JP2013249363A - Polyamide resin composition and resin metal complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition excellent in fluidity and capable of producing a molded product excellent in mechanical characteristics and metal adhesion.SOLUTION: A polyamide resin composition includes: 100 pts.wt. of a polyamide resin (A); 0.1-4 pts.wt. of a rubbery polymer (B); and 0.01-10 pts.wt. of a dendritic polyester resin (C) showing melt liquid crystallinity. The dendritic polyester resin (C) includes at least one kind of structural unit selected from the group consisting of an aromatic oxycarbonyl unit (P), an aromatic and/or aliphatic dioxy unit (Q), and an aromatic dicarboxy unit (R), and a trifunctional or higher functional organic residue (S) in an amount of 7.5-50 mol% based on the total structural units constituting the dendritic polyester.

Description

  The present invention relates to a polyamide resin composition, a molded article using the same, and a resin metal composite.

  Thermoplastic resins, especially engineering plastics that are excellent in mechanical properties and thermal properties, are used in various applications by taking advantage of the excellent properties. Polyamide resin, which is a kind of engineering plastic, has an excellent balance between mechanical properties and toughness, and is therefore used for various electrical / electronic parts, mechanical parts, automobile parts, etc. mainly in injection molding. Depending on the application, high impact resistance may be required in addition to strength and rigidity, and in recent years, development of materials using polymer alloys has been actively promoted (for example, see Patent Documents 1 and 2).

  On the other hand, it is used to meet the demands for such design freedom as the moldings become thinner and the electrical and electronic parts become smaller and more precise due to the modularization and weight reduction of large automotive parts. The material is also required to improve fluidity. On the other hand, a technique is known in which fluidity is improved by mixing a branched liquid crystalline resin with a thermoplastic resin, and various studies have been made so far (see, for example, Patent Documents 3 to 4). ).

  In recent years, due to the trend toward higher performance of electrical and electronic equipment, component design using a composite of a resin member and a metal member has become mainstream. In such a composite material, high adhesion between the resin and the metal is important in order to obtain waterproofness and sealing properties. However, it is known that the adhesion between the resin and the metal decreases due to a difference in linear expansion coefficient due to a temperature change. As a technique for improving the adhesion between the resin and the metal, a resin in which inorganic fibers are dispersed is used to suppress the expansion and contraction of the resin member during heat treatment, and the surface is modified by chemical etching of the metal surface during insert molding. Quality etc. are examined (for example, refer patent documents 5-6).

JP 2010-195853 A International Publication No. 2010/107022 JP 2008-31441 A JP 2011-195814 A JP 2010-274456 A International Publication No. 2009/151099

  However, the techniques as disclosed in Patent Documents 1 to 4 have a problem that metal adhesion is insufficient. On the other hand, the techniques disclosed in Patent Documents 5 to 6 are based on the suppression of expansion and contraction due to the addition of inorganic fibers or the surface modification of the metal, and there is still a problem that the metal adhesion is still insufficient. .

  This invention makes it a subject to provide the polyamide resin composition which can obtain the molded article which is excellent in fluidity | liquidity and excellent in a mechanical characteristic and metal adhesiveness.

  In the present invention, as a result of intensive studies to solve such problems, a polyamide resin composition comprising a polyamide resin, a rubbery polymer, and a branched liquid crystalline polyester resin having a multi-terminal structure is excellent in fluidity. The present inventors have found that it is possible to obtain a molded article that is excellent in mechanical properties and metal adhesion, and that exhibits a particularly high metal adhesion even in a wet and heat environment.

That is, the present invention has the following configuration.
1. 0.1 to 4 parts by weight of the rubbery polymer (B) and 100 parts by weight of the polyamide resin (A), and the aromatic oxycarbonyl unit (P), aromatic and / or aliphatic dioxy unit (Q) And at least one structural unit selected from aromatic dicarboxy units (R) and a trifunctional or higher functional organic residue (S), and the S content constitutes the dendritic polyester. A polyamide resin composition obtained by blending 0.01 to 10 parts by weight of a dendritic polyester resin (C) having a melt liquid crystallinity in a range of 7.5 to 50 mol% in a unit.
2. 2. The polyamide resin composition according to 1 above, wherein 0.1 to 200 parts by weight of an inorganic filler is further blended with 100 parts by weight of the polyamide resin (A).
3. 3. The polyamide resin composition according to any one of 1 to 2 above, wherein the rubber polymer (B) contains an olefin resin.
4). 4. The polyamide resin composition according to 3 above, wherein the olefin-based resin contains at least one selected from an ethylene / unsaturated carboxylic acid copolymer and an ethylene / unsaturated carboxylic acid ester copolymer.
5. The ethylene / unsaturated carboxylic acid copolymer has an ionomer structure in which at least a part of the unsaturated carboxylic acid is a metal salt and the molecules of the ethylene / unsaturated carboxylic acid copolymer are crosslinked with metal ions. 5. The polyamide resin composition according to 4.
6). A molded article obtained by melt-molding the polyamide resin composition according to any one of 1 to 5 above.
7). A resin-metal composite having a polyamide resin member and a metal member formed by melt-molding the polyamide resin composition according to any one of 1 to 5 above, wherein the metal member is in contact with the polyamide resin member body.
8). 7. A molded article for electrical / electronic parts as described in 6 above.
9. 8. The resin metal composite for electrical / electronic parts according to 7 above.

  The polyamide resin composition of the present invention can provide a molded article having excellent fluidity and excellent mechanical properties and metal adhesion.

  The polyamide resin (A) referred to in the present invention is a resin composed of a polymer having an amide bond, and mainly contains amino acids, lactams or diamines and dicarboxylic acids. By blending the polyamide resin (A), mechanical properties such as strength and rigidity of the molded product can be improved.

  Representative examples of the main components of the polyamide resin (A) include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, ε-caprolactam, ω-laurolactam, and the like. Lactam, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylene Aliphatic diamines such as diamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, aromatic diamines such as bis (aminopropyl) piperazine, aminoethylpiperazine, 1,3-bis (aminomethyl) cyclo Hexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) ) Aliphatic diamines such as methane, 2,2-bis (4-aminocyclohexyl) propane, aliphatic dicarboxylic acids such as adipic acid, peric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, Aromatic dicarboxylic acids such as 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, , 4-cyclohexanedicarboxylic acid, 1,3-cyclohexane Such Sanji carboxylic acid and 1,3-alicyclic dicarboxylic acids such as cyclopentane dicarboxylic acid. In the present invention, nylon homopolymers or copolymers derived from these raw materials can be used alone or in combination of two or more.

  In the present invention, a particularly useful polyamide resin is a polyamide resin having a melting point of 150 ° C. or more and excellent in heat resistance and strength. Specific examples include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polypentamethylene adipamide (nylon 56), polytetramethylene adipamide (nylon 46), polyhexa Methylene sebacamide (nylon 610), polypentamethylene sebacamide (nylon 510), polytetramethylene sebacamide (nylon 410), polyhexamethylene dodecamide (nylon 612), polyundecanamide (nylon 11), poly Dodecanamide (nylon 12), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6/66), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / poly Hexamethylene Rephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (nylon) 66 / 6I / 6), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / polydodecanamide copolymer (nylon 6T / 12), polyhexamethylene adipamide / Polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene adipamide (nylon XD6), polyhexamethylene tele Taramide / poly-2-methylpentamethylene terephthalamide copolymer (nylon 6T / M5T), polyhexamethylene terephthalamide / polypentamethylene terephthalamide copolymer (nylon 5T / 6T), polynonamethylene terephthalamide (nylon 9T), polydeca Examples include methylene terephthalamide (nylon 10T) and copolymers thereof. Two or more of these may be blended.

  Among these, preferred polyamide resins include hexagons such as nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 6/66, nylon 6T / 66, nylon 6T / 6I, nylon 6T / 12, and nylon 6T / 6. A polyamide resin having a methylene terephthalamide unit can be exemplified, and nylon 6, nylon 66, and nylon 610 are particularly preferable.

  The degree of polymerization of these polyamide resins is not particularly limited, but the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is in the range of 1.5 to 7.0. Particularly preferred is a polyamide resin in the range of 1.8 to 6.0.

There is no particular limitation on the amino end group concentration of the polyamide resin is preferably not more than ¹⁰ × 10 -5 mol / g, more preferably at most ^{8 × 10 -5 mol / g,} 6 × 10 -5 mol / g or less Is particularly preferred.

  In the present invention, the rubbery polymer (B) generally refers to a polymer having a glass transition temperature lower than room temperature, and some of the intermolecular molecules are caused by covalent bonds, ionic bonds, van der Waals forces, entanglement, etc. Polymers that are constrained to each other. By compounding the rubber polymer (B), the metal adhesion of the molded product can be remarkably improved by the interaction with the dendritic polyester resin (C) described later. Examples of the rubbery polymer include olefin resins, acrylic rubbers, silicon rubbers, fluorine rubbers, urethane rubbers, polyamide elastomers, and polyester elastomers. Two or more of these may be used. Among these, an olefin resin is preferably used from the viewpoint of compatibility with the polyamide resin (A).

  The olefin resin is a thermoplastic resin obtained by polymerizing or copolymerizing an olefin monomer having an unsaturated double bond such as unsaturated hydrocarbon, unsaturated carboxylic acid, acid anhydride or derivative thereof. Copolymerization of unsaturated hydrocarbons with unsaturated carboxylic acids, acid anhydrides and derivatives thereof is excellent in compatibility with the polyamide resin (A) and can further improve the impact resistance of the molded product. Preferably used.

  Examples of the unsaturated hydrocarbon include ethylene, propylene, butene, isoprene, pentene and the like. Examples of unsaturated carboxylic acids, acid anhydrides, and derivatives thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methyl fumaric acid, mesaconic acid, citraconic acid, and glutacone. Acids and metal salts of these carboxylic acids, methyl hydrogen maleate, methyl itaconic acid methyl, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, methacrylic acid 2-ethylhexyl, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- (2,2,1) -5-heptene -2,3-dicarboxylic acid Endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, glycidyl acrylate, glycidyl methacrylate, ethacryl Examples thereof include glycidyl acid, glycidyl itaconate, glycidyl citraconic acid, and 5-norbornene-2,3-dicarboxylic acid. Among these, unsaturated dicarboxylic acids and acid anhydrides thereof are preferable, and maleic acid and maleic anhydride are particularly preferable.

  Specific examples of the olefin resin include homopolymers and copolymers such as polyethylene, polypropylene, polystyrene, poly 1-pentene, polymethyl pentene, ethylene / α-olefin hydrocarbon copolymers, ethylene-unsaturated carboxylic acids. Acid ester copolymer, polyolefin obtained by hydrolyzing at least part of [copolymer of (ethylene and / or propylene) and vinyl alcohol ester], (ethylene and / or propylene) and (unsaturated carboxylic acid) And / or a copolymer of (unsaturated carboxylic acid ester), at least one of carboxyl groups of [a copolymer of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester)] Polyolefins obtained by metallization of parts, conjugated die A block copolymer of a vinyl aromatic hydrocarbon, and the like hydride of the block copolymer. Among these, from the viewpoint of compatibility with the polyamide resin (A), an ethylene-unsaturated carboxylic acid copolymer, an ethylene-unsaturated carboxylic acid ester copolymer, an ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal A salt copolymer is preferably used.

  The ethylene / α-olefin hydrocarbon copolymer referred to in the present invention is preferably a copolymer of ethylene and at least one of α-olefin hydrocarbons having 3 to 20 carbon atoms. Specific examples of the α-olefin hydrocarbon having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3- Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and The combination of these, and the like. Among these α-olefin hydrocarbons, α-olefin hydrocarbons having 3 to 12 carbon atoms are preferable from the viewpoint of further improving the mechanical strength of the molded product. From the viewpoint of compatibility with the polyamide resin (A), a copolymer of an ethylene / α-olefin hydrocarbon and an unsaturated carboxylic acid and / or a derivative thereof is more preferable. Non-conjugated dienes such as 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5-ethylidene norbornene, 5-ethyl-2,5-norbornadiene, 5- (1′-propenyl) -2-norbornene At least one of these may be copolymerized. The α-olefin hydrocarbon content of the ethylene / α-olefin hydrocarbon copolymer is preferably 1 to 30 mol%, more preferably 2 to 25 mol%, and still more preferably 3 to 20 mol%.

  The ethylene / unsaturated carboxylic acid ester copolymer referred to in the present invention is a polymer obtained by copolymerizing ethylene and an unsaturated carboxylic acid ester. Examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and glycidyl methacrylate. Specific examples of ethylene / unsaturated carboxylic acid ester copolymers include ethylene / methyl acrylate copolymers, ethylene / ethyl acrylate copolymers, ethylene / butyl acrylate copolymers, ethylene / methyl methacrylate copolymers. Copolymer, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / acrylic Examples include methyl acid / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, and the like. Of these, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, and ethylene / methyl methacrylate / glycidyl methacrylate copolymer are preferably used. The weight ratio of the ethylene component to the unsaturated carboxylic acid ester component in the ethylene / unsaturated carboxylic acid ester copolymer is not particularly limited, but is preferably 90/10 to 10/90, more preferably 85/15 to 15 / A range of 85. The number average molecular weight of the ethylene / unsaturated carboxylic acid ester copolymer is not particularly limited. It is preferable to be in the range.

  The ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid metal salt copolymer is a copolymer obtained by metallizing at least a part of the carboxyl group of a copolymer of ethylene and unsaturated carboxylic acid. By chlorinating the metal, an ionomer structure is formed in which the copolymer molecules are cross-linked by metal ions. Specific examples of the unsaturated carboxylic acid in the ethylene / unsaturated carboxylic acid copolymer and the ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid metal salt copolymer are not particularly limited. For example, (meth) Examples include acrylic acid. Examples of the unsaturated carboxylic acid metal salt in the ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid metal salt copolymer include (meth) acrylic acid metal salts. Although the metal of unsaturated carboxylic acid metal salt is not specifically limited, Preferably, alkali metals, such as sodium, alkaline-earth metals, such as magnesium, zinc etc. are mentioned. The weight ratio of the unsaturated carboxylic acid component to the unsaturated carboxylic acid metal salt component in the ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid metal salt copolymer is not particularly limited, but preferably 95/5 to 5/95, More preferably, it is the range of 90/10-10/90. The number average molecular weights of the ethylene / unsaturated carboxylic acid copolymer and the ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid metal salt copolymer are not particularly limited, but are 190 ° C. and a load of 2.degree. The MFR at 16 kg is preferably in the range of 0.9 to 5.5.

  The method for introducing the unsaturated carboxylic acid, its acid anhydride or its derivative into the polyolefin resin is not particularly limited. For example, an olefin monomer containing an unsaturated carboxylic acid, its acid anhydride, or its derivative is used. Examples thereof include a polymerization method, and a method in which an unsaturated carboxylic acid, an acid anhydride or a derivative thereof is grafted onto a polyolefin-based hydrocarbon resin using a radical initiator. The introduction amount of the unsaturated carboxylic acid, its acid anhydride and its derivative is preferably in the range of 0.001 to 40 mol%, more preferably 0.01 to 35 mol% in the total olefin monomer of the polyolefin resin. Is within.

  The compounding quantity of the rubber-like polymer (B) in the polyamide resin composition of this invention is 0.1-4 weight part with respect to 100 weight part of polyamide resin (A). When the addition amount is less than 0.1 parts by weight, sufficient toughness and metal adhesion of the molded product cannot be obtained. 0.5 parts by weight or more is preferable, and 1 part by weight or more is more preferable. On the other hand, when the blending amount of the rubber polymer (B) exceeds 4 parts by weight, the metal adhesion of the molded product is improved, but the strength rigidity is remarkably lowered, and the fluidity is lowered due to thickening. , Molding processability is reduced. When strength and rigidity are low, for example, when used for a connector for electrical and electronic parts, the insertion / extraction property tends to decrease. Moreover, when fluidity | liquidity falls, especially the molding workability in a small or thin molded article falls. 3 parts by weight or less is preferable.

  The dendritic polyester resin (C) used in the present invention is at least selected from an aromatic oxycarbonyl unit (S), an aromatic and / or aliphatic dioxy unit (T), and an aromatic dicarbonyl unit (U). A tree containing one type of structural unit and a trifunctional or higher functional organic residue (D) and having a D content in the range of 7.5 to 50 mol% in the total monomers constituting the dendritic polyester Polyester resin. By blending the dendritic polyester resin (C), the fluidity of the polyamide resin composition can be improved while maintaining the mechanical properties of the polyamide resin (A). Further, by blending a specific amount of the dendritic polyester resin (C), the metal adhesion of the molded product can be remarkably improved by the interaction with the rubber polymer (B) described above. Here, the aromatic oxycarbonyl unit (S), the aromatic and / or aliphatic dioxy unit (T), and the aromatic dicarbonyl unit (U) are structural units represented by the following formula (1), respectively. Preferably there is.

  Here, R1 and R3 are each an aromatic residue. R2 is an aromatic residue or an aliphatic residue. R1, R2, and R3 may each include a plurality of structural units. Examples of the aromatic residue include a substituted or unsubstituted phenylene group, naphthylene group, and biphenylene group. Examples of the aliphatic residue include ethylene, propylene, and butylene. R1, R2 and R3 are each preferably at least one structural unit selected from structural units represented by the following formulae.

  In the formula, Y is at least one selected from a hydrogen atom, a halogen atom and an alkyl group. Here, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms. In the formula, n is an integer of 2 to 8.

  In the polyamide resin composition of the present invention, the amount of the dendritic polyester resin (C) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the polyamide resin (A). When the compounding amount of the dendritic polyester resin (C) is less than 0.01 parts by weight, the fluidity improving effect cannot be obtained, and the metal adhesion of the molded product is not improved. 0.5 parts by weight or more is preferable, and 1 part by weight or more is more preferable. On the other hand, when the blending amount of the dendritic polyester resin (C) exceeds 10 parts by weight, the dendritic polyester is decomposed during production and molding of the resin composition and a large amount of gas is generated, which causes a problem in productivity. From the viewpoint of moderately suppressing fluidity and suppressing overpacking and burrs during molding, 5 parts by weight or less is preferable.

  In the polyamide resin composition of the present invention, the dendritic polyester has trifunctional or higher organic residues (D) directly from each other by ester bonds and / or amide bonds, or from S, T and U which are branched structure parts. The basic skeleton is a branched structure of three or more branches bonded through selected structural units. The branched structure may be formed of a single basic skeleton such as three branches and four branches, or a plurality of basic skeletons such as three branches and four branches may coexist. It is not necessary for all of the polymers to be composed of the basic skeleton, and for example, other structures may be included at the ends for end capping. When D is a trifunctional organic residue, the dendritic polyester has a structure in which all three functional groups of D are reacted, a structure in which only two are reacted, and one A structure that only reacts may be mixed. Preferably, the structure in which all three functional groups of D are reacted is preferably 15 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more with respect to the entire D. Further, when D is a tetrafunctional organic residue, the dendritic polyester has a structure in which all four functional groups of D are reacted, a structure in which only three are reacted, two A structure in which only one reacts and a structure in which only one reacts may be mixed. The structure in which all four functional groups of D are reacted is preferably 10 mol% or more with respect to the whole D, and the structure in which three functional groups are reacted is preferably 20 mol% or more, more preferably four functional groups are reacted. And the structure in which three functional groups have reacted with respect to the entire D is 30 mol% or more, and more preferably the structure in which four functional groups have reacted with respect to the entire D. 25 mol% or more and the structure in which three functional groups have reacted is 35 mol% or more with respect to the entire D.

  D is preferably an organic residue of a trifunctional compound and / or a tetrafunctional compound, and most preferably an organic residue of a trifunctional compound.

  The above three-branch basic skeleton is schematically represented by the formula (2). Further, the above four-branch basic skeleton is schematically represented by the formula (3).

  The dendritic polyester of the present invention preferably exhibits molten liquid crystallinity. The term “showing molten liquid crystallinity” means that the liquid crystal state is exhibited in a certain temperature range when the temperature is raised from room temperature. The liquid crystal state is a state showing optical anisotropy under shear.

  In order to exhibit molten liquid crystallinity, the basic skeleton in the case of three branches is composed of a structural unit in which the organic residue (D) is selected from S, T and U as shown in the following formula (4) It is preferable that they are bonded via the branch structure portion R.

  Similarly, the basic skeleton in the case of four branches is preferably a structure represented by the following formula (5).

  Although it does not specifically limit about the trifunctional organic residue represented by D, It is preferable that it is an organic residue of the compound containing the functional group chosen from a carboxyl group, a hydroxyl group, and an amino group. For example, those derived from aliphatic compounds such as glycerol, methylolpropane, tricarballylic acid, diaminopropanol, diaminopropionic acid, trimesic acid, trimellitic acid, 4-hydroxy-1,2-benzenedicarboxylic acid, phloroglucinol, α- Those derived from aromatic compounds such as resorcinic acid, β-resorcinic acid, γ-resorcinic acid, tricarboxynaphthalene, dihydroxynaphthoic acid, aminophthalic acid, 5-aminoisophthalic acid, aminoterephthalic acid, diaminobenzoic acid, melamine, cyanuric acid Can be mentioned. Among these, those derived from aromatic compounds are preferred, and those represented by the following formula (6) are more preferred. Specifically, those derived from trimesic acid and α-resorcylic acid are preferred, and those derived from trimesic acid are particularly preferred.

  Further, the tetrafunctional or higher functional organic residue D is preferably an organic residue of a compound containing a functional group selected from a carboxyl group, a hydroxyl group and an amino group. For example, erythritol, pentaerythritol, threitol, xylitol, glucitol, mannitol, 1,2,3,4-butanetetracarboxylic acid, 1,2,4,5-cyclohexanetetraol, 1,2,3,4,5- Cyclohexanepentaneol, 1,2,3,4,5,6-cyclohexanehexaneol, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4,5-cyclohexanepentacarboxylic acid, 1, Residues of aliphatic compounds such as 2,3,4,5,6-cyclohexanehexacarboxylic acid, citric acid, tartaric acid, 1,2,4,5-benzenetetraol, 1,2,3,4-benzenetetra All, 1,2,3,5-benzenetetraol, 1,2,3,4,5-benzenepentaneol, 1,2,3,4,5, Benzenehexaneol, 2,2 ′, 3,3′-tetrahydroxybiphenyl, 2,2 ′, 4,4′-tetrahydroxybiphenyl, 3,3 ′, 4,4′-tetrahydroxybiphenyl, 3,3 ', 5,5'-tetrahydroxybiphenyl, 2,3,6,7-naphthalenetetraol, 1,4,5,8-naphthalenetetraol, pyromellitic acid, merophanic acid, planitic acid, meritic acid, 2, 2 ′, 3,3′-biphenyltetracarboxylic acid, 2,2 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 5 5'-biphenyltetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthaleneteto All, 1,4,5,8-naphthalenetetraol, 1,2,4,5,6,8-naphthalenehexaol, 1,2,4,5,6,8-naphthalenehexacarboxylic acid, gallic acid, etc. Of the aromatic compound. The residue represented by the following formula (7) is more preferable.

  Specific examples of tetrafunctional organic residues of the above formula include 1,2,4,5-benzenetetraol, 1,2,3,4-benzenetetraol, 1,2,3,5-benzenetetraol. Residues such as pyromellitic acid, merophanic acid, planitic acid, and gallic acid are preferable, and residues of gallic acid are particularly preferable.

  Further, the aromatic hydroxycarbonyl unit (S), aromatic and / or aliphatic dioxy unit (T), and aromatic dicarbonyl unit (U) of the dendritic polyester resin represent the branch structure portion between the branches of the dendritic polyester. It is a unit that composes. When p, q, and r are the average contents (molar ratio) of the structural units S, T, and U, respectively, it is preferable that p + q + r = 1 to 10 when the content d of D is 1 mole. More preferably, p + q + r is in the range of 2-6. If the branch length is too long, it is not preferable because effects such as shear responsiveness based on a rigid and detailed dendritic structure are reduced. The values of p, q, and r are obtained, for example, by dissolving dendritic polyester resin in a mixed solvent of 50% by weight of pentafluorophenol and 50% by weight of chloroform and performing nuclear magnetic resonance spectrum analysis of proton nuclei at 40 ° C. It can obtain | require from the peak intensity ratio derived from each structural unit. The average content is calculated from the peak area intensity ratio of each structural unit, and the three decimal places are rounded off. From the area intensity ratio with the peak corresponding to the content d of the branched structure D, the average chain length of the branch portion R is calculated and set as the value of p + q + r. In this case, the three decimal places are rounded off.

  The ratio of p and q and the ratio of p and r (p / q, p / r) is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, more preferably 20 / 80-80 / 20. If it is this range, liquid crystallinity is easy to express and it is preferable. By setting the ratio of p / q and p / r to 95/5 or less, the melting point of the dendritic polyester resin can be within an appropriate range, and p / q and p / r should be 5/95 or more. It is preferable because the melted liquid crystallinity of the dendritic polyester resin can be expressed.

  q and r are preferably substantially equimolar, but either component can be added in excess to control the end groups. The ratio of q / r is preferably in the range of 0.7 to 1.5, more preferably 0.9 to 1.1. Equimolar here means that the molar amount in the repeating unit is equal and does not include the terminal structure. Here, the term “end structure” means the end of the branch structure portion, and when the end is blocked, it means the end of the branch structure portion closest to the end. Furthermore, R1, R2, and R3 are the structural units.

  R1 is a structure derived from an aromatic oxycarbonyl unit, and examples thereof include structural units generated from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and are preferably structural units derived from p-hydroxybenzoic acid. It is also possible to use a part of those derived from 6-hydroxy-2-naphthoic acid. Further, a structural unit derived from an aliphatic hydroxycarboxylic acid such as glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid or hydroxycaproic acid may be contained within a range not impairing the effects of the present invention.

  R2 is a structure derived from aromatic and / or aliphatic dioxy units, such as 4,4′-dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether, ethylene glycol, 1 , 3-propylene glycol, structural units generated from 1,4-butanediol, and the like. Preferred are structural units generated from 4,4′-dihydroxybiphenyl, hydroquinone, ethylene glycol, and 4,4 ′. -Dihydroxy biphe May include the Le hydroquinone or 4,4'-dihydroxybiphenyl and a structural unit derived from ethylene glycol is preferable from the viewpoint of the control of the liquid crystal.

  R3 is a structural unit generated from an aromatic dicarbonyl unit. For example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane Examples include structural units formed from -4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, and the like. It is a structural unit formed from terephthalic acid and isophthalic acid, and particularly when both are used in combination, the melting point can be easily adjusted. Moreover, a part of structural unit produced | generated from aliphatic dicarboxylic acids, such as sebacic acid and adipic acid, may be included in the range which does not impair the effect of this invention.

  The branch structure portion of the dendritic polyester resin is preferably mainly composed of a polyester skeleton, but it is also possible to introduce a carbonate structure, an amide structure, a urethane structure, etc. to such an extent that the properties are not greatly affected. Is preferably introduced. By introducing such another bond, compatibility with a wide variety of thermoplastic resins can be adjusted, which is preferable. As a method for introducing an amide bond, p-aminobenzoic acid, m-aminobenzoic acid, p-aminophenol, m-aminophenol, p-phenylenediamine, m-phenylenediamine, tetramethylenediamine pentamethylenediamine, hexamethylene Diamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m-xyl Range amine, p-xylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-Aminocyclohexyl Aliphatic, alicyclic or aromatic such as methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine It is preferable to copolymerize such an amine compound, and among them, copolymerization of p-aminophenol and p-aminobenzoic acid is preferable.

  Specific examples of the structure of R include a structural unit formed from p-hydroxybenzoic acid and a structural unit generated from 6-hydroxy-2-naphthoic acid, a structural unit generated from p-hydroxybenzoic acid, 6- A structural unit produced from hydroxy-2-naphthoic acid, a structural unit produced from 4,4′-dihydroxybiphenyl, a structure comprising a structural unit produced from terephthalic acid, a structural unit produced from p-hydroxybenzoic acid, 4,4 Structural units generated from '-dihydroxybiphenyl, structural units generated from terephthalic acid, structures composed of structural units generated from isophthalic acid, structural units generated from p-hydroxybenzoic acid, generated from 4,4'-dihydroxybiphenyl Structural unit, structural unit generated from hydroquinone, generated from terephthalic acid Structural units, structural units formed from isophthalic acid, structural units generated from p-hydroxybenzoic acid, structural units generated from ethylene glycol, structural units generated from terephthalic acid, p-hydroxybenzoic acid Structural unit generated from ethylene, structural unit generated from ethylene glycol, structural unit generated from 4,4′-dihydroxybiphenyl, structure composed of structural unit generated from terephthalic acid, structural unit generated from p-hydroxybenzoic acid, hydroquinone A structural unit generated from 4,4′-dihydroxybiphenyl, a structural unit generated from terephthalic acid, a structure consisting of a structural unit generated from 2,6-naphthalenedicarboxylic acid, generated from p-hydroxybenzoic acid Structural unit, 6-hydroxy- - structural unit derived from naphthoic acid, a structural unit derived from hydroquinone, etc. structure comprising a structural unit derived from terephthalic acid.

  Particularly preferred is R composed of the following structural units (I), (II), (III), (IV) and (V) or the following structural units (I), (II), (VI) and (IV) R).

  In the case of R composed of the structural units (I), (II), (III), (IV) and (V), the content p of the structural unit (I) is based on the total p + q + r of the structural units. It is 30 to 70%, more preferably 45 to 60%.

  Further, the content q (II) of the structural unit (II) is 60 to 75%, more preferably 65 to 73% with respect to the total q of the structural units (II) and (III). The content r (IV) of the structural unit (IV) is 60 to 92%, preferably 60 to 70%, more preferably 62 with respect to the total r of the structural units (IV) and (V). ~ 68%.

  In such a case, the shear response and the addition effect to the thermoplastic resin which are the characteristics of the present invention are remarkably exhibited, which is preferable.

  Preferably, the sum q of structural units (II) and (III) and the sum r of (IV) and (V) are substantially equimolar, but the carboxylic acid component or hydroxyl to adjust the end groups of the polymer Ingredients may be added in excess. That is, “substantially equimolar” means that the unit constituting the polymer main chain excluding the terminal is equimolar, but the unit constituting the terminal is not necessarily equimolar. Here, when the terminal is a derivative or blocked, it means the terminal of the skeleton R.

  In the case of R composed of the structural units (I), (II), (VI) and (IV), the content p of the structural unit (I) is the structural units (I), (II) and ( 30-90 mol% is preferable with respect to the sum total of VI), and 40-80 mol% is more preferable. Moreover, 70-5 mol% is preferable with respect to the sum q of (II) and (VI), and, as for content q (VI) of structural unit (VI), 60-8 mol% is more preferable. Further, the structural unit (IV) is preferably substantially equimolar to the total of the structural units (II) and (VI), but either component may be added in excess.

  The terminal of the dendritic polyester resin (C) is preferably a carboxyl group, a hydroxyl group, an amino group, or a derivative thereof. Examples of the hydroxyl derivative or carboxylic acid derivative include alkyl esters such as methyl ester and aromatic esters such as phenyl ester and benzyl ester. It is also possible to end-block using a monofunctional epoxy compound, an oxazoline compound, an ortho ester, an acid anhydride compound, or the like. The end-capping method includes adding a monofunctional organic compound in advance when synthesizing the dendritic polyester, or adding a monofunctional organic compound when the dendritic polyster skeleton is formed to some extent. The method etc. are mentioned.

  Specifically, when blocking the hydroxyl terminal or acetoxy terminal, benzoic acid, 4-t-butylbenzoic acid, 3-t-butylbenzoic acid, 4-chlorobenzoic acid, 3-chlorobenzoic acid, 4- It is possible by adding methylbenzoic acid, 3-methylbenzoic acid, 3,5-dimethylbenzoic acid, and the like.

  Moreover, the carboxyl group terminal blockade can be performed by reacting a carboxylic acid-reactive monofunctional compound. Here, the carboxylic acid-reactive monofunctional compound refers to a compound having one functional group in the molecule that can react with carboxylic acid at room temperature or when heated to form an ester, amide, urethane, or urea bond. The carboxylic acid-reactive monofunctional compound reacts with the carboxylic acid group present at the molecular end of the dendritic polyester, and the monofunctional compound is introduced at the molecular end, thereby improving the residence stability and hydrolysis resistance of the dendritic polyester. When it is improved and further kneaded with other thermoplastic resins and fillers, the decomposition of the thermoplastic resin and fillers can be suppressed, and the dispersibility of the dendritic polyester is improved, improving the fluidity and physical properties. Can be expected.

  The carboxylic acid-reactive monofunctional compound that can be used for the dendritic polyester resin is at least one compound selected from oxazoline, epoxide, orthoester, isocyanate, carbodiimide, and diazo compound. From the viewpoint of reactivity with carboxylic acid and handling properties, oxazoline, epoxide, orthoester, and isocyanate can be preferably used. The carboxylic acid-reactive monofunctional compound may be used alone or in combination of two or more carboxylic acid-reactive monofunctional compounds.

  Among the carboxylic acid-reactive monofunctional compounds that can be used in the present invention, examples of the oxazoline compound include 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline, 2-propoxy-2-oxazoline, and 2-butoxy. 2-oxazoline, 2-pentyloxy-2-oxazoline, 2-hexyloxy-2-oxazoline, 2-heptyloxy-2-oxazoline, 2-octyloxy-2-oxazoline, 2-decyloxy-2-oxazoline, 2 -Cyclopentyloxy-2-oxazoline, 2-cyclohexyl-2-oxazoline, 2-allyloxy-2-oxazoline, 2-methallyloxy-2-oxazoline, 2-phenoxy-2-oxazoline, 2-cresyl-2-oxazoline, 2-p-phenylphenoxy- -Oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-butyl-2-oxazoline, 2-pentyl-2-oxazoline, 2-hexyl-2-oxazoline 2-heptyl-2-oxazoline, 2-octyl-2-oxazoline, 2-nonyl-2-oxazoline, 2-decyl-2-oxazoline, 2-isopropyl-2-oxazoline, 2-isobutyl-2-oxazoline, 2 -Sec-butyl-2-oxazoline, 2-tert-butyl-2-oxazoline, 2-cyclopentyl-2-oxazoline, 2-cyclohexyl-2-oxazoline, 2-allyl-2-oxazoline, 2-methallyl-2-oxazoline , 2-crotyl-2-oxazoline, 2-phenyl-2- Kisazorin, 2-biphenyl-2-oxazoline. Of these, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-butyl-2 from the viewpoints of reactivity and affinity with dendritic polyester and heat resistance -Oxazoline, 2-isopropyl-2-oxazoline, 2-isobutyl-2-oxazoline, 2-sec-butyl-2-oxazoline, 2-tert-butyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-biphenyl 2-Oxazoline is preferable, and 2-phenyl-2-oxazoline is particularly preferable.

  Among the carboxylic acid-reactive monofunctional compounds that can be used in the present invention, examples of the epoxy compound include N-glycidylphthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N- Glycidyl-3-methylphthalimide, N-glycidyl-3,6-dimethylphthalimide, N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, N- Glycidylsuccinimide, N-glycidylhexahydrophthalimide, N-glycidylmaleimide, N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, N-glycidylnaphthamide, N-glycidylsteramide, o-phenylphenyl Sidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 3- (2-xenyloxy) -1,2-epoxypropane, allyl glycidyl ether, butyl glycidyl ether, lauryl glycidyl ether, benzyl glycidyl ether, cyclohexyl glycidyl ether, α -Cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, glycidyl methacrylate ether, ethylene oxide, propylene oxide, styrene oxide, octane oxide, glycidyl acetate, glycidyl propionate, glycidyl butanoate, pentanoic acid Glycidyl ester, hexanoic acid glycidyl ester, octanoic acid glycidyl ester, decanoic acid glycidyl And glycidyl ester of neodecanoic acid and glycidyl benzoate. Of these, ethylene oxide, propylene oxide, butyl glycidyl ether, phenyl glycidyl ether, and benzoic acid glycidyl ester are preferred, and benzoic acid glycidyl ester is particularly preferred from the viewpoints of reactivity and affinity with the dendritic polyester.

  Among the carboxylic acid-reactive monofunctional compounds that can be used in the present invention, ortho ester compounds include, for example, trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, tributyl orthoacetate, tribenzyl orthoacetate, trimethyl orthoformate, ortho Triethyl formate, tripropyl orthoformate, tributyl orthoformate, tribenzyl orthoformate, trimethyl orthopropionate, triethyl orthopropionate, tripropyl orthopropionate, tributyl orthopropionate, tribenzyl orthopropionate, trimethyl orthobenzoate, trimethyl orthobenzoate Triethyl, tripropyl orthobenzoate, tributyl orthobenzoate, tribenzyl orthobenzoate and the like can be mentioned. Of these, trimethyl orthoacetate, triethyl orthoacetate, trimethyl orthoformate, triethyl orthoformate are preferred, and trimethyl orthoacetate or triethyl orthoacetate is particularly preferred from the viewpoints of reactivity and affinity with dendritic polyester and handling properties. .

  Among the carboxylic acid-reactive monofunctional compounds that can be used in the present invention, examples of the isocyanate compound include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, pentyl isocyanate, hexyl isocyanate, heptyl isocyanate, octyl isocyanate, nonyl isocyanate, Examples include decyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, benzyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, 2-chloroethyl isocyanate, stearoyl isocyanate, and p-toluosulfonyl isocyanate. Of these, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, and phenyl isocyanate are preferable from the viewpoint of reactivity and affinity with the dendritic polyester, and phenyl isocyanate is particularly preferable.

  Among the carboxylic acid-reactive monofunctional compounds that can be used in the present invention, examples of the diazo compound include diazomethane, diazoethane, diazopropane, diazobutane, and trimethylsilyldiazomethane. Of these, diazomethane and trimethylsilyldiazomethane are preferably used from the viewpoint of reactivity and affinity with the dendritic polyester.

  Theoretically, it is possible to block the end by adding the organic compound used for blocking the end in an amount corresponding to the end group to be blocked. From the viewpoint of sufficiently proceeding with end-capping, the organic compound used for end-capping is preferably used in an amount equivalent to 1.005 times or more, more preferably 1.008 times equivalent or more, relative to the equivalent amount of the end group to be blocked. In addition, from the viewpoint of suppressing gas generation due to the organic compound used for terminal blocking, the amount of the organic compound used for terminal blocking is preferably 2.5 times equivalent or less.

  The content of the organic residue D indicates the blending ratio of the polyfunctional compound that generates the organic residue with respect to all monomers constituting the dendritic polyester, and the content is 7.5 mol% or more. 10 mol% or more is more preferable, More preferably, it is 20 mol% or more. In such a case, the chain length of the branch structure portion is preferable because the dendritic polyester is suitable for taking a dendritic form. The upper limit of the content of the organic residue D is 50 mol% or less, preferably 45 mol% or less, and more preferably 40 mol% or less. In addition, the dendritic polyester resin of the present invention may have a partially crosslinked structure as long as the properties are not affected.

  There is no restriction | limiting in particular in the manufacturing method of the said dendritic polyester resin used in this invention, It can manufacture according to the well-known polyester polycondensation method. After acylating the raw material monomers constituting the structural units represented by R1, R2 and R3, when the trifunctional monomer is reacted, all the addition amount (mol) of the trifunctional monomer is charged. A method of producing such that it is 7.5 mol% or more based on the monomer (mol) is preferable. The addition amount of the polyfunctional monomer is more preferably 10 mol% or more, more preferably 15 mol% or more, and further preferably 20 mol% or more. Moreover, as an upper limit of addition amount, 50 mol% or less is preferable, More preferably, it is 33 mol% or less.

  For example, in the production of a dendritic polyester resin composed of R and trimesic acid composed of the structural units (I), (II), (III), (IV) and (V), the following production method is preferred. Can be mentioned.

  (1) A liquid crystalline polyester oligomer is synthesized from p-acetoxybenzoic acid and 4,4'-diacetoxybiphenyl, diacetoxybenzene, terephthalic acid, and isophthalic acid by a deacetic acid polycondensation reaction, and trimesic acid is added to remove deacetic acid heavy A method for producing by condensation reaction.

  (2) A process for producing by deacetic acid polycondensation reaction from p-acetoxybenzoic acid and 4,4'-diacetoxybiphenyl, diacetoxybenzene, terephthalic acid, isophthalic acid and trimesic acid.

  (3) p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone and terephthalic acid, isophthalic acid is reacted with acetic anhydride to acylate the phenolic hydroxyl group, and then the liquid crystalline polyester is subjected to deacetic acid polycondensation reaction. A method in which oligomers are synthesized and trimesic acid is added and subjected to deacetic acid polycondensation reaction.

  (4) Acetic anhydride is reacted with p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid and trimesic acid to acylate the phenolic hydroxyl group, and then by deacetic acid polycondensation reaction. How to manufacture.

  (5) A liquid crystalline polyester oligomer is synthesized from a phenyl ester of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, and diphenyl ester of isophthalic acid by a dephenol polycondensation reaction, and trimesic acid is added. A method of producing by dephenol polycondensation reaction.

  (6) A method of producing by dephenol polycondensation reaction from phenyl ester of p-hydroxybenzoic acid and 4,4'-dihydroxybiphenyl, hydroquinone and terephthalic acid, diphenyl ester of isophthalic acid and phenyl ester of trimesic acid.

  (7) A predetermined amount of diphenyl carbonate is reacted with p-hydroxybenzoic acid and aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, trimesic acid, etc. to form phenyl esters, respectively, and then 4,4′-dihydroxybiphenyl, hydroquinone A method in which an aromatic dihydroxy compound such as is added and produced by a dephenol polycondensation reaction.

  Especially, the manufacturing method of (1)-(4) is preferable, More preferably, the manufacturing method of (3) or (4) is preferable from the point of chain length control and a stereoregulation.

  The amount of acetic anhydride used is preferably 0.95 equivalents or more and 1.10 equivalents or less, and more preferably 1.00 equivalents or more and 1.08 equivalents or less, in terms of chain length control, in terms of the total phenolic hydroxyl group. preferable.

  The dendritic polyester resin is characterized in that it has a reactive carboxylic acid or hydroxyl group and its derivative group at the end, and controls the amount of acetic anhydride and dihydroxy or dicarboxylic acid monomer depending on the type of thermoplastic resin to be blended. The end group can be controlled by adding excessively. In order to increase the molecular weight, it is preferable to add an excess of dihydroxy monomer equivalent to the excess amount of carboxylic acid in trimesic acid or 4,4'-dihydroxybiphenyl to match the carboxylic acid with the hydroxyl equivalent, while preferentially using carboxylic acid It is preferable not to add an excessive amount of dihydroxy monomer to the terminal group, and to preferentially leave a hydroxyl group at the terminal, the dihydroxy monomer is added in excess of the carboxylic acid equivalent of trimesic acid and anhydrous. The acetic acid molar ratio is preferably less than 1.00.

  By these methods, it is possible to selectively provide the dendritic polyester resin with a terminal group structure rich in reactivity with various thermoplastic resins. However, depending on the thermoplastic resin, in order to suppress the reactivity, it is easier to control the dispersion state by selectively generating the end and then blocking the end with a monofunctional epoxy compound, monofunctional carboxylic acid or the like. In some cases.

  When the dendritic polyester resin is produced by a deacetic acid polycondensation reaction, the reaction is carried out at a temperature at which the dendritic polyester resin melts, sometimes under reduced pressure, to distill a predetermined amount of acetic acid, thereby completing the polycondensation reaction. A melt polymerization method is preferred.

  For example, in a reaction vessel having a predetermined amount of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid, acetic anhydride, a stirring blade, a distillation pipe, and a discharge port at the bottom. After charging and heating with stirring under a nitrogen gas atmosphere to acetylate the hydroxyl group, the temperature was raised to 200 to 350 ° C. to distill acetic acid, and at the stage of distilling to 50% of the theoretical distillate, trimesic acid A predetermined amount is added, and acetic acid is distilled to 91% of the theoretical distillation amount to complete the reaction.

  The conditions for the acetylation are usually 130 to 170 ° C., preferably 135 to 155 ° C., usually 0.5 to 6 hours, preferably 135 to 145 ° C. for 1 to 2 hours.

  The polycondensation temperature is a melting temperature of the dendritic polyester resin, for example, in the range of 200 to 350 ° C, preferably a melting point of the dendritic polyester resin + 10 ° C or higher, specifically 240 to 320 ° C. preferable. When polycondensation is performed, there is no problem even under atmospheric pressure nitrogen, but it is preferable to reduce the pressure because the reaction proceeds faster and the residual acetic acid in the system decreases. The degree of vacuum is usually 0.1 mmHg (13.3 Pa) to 200 mmHg (26600 Pa), preferably 1 mmHg (133 Pa) to 100 mmHg (13300 Pa). In addition, although acetylation and polycondensation may be performed continuously in the same reaction vessel, acetylation and polycondensation may be performed in different reaction vessels.

The obtained dendritic polyester resin is pressurized at about 0.01 to 1.0 kg / cm ² (0.001 to 0.1 MPa) in the reaction vessel at a temperature at which it melts, and is provided at the lower portion of the reaction vessel. It can be discharged in the form of a strand from the discharged outlet. A mechanism that opens and closes intermittently is provided at the discharge port, and it is also possible to discharge liquid droplets. The discharged dendritic polyester resin is cooled by passing through air or water, and then cut or pulverized as necessary. The obtained pellets or granular or powdery dendritic polyester resin can further remove water, acetic acid, etc. by heat drying or vacuum drying, if necessary, to finely adjust the polymerization degree and further increase the polymerization degree. Therefore, it is possible to carry out solid phase polymerization. For example, under a nitrogen stream or under reduced pressure, the dendritic polyester resin is heated for 1 to 50 hours in the range of melting point −5 ° C. to melting point −50 ° C. (for example, 200 to 300 ° C.), and polycondensed to a desired degree of polymerization. And a method for completing the reaction.

  The polycondensation reaction of the dendritic polyester resin proceeds even without catalyst, but metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and magnesium metal can also be used.

  The dendritic polyester resin (C) used in the present invention preferably has a number average molecular weight of 1,000 to 40,000, more preferably 1,000 to 30,000, and still more preferably 1,000 to 20,000. 000.

  The number average molecular weight is a value measured by GPC-LS (gel permeation chromatography-light scattering) method using a solvent in which the dendritic polyester resin (C) is soluble.

  The melt viscosity of the dendritic polyester resin in the present invention is not particularly limited, but is preferably 0.01 to 50 Pa · s, more preferably 0.5 to 40 Pa · s, and particularly preferably 10 to 30 Pa · s. .

  In addition, this melt viscosity is a value measured by a Koka flow tester under the condition of the liquid crystal starting temperature of the dendritic polyester resin + 10 ° C. and the shear rate of 100 / s.

  The dendritic polyester resin thus obtained exhibits molten liquid crystallinity and high shear response.

  The polyamide resin composition of the present invention may further contain an inorganic filler (D). By blending the inorganic filler (D), the strength and rigidity of the molded product can be improved, and dimensional changes such as expansion and contraction due to temperature changes can be reduced, so that the metal adhesion can be improved. The shape of the inorganic filler (D) is not particularly limited, but any filler such as fibrous, plate-like, powdery, and granular can be used. Specifically, glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone koji fiber , Fibrous fillers such as metal fibers, or silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, silicon oxide, magnesium oxide, alumina, Metal compounds such as zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, ceramic beads, boron nitride, silicon carbide, phosphoric acid Hydroxides such as Lucium, Calcium hydroxide, Magnesium hydroxide, Aluminum hydroxide, Glass flakes, Glass powder, Carbon black and silica, Non-fibrous fillers such as graphite, and Montmorillonite, Viderite, Nontronite, Saponite, Smectite clay minerals such as hectorite and soconite, various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate and titanium phosphate, Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluoromica, Li-type four Layered silicates represented by swelling mica such as silicon fluorine mica are used. Two or more of these may be blended. The layered silicate may be a layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions, and examples of the organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred. As the ammonium ion, any of primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium may be used. Primary ammonium ions include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like. Secondary ammonium ions include methyl dodecyl ammonium and methyl octadecyl ammonium. Examples of tertiary ammonium ions include dimethyl dodecyl ammonium and dimethyl octadecyl ammonium. Quaternary ammonium ions include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, trioctylmethylammonium, trimethyloctylammonium, trimethyldodecylammonium, trimethyloctadecyl. Examples thereof include alkyltrimethylammonium ions such as ammonium, dimethyldialkylammonium ions such as dimethyldioctylammonium, dimethyldidodecylammonium, and dimethyldioctadecylammonium. Besides these, it is derived from aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. And ammonium ions. Among these ammonium ions, trioctylmethylammonium, trimethyloctadecylammonium, benzyldimethyloctadecylammonium, ammonium ions derived from 12-aminododecanoic acid, and the like are preferable. Layered silicates in which exchangeable cations present between layers are exchanged with organic onium ions can be produced by reacting layered silicates having exchangeable cations between layers and organic onium ions by a known method. it can. Specifically, a method by an ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method by directly reacting a layered silicate with a liquid or melted ammonium salt may be used. Among these inorganic fillers, preferred are glass fibers, talc, wollastonite, layered silicates such as montmorillonite and synthetic mica, and particularly preferred are glass fibers. The surface of the inorganic filler used in the present invention may be used after treating the surface with a known coupling agent (for example, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agents. it can. The type of glass fiber used in the present invention is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from, for example, long fiber type, short fiber type chopped strand, milled fiber, and the like. Also, weakly alkaline glass fibers are excellent in terms of mechanical strength and can be preferably used. The glass fiber is preferably treated with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, an epoxy-based resin, a urethane-based resin, an acrylic-based coating or a sizing agent, and a urethane-based resin is particularly preferable. Further, it is preferably treated with a silane-based or titanate-based coupling agent or other surface treatment agent, and an epoxysilane or aminosilane-based coupling agent is particularly preferable.

  As for the compounding quantity of the inorganic filler (D) in this invention, 0.1-200 weight part is preferable with respect to 100 weight part of polyamide resins (A). If the compounding quantity of an inorganic filler (D) is 0.1 weight part or more, the intensity | strength of a molded article, rigidity, and metal adhesiveness can be improved more. 1 part by weight or more is more preferable. On the other hand, if the compounding amount of the inorganic filler (D) is 200 parts by weight or less, the moldability and the metal adhesion of the molded product can be maintained at a high level. 100 parts by weight or less is more preferable, and 50 parts by weight or less is more preferable.

  In order to impart mechanical strength and other characteristics to the polyamide resin composition of the present invention, it is possible to further contain a flame retardant, a heat-resistant agent, and other additives. Although it does not specifically limit as a flame retardant, Specifically, it is represented by the non-halogen flame retardant which does not contain halogen atoms, such as phosphorus flame retardant, nitrogen flame retardant, and magnesium hydroxide, and a bromine flame retardant. Mention may be made of halogenated flame retardants. Two or more of these flame retardants may be blended.

  Phosphorus flame retardant is a compound containing phosphorus element, specifically, polyphosphoric compounds such as red phosphorus, ammonium polyphosphate, melamine polyphosphate, aromatic phosphate compounds, aromatic bisphosphate compounds Etc.

  Examples of the nitrogen-based flame retardant include compounds that form a salt of a triazine compound with cyanuric acid or isocyanuric acid. The salt of cyanuric acid or isocyanuric acid is an adduct of cyanuric acid or isocyanuric acid and a triazine compound, and usually has a composition of 1 to 1 (molar ratio), sometimes 1 to 2 (molar ratio). It is an adduct that has. Melamine, benzoguanamine and acetoguanamine salts are preferred.

Magnesium hydroxide is usually commercially available and is not particularly limited in terms of particle size, specific surface area, shape, etc., but preferably has a particle size of 0.1 to 20 μm and a specific surface area of 3 to 75 m ² / g. The shape is preferably spherical, needle-shaped or platelet-shaped. The surface treatment of magnesium hydroxide may or may not be performed. Examples of the surface treatment method include treatment methods such as coating formation with a thermosetting resin such as a silane coupling agent, an anionic surfactant, a polyfunctional organic acid, and an epoxy resin.

  Examples of the brominated flame retardant include ethylene bis (tetrabromophthalimide), brominated epoxy polymer, brominated polystyrene, crosslinked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate. Brominated polystyrene, crosslinked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate are more preferred. Moreover, it is also preferable to add the flame retardant adjuvant used in order to improve flame retardancy synergistically by using together with said brominated flame retardant. As the flame retardant aid, antimony trioxide and antimony pentoxide are preferable.

  Examples of the heat-resistant agent include those for maintaining thermal stability such as phenolic compounds, phosphorus compounds, and copper compounds. Moreover, it is particularly preferable to use a phenolic compound and a phosphorus compound in combination because of their large heat resistance, thermal stability and fluidity retention effect.

  As the phenolic compound, a hindered phenolic compound is preferably used, and N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane or the like is preferably used. The amount of the phenolic compound added is preferably 0.02 parts by weight or more with respect to 100 parts by weight of the polyamide resin from the viewpoint of heat resistance improvement effect, and 1 part by weight from the viewpoint of gas components generated during molding. The following is preferable.

  Examples of phosphorus compounds include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite and bis (2,4-di-t-butylphenyl) pentaerythritol-di-phos. Phyto, bis (2,4-di-cumylphenyl) pentaerythritol-di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl)- 4,4'-bisphenylene phosphite, di-stearyl pentaerythritol di-phosphite, triphenyl phosphite, 3,5-dibutyl-4-hydroxybenzyl phosphonate diethyl ester and the like. Among them, those having a high melting point are preferably used in order to reduce volatilization and decomposition of the heat-resistant agent in the polyamide resin compound. The amount of the phosphorus compound added is preferably 0.02 parts by weight or more with respect to 100 parts by weight of the polyamide resin from the viewpoint of the heat resistance improving effect. The following is preferable.

  As the copper compound, a monovalent copper compound, particularly a monovalent copper halide compound is preferable, and cuprous acetate, cuprous iodide and the like can be exemplified as particularly suitable copper compounds. The amount of the copper compound added is preferably in the range of 0.015 to 1 part by weight with respect to 100 parts by weight of the polyamide resin (A). By making the addition amount within such a range, coloring of the molded product due to liberation of metallic copper can be suppressed. It is also possible to add an alkali halide in combination with a copper compound. As the alkali halide compound, potassium iodide and sodium iodide are preferable.

  Examples of other additives include acid anhydrides as amino terminal blocking agents for the polyamide resin (A). Since the acid anhydride reacts with the amino terminal group of the polyamide resin (A), the amino terminal group concentration of the polyamide resin (A) can be reduced. As a result, the transesterification reaction between the polyamide resin and the dendritic polyester resin (C) is suppressed, and the good fluidization effect by the dendritic polyester resin (C) is more highly expressed.

  Specific examples of acid anhydrides include benzoic anhydride, isobutyric anhydride, itaconic anhydride, octanoic anhydride, glutaric anhydride, succinic anhydride, acetic anhydride, dimethylmaleic anhydride, decanoic anhydride, and trimellitic anhydride. Examples include acid, 1,8-naphthalic anhydride, phthalic anhydride, maleic anhydride and derivatives thereof. Of these, phthalic anhydride is preferably used. In the present invention, by adding an acid anhydride, the polyamide resin composition composed of the polyamide resin (A) and the rubbery polymer (B) is compared with a polyamide resin composition containing only the dendritic polyester resin (C). , While maintaining the metal adhesion, sufficient fluidity improvement effect can be expressed even if the addition amount of the dendritic polyester resin (C) is small, hydrolysis resistance of the molded product, weld characteristics, dimensional stability during molding, The deformability due to the ejection pin at the time of molding is also improved.

  In the polyamide resin composition of the present invention, the blending ratio of the acid anhydride is preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the polyamide resin (A). Preferably, it is 0.01-5 weight part, More preferably, it is 0.01-3 weight part. When the blending amount is in the above range, the above effect is remarkably obtained, which is preferable.

  Furthermore, as other additives, ultraviolet absorbers (resorcinol, salicylate, etc.), anti-coloring agents such as phosphites, hypophosphites, lubricants and mold release agents (stearic acid, montanic acid and metal salts thereof, Normal additives such as carbon black, crystal nucleating agents, plasticizers and antistatic agents such as esters, half esters thereof, stearyl alcohol, stearamide and polyethylene wax), colorants including dyes and pigments, conductive agents or colorants. Can be mentioned.

  As a method for producing the polyamide resin composition of the present invention, a method by melt kneading is preferred. A known method can be used for melt kneading. Examples of the melt kneader include a Banbury mixer, a rubber roll machine, a kneader, a single-screw or twin-screw extruder, and the like. Among these, a twin screw extruder is preferable. The kneading method is not particularly limited, but 1) a polyamide resin (A), a rubbery polymer (B), a dendritic polyester (C), an inorganic filler (D) and other additives as necessary. Method of batch kneading (collective kneading method), 2) After melt-kneading the polyamide resin (A), rubber polymer (B), dendritic polyester resin (C), and other additives as necessary, side feeder, etc. And inorganic filler (D), a method of further adding other additives as required, and melt-kneading (side feeder method). The melt kneading temperature is preferably equal to or higher than the melting temperature of the polyamide resin (A), the rubbery polymer (B), and the dendritic polyester resin (C).

  Further, the dendritic polyester resin (C) obtained by melt-kneading the polyamide resin (A), the dendritic polyester resin (C) and other additives as required in advance, discharging them in a strand form, cooling and cutting. And a pellet containing a high concentration of other additives (master pellet), then mixed in a solid state with the polyamide resin (A) and rubber polymer (B) pellets to a specified concentration and then melted A method (master pellet method) is also preferably included.

  The polyamide resin composition of the present invention can be used by being molded by a generally known method and processed into various molded products. Examples of the molding method include arbitrary melt molding methods such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, and spinning. For example, the polyamide resin composition pellets obtained by the various methods described above may be melt-molded, or the master pellets and the mixed pellets of the polyamide resin (A) and rubber polymer (B) pellets may be melt-molded. Good. As molded products, it can be used as injection molded products, extrusion molded products, blow molded products, films, sheets, fibers, etc., as films, as various films such as unstretched, uniaxially stretched, biaxially stretched, as fibers, It can be used as various fibers such as undrawn yarn, drawn yarn, and super-drawn yarn.

  The molded article of the present invention is a resin-metal composite having a polyamide resin member and a metal member obtained by melt-molding the polyamide resin composition of the present invention, and the metal member is in contact with the polyamide resin member. Resin metal composites are preferred. A molded product obtained by melt-molding the polyamide resin composition of the present invention is excellent in adhesion to metal. Therefore, when the polyamide resin composition of the present invention is combined with metal parts by insert molding or the like, high sealing performance is obtained. Can get waterproof. Although it does not specifically limit as a metal which comprises a metal member, For example, alloys, such as aluminum, copper, iron, tin, nickel, zinc, an aluminum alloy, stainless steel, etc. are mentioned. Further, those whose surface is plated with aluminum, tin, nickel, gold, silver or the like can also be preferably used.

  The polyamide resin composition and molded article of the present invention can be used in various applications such as automobile parts, electronic equipment casings, electrical / electronic parts, building materials, sports equipment, various containers, daily necessities, daily life goods and hygiene goods. Specific applications include air flow meters, air pumps, thermostat housings, engine mounts, ignition hobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, vacuum pump cases, inhibitor switches, rotations Sensor, Accelerometer, Distributor cap, Coil base, ABS actuator case, Radiator tank top and bottom, Cooling fan, Fan shroud, Engine cover, Cylinder head cover, Oil cap, Oil pan, Oil filter, Fuel cap, Fuel strainer , Distributor cap, vapor canister Automotive underhood parts such as uzing, air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, torque control lever, safety belt parts, Car interior parts such as register blade, washer lever, window regulator handle, knob of window regulator handle, passing light lever, sun visor bracket, various motor housings, roof rail, fender, garnish, bumper, door mirror stay, spoiler, food louver, Wheel covers, wheel caps, grill apron cover frames, lamp reflectors, lamp bezels, door handles, etc. Car exterior parts, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors, various automotive connectors, relay cases, coil bobbins, optical pickup chassis, motor cases, laptop computer housings and internal parts, CRT display housings and internal parts, Printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile PCs, handheld mobiles, recording medium (CD, DVD, PD, FDD, etc.) drive housings and internal parts, copier housings and internal parts And electrical / electronic parts such as facsimile housings and internal parts, parabolic antennas, and the like. Moreover, it is suitable also for electronic device housings, such as a notebook personal computer. Furthermore, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video camera, video equipment parts such as projectors, laser discs (registered trademark), compact discs (CD), CD-ROM , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts , Etc., home and office electrical appliance parts. Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, Optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders , Electrical and electronic parts such as transformer members, coil bobbins, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels, Hot walls, adjusters, plastic bundles, ceiling fishing gear, staircases, doors, floors and other building materials, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other marine products, vegetation nets, vegetation mats, weedproof bags, protection Grass net, curing sheet, slope protection sheet, fly ash holding sheet, drain sheet, water retention sheet, sludge / sludge dehydration bag, concrete formwork and other civil engineering related parts, gears, screws, springs, bearings, levers, key stems, cams , Ratchet, roller, water supply parts, toy parts, cable ties, clips, fans, tegus, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches and other mechanical parts, multi-films, tunnel films, prevention Bird sheet, Non-woven fabric for vegetation protection, Pot for seedling, Vegetation pile, Seed string tape, Germination sheet, House lining sheet, Agricultural fastener, Slow-release fertilizer, Agricultural materials such as root sheets, garden nets, insect nets, infant tree nets, print laminates, fertilizer bags, sample bags, sandbags, beast damage nets, inducement strings, windproof nets, paper diapers, sanitary wrapping materials, cotton swabs, towels , Hygiene items such as toilet seat wipes, medical non-woven fabrics (stitching reinforcements, anti-adhesion membranes, prosthetic repair materials), wound dressings, wound tape bandages, sticker base fabrics, surgical sutures, fracture reinforcements, medical Medical supplies such as film, calendar, stationery, clothing, food packaging film, tray, blister, knife, fork, spoon, tube, plastic can, pouch, container, tank, basket, etc. Fill containers, microwave cooking containers, cosmetic containers, wraps, foam buffers, paper laminates, shampoo bottles, beverage bottles, cups, candy packaging, Containers such as shrink labels, lid materials, envelopes with windows, fruit baskets, hand cut tape, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, wrapping films for electrical and electronic parts, etc. Packaging, natural fiber composites, polo shirts, T-shirts, innerwear, uniforms, sweaters, socks, ties, and other clothing, curtains, chairs, carpets, tablecloths, futons, wallpaper, furoshiki and other interior goods, carrier tape, Print lamination, heat sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather, non-woven fabric hot melt binder, magnetic material, zinc sulfide, electrode Powder binders for materials, optical elements, Electric embossed tape, IC tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, draining net, body towel, hand towel, tea pack, drainage filter, clear file, coating agent, adhesive, bag It is useful as chair, table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter and so on. It is also suitable as sports equipment, golf-related equipment such as golf clubs, shafts, grips, golf balls, sports racket-related equipment such as tennis rackets, badminton rackets and their guts, masks such as American football, baseball, softball, Body protection equipment for sports such as helmets, chest pads, elbow pads, knee pads, wear-related products such as sportswear, shoes-related products such as the bottom material of sports shoes, fishing gear-related items such as fishing rods, fishing lines, summer for surfing, etc. It is also suitably used for sports-related products, winter sports-related products such as skis and snowboards, and other indoor and outdoor sports-related products.

  Among the various uses described above, the molded article of the present invention is particularly useful for parts in contact with metals such as electrical / electronic parts and automobile parts, such as connectors or breakers, taking advantage of excellent metal adhesion.

  EXAMPLES Hereinafter, although an Example further demonstrates this invention in detail, this invention is not limited only to a following example. First, the evaluation method in an Example is demonstrated.

(1) Fluidity After the polyamide resin composition pellets obtained in each Example and Comparative Example were vacuum dried at 80 ° C. overnight, the cylinder temperature was set to 250 ° C. using SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd. An injection pressure was set to 30 MPa, a die temperature was 80 ° C., a 200 mm long × 10 mm wide × 1 mm thick rod flow test piece was injection-molded, and a rod flow length at a holding pressure of 0 was measured. The larger the flow length, the better the fluidity.

(2) Injection molding After the polyamide resin composition pellets obtained in each Example and Comparative Example were vacuum-dried at 80 ° C overnight, a cylinder temperature of 250 was used using an injection molding machine (SG75H-MIV) manufactured by Sumitomo Heavy Industries. An ASTM No. 1 type dumbbell test piece was produced by injection molding under the conditions of ℃, mold temperature 80 ° C, injection pressure lower limit pressure + 5 kgf / cm ² .

(3) Evaluation of tensile strength Using ASTM No. 1 dumbbell-shaped test piece obtained by the injection molding of (2) above, it was subjected to Tensilon UTA-2.5T (manufactured by Orientec Co., Ltd.), and according to ASTM-D638. Under an atmosphere of 23 ° C. and 50% humidity, a tensile test was performed at a distance between scores of 114 mm and a strain rate of 10 mm / min to measure the tensile strength.

(4) Evaluation of flexural modulus The ASTM No. 1 dumbbell test piece obtained by the injection molding of (2) above was used for Tensilon RTA-1T (manufactured by Orientec Corp.) and 23 ° C. according to ASTM-D790. In an atmosphere of 50% humidity, a bending test was performed at a distance between sample points of 100 mm and a strain rate of 3 mm / min, and the flexural modulus was measured.

(5) Resin / metal adhesion after hygroscopic heat drying treatment The polyamide resin composition pellets obtained in each example and comparative example were subjected to cylinder temperature using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industry Co., Ltd.). Molded at 10 mm from both ends of 5 mm x 5 mm x 50 mm long aluminum prisms at 250 ° C and mold temperature 80 ° C to cover a length of 5 mm and a length of 30 mm (molded part outer diameter is 15 mm x 15 mm) × 30 mm length), 20 moisture-absorbing and drying cycle metal adhesion test pieces were produced. Next, the obtained test piece was subjected to moisture absorption treatment at 65 ° C./90% RH for 48 hours using a constant temperature and humidity machine, and then dried at 110 ° C. for 24 hours using a hot air dryer. After the moisture absorption drying treatment, the test piece was immersed in red ink, washed with water and dried, and observed with a stereomicroscope to evaluate the presence or absence of cracks (penetration deep wound method). The number of test pieces in which ink oozing was observed from the resin and metal adhesion sites was counted. The smaller the number, the better the adhesion.

(6) Moldability After the polyamide resin composition pellets obtained in each example and comparative example were vacuum-dried at 80 ° C. overnight, a cylinder temperature of 250 was used using an injection molding machine (SG75H-MIV) manufactured by Sumitomo Heavy Industries, Ltd. An ASTM No. 1 type dumbbell test piece was produced by injection molding under the conditions of ℃, mold temperature 80 ° C, injection pressure lower limit pressure + 5 kgf / cm ² . The obtained molded product was observed to determine the presence or absence of blistering. When blisters are observed in a molded product, the amount of gas generated during molding is large and the stability during molding is low.

The polyamide resin (A) used in Reference Examples, Examples and Comparative Examples is as follows.
(A-1): Nylon 6 resin having a melting point of 225 ° C., a relative viscosity of 2.35 at 98 g in sulfuric acid at 0.01 g / ml, and an amino end group concentration of 4.4 × 10 ⁻⁵ mol / g.
(A-2): Nylon 66 resin having a melting point of 265 ° C., a relative viscosity of 3.60 in 98% sulfuric acid at 0.01 g / ml, and an amino end group concentration of 3.7 × 10 ⁻⁵ mol / g.
(A-3): Nylon 610 resin having a melting point of 225 ° C., a relative viscosity of 2.70 at 98 g in sulfuric acid at 0.01 g / ml, and an amino end group concentration of 4.0 × 10 ⁻⁵ mol / g.

The rubbery polymers (B) used in the examples and comparative examples are as follows.
(B-1): MFR 0.9 g / 10 min at 190 ° C. under a load of 2.16 kg, ethylene / methacrylic acid / zinc methacrylate copolymer “Himiran 1706” having an ionomer structure (manufactured by Mitsui DuPont Chemical)
(B-2): MFR 7 g / 10 min at 190 ° C. under a load of 2.16 kg, glycidyl methacrylate-modified polyethylene copolymer “Bond First 7L” (manufactured by Sumitomo Chemical Co., Ltd.).
(B-3): MFR 1.5 g / 10 min at 190 ° C. and a load of 2.16 kg, maleic anhydride-modified ethylene-1-butene copolymer “Tuffmer MH7020” (manufactured by Mitsui Chemicals).

The inorganic filler (D) used in the examples is as follows.
(D-1): Inorganic filler: Surface-treated glass fiber “T-249” (manufactured by Nippon Electric Glass Co., Ltd.).

Other additives used in the examples are as follows.
(E-1): Succinic anhydride (deer grade 1) (manufactured by Sigma-Aldrich).

Reference example 1
In a 500 mL reaction vessel equipped with a stirring blade and a distillation tube, 51.93 g (0.38 mol) of p-hydroxybenzoic acid, 19.1 g (0.10 mol) of 4,4′-dihydroxybiphenyl, and terephthalic acid 5. 86 g (0.035 mol), trimesic acid 21.2 g (0.10 mol), benzoic acid 5.55 g (0.045 mol), and 11.3 g (0. 059 mol) and 65.3 g of acetic anhydride (1.10 equivalents of the total phenolic hydroxyl groups) were allowed to react at 150 ° C. for 1.5 hours with stirring under a nitrogen gas atmosphere. After heating up to 290 ° C over 3 hours, the polymerization temperature was reduced to 1.0 mmHg (133 Pa) in 30 minutes while maintaining the polymerization temperature at 290 ° C, and the polymerization reaction was stopped when the stirring torque reached 2.5 kg · cm. The contents were discharged into the water. The obtained dendritic polyester (C-1) was heated and dried at 110 ° C. for 4 hours, pulverized using a blender, and washed with ethanol and deionized water. Then, it vacuum-dried at 110 degreeC using the vacuum heat dryer for 24 hours, and powdery dendritic polyester (C-1) was obtained.

  The obtained dendritic polyester (C-1) was subjected to nuclear magnetic resonance spectrum analysis. As a result, the trimesic acid content was 14 mol%.

  For the nuclear magnetic resonance spectrum, the sample was dissolved in a mixed solvent of 50% by weight of pentafluorophenol and 50% by weight of deuterated chloroform, and the nuclear magnetic resonance spectrum analysis of proton nuclei was performed at 40 ° C. 7.44 ppm and 8.16 ppm peaks derived from p-oxybenzoate units, 7.04 ppm, 7.70 ppm peaks derived from 4,4′-dioxybiphenyl units, 8.31 ppm peaks derived from terephthalate units, ethylene oxide units A peak at 4.75 ppm derived from 9.25 ppm derived from trimesic acid was detected. The trimesic acid content was calculated from the area intensity ratio of each peak, and the numbers after the decimal point were rounded off.

  The obtained dendritic polyester had a melting point of 235 ° C., a liquid crystal starting temperature of 191 ° C., and a number average molecular weight of 12,500. The melt viscosity measured using a Koka flow tester at a temperature of 270 ° C. and a shear rate of 100 / s was 18 Pa · s.

  The melting point (Tm) is 5 minutes at the temperature of Tm1 + 20 ° C. after observing the endothermic peak temperature (Tm1) observed when the polymer is measured at room temperature from 20 ° C./min in differential scanning calorimetry. After being held, the sample was once cooled to room temperature under a temperature drop condition of 20 ° C./min, and then the endothermic peak temperature (Tm) observed when measured again under a temperature rise condition of 20 ° C./min.

  The liquid crystal starting temperature is measured with a shear stress heating device (CSS-450) at a shear rate of 100 (1 / second), a heating rate of 5.0 ° C./min, and an objective lens 60 times, and the temperature at which the entire field of view starts to flow. It was measured.

The molecular weight was measured by GPC (gel permeation chromatograph) method under the following conditions.
Column: K-806M (2), K-802 (1) (Showa Denko)
Solvent: pentafluorophenol / chloroform = 35/65 (% by weight)
Flow rate: 0.8 mL / min
Sample concentration: 0.08% (wt / vol)
Injection volume: 0.200 mL
Temperature: 23 ° C
Detector: Differential refractive index (RI) detector (RI-8020 manufactured by Tosoh Corporation)
Calibration curve: Use calibration curve with monodisperse polystyrene

(Examples 1-13, Comparative Examples 1-19)
Each component shown in Tables 1 to 4 is dry blended in the proportions shown in Tables 1 to 4, and then supplied from a main feeder of TEX30 type twin screw extruder manufactured by Nippon Steel Works, with a cylinder set temperature of 250 ° C. and a screw rotation speed. Melt kneading was performed at 200 rpm. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The results of evaluating the fluidity, mechanical properties, and resin / metal adhesion after the hygroscopic heat drying treatment by the above methods are shown in Tables 1 to 4.

(Example 14)
After dry blending the polyamide resin (A-1) and the rubbery polymer (B-1) so as to be 60/40 (weight ratio), supplied from the TEX30 twin screw main feeder of Nippon Steel Works Then, melt kneading was performed at a cylinder set temperature of 250 ° C. and a screw rotation speed of 200 rpm. The gut discharged from the die is immediately cooled in a water bath and pelletized by a strand cutter, and the ratio of the polyamide resin (A-1) and the rubbery polymer (B-1) is 60/40 (weight ratio). Master pellets were obtained. Then, after dry blending the polyamide resin (A-1), the master pellet and the dendritic polyester (C-1) at a ratio of 100 / 11.1 / 2 (weight ratio), TEX30 type 2 manufactured by Nippon Steel Works The mixture was supplied from a main extruder main shaft, and melt kneading was performed at a cylinder set temperature of 250 ° C. and a screw rotation speed of 200 rpm. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. Table 2 shows the results of evaluating the fluidity, mechanical properties, and resin / metal adhesion after the hygroscopic heat drying treatment by the above method.

(Comparative Example 20)
Pellets of a polyamide resin composition were obtained in the same manner as in Example 14 except that the dendritic polyester (C-1) was not blended. Table 4 shows the results of evaluating the fluidity, mechanical properties, and resin / metal adhesion after the hygroscopic heat drying treatment by the above methods.

(Examples 15 to 17)
Furthermore, a polyamide resin composition was prepared in the same manner as in Example 3 except that glass fiber (D-1) was added as an inorganic filler at a ratio shown in Table 1 using a side feeder of TEX30 type twin screw extruder manufactured by Nippon Steel Works. Pellets were obtained. Table 2 shows the results of evaluating the fluidity, mechanical properties, and resin / metal adhesion after the hygroscopic heat drying treatment by the above method.

(Example 18)
Furthermore, it was carried out except that (E-1) succinic anhydride was supplied from the main feeder of TEX30 type twin screw extruder manufactured by Nippon Steel Co., Ltd. at the ratio shown in Table 1 as the amino terminal blocker of the polyamide resin (A-1). In the same manner as in Example 3, a polyamide resin composition pellet was obtained. Table 2 shows the results of evaluating the fluidity, mechanical properties, and resin / metal adhesion after the hygroscopic heat drying treatment by the above method.

  The polyamide resin composition comprising the polyamide resin (A), rubber polymer (B), and dendritic polyester (C-1) shown in Examples 1 to 14 in Tables 1 and 2 has high fluidity, strength and rigidity. In addition, the adhesion between the resin and the metal after the wet heat drying treatment is extremely excellent. Moreover, while the polyamide resin composition of Examples 15-17 shows the outstanding fluidity | liquidity even if glass fiber is added, the combined effect of rubber-like polymer (B-1) and dendritic polyester (C-1) is shown. Also, the resin-metal adhesion is excellent due to the effect of reducing the expansion and contraction of the resin during heat treatment by combining with glass fiber. Further, Example 18 is excellent in balance of strength and rigidity and adhesion between resin metals, and further, polyamide resin (A-1) and dendritic polyester (C-1) are blocked by amino terminal block of the polyamide resin with succinic anhydride. It can be seen that the ester amide exchange reaction is suppressed and the good fluidization effect by adding to the dendritic polyester resin (C-1) is more highly expressed.

(Comparative Examples 1-20)
Comparative Example 1 shown in Table 3 is a polyamide resin (A-1) alone, which is excellent in balance of strength and rigidity but inferior in metal adhesion. Furthermore, as shown in Comparative Examples 2-8, when only a rubber-like polymer (B) is added to a polyamide resin (A-1), fluidity | liquidity falls significantly and it is inferior also to metal adhesiveness. On the other hand, when only the dendritic polyester (C-1) is added to the polyamide resin (A-1) as shown in Comparative Examples 9 to 13, the fluidity is improved as the amount of addition increases, but the metal The adhesion was in a downward trend.

  When the addition amount of the dendritic polyester (C-1) exceeds 10 parts by weight as in Comparative Examples 14 to 16, the dendritic polyester is decomposed during melt-kneading and molding, and a large amount of gas is generated. Blistering occurred and productivity was reduced. On the other hand, when the rubbery polymer (B) exceeds 4 parts by weight as in Comparative Examples 17 to 19, fluidity, strength and rigidity of the molded product, and metal adhesion deteriorated. The decrease in fluidity causes molding defects in small and precision parts such as connectors and thin molded products, and the decrease in strength and rigidity becomes a problem that, for example, it becomes difficult to insert and remove connectors. In Comparative Example 20, the fluidity and metal adhesion decreased as compared with Example 14.

Claims (9)

0.1 to 4 parts by weight of the rubbery polymer (B) and 100 parts by weight of the polyamide resin (A), and the aromatic oxycarbonyl unit (P), aromatic and / or aliphatic dioxy unit (Q) And at least one structural unit selected from aromatic dicarboxy units (R) and a trifunctional or higher functional organic residue (S), and the S content constitutes the dendritic polyester. A polyamide resin composition obtained by blending 0.01 to 10 parts by weight of a dendritic polyester resin (C) having a melt liquid crystallinity in a range of 7.5 to 50 mol% in a unit. The polyamide resin composition according to claim 1, wherein 0.1 to 200 parts by weight of an inorganic filler is further blended with 100 parts by weight of the polyamide resin (A). The polyamide resin composition according to claim 1, wherein the rubber polymer (B) contains an olefin resin. The polyamide resin composition according to claim 3, wherein the olefin-based resin contains at least one selected from an ethylene / unsaturated carboxylic acid copolymer and an ethylene / α, β-unsaturated carboxylic acid ester copolymer. The ethylene / unsaturated carboxylic acid copolymer has an ionomer structure in which at least a part of the unsaturated carboxylic acid is a metal salt and the molecules of the ethylene / unsaturated carboxylic acid copolymer are crosslinked with metal ions. Item 5. The polyamide resin composition according to Item 4. A molded product formed by melt-molding the polyamide resin composition according to any one of claims 1 to 5. A resin metal composite comprising a polyamide resin member obtained by melt-molding the polyamide resin composition according to any one of claims 1 to 5 and a metal member, wherein the metal member is in contact with the polyamide resin member Complex. The molded product for electrical / electronic parts according to claim 6. The resin metal composite for electric / electronic parts according to claim 7.