JP2015129271A - Carbon fiber-reinforced polyamide resin composition and molded article obtained by molding the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a carbon fiber-reinforced polyamide resin composition capable of giving a molded article excellent in mechanical characteristics and adhesion to metals, and to provide a molded article obtained by molding the same.SOLUTION: The carbon fiber-reinforced polyamide resin composition contains 10-100 pts.wt. of carbon fibers (B) and 0.1-10 pts.wt. of an epoxy compound (C) having a number-average molecular weight of 10,000 or less, based on 100 pts.wt. of a semi-aromatic polyamide resin (A) which contains a dicarboxylic acid unit and a diamine unit, where the dicarboxylic acid unit contains 50-100 mol% of a terephthalic acid unit and the diamine unit contains 50-100 mol% of a C6-C18 aliphatic alkylenediamine unit.

Description

  The present invention relates to a carbon fiber reinforced polyamide resin composition excellent in metal adhesion and mechanical properties and a molded product formed by molding the same.

  Polyamide resins have excellent mechanical properties such as rigidity and strength, heat resistance, etc., and are therefore used in a wide variety of fields such as electric / electronics, automobiles, machines, and building materials. Semi-aromatic polyamides typified by polyamide 6T and polyamide 10T are excellent in heat absorption and mechanical properties, as well as low water absorption, so they are used as parts around many electric / electronic parts and automobile engines. Used in combination with other materials such as metals according to various purposes.

  In recent years, the demand for higher performance of plastics has become higher, and metal equivalent rigidity has been demanded. In order to achieve rigidity equivalent to that of metal, a method of filling a fibrous filler such as carbon fiber is generally used. So far, as a polyamide resin composition having improved moldability in addition to mechanical properties, for example, a dicarboxylic acid component mainly composed of terephthalic acid, 1,8-octanediamine, and 1,10-decanediamine A polyamide resin composition comprising a diamine component which is any one of 1,12-dodecanediamine and having a supercooling degree ΔT of 40 ° C. or less and a fibrous reinforcing material has been proposed ( For example, see Patent Document 1). Further, as a semi-aromatic polyamide resin composition pellet with improved mechanical properties, a semi-aromatic polyamide resin composed of a terephthalic acid component and a linear aliphatic diamine having 8 to 12 carbon atoms, or an inorganic fiber, A semi-aromatic polyamide resin composition pellet containing a fibrous reinforcing material that is an organic fiber whose melting point or decomposition temperature exceeds the melting point of an aromatic polyamide has been proposed (see, for example, Patent Document 2). Moreover, as a polyamide resin composition having improved long-term heat resistance in addition to mechanical properties, for example, a dicarboxylic acid unit containing 50 to 100 mol% of a terephthalic acid unit and an aliphatic diamine unit having 6 to 18 carbon atoms Is modified with an unsaturated compound having a terminal amino group content of 10 µequivalent / g or more and less than 60 µequivalent / g, a carboxyl group, and / or an acid anhydride machine. A polyamide resin composition comprising a modified resin and a filler has been proposed (see, for example, Patent Document 3). However, in these techniques, while mechanical characteristics are improved, there is a problem that metal adhesion is insufficient by blending carbon fibers.

JP 2013-28798 A JP 2013-49793 A JP 2008-179753 A

  The present invention solves the problems of the conventionally known carbon fiber reinforced polyamide resin composition and can obtain a molded article excellent in mechanical properties and metal adhesion, pellets and molding the same. It is an object of the present invention to provide a molded product.

The present invention was obtained as a result of intensive studies by the present inventors in order to solve the above problems, and has the following configuration.
(1) A polyamide resin containing a dicarboxylic acid unit and a diamine unit, wherein the dicarboxylic acid unit contains 50 to 100 mol% of a terephthalic acid unit, and the aliphatic alkylenediamine unit having 6 to 18 carbon atoms in the diamine unit. Epoxy compound (C) 0.1 to 10 having 10 to 100 parts by weight of carbon fiber (B) and a number average molecular weight of 10,000 or less with respect to 100 parts by weight of semi-aromatic polyamide resin (A) containing 50 to 100 mol%. A carbon fiber reinforced polyamide resin composition obtained by blending parts by weight.
(2) The carbon fiber reinforced polyamide resin according to (1), wherein 0.01 to 10 parts by weight of a dendritic polyester resin (D) is further blended with 100 parts by weight of the semi-aromatic polyamide resin (A). Composition.
(3) The carbon fiber reinforced polyamide resin composition according to (1) or (2), wherein the semi-aromatic polyamide resin (A) contains 50 to 100 mol% of 1,10-decanediamine units in the diamine units. .
(4) A pellet obtained by molding the carbon fiber-reinforced polyamide resin composition according to any one of (1) to (3), wherein the weight average fiber length of the carbon fiber (B) is 0.01 to 2 mm.
(5) A molded product obtained by molding the pellet according to (4).
(6) A composite molded product obtained by joining or bonding the molded product according to (5) and a metal.

  According to the carbon fiber reinforced polyamide resin composition of the present invention and pellets using the same, a molded product having excellent mechanical properties, low water absorption, and excellent metal adhesion can be obtained. Therefore, the carbon fiber reinforced polyamide resin composition of the present invention, and pellets and molded articles using the same are preferably used for electrical / electronic parts, automobile parts, and sporting goods that are joined to metals such as connectors, breakers, and bicycle pedals. Can do.

It is the schematic which shows the test piece for metal adhesiveness evaluation in an Example and a comparative example.

  The carbon fiber reinforced polyamide resin composition of the present invention (hereinafter sometimes referred to as “resin composition”) will be specifically described below.

  The resin composition of the present invention is a polyamide resin containing a dicarboxylic acid unit and a diamine unit, containing 50 to 100 mol% of a terephthalic acid unit in the dicarboxylic acid unit, and having 6 to 18 carbon atoms in the diamine unit. A semi-aromatic polyamide resin (A) containing 50 to 100 mol% of an alkylene alkylenediamine unit (hereinafter sometimes referred to as “semi-aromatic polyamide resin (A)”) is blended. By blending such a semi-aromatic polyamide resin (A), the mechanical properties and low water absorption of a molded product obtained from the resin composition can be improved.

  The dicarboxylic acid unit constituting the semiaromatic polyamide resin (A) contains 50 to 100 mol% of terephthalic acid units. When the content of the terephthalic acid unit is less than 50 mol%, properties such as heat resistance, low water absorption and surface appearance of the molded product obtained from the resin composition are deteriorated. 60-100 mol% is preferable and, as for the content rate of a terephthalic acid unit, 70-100 mol% is more preferable. Here, the dicarboxylic acid unit means a structural unit produced by polycondensation of dicarboxylic acid or its derivative constituting the polyamide resin.

  The dicarboxylic acid unit constituting the semi-aromatic polyamide resin (A) may contain a dicarboxylic acid unit other than the terephthalic acid unit as long as it is less than 50 mol%. Examples of dicarboxylic acid units other than terephthalic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, Aliphatic dicarboxylic acids such as 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, 4,4 '-Oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4, '- dicarboxylic acid, there may be mentioned units derived from aromatic dicarboxylic acids such as 4,4'-biphenyl dicarboxylic acid, can be used one or two or more of them.

  Among these, units derived from aromatic dicarboxylic acids are preferred. The content of these other dicarboxylic acid units is preferably 40 mol% or less, more preferably 30 mol% or less in the dicarboxylic acid. Further, units derived from polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid may be included within a range in which melt molding is possible.

  50-100 mol% of C6-C18 aliphatic alkylenediamine units are contained in the diamine unit which comprises a semi-aromatic polyamide resin (A). When the content of the aliphatic alkylenediamine unit having 6 to 18 carbon atoms is less than 50 mol%, the melt stability of the resin composition, the toughness of the molded product obtained from the resin composition, low water absorption, and chemical resistance Any of the characteristics such as heat resistance and surface appearance deteriorates. 60-100 mol% is preferable and, as for the content rate of a C6-C18 aliphatic alkylenediamine unit, 75-100 mol% is more preferable. Here, the diamine unit in the present invention means a structural unit produced by polycondensation of a diamine constituting a polyamide resin or a derivative thereof.

  Examples of the aliphatic alkylene diamine unit having 6 to 18 carbon atoms include 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, linear aliphatic alkylenediamine such as 1,12-dodecanediamine, 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl -1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4-butanediamine, 2,3 -Dimethyl-1,4-butanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2,5-dimethyl-1,6- Xylenediamine, 2,4-dimethyl-1,6-hexanediamine, 3,3-dimethyl-1,6-hexanediamine, 2,2-dimethyl-1,6-hexanediamine, 2,2,4-trimethyl- 1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexanediamine, 2,2-dimethyl-1,7-heptanediamine, 2, 3-dimethyl-1,7-heptanediamine, 2,4-dimethyl-1,7-heptanediamine, 2,5-dimethyl-1,7-heptanediamine, 2-methyl-1,8-octanediamine, 3- Methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,8-octanedia 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 2,2-dimethyl-1,8 -From branched aliphatic alkylene diamines such as octanediamine, 3,3-dimethyl-1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, and 5-methyl-1,9-nonanediamine Examples of the unit to be derived can be given, and one or more of these can be used.

  Among the above aliphatic alkylenediamine units, 1,6-hexanediamine, from the viewpoint of further improving the melt stability of the resin composition, the low water absorption of the molded product obtained from the resin composition, the heat resistance, and the surface appearance. Units derived from 1,8-octanediamine, 2-methyl-1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine Preferably, units derived from 2-methyl-1,8-octanediamine, 1,9-nonanediamine, and 1,10-decanediamine are more preferable. By containing a unit derived from 2-methyl-1,8-octanediamine and / or 1,9-nonanediamine, the surface appearance of the molded product can be further improved. By containing a unit derived from 1,10-decanediamine, the water absorption rate of the molded product can be further reduced, and the decrease in rigidity and dimensional change during water absorption can be suppressed.

  If the diamine unit which comprises a semi-aromatic polyamide resin (A) is 50 mol% or less, you may contain diamine units other than a C6-C18 aliphatic alkylenediamine unit. Examples of the diamine unit other than the aliphatic alkylene diamine unit having 6 to 18 carbon atoms include aliphatic diamines such as ethylenediamine, propanediamine, and 1,4-butanediamine; cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, and norbornanedimethylamine. Alicyclic diamines such as tricyclodecane dimethylamine; p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl Examples thereof include units derived from sulfones and aromatic diamines such as 4,4′-diaminodiphenyl ether, and one or more of these units can be used. The content of these other diamine units is preferably 40 mol% or less, and more preferably 25 mol% or less in the diamine unit.

  Moreover, the semi-aromatic polyamide resin (A) may further contain an aminocarboxylic acid unit in addition to the above-mentioned dicarboxylic acid unit and diamine unit. Examples of the aminocarboxylic acid unit include units derived from lactams such as caprolactam and lauryllactam; aminocarboxylic acids such as 1-aminolauric acid and 1-aminododecylic acid. The content of aminocarboxylic acid units is preferably 40 mol% or less, more preferably 20 mol% or less, based on 100 mol% of all dicarboxylic acid units constituting the semiaromatic polyamide resin (A).

  In the resin composition of the present invention, the relative viscosity (ηr) of the semiaromatic polyamide resin (A) is preferably 2.0 to 2.8. If the relative viscosity of the semi-aromatic polyamide resin (A) is 2.0 or more, the mechanical properties of the molded product can be further improved. 2.1 or more is more preferable, and 2.2 or more is more preferable. On the other hand, if the relative viscosity of the semi-aromatic polyamide resin (A) is 2.8 or less, the moldability of the resin composition can be improved. 2.7 or less is more preferable, 2.6 or less is more preferable, and 2.5 or less is more preferable. The relative viscosity of the semi-aromatic polyamide resin (A) is a value measured using an Ostwald viscometer in 98% sulfuric acid at a resin concentration of 0.01 g / ml and 25 ° C. Examples of means for setting the relative viscosity of the semi-aromatic polyamide resin (A) in such a range include, for example, a method of appropriately adjusting polymerization conditions such as pressure, temperature, polymerization time, etc. during production of the semi-aromatic polyamide resin, The method of adjusting raw material compositions, such as diamine and a terminal blocker, etc. are mentioned.

  In the semi-aromatic polyamide resin (A), it is preferable that 10% or more of the end groups of the molecular chain thereof are sealed with an end-capping agent such as benzoic acid or acetic acid. When the end sealing rate is 10% or more, the melt moldability of the resin composition can be improved. The end sealing rate is more preferably 20% or more.

  As a method for producing the semi-aromatic polyamide resin (A), for example, a diamine component and a dicarboxylic acid component or a salt as raw materials are heated to obtain a low-order condensate, and further by solid phase polymerization and / or melt polymerization. Examples thereof include a method for increasing the degree of polymerization. Two-stage polymerization in which the low-order condensate is once taken out and solid-phase polymerization and / or melt polymerization is performed. Following the production process of the low-order condensate, solid-phase polymerization and / or melt polymerization in the same reaction vessel Either of these may be used. Solid phase polymerization refers to a step of heating in a temperature range of 100 ° C. or higher and lower than the melting point under reduced pressure or in an inert gas, and melt polymerization refers to a step of heating to a melting point or higher under normal pressure or reduced pressure. Point to.

  The resin composition of this invention mix | blends a carbon fiber (B). By blending the carbon fiber (B), mechanical properties such as rigidity and strength of the molded product can be improved.

  The carbon fiber (B) in the present invention is not particularly limited, and carbon fibers produced using various known carbon fibers such as polyacrylonitrile (PAN), pitch, rayon, lignin, hydrocarbon gas, etc. Examples thereof include graphite fibers. You may use the fiber which coat | covered these fibers with metals, such as nickel, copper, and ytterbium. Of these, PAN-based carbon fibers are preferred because they are more excellent in improving mechanical properties. The carbon fiber (B) is usually in the shape of chopped strand, roving strand, milled fiber, etc., and the diameter is generally 15 μm or less, preferably 5 to 10 μm.

  The form of the carbon fiber (B) in the present invention is not particularly limited, but a carbon fiber bundle composed of several thousand to several hundred thousand carbon fibers and a milled form obtained by pulverizing the carbon fiber bundle are preferable. As for the carbon fiber bundle, it is possible to use a carbon fiber bundle obtained by a roving method using continuous fibers directly or a chopped strand cut to a predetermined length.

  The carbon fiber (B) in the present invention is preferably a chopped strand, and the number of filaments of the carbon fiber strand that is a precursor of the chopped carbon fiber is preferably 1,000 to 150,000. If the number of filaments of the carbon fiber strand is 1,000 to 150,000, the manufacturing cost can be suppressed and the stability in the production process can be ensured.

  150 GPa or more is preferable and, as for the strand elastic modulus of the carbon fiber (B) in this invention, 220 GPa or more is more preferable. On the other hand, the strand elastic modulus is preferably 1000 GPa or less, and more preferably 500 GPa or less. When the strand elastic modulus of the carbon fiber is within the above range, a resin composition that is superior in mechanical properties and moldability can be obtained.

  The strand strength of the carbon fiber (B) in the present invention is preferably 1 GPa or more, and more preferably 3 GPa or more. On the other hand, the strand strength is preferably 10 GPa or less, and more preferably 5 GPa or less. If the strand strength of the carbon fiber is within the above range, the mechanical properties of the molded product can be further improved, and the surface appearance can be further improved by reducing the waviness irregularities on the surface of the molded product.

  Here, the strand elastic modulus and strand strength refer to the elastic modulus and strength of a strand produced by impregnating and curing an epoxy resin to a continuous fiber bundle composed of 1,000 to 150,000 carbon fiber single fibers. This is a value obtained by subjecting the test piece to a tensile test according to JIS R7601.

  The carbon fiber (B) in the present invention may be subjected to surface oxidation treatment. Examples of the surface oxidation treatment include surface oxidation treatment by energization treatment, oxidation treatment in an oxidizing gas atmosphere such as ozone, and the like.

  Further, the carbon fiber (B) may have a coupling agent, a sizing agent or the like attached to the surface thereof, and can improve the wettability and handling of the semi-aromatic polyamide resin (A). it can. Examples of the coupling agent include amino-based, epoxy-based, chloro-based, mercapto-based, and cationic-based silane coupling agents, and amino-based silane coupling agents can be suitably used. Examples of the sizing agent include maleic anhydride compounds, urethane compounds, acrylic compounds, epoxy compounds, phenol compounds, derivatives of these compounds, and the like, and sizing agents containing urethane compounds and epoxy compounds. Can be suitably used. The content of the coupling agent and sizing agent in the carbon fiber (B) is preferably 0.1 to 10% by weight. When the content of the sizing agent is 0.1 to 10% by weight, the wettability with the semi-aromatic polyamide resin (A) and the handleability are excellent. More preferably, it is 0.5 to 6% by weight.

  Further, the carbon fiber (B) in the present invention may be provided with a sizing agent. Examples of a method for producing a chopped carbon fiber by applying a sizing agent to a strand of carbon fiber include, for example, a method employed in a glass fiber chopped strand in JP-B-62-9541, and JP-A-62-244606. The method described in Japanese Patent Laid-Open No. 5-261729 can be applied.

  The compounding quantity of the carbon fiber (B) in the resin composition of this invention is 10-100 weight part with respect to 100 weight part of semi-aromatic polyamide resin (A). When the blending amount of the carbon fiber (B) is less than 10 parts by weight, the rigidity, mechanical properties, metal adhesion and low water absorption of the molded product are lowered. On the other hand, when the compounding amount of the carbon fiber (B) exceeds 100 parts by weight, the productivity and moldability of the resin composition are lowered, and the surface appearance, impact resistance and metal adhesion of the molded product are lowered. 90 parts by weight or less is preferable, and 80 parts by weight or less is more preferable.

  The resin composition of the present invention comprises an epoxy compound (C) having a number average molecular weight of 10,000 or less (hereinafter sometimes referred to as “epoxy compound”). By mix | blending an epoxy compound (C), the interface adhesiveness of semi-aromatic polyamide and carbon fiber can be improved, and the mechanical characteristic and metal adhesiveness of the molded article obtained from a resin composition can be improved.

  The number average molecular weight of the epoxy compound (C) in the present invention is 10,000 or less. When the number average molecular weight exceeds 10,000, the viscosity of the resin composition increases, the moldability decreases, and the metal adhesiveness decreases. The number average molecular weight is preferably 5000 or less, more preferably 4000 or less, and still more preferably 3000 or less. On the other hand, from the viewpoint of improving the moldability of the resin composition, the number average molecular weight of the epoxy compound (C) is preferably 100 or more, more preferably 500 or more, and even more preferably 1000 or more. In addition, the number average molecular weight of an epoxy compound (C) is computable by specifying structural formula with a normal analysis method (for example, combination of NMR, FT-IR, GC-MS etc.). In the case of a high molecular compound, it can be calculated by gel permeation chromatography (GPC).

  The epoxy compound (C) in the present invention refers to a compound having at least one epoxy group in one molecule. A compound having two or more epoxy groups in one molecule is preferable because it is excellent in the moldability of the resin composition, the mechanical properties of the molded article, and the bonding adhesiveness to metal.

  Examples of the epoxy compound (C) include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetrabromobisphenol A, resorcinol, hydroquinone, olocaterol, saligenin, 1,3,5-trihydroxybenzene, trihydroxy-diphenyldimethyl. Bisphenol-type epoxy compounds such as methane, 4,4′-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, ethylene glycol, propylene glycol, Diglycidyl ether epoxy compounds of diols such as neopentyl glycol, diglycol of polyether diols such as polypropylene glycol and polyethylene glycol Dil ether type epoxy compound, glycidyl ester type epoxy compound, glycidyl amine type epoxy compound, phenol type epoxy compound, cresol type epoxy compound, alicyclic epoxy compound, silicon modified epoxy compound, rubber modified epoxy compound, epoxidized polyolefin, epoxidized Examples include soybean oil, epoxy compounds having a naphthalene skeleton, epoxy compounds having a dicyclopentanediene skeleton, and epoxy compounds having a limonene skeleton. Two or more of these epoxy compounds (C) may be blended.

  Among these, a bisphenol type epoxy compound and a diglycidyl ether type epoxy compound are preferable, and a bisphenol type epoxy compound is more preferable because the moldability of the resin composition and the metal adhesion of the molded product are more excellent.

  The compounding quantity of the epoxy compound (C) in the resin composition of this invention is 0.1-10 weight part with respect to 100 weight part of semi-aromatic polyamide resin (A). When the compounding amount of the epoxy compound (C) is less than 0.1 parts by weight, the mechanical properties and metal adhesion of the molded product are deteriorated. The compounding amount of the epoxy compound (C) is preferably 0.2 parts by weight or more, and more preferably 0.5 parts by weight or more. On the other hand, when the compounding quantity of an epoxy compound (C) exceeds 10 weight part, the residence stability of a resin composition and the mechanical characteristic of a molded article will fall. The amount of the epoxy compound (C) is preferably 8 parts by weight or less, and more preferably 5 parts by weight or less.

  A dendritic polyester resin (D) can be mix | blended with the resin composition of this invention. By blending the dendritic polyester resin (D), the moldability of the resin composition can be greatly improved.

  The dendritic polyester resin (D) in the present invention comprises an aromatic oxycarbonyl unit (P), an aromatic and / or aliphatic dioxy unit (Q), an aromatic dicarbonyl unit (R), and a trifunctional or higher functional organic compound. Residue (S) is included, and the content of (S) is in the range of 7.5 to 50 mol% with respect to all monomers constituting the dendritic polyester resin, and exhibits melt liquid crystallinity. preferable.

  Here, the aromatic oxycarbonyl unit (P), the aromatic and / or aliphatic dioxy unit (Q), and the aromatic dicarbonyl unit (R) are structures represented by the following general formula (3), respectively. Preferably it is a unit.

Here, R ₁ and R ₃ are each an aromatic residue. R ₂ is an aromatic residue or an aliphatic residue. R ₁ , R ₂ and R ₃ 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. R ₁ , R ₂ and R ₃ are each preferably at least one selected from structural units represented by the following structural formula (4).

  In the formula, Y is at least one selected from a hydrogen atom, a halogen atom and an alkyl group. As an alkyl group, a C1-C4 alkyl group is preferable. In the formula, n is an integer of 2 to 8.

  In the dendritic polyester resin (D) of the present invention, the trifunctional or higher functional organic residue (S) consists of the above-mentioned P, Q and R which are directly or mutually branched by an ester bond and / or an amide bond. The basic skeleton is a branched structure of three or more branches connected through a structural unit. It is not necessary for all of the polymers to be composed of the basic skeleton, and other structures may be included at the ends, for example, for end capping. The dendritic polyester resin may contain a structure in which all functional groups of (S) are reacted, a structure in which only two are reacted, and a structure in which only one is reacted. . The structure in which all the functional groups of (S) have reacted is preferably 30 mol% or more with respect to the entire (S).

  The dendritic polyester resin (D) in 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.

  The trifunctional organic residue (S) is preferably an organic residue of a compound having a carboxyl group, a hydroxyl group or an amino group. It may be an organic residue of a compound having two or more of these groups. For example, aliphatic compounds such as glycerol, 1,2,3-tricarboxypropane, diaminopropanol, diaminopropionic acid, trimesic acid, trimellitic acid, 4-hydroxy-1,2-benzenedicarboxylic acid, phloroglucinol, Residues of aromatic compounds such as resorcinic acid, tricarboxynaphthalene, dihydroxynaphthoic acid, aminophthalic acid, 5-aminoisophthalic acid, aminoterephthalic acid, diaminobenzoic acid and melamine are preferably used. A residue of an aromatic compound represented by the following general formula (5) is more preferable.

  Specific examples of the above trifunctional organic residues include residues such as phloroglucinol, trimesic acid, trimellitic acid, trimellitic anhydride, α-resorcylic acid, 4-hydroxy-1,2-benzenedicarboxylic acid Is more preferable, and a residue of trimesic acid is more preferable.

  In addition, the aromatic hydroxycarbonyl unit (P), aromatic and / or aliphatic dioxy unit (Q), and aromatic dicarbonyl unit (R) of the dendritic polyester resin (D) are between the branches of the dendritic polyester resin. It is a unit constituting a branch structure part. p, q, and r are the average contents (molar ratio) of the structural units P, Q, and R, respectively, and in the range of p + q + r = 2 to 6 mol with respect to 1 mol of the content d of (S). Is preferred. When the branch chain length is in the above range, effects such as shear responsiveness based on a rigid and detailed dendritic structure are sufficiently exhibited.

  The values of p, q, and r are, for example, in the nuclear magnetic resonance spectrum of proton nuclei at 40 ° C. in a solution of dendritic polyester resin dissolved in a mixed solvent of 50% by weight of pentafluorophenol: 50% by weight of deuterated chloroform. It can obtain | require from the peak intensity ratio derived from a 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 respect to the peak corresponding to the content d of the branched structure D, the average chain length of the branched structure portion is calculated and set as the value of p + q + r. In this case, the three decimal places are rounded off.

  The ratio between p and q and the ratio between p and r (p / q, p / r) are preferably in the range of 5/95 to 95/5. 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 set to an appropriate range. Further, by setting p / q and p / r to be 5/95 or more, the melt liquid crystallinity of the dendritic polyester resin can be expressed more effectively.

  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 0.9 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.

In the general formula (3), R ₁ is a structural unit derived from an aromatic oxycarbonyl unit, preferably a structural unit derived from p-hydroxybenzoic acid, and a part of the structural unit derived from 6-hydroxy-2-naphthoic acid. It can also be used in combination. In addition, a structural unit derived from an aliphatic hydroxycarboxylic acid such as glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid and the like may be contained as long as the effects of the present invention are not impaired.

R ₂ is a structural unit derived from an aromatic and / or aliphatic dioxy unit and includes a structural unit derived from 4,4′-dihydroxybiphenyl and hydroquinone or 4,4′-dihydroxybiphenyl and ethylene glycol. It is preferable from the viewpoint of control.

R ₃ is a structural unit derived from an aromatic dicarbonyl unit, and is preferably a structural unit derived from terephthalic acid or isophthalic acid. Particularly, when both are used in combination, the melting point can be easily adjusted. A part of the structural unit derived from aliphatic dicarboxylic acid such as sebacic acid or adipic acid may be contained.

  The branch structure portion of the dendritic polyester resin (D) in the present invention 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 characteristics are not greatly affected. Is possible. By introducing such another bond, compatibility with a wide variety of thermoplastic resins can be adjusted. Among them, it is preferable to introduce an amide structure. Examples of the method for introducing an amide bond include a method of copolymerizing an aliphatic, alicyclic, or aromatic amine compound. Examples of the aliphatic amine compound include tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, 2-methylpentamethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4- / 2, Examples include 4,4-trimethylhexamethylenediamine and 5-methylnonamethylenediamine. Examples of the alicyclic amine compound include 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, Examples thereof include bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine and the like. Examples of the aromatic amine compound include p-aminobenzoic acid, m-aminobenzoic acid, p-aminophenol, m-aminophenol, p-phenylenediamine, m-phenylenediamine, and the like. Two or more of these may be used. Of these, p-aminophenol or p-aminobenzoic acid is preferred.

  As the branch structure portion of the dendritic polyester resin, those composed of the following structural units (I), (II), (III), (IV) and (V), or the following structural units (I), (II ), (VI) and (IV) are preferred.

  When the branch structure part is composed of the structural units (I), (II), (III), (IV) and (V), the content p of the structural unit (I) 45-60 mol% is preferable with respect to total p + q + r. In addition, the content q (II) of the structural unit (II) is preferably 65 to 73 mol% with respect to the total content q of the structural units (II) and (III). The content r (IV) of the structural unit (IV) is preferably 62 to 68 mol% with respect to the total content r of the structural units (IV) and (V). In such a case, the moldability can be further improved.

  As described above, the total content q of the structural units (II) and (III) and the total content r of (IV) and (V) are preferably substantially equimolar. An excess may be added.

  When the branch structure portion is composed of the structural units (I), (II), (VI) and (IV), the content p of the structural unit (I) is 40 to 80 with respect to p + q + r. Mole% is preferred. The content q (VI) of the structural unit (VI) is preferably 8 to 60 mol% with respect to the total content q of (II) and (VI). As described above, the content r of the structural unit (IV) is preferably substantially equimolar to the total content q of the structural units (II) and (VI). May be added.

  Moreover, it is preferable that the terminal of the dendritic polyester resin (D) in this invention is a carboxyl group, a hydroxyl group, an amino group, or the residue of those derivatives. Examples of the hydroxyl group 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 acid anhydride compound, or the like. The end-capping method includes adding a monofunctional organic compound in advance when synthesizing a dendritic polyester resin, or adding a monofunctional organic compound when the dendritic polyster skeleton is formed to some extent. The method of doing is 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- Methyl benzoic acid, 3-methyl benzoic acid, 3,5-dimethyl benzoic acid and the like are preferably added.

  When blocking the carboxyl group end, acetoxybenzene, 1-acetoxy-4-t-butylbenzene, 1-acetoxy-3-t-butylbenzene, 1-acetoxy-4-chlorobenzene, 1-acetoxy-3 It is preferable to add -chlorobenzene, 1-acetoxy-4-cyanobenzene or the like.

  Theoretically, the end-capping is possible by adding an amount of the organic compound used for end-capping corresponding to the end group to be capped. From the viewpoint of effectively performing end-capping, it is preferable to use 1.008-fold equivalent or more of the organic compound used for end-capping with respect to the equivalent amount of the end group to be capped. On the other hand, from the viewpoint of suppressing a reduction in reaction rate and gas generation due to an excessive end-capping agent remaining in the system, the amount of organic compound used for end-capping is preferably 1.5 times equivalent or less.

  Moreover, content of an organic residue (S) is 7.5 mol% or more with respect to content of all the monomers which comprise dendritic polyester resin (D), and 20 mol% or more is preferable. In such a case, the chain length of the branch structure portion is preferable because the dendritic polyester resin is suitable for taking a dendritic form. As an upper limit of content of an organic residue (S), it is 50 mol% or less, and 40 mol% or less is preferable.

  Moreover, the dendritic polyester resin (D) in this invention may have a crosslinked structure partially in the range which does not affect a characteristic.

In the present invention, the production method of the dendritic polyester resin (D) is not particularly limited, and for example, a method disclosed in Japanese Patent No. 5182914 can be used according to a known polyester polycondensation method. For example, a monomer containing a structural unit represented by the R _1, monomer containing a structural unit represented by the R _2, monomers and trifunctional a structural unit represented by R ₃ The method of making a monomer react is mentioned, The addition amount (mol) of a trifunctional monomer shall be 7.5 mol% or more with respect to all the monomers (mol) which comprise dendritic polyester resin. The method is preferred. The addition amount of the trifunctional monomer is more preferably 20 mol% or more.

In the above reaction, an embodiment in which a trifunctional monomer is reacted after acylating a monomer containing at least one selected from structural units represented by R ₁ , R ₂ and R ₃ is also preferred. Also preferred is an embodiment in which a monomer containing at least one selected from structural units represented by R ₁ , R ₂ and R ₃ and a trifunctional monomer are acylated and then subjected to a polymerization reaction.

  In the case of producing a dendritic polyester resin composed of the structural units (I), (II), (III), (IV) and (V) and a trimesic acid residue, p-hydroxybenzoic acid is taken as an example. , 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid and isophthalic acid are reacted with acetic anhydride to acylate the phenolic hydroxyl group, and then a liquid crystalline polyester oligomer is synthesized by a deacetic acid polycondensation reaction. Further, trimesic acid Is preferable from the viewpoints of chain length control and steric regulation.

  The blending amount of acetic anhydride is preferably 0.95 equivalents or more and 1.10 equivalents or less of the total of phenolic hydroxyl groups from the viewpoint of chain length control. It is possible to adjust the terminal group by adjusting the amount of acetic anhydride, adding an excess of either a dihydroxy monomer or a dicarboxylic acid monomer, or the like.

  In order to increase the molecular weight, an amount of dihydroxy monomer such as hydroquinone or 4,4′-dihydroxybiphenyl is excessively added to the dicarboxylic acid monomer by an amount corresponding to the amount of carboxylic acid of trimesic acid. The acid and the hydroxyl equivalent are preferably combined. On the other hand, when the carboxylic acid is intentionally left in the terminal group, it is preferable not to add the dihydroxy monomer as described above excessively. Furthermore, when the hydroxyl group is intentionally left at the terminal, the dihydroxy monomer is added in excess of the carboxylic acid equivalent of trimesic acid, and the amount of acetic anhydride used is less than 1.00 equivalent of the phenolic hydroxyl group. preferable.

  By these methods, the dendritic polyester resin (D) in the present invention can be selectively provided with a terminal group structure rich in reactivity with the (A) semi-aromatic polyamide resin in the present invention. However, depending on the structure of the (A) semi-aromatic polyamide resin, in order to suppress excessive reactivity, it may be easier to control the dispersion state by blocking the end with a monofunctional epoxy compound or the like.

  In the case of performing the deacetic acid polycondensation reaction, a melt polymerization method is preferable in which the dendritic polyester resin is reacted at a temperature at which the dendritic polyester resin is melted, sometimes under reduced pressure, and a predetermined amount of acetic acid is distilled to complete the polycondensation reaction. . Specifically, the following method is mentioned, for example. A predetermined amount of p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid, and acetic anhydride are charged into a reaction vessel equipped with a stirring blade and a distillation pipe and having a discharge port at the bottom. . The mixture in the reaction vessel is heated with stirring under a nitrogen gas atmosphere to acetylate the hydroxyl group, and then heated to 200 to 350 ° C. to perform a deacetic acid polycondensation reaction to distill acetic acid. When acetic acid is distilled to 50% of the theoretical distillation amount, a predetermined amount of trimesic acid is added, and acetic acid is distilled to 91% of the theoretical distillation amount to complete the reaction.

  As acetylation reaction conditions, the reaction temperature is preferably 135 to 155 ° C., and the reaction time is preferably 1 to 2 hours.

  The polycondensation reaction temperature is a temperature at which the dendritic polyester resin is melted, and is preferably a melting point of the dendritic polyester resin + 10 ° C. or higher. Specifically, 240-280 degreeC is preferable. The atmosphere for polycondensation is satisfactory even under atmospheric pressure nitrogen, but a reduced pressure is preferable because the reaction proceeds faster and the residual acetic acid in the system decreases. The degree of vacuum is preferably 1330 Pa to 13300 Pa. In addition, acetylation and polycondensation may be performed continuously in the same reaction vessel, or acetylation and polycondensation may be performed in different reaction vessels.

  After the polycondensation reaction is completed, the inside of the reaction vessel is kept at a temperature at which the dendritic polyester resin melts, and is pressurized to, for example, 0.001 to 0.1 MPa, and the dendritic polyester is discharged from the discharge port provided at the lower portion of the reaction vessel. It is preferable to discharge the resin in a strand shape. A mechanism that opens and closes intermittently is provided at the discharge port, and it is also possible to discharge liquid droplets. In general, the discharged dendritic polyester resin is cooled by passing through air or water, and then is cut or pulverized as necessary.

  It is preferable that the obtained pellet-like, granular or powdery dendritic polyester resin (D) further removes water, acetic acid and the like by heat drying or vacuum drying, if necessary. Further, in order to finely adjust the degree of polymerization, or to further increase the degree of polymerization, solid phase polymerization can also be performed. As the solid-phase polymerization method, for example, the dendritic polyester resin obtained as described above is melted at a melting point of −5 ° C. to a melting point of −50 ° C. (for example, 200 to 300 ° C.) under a nitrogen stream or under reduced pressure. ) In the temperature range of 1 to 50 hours.

  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 number average molecular weight of the dendritic polyester resin (D) used in the present invention is preferably 1,000 to 40,000, and more preferably 1,000 to 5,000. This number average molecular weight was adjusted to a concentration of 0.08% (wt / vol) using a mixed solvent of pentafluorophenol / chloroform = 35/65% by weight, which is a solvent in which the dendritic polyester resin is soluble. It is the value which measured the glass-like polyester resin solution as an absolute molecular weight by GPC-LS (gel permeation chromatography-light scattering) method. As measurement conditions here, a column uses Shodex KG, Shodex K-806M × 2, Shodex K-802, a flow rate of 0.8 mL / min, a temperature of 23 ° C., a detector is a differential refractometer (RI), Multi-angle light scattering (MALS).

  Moreover, 0.01-30 Pa.s is preferable and, as for the melt viscosity of the dendritic polyester resin (D) in this invention, 1-10 Pa.s is more preferable. In addition, this melt viscosity is a value measured by a Koka flow tester under a condition of a liquid crystal starting temperature of the dendritic polyester resin + 10 ° C. and a shear rate of 100 / s.

  The compounding quantity of the dendritic polyester resin (D) in this invention is 0.01-10 weight part with respect to 100 weight part of (A) semi-aromatic polyamide resin. The moldability of a resin composition can be improved because the compounding quantity of dendritic polyester resin (D) shall be 0.01 weight part or more. 0.05 parts by weight or more is more preferable, and 0.5 parts by weight or more is more preferable. On the other hand, when the blending amount of the dendritic polyester resin (D) is 10 parts by weight or less, the mechanical properties and metal adhesion of the molded product can be further improved. 8 parts by weight or less is more preferable, and 5 parts by weight or less is more preferable.

  The resin composition of the present invention includes a stabilizer, a mold release agent, an ultraviolet absorber, a colorant, a flame retardant aid, an anti-drip agent, a lubricant, a fluorescent whitening agent, and a phosphorescent substance as long as the effects of the present invention are not impaired. Additives such as pigments, fluorescent dyes, flow modifiers, impact modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents, infrared absorbers and photochromic agents, fillers other than carbon fibers A thermoplastic resin other than the semi-aromatic polyamide resin (A) in the present invention, a thermosetting resin, or the like can be blended.

  Although the manufacturing method of the resin composition of this invention is not specifically limited as long as the requirements prescribed | regulated by this invention are satisfy | filled, the carbon fiber chop which cut | disconnected carbon fiber, a semi-aromatic polyamide resin (A), an epoxy compound ( C) and, if necessary, a method of melt-kneading other components with a single-screw or twin-screw extruder, or introducing a carbon fiber bundle into the extruder, a semi-aromatic polyamide resin (A), an epoxy compound (C) and Examples include a method of melting and kneading other components as necessary, and cutting and kneading carbon fibers with a screw in an extruder.

  Next, the pellet of the present invention will be described. The pellet of the present invention is formed by molding the above resin composition, and the weight average fiber length of the carbon fiber in the pellet is preferably 0.01 to 2 mm. When the weight average fiber length of the carbon fibers in the pellet is within the above range, the moldability of the pellet is improved, and a molded product having an excellent surface appearance can be obtained.

Here, the weight average fiber length of the carbon fibers in the pellet can be measured by the following method. First, the pellet is fired at 500 ° C. for 1 hour, and the obtained ash is dispersed in water, followed by filtration, and the residue is observed with an optical microscope. The length of 1,000 carbon fibers selected at random is measured, and the weight average fiber length is calculated. Specifically, by putting about 10 g of resin composition pellets in a crucible, steaming until no flammable gas is generated on an electric stove, and then baking for another hour in an electric furnace set at 500 ° C. Only the carbon fiber residue is obtained. Observe an image of the residue magnified 50 to 100 times with an optical microscope, measure the length of 1,000 randomly selected lengths, and give the measured value (mm) (2 digits for the decimal point). And calculated based on the following Equation 1 or Equation 2.
Weight average fiber length (Lw) = Σ (Wi × Li) / ΣWi = Σ (π × ri ² × Li × ρ × ni × Li) / Σ (π × ri ² × Li × ρ × ni) ( Formula 1)

  Here, Li is the fiber length of the carbon fiber, ni is the number of carbon fibers of the fiber length Li, Wi is the weight of the carbon fiber of the fiber length Li, ri is the fiber diameter of the carbon fiber of the fiber length Li, and ρ is the carbon fiber Density, π, indicates a circular ratio, and the cross-sectional shape of the carbon fiber is approximated to a perfect circle having a fiber diameter ri.

When the fiber diameter ri and the density ρ are constant, the above equation 1 is approximated as follows, and the weight average fiber length can be obtained by the following equation 2.
Weight average fiber length (Lw) = Σ (Li ² × ni) / Σ (Li × ni) (Formula 2)

  As a means for making the weight average fiber length of the carbon fibers in the pellet into such a range, for example, when producing pellets by melt kneading using a single screw or twin screw extruder, cylinder temperature, screw rotation speed, production speed, etc. The method of adjusting the production conditions is mentioned.

  The resin composition of the present invention can be molded using, for example, the above pellets to produce various molded products. Examples of the molding method include generally known injection molding, compression molding, extrusion molding, blow molding, press molding, spinning, and the like, which can be processed into various molded products and used. Examples of the molded products include injection molded products, extrusion molded products, blow molded products, various films such as uniaxially drawn and biaxially drawn, sheets, various fibers such as undrawn yarn, drawn yarn, and superdrawn yarn.

  The resin composition of the present invention preferably produces various molded products by injection molding the pellets produced as described above. Injection molding methods include, for example, injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including those by supercritical fluid injection), insert molding, in-mold coating molding, heat insulating mold molding, and rapid heating. Cooling die molding, two-color molding, sandwich molding, ultra-high speed injection molding, and the like can be mentioned, and can be appropriately selected according to the purpose. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for forming.

  Although the weight average fiber length of the carbon fiber in the molded article obtained by shape | molding the resin composition of this invention is not specifically limited, It is preferable that it is the range of 0.1-0.7 mm.

  Here, the weight average fiber length of the carbon fibers in the molded product can be measured by the following method. First, a sample cut out from a molded product is calcined at 500 ° C. for 1 hour, the obtained ash is dispersed in water, filtered, and the residue is observed with an optical microscope. The length of 1,000 carbon fibers selected at random is measured, and the weight average fiber length is calculated. Specifically, about 10 g of a sample obtained by cutting out a molded product of the resin composition is put in a crucible, steamed until no flammable gas is generated on an electric stove, and further in an electric furnace set at 500 ° C. By baking for a period of time, only carbon fiber residue is obtained. Observe an image of the filtered residue dispersed in ion-exchanged water and magnified 50 to 100 times with an optical microscope, measure the length of 1,000 randomly selected, and the measured value (mm) ( The calculation is performed based on the above-described Equation 1 or Equation 2 using two significant digits).

  Since the molded product of the present invention is excellent in metal adhesion, it can be suitably used as a composite molded product bonded or bonded to a metal.

  The resin composition and molded product thereof of the present invention are preferably used for various applications such as electronic parts, electrical parts, household goods, office supplies, automobile / vehicle-related parts, building materials, sports goods, etc., taking advantage of their excellent characteristics. The

  Applications for electronic components include, for example, connectors, coils, sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable capacitor cases, optical pickup chassis, oscillators, various terminal boards, transformers, and plugs. , Printed circuit board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, transformer member, parabolic antenna, computer related parts, etc. The

  Electrical component applications include, for example, generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, breakers, knife switches, other pole rods, electrical components, For motor cases, notebook PC 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, various gears, various cases, cabinets, etc. Preferably used.

  Household and office supplies applications include, for example, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio, laser discs (registered trademark), compact discs, DVDs, etc.・ Video equipment parts, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, housings for electronic devices such as personal computers and laptops, office computer related parts, telephone related parts, facsimile related parts, copier related parts It is preferably used for cleaning jigs, motor parts, lighters, typewriters, microscopes, binoculars, cameras, watches, and the like.

  Automotive / vehicle-related parts include, for example, alternator terminals, alternator connectors, IC regulators, potentiometer bases for light dials, various valves such as exhaust gas valves, fuel-related / cooling systems / brake systems / wiper systems / exhaust systems・ Various intake pipes, hoses, tubes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, Throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, battery peripheral parts, thermostat base for air conditioner, heating temperature Flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, transmission wire harness, transmission oil pan, window washer nozzle, air conditioner panel switch board , Fuel-related electromagnetic valve coils, wire harness connectors, SMJ connectors, PCB connectors, door grommets connectors, fuse connectors and other connectors, horn terminals, electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings , Brake piston, solenoid bobbin, engine oil pan, engine oil filter, Fire equipment case, torque control lever, safety belt parts, register blade, washer lever, window regulator handle, window regulator handle knob, passing light lever, sun visor bracket, instrument panel, airbag peripheral parts, door pad, pillar, console Box, motor housing, roof rail, fender, garnish, roof panel, hood panel, trunk lid, door mirror stay, spoiler, hood louver, wheel cover, wheel cap, grill apron cover frame, lamp bezel, door handle, door molding, rear finisher It is preferably used for wipers and the like.

  Examples of building material applications include civil engineering building walls, roofs, ceiling material-related parts, window material-related parts, heat insulating material-related parts, flooring-related parts, seismic isolation / vibration control parts-related parts, lifeline-related parts, etc. Preferably used.

  Examples of sports equipment include golf-related equipment such as golf clubs and shafts, masks such as American football and baseball, softball, body protection equipment for sports such as helmets, breast pads, elbow pads, knee pads, and the bottom of sports shoes. Shoes-related items such as materials, fishing rods, fishing line, fishing gear-related items such as reels, summer sports-related items such as surfing, winter sports-related items such as skis and snowboards, cycle-related items such as bicycle pedals, other indoor and outdoor sports It is preferably used for related products.

  Among the various uses described above, the resin composition of the present invention and a molded product are made of metal such as a connector, breaker, bicycle pedal and the like, taking advantage of excellent mechanical properties, low water absorption and metal adhesion. The composite molded body obtained by bonding or bonding can be particularly preferably used for electric / electronic parts, automobile parts, and sports equipment.

  In order to describe the present invention more specifically, examples and comparative examples will be described below, but the present invention is not limited to these examples. Various characteristics in the examples were evaluated by the following methods.

(1) Bending elastic modulus and bending strength of molded product The resin composition pellets obtained in each of the examples and comparative examples were subjected to a cylinder temperature of polyamide using a 75-ton injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. A bending test piece was injection-molded under the conditions of a melting point of the resin + 22 ° C. and a mold temperature of 80 ° C., and bending strength and bending elastic modulus were evaluated at 23 ° C. in accordance with ISO178.

(2) Impact resistance of molded product Using the resin composition pellets obtained in each example and comparative example, using a 75-ton injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., the cylinder temperature is the melting point of the polyamide resin. The Charpy impact test piece was injection-molded at a mold temperature of 80 ° C. at + 22 ° C., and Charpy impact strength (notched) was evaluated at 23 ° C. according to ISO179.

(3) Water Absorption Rate of Molded Product Using the resin composition pellets obtained in each example and comparative example, using a 75-ton injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., the cylinder temperature is the melting point of the polyamide resin +22 A dumbbell test piece was injection-molded under the conditions of a mold temperature of 80 ° C. Using the obtained dumbbell test piece, a water absorption test is performed in which the sample is left standing at 60 ° C. and 95% RH to measure a change in weight over time. The weight after drying (before the water absorption test) and after 500 hours has elapsed. Was measured, and the water absorption was determined from the following equation. In addition, in the following formula | equation, the weight at the time of drying is an initial weight of the dumbbell test piece before using for a water absorption test.
Water absorption rate (%) = [(95% RH after 1000 hours-dry weight) / dry weight] × 100

(4) Surface appearance of molded product Using the resin composition pellets obtained in each of the examples and comparative examples, using a 75-ton injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., the cylinder temperature is the melting point of the polyamide resin +22 A square plate test piece of 80 mm × 80 mm × thickness 3 mm was prepared under conditions of a mold temperature of 130 ° C., an injection time of 10 seconds, and a cooling time of 20 seconds, and a surface roughness measuring device (manufactured by ACCRTECH) was used. The arithmetic average height (Wa) value of the waviness curve on the surface of the molded article was evaluated under the measurement conditions of an evaluation length of 20 mm and a test speed of 0.6 mm / sec.

(5) Metal Adhesiveness of Molded Product FIG. 1 is a schematic view of a test piece for evaluating metal adhesion. An aluminum prism 1 having the shape shown in FIG. 1 was manufactured and charged into a mold. Using a 75-ton injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., the cylinder temperature is set to the melting point of the polyamide resin + 22 ° C., the mold temperature is 130 ° C., the injection speed is 100 mm / sec, and the injection pressure is the lower limit pressure + 3 MPa. Under the conditions described above, injection molding was performed from the gate 3 so that the resin 2 was joined to the aluminum prism 1, and three test pieces for metal adhesion evaluation shown in FIG. 1 were produced.

  Next, using a tensile tester (manufactured by Shimadzu AG-2000C), a tensile test was performed under the conditions of a measurement temperature of 23 ° C., a strain rate of 10 mm / min, and a distance between sample specimens of 50 mm, and the tensile strength was measured. The average value of the tensile strength of the three molded articles was calculated as the value of metal adhesion.

(6) Formability Using a 75-ton injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., the cylinder temperature is the melting point of polyamide resin + 22 ° C., the mold temperature is 130 ° C., the injection pressure is 55 MPa, the injection time is 5 seconds, the molded product. The bar flow flow length was measured under the condition of a thickness of 0.7 mm. The larger this value, the better the moldability.

(7) Weight average fiber length of carbon fibers in pellets 10 g of pellets are put in a crucible, steamed until no flammable gas is generated on an electric stove, and then further fired in an electric furnace set at 500 ° C. for 1 hour. did. The residue obtained by dispersing and filtering in ion-exchanged water was observed with an optical microscope at an magnification of 50 to 100 times, and the length of 1000 randomly selected was measured. A fiber length (mm) was obtained.
Weight average fiber length (Lw) = Σ (Li ² × ni) / Σ (Li × ni) (Formula 2)
Here, Li represents the fiber length of the carbon fiber, and ni represents the number of carbon fibers having the fiber length Li.

(Production Example 1) Production of semi-aromatic polyamide resin (A-1) Decamethylenediamine (manufactured by Tokyo Chemical Industry) and terephthalic acid (manufactured by Tokyo Chemical Industry) are added in equimolar amounts so that the total amount becomes 10 kg, An excess of 0.5 mol% of decamethylenediamine is added to the total amount of decamethylenediamine, and 0.5 parts by weight of benzoic acid and 30 parts by weight of water are added as end-capping agents to a total of 70 parts by weight of these raw materials. Then, the mixture was charged into a pressure vessel, sealed, and purged with nitrogen. After heating was started and the internal pressure of the can reached 2.0 MPa, the internal pressure of the can was maintained at 2.0 MPa and the internal temperature of 240 ° C. for 2 hours while releasing moisture out of the system. Thereafter, the contents were discharged from the pressurized container to obtain a polyamide oligomer. The obtained polyamide oligomer is pulverized, vacuum-dried at 100 ° C. for 24 hours, solid-phase polymerized at 50 Pa and 240 ° C., containing 100 mol% of terephthalic acid units in dicarboxylic acid units, and decamethylenediamine units as diamine units. Polyamide 10T (A-1) containing 100 mol% was obtained. For polyamide 10T (A-1), the relative viscosity measured in Ostwald viscosity at 25 ° C. in 98% sulfuric acid at a resin concentration of 0.01 g / ml was 2.30. The melting point measured using a differential scanning calorimeter (Seiko Instruments Co., Ltd. robot DSC, EXSTAR 6000 system) at a temperature rising / falling rate of 20 ° C./min was 318 ° C.

(Production Example 2) Production of semi-aromatic polyamide resin (A-2) 4539.3 g (27.3 mol) of terephthalic acid, (a) 1,9-nonanediamine and (b) 2-methyl-1,8-octane Mixture of diamine [(a) / (b) = 50/50 (molar ratio)] 4478.8 g (28.3 mol), benzoic acid 101.6 g (0.83 mol), sodium hypophosphite monohydrate 9.12 g (0.1% by mass with respect to the total mass of the raw material) and 2.5 liters of water were added and mixed, charged into a pressure vessel, sealed, and purged with nitrogen. This mixture was stirred at 100 ° C. for 30 minutes, and the temperature inside the autoclave was increased to 220 ° C. over 2 hours. At this time, the pressure inside the autoclave was increased to 2 MPa. The reaction was continued as it was for 2 hours, then the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and keeping the pressure at 2 MPa. Next, the pressure was reduced to 1 MPa over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer.

  The obtained prepolymer was dried at 100 ° C. under reduced pressure for 12 hours, pulverized to a particle size of 2 mm or less, solid-phase polymerized at 230 ° C. and 13 Pa (0.1 mmHg) for 8 hours, and a melting point of 262 ° C. The relative viscosity is 2.13, the terephthalic acid unit is contained in 100 mol% in the dicarboxylic acid unit, and the 1,9-nonanediamine unit and the 2-methyl-1,8-octanediamine unit are each 50 mol% in the diamine unit. A white polyamide resin (A-2) was obtained.

(Production Example 3) Production of semi-aromatic polyamide resin (A-3) The molar ratio of a mixture of (a) 1,9-nonanediamine and (b) 2-methyl-1,8-octanediamine is (a) / ( b) In the same manner as in Production Example 2, except that it was changed to 80/20, 100 mol% of the terephthalic acid unit was contained in the dicarboxylic acid unit, and 80 mol% of the 1,9-nonanediamine unit was contained in the diamine unit. A polyamide resin (A-3) containing 20 mol% of 2-methyl-1,8-octanediamine unit in the diamine unit was produced. (A-3) had a melting point of 302 ° C. and a relative viscosity of 2.15.

Production Example 5 Production of Dendritic Polyester Resin (D-1) In a 500 mL reaction vessel equipped with a stirring blade and a distilling tube, 66.3 g (0.48 mol) of p-hydroxybenzoic acid, 4,4 ′ -8.38 g (0.045 mol) of dihydroxybiphenyl, 7.48 g (0.045 mol) of terephthalic acid, 14.41 g (0.075 mol) of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dL / g and acetic anhydride 62 .48 g (1.00 equivalent of the total of phenolic hydroxyl groups) was added and reacted at 145 ° C. for 2 hours with stirring under a nitrogen gas atmosphere. Thereafter, 31.52 g (0.15 mol) of trimesic acid was added, the temperature was raised to 260 ° C., and the mixture was stirred for 3 hours. When 91% of acetic acid was distilled from the theoretical distillate, heating and stirring were stopped. The product was discharged into cold water to obtain a dendritic polyester resin (D-1).

  The obtained dendritic polyester resin (D-1) was subjected to nuclear magnetic resonance spectrum analysis. As a result, the content p of p-oxybenzoate units was 2.66, 4,4′- with respect to the trimesic acid residue. The content q of dioxybiphenyl units and ethylene oxide units was 0.66, the content r of terephthalate units was 0.66, and p + q + r = 4. At the end, carboxylic acid and acetyl groups were present in a ratio of 64:36.

  The nuclear magnetic resonance spectrum was obtained by analyzing the nuclear magnetic resonance spectrum of the proton nucleus at 40 ° C. using a solution obtained by dissolving the dendritic polyester resin (D-1) in 50% pentafluorophenol: 50% deuterated chloroform. . 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 content ratio of each structural unit was calculated from the area intensity ratio of each peak, and the three decimal places were rounded off. From the ratio of the peak area intensity derived from the branch structure portions P, Q, and R and the peak area intensity derived from the organic residue S, the contents p, q, r, and the content of the branch point S were calculated. Further, the presence or absence of the reaction of carboxylic acid was determined from the peak shift of the three protons of trimesic acid, and the degree of branching was calculated to be 0.68 (rounded to the third decimal place). The degree of branching was determined by calculating the ratio of those in which all three functional groups of trimesic acid were reacted.

  The obtained dendritic polyester resin (D-1) had a melting point Tm of 185 ° C., a liquid crystal starting temperature of 159 ° C., and a number average molecular weight of 2,300. In addition, melting | fusing point (Tm) is observation of the endothermic peak temperature (Tm1) observed when dendritic polyester resin (D-1) is measured on 20 degreeC / min temperature rising conditions in differential calorimetry. Thereafter, the temperature is maintained at a temperature of Tm1 + 20 ° C. for 5 minutes, once cooled to room temperature under a temperature decrease condition of 20 ° C./min, and again measured with an endothermic peak temperature (Tm) measured at a temperature increase condition of 20 ° C./min. did. The liquid crystal starting temperature is the temperature at which the entire field of view starts to flow with a shear stress heating device (CSS-450) under conditions of a shear rate of 100 (1 / second), a heating rate of 5.0 ° C./min, and an objective lens 60 times. It was.

  The dendritic polyester resin (D-1) has a number average molecular weight adjusted to a concentration of 0.08% (wt / vol) using a mixed solvent of pentafluorophenol / chloroform = 35/65% by weight. The polyester resin solution was measured as an absolute molecular weight by GPC-LS (gel permeation chromatography-light scattering) method. As measurement conditions here, a column uses Shodex KG, Shodex K-806M × 2, Shodex K-802, a flow rate of 0.8 mL / min, a temperature of 23 ° C., a detector is a differential refractometer (RI), Multi-angle light scattering (MALS) was used.

Other raw materials used in Examples and Comparative Examples are shown below.
(A ′) Polyamide resin other than semi-aromatic polyamide (A′-1) Polyamide 6 resin “Amilan” (registered trademark) CM1001 (manufactured by Toray Industries, Inc.)
Melting point 222 ° C
(B) Carbon fiber (B-1) PAN-based carbon fiber “Torayca” (registered trademark) cut fiber TV14-006 (manufactured by Toray Industries, Inc., original yarn T700SC-12K)
(C) Epoxy compound (C-1) Bisphenol-type epoxy compound “jER1004” (manufactured by Mitsubishi Chemical Corporation), molecular weight 1650, epoxy equivalent 875-975 (q / eq)
(C-2) Bisphenol type epoxy compound “jER1009” (manufactured by Mitsubishi Chemical Corporation), molecular weight 3850, epoxy equivalent 2400-3300 (q / eq)
(C-3) Bisphenol type epoxy compound “jER1010” (manufactured by Mitsubishi Chemical Corporation), molecular weight 5500, epoxy equivalent 1000 to 5000 (q / eq)
(C-4) Bisphenol type epoxy compound “jER828” (manufactured by Mitsubishi Chemical Corporation), molecular weight 370, epoxy equivalent 184 to 194 (q / eq)
(C-5) Bisphenol type epoxy compound “jER1001” (manufactured by Mitsubishi Chemical Corporation), molecular weight 900, epoxy equivalent 450 to 500 (q / eq)
(C-6) Glycidyl ether type epoxy compound “Epiol E-1000” (manufactured by NOF Corporation), molecular weight 1140, epoxy equivalent 570 (q / eq)

[Examples 1-17, Comparative Examples 1-12]
A twin screw extruder (TEX30α manufactured by Nippon Steel) with the cylinder temperature set to the melting point of the polyamide resin + 22 ° C. and the screw rotation speed set to 200 rpm was used. A polyamide resin, an epoxy compound and a dendritic polyester resin were supplied from the main hopper in the formulations shown in Tables 1 and 2, and carbon fibers were supplied from the side feeder into the molten resin and melt kneaded. The strand discharged from the die was cooled in water, cut into a length of 3.0 mm by a strand cutter, and pelletized to obtain a carbon fiber reinforced polyamide resin composition pellet. Various characteristics evaluation was performed by the method mentioned above using the produced pellet. The results are shown in Tables 1-2.

  The carbon fiber reinforced polyamide resin compositions shown in Examples 1 to 17 have high flexural modulus and flexural strength, excellent impact resistance, low water absorption, surface appearance, metal adhesion, and moldability. Recognize. On the other hand, any of the characteristics of Comparative Examples 1 to 12 was insufficient. Moreover, it turns out that the carbon fiber reinforced polyamide resin composition shown in Example 16 is more excellent in moldability without deteriorating mechanical properties such as bending elastic modulus and bending strength.

  According to the carbon fiber reinforced polyamide resin composition of the present invention, a molded product excellent in mechanical properties, low water absorption and metal adhesion can be obtained. Therefore, the carbon fiber reinforced polyamide resin composition of the present invention, and pellets and molded articles using the same are preferably used for electrical / electronic parts, automobile parts, and sporting goods that are joined to metals such as connectors, breakers, and bicycle pedals. Can do.

1 Aluminum prism 2 Resin 3 Gate

Claims (6)

A polyamide resin containing a dicarboxylic acid unit and a diamine unit, wherein the dicarboxylic acid unit contains 50 to 100 mol% of a terephthalic acid unit, and the diamine unit contains 50 to 100 aliphatic alkylenediamine units having 6 to 18 carbon atoms. 10 to 100 parts by weight of carbon fiber (B) and 0.1 to 10 parts by weight of epoxy compound (C) having a number average molecular weight of 10,000 or less with respect to 100 parts by weight of semi-aromatic polyamide resin (A) containing mol% A carbon fiber reinforced polyamide resin composition obtained by blending. The carbon fiber-reinforced polyamide resin composition according to claim 1, wherein 0.01 to 10 parts by weight of a dendritic polyester resin (D) is further blended with 100 parts by weight of the semi-aromatic polyamide resin (A). The carbon fiber-reinforced polyamide resin composition according to claim 1 or 2, wherein the semi-aromatic polyamide resin (A) contains 50 to 100 mol% of 1,10-decanediamine units in diamine units. The pellet whose carbon fiber (B) weight average fiber length obtained by shape | molding the carbon fiber reinforced polyamide resin composition in any one of Claims 1-3 is 0.01-2 mm. A molded product formed by molding the pellet according to claim 4. A composite molded product obtained by joining or bonding the molded product according to claim 5 and a metal.

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