JP2015071668A - Polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition which has both high fluidity and retention stability, has excellent adhesion to metal, and can provide a molded article with reduced warping under a heating condition, and to provide electric and electronic parts using the polyamide resin composition.SOLUTION: There is provided the polyamide resin composition containing: 50 to 95 pts.wt. of a semi-aromatic polyamide (A) using as raw materials, a dicarboxylic acid component including terephthalic acid and/or isophthalic acid as a main component, and a diamine component including at least one selected from the group consisting of 1,8-octane diamine, 1,10-decane diamine, and 1,12-dodecane diamine as a main component; and 5 to 50 pts.wt. of an aliphatic polyamide (B) (however, a total amount of (A) and (B) is set at 100 pts.wt.) using as raw materials a dicarboxylic acid component including an aliphatic dicarboxylic acid having 8 to 12 carbon atoms as a main component, and a diamine component including an aliphatic diamine having 4 to 8 carbon atoms as a main component.

Description

  The present invention relates to a polyamide resin composition containing a semi-aromatic polyamide and an aliphatic polyamide, and an electric / electronic component formed by molding the same.

  Polyamide resins typified by polyamide 6 and polyamide 66 have been adopted as various mechanical parts, electrical / electronic parts, and automobile parts by taking advantage of their excellent characteristics. Among them, particularly in connector applications, the demand for higher toughness is increased from the viewpoint of insertion / extraction, and polyamide resins are widely used.

  In recent years, with the generalization of the portability of electrical / electronic devices, opportunities for contact between these electrical / electronic devices and water are increasing. In the unlikely event that water enters the inside of the device, it may cause a failure. For example, connectors used in these electric / electronic devices are also required to have a resin-metal adhesion. In addition, along with the reduction in size and weight of electrical and electronic equipment, there is a demand for further thinning of the parts and complicated shapes. In response to these requirements, if the resin has insufficient fluidity, unfilled parts with thin or complex shapes may occur, and parts may have residual stress due to the high filling pressure required during molding. Therefore, improvement in resin fluidity is demanded. In recent years, many electrical and electronic products that are compatible with lead-free soldering have been seen due to environmental considerations. However, when reflowing parts with residual stress, the residual stress is relieved. A sled will occur.

  In response to these requirements, as a method for improving moldability and fluidity, a dicarboxylic acid unit containing a terephthalic acid unit and a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit are used. A semi-aromatic polyamide comprising a dicarboxylic acid unit and a polyamide composition comprising an aliphatic polyamide having 7 to 12 carbon atoms per amide group (for example, see Patent Document 1), and the dicarboxylic acid component is terephthalic acid And a polyamide containing a semi-aromatic polyamide resin, an aliphatic polyamide resin and a flame retardant, wherein the diamine component is any one of 1,8-octanediamine, 1,10-decanediamine, and 1,12-dodecanediamine A resin composition (see, for example, Patent Document 2) has been proposed. As a method for improving mechanical properties, the dicarboxylic acid component is mainly terephthalic acid, and the diamine component is any of 1,8-octanediamine, 1,10-decanediamine, and 1,12-dodecanediamine. A polyamide resin composition containing a semi-aromatic polyamide resin, an aliphatic polyamide resin and a fibrous reinforcing material (for example, see Patent Document 3) has been proposed.

Japanese Patent Laid-Open No. 2003-411117 JP 2013-64032 A JP 2013-60534 A

  However, the polyamide resin composition in which polyamide 612 or 99 is blended with the polyamide 9T described in Patent Document 1 also has insufficient thin-wall fluidity and requires high molding pressure. There has been a problem that warping deformation is caused. In addition, the mechanical strength of the molded product is insufficient because of low crystallinity, and the exchange reaction proceeds due to retention under a high temperature condition of 300 ° C. or higher, so that the retention stability and metal adhesion are insufficient. was there.

  The polyamide resin composition in which polyamide 6 or 66 is blended with polyamide 10T described in Patent Documents 2 and 3 above is decomposed during high-temperature processing, and a large amount of gas is generated during molding, resulting in fluidity, metal adhesion and There was a problem that the retention stability was insufficient.

  In view of the problems of these prior arts, the present invention provides a polyamide resin composition having high fluidity and retention stability, excellent metal adhesion, and capable of obtaining a molded product with reduced warpage under heating conditions, and the polyamide resin composition It is an object of the present invention to provide an electrical / electronic component using the above.

In order to solve this problem, the present invention mainly has the following configuration.
(1) At least one selected from the group consisting of a dicarboxylic acid component mainly composed of terephthalic acid and / or isophthalic acid, and 1,8-octanediamine, 1,10-decanediamine, and 1,12-dodecanediamine. 50 to 95 parts by weight of a semi-aromatic polyamide (A) whose raw material is a diamine component containing as a main component, a dicarboxylic acid component whose main component is an aliphatic dicarboxylic having 8 to 12 carbon atoms, and a carbon number of 4 to 8 Polyamide resin containing 5 to 50 parts by weight of an aliphatic polyamide (B) (provided that the total of (A) and (B) is 100 parts by weight) using a diamine component containing as a main component an aliphatic diamine Composition.
(2) The polyamide resin according to (1), further containing 5-200 parts by weight of an inorganic filler (C) with respect to a total of 100 parts by weight of the semi-aromatic polyamide (A) and the aliphatic polyamide (B). Composition.
(3) (1) or (2) description which further contains 1-50 weight part of flame retardants (D) with respect to a total of 100 weight part of said semi-aromatic polyamide (A) and said aliphatic polyamide (B). Polyamide resin composition.
(4) The polyamide resin composition according to (3), wherein the flame retardant (D) contains at least a phosphorus-containing compound.
(5) The polyamide resin composition according to any one of (1) to (4), wherein the aliphatic polyamide (B) includes polyamide 410, polyamide 510, and / or polyamide 610.
(6) An electrical / electronic component formed by molding the polyamide resin composition according to (1) to (5).

  The polyamide resin composition of the present invention has high fluidity and residence stability. According to the polyamide resin composition of the present invention, it is possible to provide an electric / electronic component having excellent metal adhesion and reduced warpage even under heating conditions.

It is the schematic which shows the test piece for metal adhesion | attachment evaluation used in the Example of this invention. It is the schematic which shows the molded article of the 0.8mm pitch 100 core fine pitch connector (insulator) used in the Example of this invention.

  Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

  The semi-aromatic polyamide (A) in the present invention is a dicarboxylic acid component mainly composed of terephthalic acid and / or isophthalic acid, 1,8-octanediamine, 1,10-decanediamine, and 1,12-dodecanediamine. It is polyamide comprised from the diamine which has as a main component at least 1 sort (s) selected from the group which consists of. Here, the main component refers to a component occupying 50% by weight or more in the dicarboxylic acid component or the diamine component, and the same shall apply hereinafter.

  By making the carbon number of the main component of the aliphatic diamine constituting the semi-aromatic polyamide (A) in the present invention 8 or more, gas generation at the time of molding at high temperature is suppressed, and fluidity and residence stability are improved. The metal adhesion of the molded product can be improved. On the other hand, by setting the carbon number of the main component of the aliphatic diamine constituting the semi-aromatic polyamide (A) to 12 or less, it is possible to suppress the decomposition of the polyamide at high temperature, improve the residence stability, and mold Warpage of the product under heating conditions can be reduced. In addition, the semi-aromatic polyamide (A) in the present invention can improve crystallinity by using terephthalic acid and / or isophthalic acid as a main component as a dicarboxylic acid component, and improve metal adhesion of a molded product. be able to. On the other hand, the semi-aromatic polyamide resin composed of these dicarboxylic acid components has low crystallinity and a high temperature of 300 ° C. or higher when the main component is an aliphatic diamine having an odd number of carbon atoms from the viewpoint of the odd-even effect. Since the exchange reaction proceeds due to residence under conditions, the residence stability is lowered, and the metal adhesion of the molded product and warpage under heating conditions increase. Therefore, the semi-aromatic polyamide (A) in the present invention is a diamine mainly composed of at least one selected from the group consisting of 1,8-octanediamine, 1,10-decanediamine and 1,12-dodecanediamine. It is important to use

  If the total amount of terephthalic acid and / or isophthalic acid is 50% by weight or more in the dicarboxylic acid component, another dicarboxylic acid component may be used as the raw material for the semiaromatic polyamide (A) in the present invention. Examples of other dicarboxylic acid components include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, tetradecanediic acid. Examples thereof include aliphatic dicarboxylic acids such as acids, pentadecanedioic acid and octadecanedioic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, aromatic dicarboxylic acids such as phthalic acid and naphthalenedicarboxylic acid, and derivatives thereof. Moreover, the raw material of the semi-aromatic polyamide (A) in the present invention includes at least one selected from the group consisting of 1,8-octanediamine, 1,10-decanediamine and 1,12-dodecanediamine in the diamine component. If the total amount of seeds is 50% by weight or more, another diamine component may be further used. Examples of other diamine components include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,9- Diaminononane, 1,11-diaminoundecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18- Fatty substances such as diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, aliphatic diamines such as 2-methyl-1,5-diaminopentane, cyclohexanediamine, and bis- (4-aminocyclohexyl) methane Aromatic diamines such as cyclic diamine and xylylenediamine Etc., and the like.

  Specific examples of the semi-aromatic polyamide (A) in the present invention include polyoctamethylene terephthalamide (polyamide 8T), polydecamethylene terephthalamide (polyamide 10T), polydodecamethylene terephthalamide (polyamide 12T), polyoctamethylene isophthalate. Amide (polyamide 8I), polydecamethylene isophthalamide (polyamide 10I), polydodecamethylene isophthalamide (polyamide 12I), polydecamethylene terephthalamide / polydodecamethylene terephthalamide copolymer (polyamide 10T / 12T), polydecamethylene terephthalamide / Polydecamethylene isophthalamide copolymer (Polyamide 10T / 10I), Polydodecamethylene terephthalamide / Polydodecamethylene terephthalami The total amount of terephthalic acid and isophthalic acid in the copolymer (polyamide 12T / 12I) and dicarboxylic acid component is 50% by weight or more, and in the diamine component, 1,8-octanediamine, 1,10-decanediamine and 1,12 A polydecamethylene terephthalamide / polyhexamethylene terephthalamide copolymer (polyamide 10T / 6T), polydecamethylene terephthalamide / polypenta, wherein the total amount of at least one selected from the group consisting of dodecanediamine is 50% by weight or more Methylene terephthalamide copolymer (polyamide 10T / 5T), polydecamethylene terephthalamide / polytetramethylene terephthalamide copolymer (polyamide 10T / 4T), polydodecamethylene terephthalamide / polyhexamethylene tele Taramide copolymer (polyamide 12T / 6T), polydodecamethylene terephthalamide / polypentamethylene terephthalamide copolymer (polyamide 12T / 5T), polydodecamethylene terephthalamide / polytetramethylene terephthalamide copolymer (polyamide 12T / 4T), polydeca Examples include methylene terephthalamide / polydecamethylene phthalamide copolymer (polyamide 10T / 10P), polydecamethylene terephthalamide / polydecamethylene naphthalamide copolymer (polyamide 10T / 10N), and the like. Two or more of these may be contained. Here, “/” indicates a copolymer. Among these semi-aromatic polyamides (A), polydecamethylene terephthalamide (polyamide 10T) is more preferable from the viewpoints of melting point and mechanical strength.

  The aliphatic polyamide (B) in the present invention includes a dicarboxylic acid component mainly composed of an aliphatic dicarboxylic having 8 to 12 carbon atoms and an aliphatic diamine component mainly composed of an aliphatic diamine having 4 to 8 carbon atoms. Polyamide constructed as a raw material.

  By making the main component of the aliphatic dicarboxylic acid constituting the aliphatic polyamide (B) in the present invention 8 or more, the decomposition of the polyamide during high temperature processing and the generation of gas during molding at high temperature are suppressed. In addition, fluidity and residence stability can be improved, metal adhesion of the molded product can be improved, and warpage under heating conditions can be reduced. On the other hand, by making the main component of the aliphatic dicarboxylic acid constituting the aliphatic polyamide (B) 12 or less, compatibility with the aromatic polyamide (A) is improved and metal adhesion of the molded product is improved. And warpage under heating conditions can be reduced. In addition, by making the number of carbons of the main component of the aliphatic diamine constituting the aliphatic polyamide (B) 4 or more, the amide group concentration can be reduced, the water absorption resistance can be increased, and the residence stability can be improved. The metal adhesion under heating conditions of the molded product can be improved. On the other hand, by setting the number of carbon atoms of the aliphatic diamine constituting the aliphatic polyamide (B) to 8 or less, the heat resistance can be increased and the warpage of the molded product under heating conditions can be reduced. From the viewpoint of further reducing gas generation during the molding process, the aliphatic dicarboxylic acid preferably has 10 to 12 carbon atoms, and the aliphatic diamine acid has preferably 4 to 6 carbon atoms.

  As the raw material of the aliphatic polyamide (B) in the present invention, another dicarboxylic acid component may be used as long as the total amount of the aliphatic dicarboxylic acid having 8 to 12 carbon atoms is 50% by weight or more in the dicarboxylic acid component. . Other dicarboxylic acid components include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, brassic acid, tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid and other aliphatic dicarboxylic acids, cyclohexane Examples thereof include alicyclic dicarboxylic acids such as dicarboxylic acids, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and derivatives thereof. Further, in the raw material of the aliphatic polyamide (B) in the present invention, if the total amount of aliphatic diamine having 4 to 8 carbon atoms in the diamine component is 50% by weight or more, another diamine component may be used. . Examples of other diamine components include ethylenediamine, 1,3-diaminopropane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and 1,13-diamino. Tridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20 -Aliphatic diamines such as aliphatic diamines such as diaminoeicosane and 2-methyl-1,5-diaminopentane, cyclohexanediamine and bis- (4-aminocyclohexyl) methane, and aromatic diamines such as xylylenediamine Can be mentioned.

  Specific examples of the aliphatic polyamide (B) in the present invention include polytetramethylene sebacamide (polyamide 410), polypentamethylene sebacamide (polyamide 510), polyhexamethylene sebacamide (polyamide 610), and polytetramethylene sebacamide (polyamide 410). Examples include methylene dodecamide (polyamide 412), polypentamethylene dodecamide (polyamide 512), polyhexamethylene dodecamide (polyamide 612), and the like. In the dicarboxylic acid component, the total amount of aliphatic dicarboxylic acid having 8 to 12 carbon atoms is 50% by weight or more, and in the diamine component, the total amount of aliphatic diamine having 4 to 8 carbon atoms is 50% by weight or more. Tetramethylene sebacamide / polyhexamethylene adipamide copolymer (polyamide 410/66), polypentamethylene sebacamide / polyhexamethylene adipamide copolymer (polyamide 510/66), polyhexamethylene sebacamide / polyhexa Methylene adipamide copolymer (polyamide 610/66), polytetramethylene sebacamide / polydecamethylene sebamide polymer (polyamide 410/1010), polypentamethylene sebacamide / polydecamethylene sebacamide polymer (polyamide 510) / 1010), polyhexamethylene sebaka / Polydecamethylene sebacamide polymer (polyamide 610/1010), polytetramethylene sebacamide / polydodecamethylene sebacamide polymer (polyamide 410/1210), polypentamethylene sebacamide / polydodecamethylene sebacamide Examples thereof include a polymer (polyamide 510/1210), a polyhexamethylene sebacamide / polydodecamethylene sebacamide polymer (polyamide 610/1210), and the like. Two or more of these may be contained. Here, “/” indicates a copolymer.

  Among these aliphatic polyamides (B), polytetramethylene sebacamide (polyamide 410), polypentamethylene sebacamide (polyamide 510), and polyhexamethylene sebacamide (polyamide 610) are preferable, and the polyamide resin composition It is possible to further improve the fluidity and residence stability of the molded product, and to further reduce warpage of the molded product under heating conditions. Polytetramethylene sebacamide (polyamide 410) and polyhexamethylene sebacamide (polyamide 610) are more preferred.

  In this invention, it contains 50-95 weight part of semi-aromatic polyamide (A) and 5-50 weight part of aliphatic polyamide (B) with respect to a total of 100 weight part of (A) and (B). Features. When the content of the semi-aromatic polyamide (A) is less than 50 parts by weight and the content of the aliphatic polyamide (B) exceeds 50 parts by weight, the residence stability is lowered and warping under heating conditions is increased. Also, metal adhesion is greatly reduced. The content of the semi-aromatic polyamide (A) is preferably 55 parts by weight or more, the content of the aliphatic polyamide (B) is preferably 45 parts by weight or less, and the content of the semi-aromatic polyamide (A) is 60 parts by weight. As described above, the content of the aliphatic polyamide (B) is more preferably 40 parts by weight or less. On the other hand, when the content of the semi-aromatic polyamide (A) exceeds 95 parts by weight and the content of the aliphatic polyamide (B) is less than 5 parts by weight, the fluidity, residence stability and molding of the polyamide resin composition The metal adhesion of the product decreases, and warpage under heating conditions increases. From the viewpoint of further improving the metal adhesion, the content of the semi-aromatic polyamide (A) is preferably 85 parts by weight or less, and the content of the aliphatic polyamide (B) is preferably 15 parts by weight or more. From the viewpoint of further improvement, it is more preferable that the content of the semi-aromatic polyamide (A) is 75 parts by weight or less and the content of the aliphatic polyamide (B) is 25 parts by weight or more.

  In the polyamide resin composition of the present invention, the relative viscosity (ηr) of the whole polyamide composed of the semi-aromatic polyamide (A) and the aliphatic polyamide (B) is preferably 2.1 to 2.6, and from the viewpoint of moldability From 2.3 to 2.5 is more preferable. In the following, the relative viscosity ηr is the relative viscosity of polyamide measured using an Ostwald viscometer at 98 ° C. in sulfuric acid at a concentration of 0.01 g / ml at 25 ° C.

  As a manufacturing method of the semi-aromatic polyamide (A) and the aliphatic polyamide (B) used in the present invention, for example, a diamine component and a dicarboxylic acid component or a salt thereof as raw materials are heated to obtain a low-order condensate. Furthermore, a method of increasing the degree of polymerization by solid phase polymerization and / or melt polymerization can be used. 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 polyamide resin composition of the present invention may further contain an inorganic filler (C). By containing the inorganic filler (C), the mechanical strength and rigidity of the molded product can be improved. Furthermore, since dimensional changes such as expansion and contraction due to temperature changes can be reduced, dimensional accuracy can be improved, and warpage under heating conditions can be further reduced.

  Examples of the inorganic filler (C) include inorganic fillers such as fibers, plates, powders, and granules, and the shape is not particularly limited. Specifically, glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone koji fiber, metal fiber Fibrous inorganic fillers such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate and other metal silicates, silicon oxide, magnesium oxide, alumina, zirconium oxide , Metal oxides such as titanium oxide and iron oxide, metal carbonates such as calcium carbonate, magnesium carbonate and dolomite, metal sulfates such as calcium sulfate and barium sulfate, glass beads, ceramic beads, boron nitride, silicon carbide, phosphoric acid Karshi Metal hydroxide such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, glass flakes, glass powder, carbon black, silica, non-fibrous reinforcement such as graphite, montmorillonite, beidellite, 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 Examples thereof include layered silicates typified by swelling mica such as silicon fluorine mica. Two or more of these may be contained. The inorganic filler (C) may have a surface treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.) or other surface treatment agent. .

  Among these inorganic fillers, layered silicates such as glass fiber, talc, mica, wollastonite, montmorillonite or synthetic mica are preferable. Glass fiber is more preferable, and the mechanical strength and rigidity of the molded product can be further improved, and warpage under heating conditions can be further reduced.

  The glass fiber used in the present invention is preferably treated with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, an epoxy-based, urethane-based, acrylic-based coating agent or sizing agent, and a urethane-based coating. More preferably, it is treated with an agent or a sizing agent.

  The content of the inorganic filler (C) in the polyamide resin composition of the present invention is preferably 5 to 200 parts by weight with respect to a total of 100 parts by weight of the semi-aromatic polyamide (A) and the aliphatic polyamide (B). By setting the content of the inorganic filler (C) to 5 parts by weight or more, the mechanical strength and rigidity of the molded product can be further improved, and warpage under heating conditions can be further reduced. On the other hand, when the content of the inorganic filler (C) is 200 parts by weight or less, the fluidity of the polyamide resin and the metal adhesion of the molded product can be maintained at a high level. From the viewpoint of further improving the metal adhesion, it is more preferably 150 parts by weight or less, and more preferably 100 parts by weight or less.

  The polyamide resin composition of the present invention may further contain a flame retardant (D). By containing the flame retardant (D), flame retardancy can be improved.

  Examples of the flame retardant (D) include non-halogen flame retardants that do not contain halogen atoms, such as phosphorus flame retardants (phosphorus-containing compounds), nitrogen flame retardants, and metal hydroxide flame retardants, and bromine flame retardants. Examples thereof include halogen-based flame retardants. Two or more of these may be contained.

  Among these flame retardants (D), it is preferable to contain a phosphorus-containing compound, which can further improve the retention stability of the polyamide resin composition and further reduce warpage of the molded product under heating conditions.

  Specific examples of phosphorus-containing compounds include polyphosphoric acid compounds such as red phosphorus, ammonium polyphosphate, and melamine polyphosphate, (di) phosphinic acid metal salts, phosphazene compounds, aromatic phosphoric esters, and aromatic condensed phosphoric acids. Examples include esters and halogenated phosphates. Two or more of these may be contained. Among these flame retardants containing phosphorus-containing compounds, (di) phosphinic acid metal salts are more preferable from the viewpoint of further improving heat resistance and residence stability.

  The content of the flame retardant (D) in the polyamide resin composition of the present invention is preferably 1 to 50 parts by weight with respect to a total of 100 parts by weight of the semi-aromatic polyamide (A) and the aliphatic polyamide (B). By setting the content of the flame retardant (D) to 1 part by weight or more, flame retardancy can be effectively expressed. 20 parts by weight or more is more preferable. On the other hand, by setting the content of the flame retardant (D) to 50 parts by weight or less, the residence stability of the polyamide resin composition is maintained at a higher level, and the warpage of the molded product under heating conditions is further reduced. Can do.

  The polyamide resin composition of the present invention may contain other polyamide resins as necessary within a range not impairing the characteristics. Specific examples of other polyamide resins include polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polytetramethylene adipamide (polyamide 46), and polypentamethylene adipamide (polyamide). 56), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (polyamide 66 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6T / 6I) , Polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 6T / 6I), polyxylylene adipamide (polyamide XD6), and copolymers thereof. Two or more of these may be contained. By containing other polyamide resins, the fluidity can be further improved. From the viewpoint of maintaining the general physical properties of the polyamide resin composition, the content of the other polyamide resin is 20 parts by weight or less with respect to 100 parts by weight in total of the aromatic polyamide resin (A) and the aliphatic polyamide resin (B). Preferably, 5 parts by weight or less is more preferable.

  The polyamide resin composition of the present invention may further contain a dendritic polyester resin as long as the characteristics are not impaired, and the fluidity can be further improved. From the viewpoint of further improving the fluidity, the content of the dendritic polyester resin is preferably 1 part by weight or more with respect to a total of 100 parts by weight of the aromatic polyamide resin (A) and the aliphatic polyamide resin (B). On the other hand, from the viewpoint of maintaining the general physical properties of the polyamide resin composition, the content of the dendritic polyester resin is 5% with respect to a total of 100 parts by weight of the aromatic polyamide resin (A) and the aliphatic polyamide resin (B). Part or less is preferred.

  The dendritic polyester resin includes an aromatic oxycarbonyl unit (S) represented by the following general formula (1), an aromatic and / or aliphatic dioxy unit (T), and an aromatic dicarbonyl unit (U). Including at least one structural unit selected from the group consisting of an organic residue (D) having three or more functional groups, and a D content of 7.5 to all monomers constituting the dendritic polyester. Dendritic polyester resins in the range of 50 mol% are preferred.

  Here, R1 and R3 are each an aromatic residue. R2 is an aromatic residue or an aliphatic residue. In the general formula (1), a plurality of R1, R2 and R3 may be the same or different. R1, R2 and R3 each preferably have a structure represented by the following formula.

  However, Y may be the same or different and is a hydrogen atom, a halogen atom or an alkyl group. As for carbon number of an alkyl group, 1-4 are preferable. In the formula, n is an integer of 2 to 8.

  Specifically, R1 is a structure derived from an aromatic oxycarbonyl unit, preferably a structural unit derived from p-hydroxybenzoic acid, and partially contains a structural unit derived from 6-hydroxy-2-naphthoic acid. It is also possible. R2 is a structure derived from an aromatic and / or aliphatic dioxy unit, and includes a structural unit generated from 4,4′-dihydroxybiphenyl and hydroquinone or 4,4′-dihydroxybiphenyl and ethylene glycol. It is preferable from the point of control. R3 is a structural unit produced from an aromatic dicarbonyl unit, preferably a structural unit produced from terephthalic acid or isophthalic acid, and is particularly preferred when both are used in combination, since the melting point can be easily adjusted. Moreover, you may contain in part the structural unit produced | generated from aliphatic dicarboxylic acids, such as sebacic acid and adipic acid, in the range which does not impair the effect of this invention.

  In the dendritic polyester resin of the present invention, a trifunctional or higher functional organic residue (D) is a structural unit selected from S, T and U which are directly or mutually branched by an ester bond and / or an amide bond. A basic skeleton is a branched structure of three or more branches connected through each other. The branched structure may be formed of a single basic skeleton such as 3-branch and 4-branch, or may be formed of a plurality of basic skeletons such as 3-branch and 4-branch. 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. When D is a trifunctional organic residue, the dendritic polyester resin has a structure in which all three functional groups of D are reacted, a structure in which only two are reacted, and 1 A structure that reacts with only one may be mixed. The structure in which all three functional groups of D have reacted is preferably 30 mol% or more with respect to the entire D. Further, when D is a tetrafunctional organic residue, the dendritic polyester resin 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 have reacted is preferably 25 mol% or more with respect to the entire D, and the structure in which three functional groups have reacted is preferably 35 mol% or more.

  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 dendritic polyester resin in the present invention preferably exhibits molten liquid crystallinity. The term “showing melt 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 represented by a structural unit in which the organic residue (D) is selected from the group consisting of S, T, and U as represented by the following formula (2): It is preferable that they are bonded via the constituted branch structure portion R. Similarly, the basic skeleton in the case of four branches is preferably a structure represented by the following formula (3).

  The trifunctional organic residue represented by D is not particularly limited, but may be an organic residue of a compound containing at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an amino group. preferable. Residues of trimesic acid and α-resorcylic acid are preferable, and residues derived from trimesic acid are particularly preferable.

  Further, the tetrafunctional or higher functional organic residue D is preferably an organic residue of a compound containing at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an amino group. 1,2,4,5-benzenetetraol, 1,2,3,4-benzenetetraol, 1,2,3,5-benzenetetraol, pyromellitic acid, merophanic acid, planitic acid, gallic acid, etc. Residues are preferred, and residues of gallic acid are particularly preferred.

  The branch structure portion of the dendritic polyester resin 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. Among them, it is preferable to introduce an amide structure. By introducing such another bond, compatibility with a wide variety of thermoplastic resins can be adjusted. As a method for introducing the amide structure, a method of copolymerizing p-aminophenol and p-aminobenzoic acid is preferable.

  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. More specifically, for example, a method for producing a dendritic polyester resin described in JP2011-195814A can be used.

  Moreover, the dendritic polyester resin in this invention may be terminal-blocked. Examples of the end-capping method include a method of adding a monofunctional organic compound in advance when synthesizing a dendritic polyester resin, or a monofunctional organic compound at a stage where the skeleton of the dendritic polyester resin is formed to some extent. The method of adding etc. is mentioned.

  Examples of the monofunctional organic compound used for end-capping include monofunctional epoxy compounds, oxazoline compounds, orthoesters, and acid anhydride compounds. When blocking the hydroxyl end or acetoxy end, monofunctional organic compounds include benzoic acid, 4-t-butylbenzoic acid, 3-t-butylbenzoic acid, 4-chlorobenzoic acid, 3-chlorobenzoic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, 3,5-dimethylbenzoic acid and the like are preferably used. Moreover, when blocking the carboxyl group terminal, as a monofunctional organic compound, it has 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. A compound is preferably used. By blocking the end of the dendritic polyester resin, the retention stability and hydrolysis resistance of the dendritic polyester resin can be improved. In addition, further improvement in fluidity and physical properties can be expected by improving the dispersibility of the dendritic polyester in the polyamide resin composition.

  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 preferably 7.5 mol% or more. 13 mol% or more is more preferable. As an upper limit of content of the organic residue D, 50 mol% or less is preferable and 40 mol% or less is more preferable. In addition, the dendritic polyester resin of the present invention may have a partially crosslinked structure as long as the properties are not affected.

  Moreover, it is preferable that the terminal of the dendritic polyester resin in the present invention is a residue of a carboxyl group, a hydroxyl group, an amino group or a derivative having these groups. Examples of the derivative having a hydroxyl group or a carboxyl group include alkyl esters such as methyl ester and aromatic esters such as phenyl ester and benzyl ester.

  The polyamide resin composition of the present invention may contain components other than the components (A) to (D), such as various additives, as necessary, as long as the properties are not impaired. By further containing components other than (A) to (D), fluidity and residence stability of the polyamide resin composition, mechanical properties, heat aging resistance, and surface appearance of a molded product obtained using the polyamide resin composition In some cases, the metal adhesion can be further improved. Examples of such various additives include crystal nucleating agents, coloring agents, antioxidants (thermal stabilizers), sliding agents, weathering agents, mold release agents, plasticizers, lubricants, dye-based coloring agents, and pigment-based coloring. Agents, antistatic agents, foaming agents and the like. Two or more of these may be contained.

  As a manufacturing method of the polyamide resin composition of this invention, the manufacturing method in a molten state, the manufacturing method in a solution state, etc. are mentioned, for example. As a production method in a molten state, melt kneading with an extruder, melt kneading with a kneader, or the like can be used. From the viewpoint of productivity, melt kneading with an extruder that can be continuously produced is preferable. As the extruder, one or more extruders such as a single screw extruder, a twin screw extruder, a multi screw extruder such as a four screw extruder, and a twin screw single screw compound extruder can be used. From the viewpoint of improving productivity, a multi-screw extruder such as a twin-screw extruder or a four-screw extruder is preferable, and a twin-screw extruder is more preferable.

  As a melt-kneading method, a semi-aromatic polyamide resin (A) and an aliphatic polyamide (B), an inorganic filler (C), a flame retardant (D), and other additives are kneaded at once (collective kneading). Method), semi-aromatic polyamide resin (A), aliphatic polyamide (B), and other additives, if necessary, after melt-kneading, using a side feeder or the like, if necessary, inorganic filler (C), difficult A method in which a flame retardant (D) and other additives are further added and melt-kneaded (side feeder method-1), a semi-aromatic polyamide resin (A) and an aliphatic polyamide (B), and a flame retardant (D) as necessary And other additives are melt-kneaded, then the inorganic filler (C) and other additives are further added using a side feeder or the like, and melt-kneaded (side feeder method-2). It is. After semi-aromatic polyamide resin (A) and aliphatic polyamide (B) are melt-kneaded in advance, the two components interact with each other to improve compatibility, and then inorganic filler (C), flame retardant (D), etc. are added. The side feeder method is preferable in that it can be supplied.

  When producing a polyamide resin composition by melt-kneading using a twin screw extruder, the ratio (L / D) of the total screw length L and screw diameter D of the twin screw extruder is preferably 25 or more, More than 30 is more preferable. When the L / D is 25 or more, the semi-aromatic polyamide (A) and the aliphatic polyamide (B) are sufficiently kneaded, and then an inorganic filler (C), a flame retardant (D) and other additives are added as necessary. It becomes easy to supply the agent. As a result, it is considered that the semi-aromatic polyamide (A) and the aliphatic polyamide (B) are mixed more uniformly, and the fluidity and residence stability of the polyamide resin composition can be further improved.

  The polyamide resin composition of the present invention can be molded by any method such as generally known injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, and spinning, and can be processed into various molded products. Can be used. Examples of the molded product include injection molded products, extrusion molded products, blow molded products, films, sheets, fibers and the like. The film can be used as various films such as unstretched, uniaxially stretched, and biaxially stretched, and the fiber can be used as various fibers such as unstretched yarn, stretched yarn, and superstretched yarn. In particular, in the present invention, taking advantage of its excellent fluidity, it is also suitable for processing into small injection molded products such as electric and electronic parts and injection molded products having a thin part with a thickness of 0.01 to 1.0 mm. .

  The polyamide resin composition and molded product of the present invention are used in various applications such as electronic parts, electrical parts, household goods, office supplies, automobile / vehicle-related parts, building materials, sporting 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. It is preferably used for footwear related products such as materials, fishing gear related products such as fishing rods and fishing lines, summer sports related products such as surfing, winter sports related products such as skiing and snowboarding, and other indoor and outdoor sports related products.

  Among the various uses described above, the polyamide resin composition of the present invention and a molded product obtained from the above are used for electric / electronic parts by taking advantage of the fact that warpage is reduced under heating conditions and excellent metal adhesion. It is particularly preferably used for parts in contact with metal such as automobile parts, for example, connectors or breakers.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely in detail, this invention is not limited only to a following example. The semi-aromatic polyamide (X) and the aliphatic polyamide (Y) used in the examples and comparative examples are as follows.

Production Example 1: (X-1) Polyamide 10T
Decamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and terephthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are added in an equimolar amount so that the total amount is 10 kg, and 0.5 mol% of decamethylenediamine is excessive with respect to the total amount of decamethylenediamine. 30 parts by weight of water was added to and mixed with 70 parts by weight of these raw materials, charged in 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 was pulverized, vacuum dried at 100 ° C. for 24 hours, and solid-phase polymerized at 50 Pa and 240 ° C. to obtain polyamide 10T having ηr = 2.30 and a melting point of 318 ° C.

Production Example 2: (X-2) Polyamide 9T
Nonamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2-methyl-1,8-octanediamine are added so that the molar percentage is 85:15, and the mixture and terephthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are brought to a total amount of 10 kg. Further, equimolar amounts were added so that 0.5 mol% of nonamethylenediamine and 2-methyl-1,8-octanediamine was mixed with respect to the total amount of nonamethylenediamine and 2-methyl-1,8-octanediamine. The liquid (85/15 mol% ratio) was added in excess, and 30 parts by weight of water was added to and mixed with 70 parts by weight of these raw materials. The mixture was charged in a pressure vessel, sealed, and purged with nitrogen. After the 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 230 ° 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 was pulverized, vacuum dried at 100 ° C. for 24 hours, and solid-phase polymerized at 50 Pa and 240 ° C. to obtain polyamide 9T having ηr = 2.43 and a melting point of 308 ° C.

Production Example 3: (X-3) Polyamide 6T
50 equimolar salts (M5T) of 2-methylpentamethylenediamine (manufactured by Tokyo Chemical Industry) and terephthalic acid (manufactured by Tokyo Chemical Industry), 50 equimolar salts of hexamethylenediamine (manufactured by Tokyo Chemical Industry) and terephthalic acid (6T) / 50 wt% ratio. An excess of 0.5 mol% of a mixture of 2-methylpentamethylenediamine and hexamethylenediamine (50/50 wt% ratio) with respect to the total amount of 2-methylpentamethylenediamine and hexamethylenediamine was added, and the total of these raw materials 30 parts by weight of water was added to 70 parts by weight, mixed, charged in a pressure vessel, sealed, and purged with nitrogen. After heating was started and the internal temperature of the can reached 214 ° C. and the internal pressure of 1.7 MPa, the internal pressure of the can was maintained at 1.7 MPa for 2 hours while distilling water, and the internal temperature of the can increased to 241 ° C. did. Thereafter, the contents were discharged from the pressurized container to obtain a polyamide oligomer. The obtained polyamide oligomer was pulverized, vacuum dried at 100 ° C. for 24 hours, and solid-phase polymerized at 40 Pa and 240 ° C. to obtain polyamide 6T having ηr = 2.20 and a melting point of 302 ° C.

Production Example 4: (Y-1) Polyamide 610
Hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and a 50% by weight aqueous solution of an equimolar salt of sebacic acid (manufactured by Tokyo Chemical Industry Co., Ltd .: 2.36 mol) and hexamethylenediamine (0.0141 mol) were charged into a 3 L pressure vessel and sealed. And replaced with nitrogen. After heating was started and the internal pressure of the can reached 1.75 MPa, the internal pressure of the can was maintained at 1.75 MPa for 1.5 hours while releasing moisture out of the system. Thereafter, the internal pressure of the can was returned to normal pressure over 1 hour, and further reacted at 265 ° C. for 1 hour under 80.0 kPa to complete the polymerization. Thereafter, the polymer in a lump was taken out from the pressure vessel and freeze-ground. This was vacuum-dried at 80 ° C. for 24 hours to obtain polyamide 610 having ηr = 2.69 and Tm = 225 ° C.

Production Example 5: (Y-2) Polyamide 510
A 50% by weight aqueous solution of pentamethylene sebacamide salt and an excess of 1,5-diaminopentane (24.67 mmol) were placed in the polymerization vessel, and the inside of the polymerization vessel was thoroughly purged with nitrogen. did. After the internal pressure of the can reached 1.75 MPa, the internal pressure of the can was maintained at 1.75 MPa for 74 minutes, and then the internal pressure of the can was returned to normal pressure over 1 hour. At this time, the inside temperature of the can reached 264 ° C. Furthermore, the polymerization was completed by reacting at 264 ° C. for 40 minutes under 80.0 kPa. Thereafter, the block polymer was taken out from the polymerization can and freeze-pulverized. This was vacuum-dried at 80 ° C. for 24 hours to obtain polypentamethylene sebacamide (polyamide 510, ηr = 2.71).

Production Example 6: (Y-3) Polyamide 410
Polyamide 410 salt, tetramethylenediamine (1.00 mol% with respect to polyamide 410 salt), sodium hypophosphite (0.05 wt% with respect to the weight of the produced polymer) were charged into a 3 L pressure vessel and sealed, and nitrogen was added. Replaced. After heating was started and the internal pressure of the can reached 0.5 MPa, the internal pressure of the can was maintained at 0.5 MPa for 1.5 hours while releasing moisture out of the system. Thereafter, the internal pressure of the can was returned to normal pressure over 10 minutes, and the reaction was further continued for 1.5 hours under a nitrogen flow to complete the polymerization. Thereafter, the polymer in a lump was taken out from the pressure vessel and freeze-ground. This was vacuum-dried at 80 ° C. for 24 hours to obtain polytetramethylene sebacamide (polyamide 410, ηr = 2.84).

Production Example 7: (Y-4) Polyamide 612
Hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.), dodecanedioic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.5 mol% of hexamethylenediamine with respect to the total amount of hexamethylenediamine are added in excess and charged into a 3 L pressure vessel. Sealed and purged with nitrogen. After heating was started and the internal pressure of the can reached 1.7 MPa, the internal pressure of the can was maintained at 1.7 MPa for 1.5 hours while moisture was released out of the system. Thereafter, the internal pressure of the can was returned to normal pressure over 10 minutes, and the reaction was further continued for 1.5 hours under a nitrogen flow to complete the polymerization. Thereafter, the polymer in a lump was taken out from the pressure vessel and freeze-ground. This was vacuum-dried at 80 ° C. for 24 hours to obtain polyamide 612 (ηr = 2.51, melting point 191 ° C.).

(Y-5) Polyamide 66
Polyamide 66 (“Amilan” (registered trademark) CM3001-N manufactured by Toray Industries, Inc.).

(Y-6): Polyamide 6
Polyamide 6 (“Amilan” (registered trademark) CM1010 manufactured by Toray Industries, Inc.).

The inorganic filler (C) used in the examples and comparative examples is as follows.
(C-1) Glass fiber “T-275H” (manufactured by Nippon Electric Glass Co., Ltd.) treated with a urethane sizing agent.

The flame retardant (D) used in the examples and comparative examples is as follows.
(D-1) Phosphorus flame retardant Aluminum diethylphosphinate “OP1230” (manufactured by Clariant).

  Characteristic evaluation in each example and comparative example was performed according to the following method.

[Liquidity]
The pellets obtained in each of the examples and comparative examples were dried under reduced pressure at 140 ° C. for 12 hours, and the mold temperature was set to 140 ° C. using ROBOSHOTα-30C (manufactured by FANUC). Ten molded products having a width of 10 mm × 0.5 mm were injection molded under the conditions of the resin temperature, the injection speed being 100 mm / sec, and the injection pressure being 98 MPa. The average value of the flow lengths of 10 molded articles was calculated as the fluidity value. The longer the flow length, the better the fluidity.

[Stay stability]
Capillograph 1C (made by Toyo Seiki Co., Ltd.) using a die having a hole length of 10.00 mm and a hole diameter of 1.00 mm was charged with 20 g of pellets obtained in each Example and Comparative Example and dried under reduced pressure at 140 ° C. for 12 hours. The melt viscosity after residence for 5 minutes and after residence for 30 minutes was measured at the resin temperatures shown in Tables 1-4. The relationship of the resulting shear rate ^{(sec -1)} and the melt viscosity, to calculate the melt viscosity at a shear rate of 1,000 sec ^-1, was calculated melt viscosity retention at the following equation. The melt viscosity after 5 minutes residence and after 30 minutes residence was measured twice, and the average value was calculated as the value of melt viscosity at each residence time. It can be said that the greater the melt viscosity retention, the better the retention stability.
Melt viscosity retention [%] = (melt viscosity after staying for 30 minutes [Pa · s] / 5 melt viscosity after staying for 5 minutes [Pa · s]) × 100.

[Metal adhesion]
FIG. 1 shows a schematic diagram of a test piece for metal adhesion evaluation. An aluminum prism 1 having the shape shown in FIG. 1 was manufactured and charged into a mold. The pellets obtained in each of the examples and comparative examples were dried under reduced pressure at 140 ° C. for 12 hours, and the mold temperature was set to 140 ° C. using ROBOSHOTα-30C (manufactured by FANUC). The resin temperature was injection-molded from the gate 3 so that the resin 2 was bonded to the aluminum prism 1 under the conditions that the injection speed was 100 mm / sec and the injection pressure was the lower limit pressure + 0.49 MPa. Three test pieces were prepared each. Next, using a metal adhesion evaluation AG-2000C (manufactured by Shimadzu Corp.), a tensile test was performed under the conditions of a measurement environment temperature of 23 ° C., 50% RH, a strain rate of 10 mm / min, and a distance between sample gauge points of 50 mm. Was measured. The average value of the tensile strength of three molded articles was calculated as the value of metal adhesion.

[Sleigh under heating conditions]
The pellets obtained in each of the examples and comparative examples were dried under reduced pressure at 140 ° C. for 12 hours, and the mold temperature was set to 140 ° C. using ROBOSHOTα-30C (manufactured by FANUC). Injection molding was performed under the conditions that the resin temperature was an injection speed of 100 mm / sec and the injection pressure was 49 MPa, to obtain a molded product of a 0.8 mm pitch 100-core fine pitch connector (insulator) shown in FIG. Thereafter, the molded product was placed on a horizontal surface plate and observed using a universal projector, and the maximum displacement amount of the connector bottom surface 4 with respect to the horizontal surface plate was defined as a warp deformation amount and measured. In addition, it was set as "deformation measurement impossible" when it cannot measure by softening deformation.

[Flame retardance]
The pellets obtained in Examples 9 to 12 and Comparative Examples 9 to 12 were dried under reduced pressure at 140 ° C. for 12 hours. Using ROBOSHOTα-30C (manufactured by FANUC), the mold temperature was 140 ° C., and the resin temperature was expressed. The resin temperature described in 1-4 was injection-molded under the conditions where the injection speed was 100 mm / sec and the injection pressure was the lower limit pressure + 1.0 MPa, and five 0.38 mm-thick UL test pieces were produced. Evaluation was carried out by a vertical combustion method in conformity with UL94 (standard established by Under WriterLaboratories Inc., USA). According to the test method of UL94, after the flame of the gas burner was contacted to the lower end of the sample held vertically for 10 seconds, if the combustion stopped within 10 seconds, the indirect flame was further continued for 10 seconds, and this two contact The total flame time was evaluated as a flame retardance index in the present invention, where the total flame time was defined as the combustion time, and the total combustion time evaluated for the five flames.

(Examples 1-5, Comparative Examples 1-6)
After dry blending the semi-aromatic polyamide and the aliphatic polyamide shown in Table 1, the TEX30 type twin screw extruder (L / L) manufactured by Nippon Steel Co., Ltd. was set to the resin temperature shown in Table 1 and the screw rotation speed was set to 200 rpm. D = 35) was supplied from the main feeder and melt-kneaded. This main feeder is connected to a position 0 when viewed from the upstream side when the total length of the screw is 1.0, that is, a position of an end portion on the upstream side of the screw segment. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The results evaluated by the above method are shown in Table 1.

  The polyamide resin compositions of Examples 1 to 5 were excellent in fluidity and residence stability, had high metal adhesion, and were able to obtain molded articles with little warpage under heating conditions. On the other hand, in Comparative Example 1, since the content of the aliphatic polyamide was as very small as 2 parts by weight, the fluidity, residence stability and metal adhesion decreased, and warpage under heating conditions increased. In Comparative Example 2, since the aliphatic polyamide content was as high as 67 parts by weight, the retention stability was low, and the warpage of the molded product under heating conditions increased. Since Comparative Examples 3 to 4 did not contain the predetermined aromatic polyamide, fluidity, residence stability, and metal adhesion of the molded product were lowered, and the molded product was softened under heating conditions or warpage was increased. Since Comparative Examples 5 to 6 did not contain the predetermined aliphatic polyamide, fluidity, residence stability, and metal adhesion of the molded product were lowered, and warpage was increased under heating conditions.

(Examples 6-8, Comparative Examples 7-8)
After dry blending the semi-aromatic polyamide and the aliphatic polyamide shown in Table 2, the cylinder set temperature is set to the resin temperature shown in Table 2, and the screw rotation speed is set to 200 rpm. Supplied from the main feeder of the machine (L / D = 35). The main feeder is connected to a position 0 when viewed from the upstream side when the total length of the screw is 1.0. Subsequently, the inorganic filler shown in Table 2 was supplied from the side feeder to the twin screw extruder, and melt kneaded. This side feeder is connected to a position of 0.65 when viewed from the upstream side when the total length of the screw is 1.0. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The results evaluated by the above method are shown in Table 2.

  The polyamide resin compositions of Examples 6 to 8 were excellent in fluidity and retention stability, had high metal adhesion, and were able to obtain molded articles with little warpage under heating conditions. On the other hand, since Comparative Example 7 did not contain a predetermined aromatic polyamide, fluidity, residence stability and metal adhesion of the molded product were lowered, and the molded product was softened under heating conditions. Since Comparative Example 8 did not contain a predetermined aliphatic polyamide, fluidity, retention stability and metal adhesion of the molded product were lowered, and warpage was increased under heating conditions.

(Examples 9 to 10, Comparative Examples 9 to 10)
After dry blending the semi-aromatic polyamide, the aliphatic polyamide and the flame retardant shown in Table 3, the TEX30 type twin screw extruder manufactured by Nippon Steel Co., Ltd. was set to the resin temperature shown in Table 3 and the screw rotation speed was set to 200 rpm. It was supplied from a main feeder (L / D = 35) and melt kneaded. The main feeder is connected to a position 0 when viewed from the upstream side when the total length of the screw is 1.0. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The results evaluated by the above method are shown in Table 3.

  The polyamide resin compositions of Examples 9 to 10 are excellent in fluidity and residence stability, have high metal adhesion, have little warpage under heating conditions, and can obtain a molded product having excellent flame retardancy. did it. On the other hand, since Comparative Example 9 did not contain the predetermined semi-aromatic polyamide, fluidity, retention stability and metal adhesion of the molded product were lowered, and the molded product was softened under heating conditions. Since Comparative Example 10 did not contain a predetermined aliphatic polyamide, fluidity, retention stability and metal adhesion of the molded product were lowered, and warpage was increased under heating conditions.

(Examples 11-12, Comparative Examples 11-12)
After dry blending the semi-aromatic polyamide, the aliphatic polyamide and the flame retardant shown in Table 4, the cylinder set temperature is set to the resin temperature shown in Table 4, and the screw rotation speed is set to 200 rpm. Supplied from the main feeder of a twin screw extruder (L / D = 35). The main feeder is connected to a position 0 when viewed from the upstream side when the total length of the screw is 1.0. Subsequently, the inorganic filler shown in Table 4 was supplied from the side feeder to the twin screw extruder and melt-kneaded. This side feeder is connected to a position of 0.65 when viewed from the upstream side when the total length of the screw is 1.0. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The results evaluated by the above method are shown in Table 4.

  The polyamide resin compositions of Examples 11 to 12 are excellent in fluidity and residence stability, have high metal adhesion, have little warpage under heating conditions, and can obtain molded articles having excellent flame retardancy. did it. On the other hand, since Comparative Example 11 did not contain the predetermined semi-aromatic polyamide, fluidity, retention stability, and metal adhesion of the molded product were lowered, and the molded product was softened under heating conditions. Since Comparative Example 12 did not contain a predetermined aliphatic polyamide, fluidity, retention stability and metal adhesion of the molded product were lowered, and warpage was increased under heating conditions.

1 Aluminum prism 2 Resin 3 Gate 4 Connector bottom

Claims (6)

Main component is at least one selected from the group consisting of a dicarboxylic acid component mainly composed of terephthalic acid and / or isophthalic acid, and 1,8-octanediamine, 1,10-decanediamine and 1,12-dodecanediamine. 50 to 95 parts by weight of a semi-aromatic polyamide (A) using a diamine component as a raw material, a dicarboxylic acid component mainly composed of an aliphatic dicarboxylic having 8 to 12 carbons, and an aliphatic having 4 to 8 carbons A polyamide resin composition containing 5 to 50 parts by weight of an aliphatic polyamide (B) made from a diamine component mainly composed of diamine (provided that the total of (A) and (B) is 100 parts by weight). The polyamide resin composition according to claim 1, further comprising 5 to 200 parts by weight of an inorganic filler (C) with respect to a total of 100 parts by weight of the semi-aromatic polyamide (A) and the aliphatic polyamide (B). The polyamide resin composition according to claim 1 or 2, further comprising 1 to 50 parts by weight of a flame retardant (D) with respect to a total of 100 parts by weight of the semi-aromatic polyamide (A) and the aliphatic polyamide (B). . The polyamide resin composition according to claim 3, wherein the flame retardant (D) contains at least a phosphorus-containing compound. The polyamide resin composition according to any one of claims 1 to 4, wherein the aliphatic polyamide (B) includes polyamide 410, polyamide 510, and / or polyamide 610. An electrical / electronic component formed by molding the polyamide resin composition according to claim 1.

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