulfonyl groups described in Japanese Patent Application Publication No. 6-345927, or block polymers having a polyolefin portion and an aromatic vinyl polymer portion.

[0145] Further preferred compatibilizers include acid anhydride-modified polyolefins such as maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, itaconic anhydride-modified polyethylene, and itaconic anhydride-modified polypropylene.

[0146] The compatibilizer may be blended into the mechanical properties enhancer of the present invention, or it may be used by blending it with the mechanical properties enhancer of the present invention in a thermoplastic resin. The amount of compatibilizer blended is preferably 0.1 to 15 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the mechanical properties enhancer of the present invention.

[0147] The mechanical properties improving agent composition of the present invention may contain other components as optional components, in addition to the mechanical properties improving agent of the present invention and the components listed above, as long as the effects of the present invention are not impaired. These other components may be directly incorporated into the mechanical properties improving agent composition, or they may be incorporated into a thermoplastic resin when the mechanical properties improving agent or the mechanical properties improving agent composition of the present invention is incorporated into a thermoplastic resin and used as a thermoplastic resin composition.

[0148] In the present invention, when a mechanical properties improving agent composition is blended into a thermoplastic resin composition containing fibrous filler, the amount blended is preferably 0.011 to 22.7 parts by mass, more preferably 0.022 to 11.4 parts by mass, even more preferably 0.055 to 5.8 parts by mass, and even more preferably 0.11 to 3.5 parts by mass, per 100 parts by mass of the total of the fibrous filler and thermoplastic resin, from the viewpoint of improving mechanical properties.

[0149] "Thermoplastic resin composition" Next, the thermoplastic resin composition of the present invention will be described. The thermoplastic resin composition of the present invention is characterized in that it is blended with a thermoplastic resin, a fibrous filler, and the mechanical properties enhancer of the present invention. Furthermore, another thermoplastic resin composition of the present invention is characterized in that it is blended with a thermoplastic resin, a fibrous filler, and the mechanical properties enhancer composition of the present invention. Hereinafter, the thermoplastic resin composition of the present invention and the other thermoplastic resin composition of the present invention will be collectively referred to as the thermoplastic resin composition of the present invention.

[0150] Examples of thermoplastic resins include polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, cross-linked polyethylene, ultra-high molecular weight polyethylene, α-olefin polymers such as polybutene-1, poly-3-methylpentene, poly-4-methylpentene, or polyolefin resins and copolymers thereof such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-propylene copolymer; polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid copolymer, vinyl chloride-maleic acid copolymer, vinyl chloride-cyclohexylmaleimide copolymer, and other halogen-containing resins; petroleum resins, coumarone resins, polystyrene, polyvinyl acetate, acrylic resins, styrene and / or α-methylstyrene and other monomers (e.g., maleic anhydride, phenylmaleimide, me) Copolymers with methyl tacrylate, butadiene, acrylonitrile, etc. (e.g., acrylonitrile-styrene copolymer (AS) resin, ABS resin, acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS) resin, styrene-butadiene-styrene block copolymer (SBS) resin, methyl methacrylate-butadiene-styrene copolymer (MBS) resin, heat-resistant ABS resin, etc.); polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; polyethylene terephthalate, polybutylene Aromatic polyesters such as polyalkylene terephthalates like polychlorohexanedimethylene terephthalate, polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate, and linear polyesters such as polytetramethylene terephthalate; biodegradable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid (PLA resin), polymalic acid, polyglycolic acid, polydioxane, and poly(2-oxetanone);Examples include polyamides such as polyphenylene oxide, polycaprolactam, and polyhexamethylene adipamide; polycarbonate (PC); polycarbonate / ABS resin; branched polycarbonate; polyacetal; polyphenylene sulfide; polyurethane; crystalline resins; polyimide resins; polysulfone; polyphenylene ether; polyether ketone; polyether ether ketone; liquid crystal polymers; thermoplastic resins; and blends thereof.

[0151] Furthermore, the thermoplastic resin may be an elastomer such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber, olefin-based elastomer, styrene-based elastomer, polyester-based elastomer, nitrile-based elastomer, nylon-based elastomer, vinyl chloride-based elastomer, polyamide-based elastomer, or polyurethane-based elastomer. Examples of thermoplastic resins that can be used in the present invention include fluororesins and silicone resins. In the resin composition of the present invention, these thermoplastic resins may be used individually or in combination of two or more. The thermoplastic resin may also be alloyed.

[0152] These thermoplastic resins can be used regardless of molecular weight, degree of polymerization, density, softening point, proportion of insoluble matter in the solvent, degree of stereoregularity, presence or absence of catalyst residue, type and blending ratio of raw material monomers, type of polymerization catalyst (e.g., Ziegler catalyst, metallocene catalyst, etc.), polymerization method (e.g., bulk polymerization, suspension polymerization, etc.).

[0153] Furthermore, the thermoplastic resin may be obtained from raw material monomers derived from fossil fuels, or from raw material monomers derived from biomass, and may also be a recycled resin obtained by methods such as material recycling or chemical recycling.

[0154] Among these thermoplastic resins, polyamide resins, polyester resins, polypropylene resins, and polycarbonate resins are preferred from the viewpoint of improving mechanical properties, with polyamide resins being more preferred.

[0155] Polyamide resins are polymers containing amide bonds, primarily made from amino acids, lactams, or diamines and dicarboxylic acids.

[0156] Examples of raw materials for polyamide resins include amino acids such as 6-aminocaproic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and para-aminomethylbenzoic acid; lactams such as γ-butyrolactam, δ-valerolactam, ε-caprolactam, and ω-laurolactam; ethylenediamine, 1,3-diaminopropane, tetramethylenediamine (1,4-diaminobutane), pentamethylenediamine (1,5-diaminopentane), hexamethylenediamine (1,6-diaminohexane), and heptamine. Methylenediamine (1,7-diaminoheptane), octamethylenediamine (1,8-diaminooctane), nonamethylenediamine (1,9-diaminononane), decamethylenediamine (1,10-diaminodecane), 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane Aliphatic diamines such as 1,20-diaminoeicosane, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclo Alicyclic diamines such as hexyl)propane, bis(aminopropyl)piperazine, aminoethylpiperazine, aromatic diamines such as metaxylylenediamine, paraxylylenediamine, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanediic acid, 1,3-cyclohexanedicarboxylic acid, 1,Examples include alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfisoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid, among other aromatic dicarboxylic acids. The polyamide resin may be a polyamide homopolymer derived from one of the above raw materials, or a copolymer derived from two or more of the above raw materials.

[0157] Specific examples of polyamide resins include polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polypentamethylene adipamide (polyamide 56), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebaamide (polyamide 610), polypentamethylene sebaamide (polyamide 510), polytetramethylene pimeraamide (nylon 47), polytetramethylene sveramide (polyamide 48), polytetramethylene azeramide (polyamide 49), and polytetramethylene sebaamide (poly Polyamide 410), Polytetramethylene undecamide (Polyamide 411), Polytetramethylene dodecamide (Polyamide 412), Polytetramethylene tridecanamide (Polyamide 413), Polytetramethylene tetradecanamide (Polyamide 414), Polytetramethylene pentadecanamide (Polyamide 415), Polytetramethylene hexadecanamide (Polyamide 416), Polytetramethylene heptadecanamide (Polyamide 417), Polytetramethylene octadecanamide (Polyamide 418), Polyhexamethylene dodeca Polyamide 612, Polyundecaneamide (Polyamide 11), Polydodecaneamide (Polyamide 12), Polycaproamide / Polyhexamethylene adipamide copolymer (Polyamide 6 / 66), Polycaproamide / Polyhexamethylene terephthalamide copolymer (Polyamide 6 / 6T), Polyhexamethylene adipamide / Polyhexamethylene terephthalamide copolymer (Polyamide 66 / 6T), Polyhexamethylene adipamide / Polyhexamethylene isophthalamide copolymer (Polyamide 66 / 6I), Polyhexamethylene Dipamide / Polyhexamethylene isophthalamide / Polycaproamide copolymer (Polyamide 66 / 6I / 6), Polyhexamethylene terephthalamide / Polyhexamethylene isophthalamide copolymer (Polyamide 6T / 6I), Polyhexamethylene terephthalamide / Polydecaneamide copolymer (Polyamide 6T / 12), Polyhexamethylene adipamide / Polyhexamethylene terephthalamide / Polyhexamethylene isophthalamide copolymer (Polyamide 66 / 6T / 6I), Polymetaxylylene adipamide (Polyamide MXD6),Polymeta-xylylene sebamid (polyamide MXD10), polypara-xylylene adipamide (polyamide PXD6), polypara-xylylene sebamid (polyamide PXD10), polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer (polyamide 6T / M5T), polyhexamethylene terephthalamide / polypentamethylene terephthalamide copolymer (polyamide 6T / 5T), polypentamethylene terephthalamide / polypentamethylene adipamide copolymer (5T / 56), polynonameethylene terephthalamide Examples include polyamide (polyamide 9T), polynonameethylene terephthalamide / poly2-methyl-1,8-octamethylene terephthalamide copolymer (polyamide 9T / M8T), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene terephthalamide / polyhexamethylene adipamide copolymer (polyamide 10T / 66), polydecamethylene terephthalamide / polyhexamethylene dodecamide copolymer (polyamide 10T / 612), polydodecamethylene terephthalamide (polyamide 12T), and copolymers thereof. Here, " / " indicates a copolymer, and the same applies hereafter. One of these polyamide resins may be used alone, or two or more may be used in combination.

[0158] Examples of fibrous fillers contained in the thermoplastic resin composition of the present invention include glass fibers, carbon fibers, graphite fibers, stainless steel fibers, metal fibers such as aluminum fibers and brass fibers, slag fibers, gypsum fibers, ceramic fibers, zirconia fibers, alumina fibers, silica fibers, silica-alumina fibers, titanium oxide fibers, boron nitride fibers, silicon nitride fibers, silicon carbide fibers, boron fibers, cellulose fibers, cellulose nanofibers, and rock wool.

[0159] Among these, glass fibers are preferred from the viewpoint of improving mechanical properties. The glass fibers may be treated with a surface treatment agent. Examples of such surface treatment agents include silane-based, titanate-based, aluminum-based, chromium-based, zirconium-based, and borane-based coupling agents, but among these, silane-based and titanate-based coupling agents are preferred, and silane-based coupling agents are particularly preferred. Examples of silane coupling agents include triethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-chloropropyltrimethoxysilane.

[0160] Furthermore, a consolidating agent may be used to bind the glass fibers together. Examples of consolidating agents include polypropylene resin, polyurethane resin, polyester resin, acrylic resin, epoxy resin, starch, and vegetable oil.

[0161] Glass fibers can also be used in the form of chopped strands, which are made by bundling single fibers together.

[0162] In the present invention, in a thermoplastic resin composition containing a fibrous filler into which a mechanical properties enhancer is blended, the content of the fibrous filler relative to the thermoplastic resin is preferably 1 to 80 parts by mass, more preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, even more preferably 15 to 55 parts by mass, and even more preferably 20 to 50 parts by mass, per 100 parts by mass of the total of the thermoplastic resin and the fibrous filler.

[0163] In the present invention, when a mechanical property enhancer is blended into a thermoplastic resin composition containing fibrous fillers, the amount blended is preferably 0.01 to 20 parts by mass, more preferably 0.02 to 10 parts by mass, even more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total of the fibrous filler and the thermoplastic resin, from the viewpoint of improving mechanical properties.

[0164] In the present invention, when a mechanical properties improving agent composition is blended into a thermoplastic resin composition containing fibrous filler, the amount blended is preferably 0.011 to 22.7 parts by mass, more preferably 0.022 to 11.4 parts by mass, even more preferably 0.055 to 5.8 parts by mass, and even more preferably 0.11 to 3.5 parts by mass, based on 100 parts by mass of the total of the fibrous filler and the thermoplastic resin, from the viewpoint of improving mechanical properties.

[0165] The method for compounding the mechanical property enhancer or mechanical property enhancer composition of the present invention into a thermoplastic resin is not particularly limited, and any commonly used method can be used. For example, it may be compounded by mixing and kneading using roll kneading, bumper kneading, an extruder, a kneader, etc. Furthermore, the mechanical property enhancer of the present invention may be added directly to the thermoplastic resin, or it may be added after impregnating a carrier as needed. To impregnate the carrier, it may be heated and mixed as is, or, as needed, it may be diluted with an organic solvent, impregnated into the carrier, and then the solvent may be removed. As such carriers, those known as fillers or fillers for thermoplastic resins, or flame retardants or light stabilizers that are solid at room temperature can be used. Examples include calcium silicate powder, silica powder, talc powder, alumina powder, titanium oxide powder, or carriers whose surfaces have been chemically modified, or solid flame retardants and antioxidants listed below. Among these carriers, those whose surfaces have been chemically modified are preferred, and those whose surfaces have been chemically modified silica powder are more preferred. These carriers are preferably those with an average particle size of 0.1 to 100 μm, and more preferably those with an average particle size of 0.5 to 50 μm.

[0166] As a method for compounding the mechanical properties enhancer of the present invention into a thermoplastic resin, a polymer compound (E) may be synthesized and compounded by kneading a block polymer (C) and an epoxy compound (D) having two or more epoxy groups simultaneously with the thermoplastic resin, and at that time, one or more selected from the group of alkali metal salts (F) and ionic liquids (G) may also be kneaded simultaneously. Alternatively, the mechanical properties enhancer of the present invention may be compounded by mixing it with the thermoplastic resin during molding, such as injection molding, to obtain a molded product, and at that time, one or more selected from the group of alkali metal salts (F) and ionic liquids (G) may also be compounded. Furthermore, a masterbatch of the mechanical properties enhancer of the present invention and a thermoplastic resin may be prepared in advance, and this masterbatch may be compounded, and at that time, one or more selected from the group of alkali metal salts (F) and ionic liquids (G) may also be compounded.

[0167] The thermoplastic resin composition of the present invention may optionally contain various additives such as phenolic antioxidants, phosphorus-based antioxidants, thioether-based antioxidants, ultraviolet absorbers, and hindered amine-based light stabilizers, thereby stabilizing the thermoplastic resin composition of the present invention.

[0168] These various additives, such as antioxidants, may be incorporated into the mechanical property enhancer or mechanical property enhancer composition of the present invention before being blended into the thermoplastic resin. Furthermore, they may be incorporated during the production of the polymer compound (E). In particular, incorporating antioxidants during the production of the polymer compound (E) is preferable because it can prevent oxidative degradation of the polymer compound (E) during production.

[0169] Examples of phenolic antioxidants include 2,6-diter-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl(3,5-diter-butyl-4-hydroxybenzyl)phosphonate, 1,6-hexamethylenebis[(3,5-diter-butyl-4-hydroxyphenyl)propionamide], 4,4'-thiobis(6-terter-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-terter-butylphenol), 2,2'-methylenebis(4-ethyl-6-terter-butylphenol), and 4,4'- Tylidenebis(6-tertiary butyl-m-cresol), 2,2'-ethylidenebis(4,6-ditertiary butylphenol), 2,2'-ethylidenebis(4-secondary butyl-6-tertiary butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tertiary butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tertiary butylbenzyl) isocyanurate, 1,3,5-tris(3,5-ditertiary butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-ditertiary butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-ditertiary butyl-4-hydroxybenzyl) Zyl)-2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, stearyl(3,5-ditert-butyl-4-hydroxyphenyl)propionate, tetrakis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate methyl]methane, thiodiethylene glycol bis[(3,5-ditert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene bis[(3,5-ditert-butyl-4-hydroxyphenyl)propionate] ], bis[3,3-bis(4-hydroxy-3-tertiary butylphenyl)butyric acid] glycol ester, bis[2-tertiary butyl-4-methyl-6-(2-hydroxy-3-tertiary butyl-5-methylbenzyl)phenyl] terephthalate, 1,3,5-tris[(3,5-ditertiary butyl-4-hydroxyphenyl)propionyloxyethyl] isocyanurate, 3,9-bis[1,1-dimethyl-2-{(3-tertiary butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5) Examples include undecane, triethylene glycol bis[(3-tertiary butyl-4-hydroxy-5-methylphenyl)propionate], etc. The amount of these phenolic antioxidants added is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of thermoplastic resin.

[0170] Examples of phosphorus-based antioxidants include trisnonylphenyl phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tridecyl phosphite, octyldiphenyl phosphite, di(decyl)monophenyl phosphite, di(tridecyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, bis(2,4-ditert-butylphenyl)pentaerythritol diphosphite, bis(2,6-ditert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4-tritert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tetra(tridecyl)isopropylidenediphenol diphosphite, tetra(tridecyl)-4,4'-n-butylidenebis(2- (Third-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tertiary butylphenyl)butane triphosphite, tetrakis(2,4-ditertiary butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis(4,6-tertiary butylphenyl)-2-ethylhexyl phosphite, 2 Examples include 2'-methylenebis(4,6-tertiary butylphenyl)-octadecyl phosphite, 2,2'-ethylidenebis(4,6-ditertiary butylphenyl)fluorophosphite, tris(2-[(2,4,8,10-tetrakistertiary butyldibenzo[d,f][1,3,2]dioxaphosphine-6-yl)oxy]ethyl)amine, and phosphites of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritertiary butylphenol. The amount of these phosphorus-based antioxidants added is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of thermoplastic resin.

[0171] Examples of thioether-based antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, as well as pentaerythritol tetra(β-alkylthiopropionic acid) esters. The amount of these thioether-based antioxidants added is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of thermoplastic resin.

[0172] Examples of UV absorbers include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-diter-butylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'- 2-(2'-hydroxyphenyl)benzotriazoles such as tertiary butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tertiary octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tertiary octyl-6-(benzotriazolyl)phenol), and 2-(2'-hydroxy-3'-tertiary butyl-5'-carboxyphenyl)benzotriazole; phenyl Benzoates such as lysilate, resorcinol monobenzoate, 2,4-diter-butylphenyl-3,5-diter-butyl-4-hydroxybenzoate, 2,4-diter-amylphenyl-3,5-diter-butyl-4-hydroxybenzoate, hexadecyl-3,5-diter-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β,β-diphenylacrylate, methyl Examples include cyanoacrylates such as 2-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; and triaryltriazines such as 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-diter-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, and 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-diter-butylphenyl)-s-triazine. The amount of these UV absorbers added is preferably 0.001 to 30 parts by mass, and more preferably 0.05 to 10 parts by mass, per 100 parts by mass of thermoplastic resin.

[0173] Examples of hindered amine-based light stabilizers include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, and tetrakis(2,2,6,6-tetramethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)·bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)·bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tertiary buty (4-hydroxybenzyl)malonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], 1,2,3,4-butanecarboxylic acid / 2,2-bis(hydroxymethyl)-1,3-propanediol / 3-hydroxy-2,2-dimethylpropanal / 1,2,2,6,6 -Pentamethyl-4-piperidinyl ester polycondensate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)=decandioate / methyl=1,2,2,6,6-pentamethyl-4-piperidyl=sebacate mixture, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / dibromoethane polycondensate, 1,6-bis(2,2,6,6-Tetramethyl-4-piperidylamino)hexane / 2,4-Dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-Dichloro-6-tertiaryoctylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl]-1 ,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-6-yl]-1,5,8,12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-ylamino]undecane, 1,6,11-tris[ 2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-6-ylamino]undecane, 3,9-bis[1,1-dimethyl-2-{tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonyl)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis[1,1-dimethyl-2-{tris(1,2,2,6, Examples of hindered amine compounds include 6-pentamethyl-4-piperidyloxycarbonyl)butylcarbonyloxyethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, bis(1-undecyloxy-2,2,6,6-tetramethylpiperidine-4-yl)carbonate, 2,2,6,6-tetramethyl-4-piperidylhexadecanoate, and 2,2,6,6-tetramethyl-4-piperidyloctadecanoate. The amount of these hindered amine-based light stabilizers added is preferably 0.001 to 30 parts by mass, and more preferably 0.05 to 10 parts by mass, per 100 parts by mass of thermoplastic resin.

[0174] Furthermore, when using a polyolefin resin as the thermoplastic resin, it is preferable to add a known neutralizing agent to neutralize the residual catalyst in the polyolefin resin as needed, to the extent that it does not impair the effects of the present invention. Examples of neutralizing agents include fatty acid metal salts such as calcium stearate, lithium stearate, and sodium stearate, or fatty acid amide compounds such as ethylenebis(stearoamide), ethylenebis(12-hydroxystearoamide), and stearamide, and these neutralizing agents may be used in mixtures.

[0175] The thermoplastic resin composition of the present invention may also contain, as necessary, other additives, to the extent that they do not impair the effects of the present invention, such as nucleating agents including aromatic carboxylate metal salts, alicyclic alkyl carboxylate metal salts, p-ter-butylbenzoate aluminum, aromatic phosphate ester metal salts, dibenzylidene sorbitols, metal soaps, hydrotalcite, triazine ring-containing compounds, metal hydroxides, phosphate ester flame retardants, condensed phosphate ester flame retardants, phosphate flame retardants, inorganic phosphorus flame retardants, (poly)phosphate flame retardants, halogenated flame retardants, silicon flame retardants, antimony oxide such as antimony trioxide, other inorganic flame retardant aids, other organic flame retardant aids, fillers, pigments, lubricants, processing aids, plasticizers, reinforcing materials, antioxidants, wood flour, foaming agents, etc.

[0176] Examples of triazine ring-containing compounds include melamine, ammeline, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornenediguanamine, methylenediguanamine, ethylenedimelamine, trimethylenedimelamine, tetramethylenedimelamine, hexamethylenedimelamine, and 1,3-hexylenedimelamine.

[0177] Examples of metal hydroxides include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, and Kissmer 5A (magnesium hydroxide: manufactured by Kyowa Chemical Industry Co., Ltd.).

[0178] Examples of phosphate ester-based flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, trixylenyl phosphate, octyldiphenyl phosphate, xylenyldiphenyl phosphate, trisisopropylphenyl phosphate, 2-ethylhexyldiphenyl phosphate, t-butylphenyldiphenyl phosphate, bis-(t-butylphenyl)phenyl phosphate, tris-(t-butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis-(isopropylphenyl)diphenyl phosphate, and tris-(isopropylphenyl) phosphate.

[0179] Examples of condensed phosphate ester flame retardants include 1,3-phenylenebis(diphenyl phosphate), 1,3-phenylenebis(dixylenyl phosphate), and bisphenol Abis(diphenyl phosphate).

[0180] Examples of (poly)phosphate flame retardants include ammonium salts and amine salts of (poly)phosphates such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melamine pyrophosphate, and piperazine pyrophosphate.

[0181] Other inorganic flame retardants include, for example, inorganic compounds such as titanium dioxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, and montmorillonite, as well as surface-treated products thereof. Various commercially available products can be used, such as TIPAQUE R-680 (titanium dioxide: manufactured by Ishihara Sangyo Co., Ltd.), Kyowa Mag 150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.), and Alkamizer 4 (zinc-modified hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.). Other organic flame retardants include, for example, pentaerythritol.

[0182] Anti-aging agents include naphthylamines, diphenylamines, p-phenyldiamines, quinolines, hydroquinone derivatives, monophenols, thiobisphenols, hindered phenols, and phosphite esters.

[0183] Examples of nucleating agents include inorganic and organic nucleating agents. Specific examples of inorganic nucleating agents include kaolinite, synthetic mica, clay, zeolite, silica, graphite, carbon black, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, barium sulfate, aluminum oxide, neodymium oxide, and metal salts such as phenylphosphonate. These inorganic nucleating agents may be modified with organic substances to improve their dispersibility in the composition.

[0184] Specific examples of organic 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, barium stearate, sodium montanaate, calcium montanaate, sodium tolulate, sodium salicylate, potassium salicylate, zinc salicylate, and Examples include metal salts of organic carboxylic acids such as luminium dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, and sodium cyclohexanecarboxylate; organic sulfonates such as sodium p-toluenesulfonate and sodium sulfisophthalate; carboxylic acid amides such as stearic acid amide, ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, and tris(t-butylamide) trimesinate; benzylidene sorbitol and its derivatives; metal salts of phosphorus compounds such as sodium-2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate; and sodium 2,2-methylbis(4,6-di-t-butylphenyl).

[0185] Examples of lubricants include pure hydrocarbon lubricants such as liquid paraffin, natural paraffin, microwax, synthetic paraffin, low molecular weight polyethylene, and polyethylene wax; halogenated hydrocarbon lubricants; fatty acid lubricants such as higher fatty acids and oxy fatty acids; fatty acid amide lubricants such as fatty acid amides and bis-fatty acid amides; ester lubricants such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, and fatty alcohol esters of fatty acids (ester waxes); lubricants such as metal soaps, fatty alcohols, polyhydric alcohols, polyglycols, polyglycerols, partial esters of fatty acids and polyhydric alcohols, partial esters of fatty acids and polyglycols, and polyglycerols; as well as silicone oils and mineral oils.

[0186] Examples of processing aids include acrylic processing aids, which can be obtained by polymerizing one type of (meth)acrylic acid ester or copolymerizing two or more types. Examples of (meth)acrylic acid esters to be polymerized or copolymerized include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, isobutyl acrylate, t-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, and other (meth)acrylic acid esters. In addition to the above, (meth)acrylic acid and (meth)acrylic acid esters containing hydroxyl groups can also be used.

[0187] Examples of plasticizers include polyester-based plasticizers, glycerin-based plasticizers, polycarboxylic acid ester-based plasticizers, polyalkylene glycol-based plasticizers, ether ester-based plasticizers, and epoxy-based plasticizers.

[0188] Examples of fillers include talc, calcium carbonate, silica, clay, kaolin, alumina, and carbon black. These fillers may be subjected to processing such as pulverization or micronization, or surface treatment. The fillers are not fibrous, but rather in the form of plates or granules.

[0189] Wood powder is used to impart the wood grain pattern and texture of natural wood to molded articles obtained from thermoplastic resin compositions, giving them a color tone and texture close to that of natural wood. It is used for building materials such as interior materials for vehicles, side moldings, interior materials for houses, exterior building materials, flooring materials such as terraces, balconies, and decking, civil engineering materials, wooden walkways in wetlands in nature parks, handrails covered on steel pipes, table frames, gaskets, etc. The average particle size of the wood powder is preferably 30 to 500 μm, and more preferably 100 to 200 μm. An average particle size exceeding 500 μm tends to result in a poor surface condition of the molded article, which is undesirable. The type of wood used for the wood powder is not particularly limited, but coniferous trees such as cedar, lauan, hemlock, and cypress are preferred. Wood powder obtained from hardwoods can also be used depending on the intended use. In addition, finely ground sawdust, rice husks, and surface polishing powder of particleboard can also be used. There are no particular limitations on the method for turning wood powder into a fine powder; for example, one method is to finely grind chipped wood using a dry pulverizer.

[0190] In addition, the thermoplastic resin of the present invention may, as necessary and within limits that do not impair the effects of the present invention, contain additives commonly used in thermoplastic resins, such as crosslinking agents, antifogging agents, plate-out inhibitors, surface treatment agents, flame retardants other than those described above, fluorescent agents, antifungal agents, disinfectants, metal deactivators, mold release agents, pigments, antioxidants other than those described above, and light stabilizers other than those described above, within limits that do not impair the effects of the present invention.

[0191] The additives incorporated into the thermoplastic resin of the present invention may be added directly to the thermoplastic resin, or they may be incorporated into the mechanical properties enhancer or mechanical properties enhancer composition of the present invention before being added to the thermoplastic resin.

[0192] "Molded body" Next, the molded article of the present invention will be described. The molded articles of the present invention can be obtained by molding the thermoplastic resin composition of the present invention. The molding method is not particularly limited and includes extrusion, calendering, injection molding, roll molding, compression molding, blow molding, rotational molding, etc. Various shapes of molded articles such as resin plates, sheets, films, bottles, fibers, and irregularly shaped products can be manufactured.

[0193] Molded articles obtained using the thermoplastic resin composition of the present invention exhibit excellent mechanical properties such as flexural strength, flexural modulus, Izod impact strength, and heat distortion temperature.

[0194] The thermoplastic resin composition of the present invention and molded articles using the same can be used in a wide range of industrial fields, including electrical and electronic communications, agriculture, forestry and fisheries, mining, construction, food, textiles, clothing, medical, coal, petroleum, rubber, leather, automobiles, precision instruments, timber, building materials, civil engineering, furniture, printing, and musical instruments.

[0195] More specifically, the thermoplastic resin composition of the present invention and molded articles using the same are used in applications such as printers, personal computers, word processors, keyboards, PDAs (personal digital assistants), telephones, photocopiers, facsimile machines, ECRs (electronic cash registers), calculators, electronic organizers, cards, holders, stationery, and other office and OA equipment; home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, game consoles, irons, and kotatsu (heated tables); AV equipment such as TVs, VTRs, video cameras, radio cassette players, tape recorders, MiniDiscs, CD players, speakers, and liquid crystal displays; electrical and electronic components and communication equipment such as connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulating materials, LED encapsulating materials, electric wires, cables, transformers, deflection yokes, distribution boards, and clocks; automotive interior and exterior materials; printing plates, adhesive films, bottles, food containers, food packaging films, pharmaceutical and medical wrap films, product packaging films, agricultural films, agricultural sheets, and greenhouse films.

[0196] Furthermore, the thermoplastic resin composition of the present invention and molded articles using the same can be used for (filling, surface materials, etc.), belts, ceiling coverings, convertible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, wheel covers, mattress covers, airbags, insulating materials, handrails, handrail straps, wire coverings, electrical insulating materials, paints, coatings, upholstery materials, flooring materials, corner walls, carpets, wallpaper, wall coverings, exterior materials, interior materials, roofing materials, decking materials, and walls. It can be used for a variety of applications, including materials for automobiles, vehicles, ships, aircraft, buildings, houses and construction, civil engineering materials such as lumber, pillars, baseboards, fence materials, frameworks and moldings, window and door profiles, shingles, paneling, terraces, balconies, soundproofing boards, insulation boards, window materials, etc., as well as household goods and sports equipment such as clothing, curtains, sheets, nonwoven fabrics, plywood, synthetic fiberboards, carpets, doormats, sheets, buckets, hoses, containers, eyeglasses, bags, cases, goggles, skis, rackets, tents, musical instruments, and more. [Examples]

[0197] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following examples, "%", "ppm", and "parts" are based on mass unless otherwise specified.

[0198] Polymer compound (E) was manufactured according to the manufacturing example below. In the manufacturing example below, the number-average molecular weight of compound (b) was calculated according to the method for calculating the number-average molecular weight from the hydroxyl value described below, and the number-average molecular weights of compounds other than compound (b) were calculated according to the method for measuring the number-average molecular weight in polystyrene equivalent described below.

[0199] <Method for calculating the number-average molecular weight from the hydroxyl value> The hydroxyl value was measured according to the method for measuring hydroxyl value described below, and the number-average molecular weight was determined according to the formula below. Number-average molecular weight = (56110 × 2) / hydroxyl value

[0200] <Method for measuring hydroxyl value> • Reagent A (acetylating agent) (1) Triethyl phosphate 1560 mL (2) Acetic anhydride 193 mL (3) Perchloric acid (60%) 16g The reagents listed above were mixed in the order of (1) → (2) → (3). Reagent B Pyridine and pure water were mixed in a volume ratio of 3:1. Reagent C 500 mL of isopropyl alcohol was mixed with 2-3 drops of phenolphthalein solution and neutralized with 1N-KOH aqueous solution.

[0201] First, 2 g of the sample was weighed into a 200 mL Erlenmeyer flask, 10 mL of triethyl phosphate was added, and it was heated until dissolved. 15 mL of reagent A was added, the flask was stoppered, and the mixture was shaken vigorously. 20 mL of reagent B was added, the flask was stoppered, and the mixture was shaken vigorously. 50 mL of reagent C was added. The solution was titrated with 1N KOH aqueous solution and calculated according to the following formula.

[0202] Hydroxyl value [mgKOH / g] = 56.11 × f × (TB) / S f: Factor of 1N-KOH aqueous solution B: Blank titration volume [mL] T: Titration volume for this test [mL] S: Sample volume [g]

[0203] <Method for measuring the number-average molecular weight based on polystyrene equivalent> The number-average molecular weight (Mn) was measured by the GPC method. The measurement conditions for Mn were as follows:

[0204] Equipment: GPC instrument manufactured by JASCO Corporation Solvent: Chloroform Reference material: Polystyrene Detector: Differential refractometer (RI detector) Column stationary phase: Shodex LF-804 manufactured by Showa Denko Corporation Column temperature: 40℃ Sample concentration: 1 mg / 1 mL Flow rate: 0.8mL / min. Injection volume: 100μL

[0205] [Manufacturing Example 1] Manufacturing of polymer compound (E)-1 In a separable flask, 122 g (1.35 mol) of 1,4-butanediol (a1)-1 and 168 g (1.42 mol) of succinic acid (a2)-1 were polymerized at atmospheric pressure for 3 hours while gradually increasing the temperature from 140°C to 190°C, in the presence of 0.2 g of an antioxidant (tetrakis[3-(3,5-diter-butyl-4-hydroxyphenyl)propionyloxymethyl]methane, ADEKA Stab AO-60, manufactured by ADEKA Corporation), to obtain polyester (a)-1. The number-average molecular weight Mn of the obtained polyester (a)-1 was 3,000.

[0206] Next, 250 g of the obtained polyester (a)-1, 160 g of polyethylene glycol (b)-1 with a number average molecular weight of 3,300 as compound (b) having hydroxyl groups at both ends, 0.2 g of antioxidant (Adekastab AO-60), and 0.4 g of zirconium octate were added, and polymerization was carried out at 200°C for 3 hours under reduced pressure to obtain 400 g of block polymer (C)-1 having a structure with carboxyl groups at both ends. The number average molecular weight Mn of this block polymer (C)-1 having a structure with carboxyl groups at both ends was 16,500.

[0207] 400 g of the resulting block polymer (C)-1, which has a structure with carboxyl groups at both ends, was charged with 3 g of bisphenol F diglycidyl ether (epoxy equivalent 170 g / eq) as epoxy compound (D)-1 having two or more epoxy groups, and polymerized under reduced pressure at 220°C for 5 hours to obtain polymer compound (E)-1.

[0208] [Manufacturing Example 2] Manufacturing of Polymer Compound (E)-2 In a separable flask, 656 g of 1,4-cyclohexanedimethanol(a1)-2, 708 g of adipic acid(a2)-2, 0.7 g of phthalic anhydride(a2)-3, and 0.7 g of antioxidant (tetrakis[3-(3,5-diter-butyl-4-hydroxyphenyl)propionyloxymethyl]methane, ADEKA stab AO-60, manufactured by ADEKA Corporation) were charged. Polymerization was carried out at atmospheric pressure for 4 hours while gradually increasing the temperature from 160°C to 210°C, and then at 210°C under reduced pressure for 3 hours to obtain polyester(a)-2. The number-average molecular weight Mn of the obtained polyester(a)-2 was 5,400.

[0209] Next, 600 g of the obtained polyester (a)-2, 300 g of polyethylene glycol (b)-2 with a number average molecular weight of 4,000 as compound (b) having hydroxyl groups at both ends, 0.5 g of antioxidant (Adekastab AO-60), and 0.8 g of zirconium octate were added, and polymerization was carried out at 210°C for 7 hours under reduced pressure to obtain block polymer (C)-2 having a structure with carboxyl groups at both ends. The number average molecular weight Mn of this block polymer (C)-2 having a structure with carboxyl groups at both ends was 12,000.

[0210] 360 g of the resulting block polymer (C)-2, which has a structure with carboxyl groups at both ends, was charged with 6 g of bisphenol F diglycidyl ether (epoxy equivalent 170 g / eq) as epoxy compound (D)-1, and polymerized under reduced pressure at 240°C for 3 hours to obtain polymer compound (E)-2.

[0211] [Manufacturing Example 3] Manufacturing of Polymer Compound (E)-3 In a separable flask, 111 g of 1,4-cyclohexanedimethanol(a1)-3, 122 g of adipic acid(a2)-2, 0.1 g of phthalic anhydride(a2)-3, and 0.4 g of antioxidant (tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane, ADEKA stab AO-60, manufactured by ADEKA Corporation) were charged. Polymerization was carried out at atmospheric pressure for 4 hours while gradually increasing the temperature from 170°C to 215°C, and then at 215°C under reduced pressure for 3 hours to obtain polyester(a)-3. The number-average molecular weight Mn of the obtained polyester(a)-3 was 2931.

[0212] Next, 205 g of the obtained polyester (a)-3, a mixture (b)-3 consisting of 144 g of polyethylene glycol with a number average molecular weight of 3650 and 40 g of polytetramethylene glycol with a number average molecular weight of 3042 (the proportion of polytetramethylene glycol being 25 mol% of the total number of moles of polyethylene glycol and polytetramethylene glycol), 0.4 g of antioxidant (Adekastab AO-60), and 3.4 g of zirconium octate were charged together. Polymerization was carried out under reduced pressure for 7 hours while gradually increasing the temperature from 215°C to 240°C to obtain block polymer (C)-3 having a structure with carboxyl groups at both ends. The number average molecular weight Mn of this block polymer (C)-3 having a structure with carboxyl groups at both ends was 22109.

[0213] 392 g of the resulting block polymer (C)-3, which has a structure with carboxyl groups at both ends, was charged with 4.0 g of polypropylene glycol diglycidyl ether (number average molecular weight 530, epoxy equivalent 300 g / eq) as epoxy compound (D)-2, and polymerized under reduced pressure at 240°C for 3 hours to obtain 396 g of polymer compound (E)-3.

[0214] [Examples 1-26, Comparative Examples 1-6] Test specimens were obtained using the thermoplastic resin compositions of each example and comparative example, blended according to the proportions (parts by mass) listed in Tables 1 to 5 below, and following the specimen preparation conditions shown below. The Charpy impact strength, flexural strength, flexural modulus, and heat distortion temperature were measured using the obtained test specimens under the following conditions. The results are shown in Tables 1 to 5.

[0215] <Conditions for preparing test specimens of polyamide resin (polyamide 66) composition> Based on the blending amounts shown in Tables 1-5 below, the polyamide resin composition was granulated using a twin-screw segment extruder (2D30W2) manufactured by Toyo Seiki Co., Ltd. at 270°C and 3 kg / hour to obtain pellets.

[0216] The obtained pellets were molded using a horizontal injection molding machine (NEX80: manufactured by Nissei Plastic Industrial Co., Ltd.) under processing conditions of resin temperature 270°C and mold temperature 85°C to obtain test specimens (80 mm × 10 mm × 4 mm) for flexural strength, flexural modulus, Charpy impact strength, and thermal deformation temperature. Polyamide 66 used was Leona 1042S, manufactured by Asahi Kasei Corporation.

[0217] <Charpy impact strength> Measurements were taken in accordance with ISO 179-1 (with notches).

[0218] <Bending strength> Measurements were taken in accordance with ISO 178.

[0219] <Flexural modulus> Measurements were taken in accordance with ISO 178.

[0220] <Heat distortion temperature> Measurements were taken in accordance with ISO 75-2.

[0221] [Table 1] *1: Manufactured by Asahi Kasei Corporation. Product name: Leona 1042S *2: CS3PE-455S manufactured by Nitto Boseki Co., Ltd. *3: Sodium dodecylbenzenesulfonate *4: 1-Ethyl-3-methylimidazolium dodecylbenzene sulfonate

[0222] [Table 2] *1: Manufactured by Asahi Kasei Corporation. Product name: Leona 1042S *2: CS3PE-455S manufactured by Nitto Boseki Co., Ltd. *3: Sodium dodecylbenzenesulfonate *4: 1-Ethyl-3-methylimidazolium dodecylbenzene sulfonate

[0223] [Table 3] *1: Manufactured by Asahi Kasei Corporation. Product name: Leona 1042S *2: CS3PE-455S manufactured by Nitto Boseki Co., Ltd. *3: Sodium dodecylbenzenesulfonate *4: 1-Ethyl-3-methylimidazolium dodecylbenzene sulfonate

[0224] [Table 4] *1: Manufactured by Asahi Kasei Corporation. Product name: Leona 1042S *2: CS3PE-455S manufactured by Nitto Boseki Co., Ltd. *3: Sodium dodecylbenzenesulfonate *4: 1-Ethyl-3-methylimidazolium dodecylbenzene sulfonate

[0225] [Table 5] *1: Manufactured by Asahi Kasei Corporation. Product name: Leona 1042S *2: CS3PE-455S manufactured by Nitto Boseki Co., Ltd. *3: Sodium dodecylbenzenesulfonate *4: 1-Ethyl-3-methylimidazolium dodecylbenzene sulfonate

[0226] From the above, it can be seen that the mechanical property enhancer of the present invention can improve the mechanical properties of thermoplastic resins containing fibrous fillers, and can provide molded articles with excellent mechanical properties.

Claims

1. A mechanical property enhancer for a thermoplastic resin composition containing fibrous fillers, characterized by containing one or more polymer compounds (E) obtained by reacting a polyester (a) obtained by reacting a diol (a1) and a dicarboxylic acid (a2), a compound (b) having hydroxyl groups at both ends, and an epoxy compound (D) having two or more epoxy groups.

2. The polymer compound (E) comprises a polyester block (A) composed of the polyester (a) and a polyether block (B) composed of the compound (b), A mechanical property enhancer for a fibrous filler-containing thermoplastic resin composition according to claim 1, having a structure in which the polyester block (A), the polyether block (B), and the epoxy compound (D) are linked via ester bonds or ether bonds.

3. A mechanical property enhancer for a fibrous filler-containing thermoplastic resin composition according to claim 2, wherein the polymer compound (E) has a structure in which a block polymer (C) having carboxyl groups at both ends is formed by repeatedly and alternately bonding a polyester block (A) and a polyether block (B) via ester bonds, and the epoxy compound (D) is bonded via ester bonds.

4. A mechanical property improving agent composition for a fibrous filler-containing thermoplastic resin composition, characterized by containing one or more selected from the group consisting of alkali metal salts (F) and ionic liquids (G), and a mechanical property improving agent according to any one of claims 1 to 3.

5. A thermoplastic resin composition characterized by containing a thermoplastic resin, a fibrous filler, and a mechanical property enhancer according to any one of claims 1 to 3.

6. A thermoplastic resin composition characterized by containing a thermoplastic resin, a fibrous filler, and the mechanical property improving agent composition according to claim 4.

7. A molded article characterized by being obtained from the thermoplastic resin composition described in claim 5.

8. A molded article characterized by being obtained from the thermoplastic resin composition described in claim 6.

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