WO2014132883A1

WO2014132883A1 - Flame-retardant polyamide resin composition to be used in surface mount type electric/electronic component

Info

Publication number: WO2014132883A1
Application number: PCT/JP2014/054121
Authority: WO
Inventors: 誠玉津島; 順一中尾; 貴司清水
Original assignee: 東洋紡株式会社
Priority date: 2013-02-26
Filing date: 2014-02-21
Publication date: 2014-09-04
Also published as: JPWO2014132883A1

Abstract

A flame-retardant polyamide resin composition that has a high solder heat resistance, a high flame retardancy, a low water absorbency and excellent mechanical properties and is appropriately usable in a surface mount type electric/electronic component, said flame-retardant polyamide resin composition comprising: copolymerized polyamide resin (A) that comprises 55-75 mol% of structural unit (a) obtained from hexamethylenediamine and terephthalic acid and 45-25 mol% of structural unit (b) comprising 11-aminoundecanoic acid or undecane lactam; flame retardant (B) that comprises a phosphinic acid metal salt; flame retardant (C) that comprises a nitrogen-containing phosphoric acid-based compound; reinforcing agent (D) that is selected from a fibrous reinforcing agent and a needle-type reinforcing agent; and non-fibrous or non-needle-type filler (E), wherein, per 100 parts by mass of copolymerized polyamide resin (A), flame retardants (B) and (C) are contained in a total amount of 30-80 parts by mass, reinforcing agent (D) is contained in an amount of 30-200 parts by mass, and filler (E) is contained in an amount of 0-5 parts by mass, and the ratio by mass of flame retardant (B)/flame retardant (C) is 5-50.

Description

Flame retardant polyamide resin composition for use in surface mount electrical and electronic parts

The present invention relates to a non-halogen flame-retardant polyamide resin composition suitable for use in a surface-mount type electric / electronic component having excellent flame retardancy, low water absorption, solder heat resistance, and mechanical properties.

In recent years, in the mounting of electrical and electronic components, surface mounting methods (flow method, reflow method) have rapidly increased due to the miniaturization of components accompanying the reduction in product size, higher mounting density, simplification of processes, and lower costs. Penetrating. In the surface mounting method, since the process atmosphere temperature is equal to or higher than the solder melting temperature (240 to 260 ° C.), the resin to be used is inevitably required to have heat resistance at the above atmospheric temperature. Further, in the surface mounting process, the swelling and deformation of the mounting component due to the water absorption of the resin may be a problem, and the resin used is required to have low water absorption. As resins satisfying these characteristics, there are 6T polyamide and 9T polyamide, and Patent Document 1 and Patent Document 2 show that these aromatic polyamides can be used for surface mount type electric and electronic parts.

On the other hand, it is desirable that the polyamide resin as a raw material is not limited to electrical and electronic parts, but has flame retardancy based on the UL-94 standard depending on the location and environment of use. In response to such a need, various technical developments for imparting flame retardancy to polyamide resins have been performed so far. As a technique for flame-retarding a polyamide resin, a combined use of a halogenated organic compound such as brominated polystyrene as a flame retardant and an antimony compound that works as a flame retardant aid is common. However, while this technology can provide excellent flame retardancy, it has problems such as generation of hydrogen halide during combustion and a large amount of smoke generation. Furthermore, since the use of plastic products using some halogenated flame retardants is being regulated, non-halogen flame retardant polyamide resins are being actively studied.

As non-halogen flame retardant technologies, those using metal hydroxides or phosphorus compounds as flame retardants are common, but the former requires a large amount of addition to obtain sufficient flame retardancy, As a result, there is a problem that the mechanical properties are remarkably deteriorated.

On the other hand, in the latter, for example, in Patent Document 3, a high flame retardancy is imparted to polyamide 66 by using a phosphorus compound containing melamine, melam, and melem, which are triazine compounds, as a structural unit as a flame retardant. Non-halogen flame retardant polyamide resin compositions have been proposed. Patent Document 4 proposes a non-halogen flame-retardant polyamide resin composition that imparts high flame retardancy to polyamide 12 that is a long-chain aliphatic polyamide by using a condensed or non-condensed phosphorus flame retardant. ing. However, these flame retardant polyamide resin compositions have a melting point near or below the solder melting temperature, and therefore cannot be applied to surface mount type electric / electronic components. In addition, regarding the flame retardant technology, due to the heat resistance problem of the flame retardant itself, it is not effective for polyamide resins corresponding to surface mount type electric and electronic parts typified by 6T polyamide. There is room for improvement in the study of resins.

As a non-halogen flame retardant resin composition corresponding to a surface mount type electric / electronic component, for example, in Patent Document 5, a thermoplastic flame retardant composition composed of 6T polyamide and polyphenylene sulfide is used as a flame retardant. A non-halogen flame retardant thermoplastic resin composition having the above formula is proposed. Patent Document 6 proposes a non-halogen flame retardant polyamide resin composition in which flame resistance is imparted to the polyamide 46 by the combined use of a nitrogen-containing compound and a phosphorus flame retardant. However, these resin compositions have a high saturated water absorption of 6% or more, and absorb moisture in the atmosphere during transportation and storage of products, causing problems such as product blistering in the surface mounting process. Have.

Furthermore, Patent Document 7 proposes a flame retardant polyamide resin composition in which flame retardancy is imparted to polyamide 9T by using red phosphorus and magnesium hydroxide together without using a large amount of metal hydroxide. Although this polyamide resin exhibits low water absorption and the problem of blistering in the surface mounting process found in 6T polyamide is extremely suppressed, the glass transition temperature of the resin is 130 ° C. In order to complete crystallization, it is necessary to set the mold temperature to a high temperature of 140 ° C. or higher, and there is room for improvement in terms of moldability.

As described above, the non-halogen flame retardant polyamide resins that have been proposed so far do not satisfy all of the mechanical properties, solder heat resistance, low water absorption, moldability, and flame retardancy, and are used with problems. It is the actual situation.

Japanese Patent Laid-Open No. 3-88846 Japanese Patent No. 3474246 JP 2004-43647 A JP-A-11-302656 International Publication WO2010 / 073595 Pamphlet Japanese Patent No. 4454146 JP 2000-230118 A

The present invention was devised in view of the above-mentioned problems of the prior art, and its purpose is to be used for a surface mount type electric / electronic component excellent in solder heat resistance, flame retardancy, low water absorption, and mechanical properties. Another object of the present invention is to provide a flame retardant polyamide resin composition suitable for the above.

In order to achieve the above-mentioned object, the present inventor has intensively studied the composition of polyamide that can impart flame retardancy while satisfying the characteristics as an electric / electronic component and can advantageously perform injection molding and reflow soldering process. The present invention has been completed.

That is, the present invention has the following configurations (1) to (4).
(1) A flame-retardant polyamide resin composition for use in a surface-mounted electrical / electronic component, wherein (a) a structural unit 55 to 75 mol% obtained from an equimolar salt of hexamethylenediamine and terephthalic acid; (B) a copolymerized polyamide resin (A) comprising 45 to 25 mol% of a structural unit obtained from 11-aminoundecanoic acid or undecane lactam, a flame retardant (B) comprising a metal salt of phosphinic acid, a nitrogen-containing phosphoric acid series Contains at least one reinforcing material (D) selected from the group consisting of a flame retardant (C) composed of a compound, a fibrous reinforcing material and an acicular reinforcing material, and a non-fibrous or non-acicular filling material (E) The total of the flame retardants (B) and (C) is 30 to 80 parts by mass, the reinforcing material (D) is 30 to 200 parts by mass, and the filler (E ) Is the proportion of 0-5 parts by mass It contained, and the weight ratio of the flame retardant (B) / (C) is a flame-retardant polyamide resin composition, wherein the 5 to 50.
(2) The flame retardant polyamide resin composition according to (1), wherein the polyamide resin composition has an underwater equilibrium water absorption of 3.0% or less.
(3) The melting point (Tm) of the polyamide resin composition is 300 to 330 ° C, and the temperature-rising crystallization temperature (Tc1) is 90 to 120 ° C, as described in (1) or (2) Flame retardant polyamide resin composition.
(4) The non-fibrous or non-needle filler (E) is talc, and is contained at a ratio of 0.1 to 5 parts by mass of talc with respect to 100 parts by mass of the copolymerized polyamide resin (A). The flame-retardant polyamide resin composition according to any one of (1) to (3).
(5) The copolymerized polyamide resin (A) is (c) a structural unit obtained from an equivalent molar salt of a diamine other than the structural unit of (a) and a dicarboxylic acid, or an amino group other than the structural unit of (b). The flame-retardant polyamide resin composition according to any one of (1) to (4), which contains up to 20 mol% of a structural unit obtained from carboxylic acid or lactam.

The flame-retardant polyamide resin composition of the present invention uses a specific copolymerized polyamide resin that is excellent in processability such as moldability during injection molding and solder heat resistance in addition to high heat resistance, low water absorption, and flame retardancy. Therefore, it is possible to industrially advantageously manufacture a surface mount type electric / electronic component that highly satisfies all necessary characteristics.

The polyamide resin composition of the present invention is intended to be used for surface-mounted electrical and electronic parts. Examples of the surface mount type electric / electronic components include connectors, switches, IC / LED housings, sockets, relays, resistors, capacitors, coil bobbins, etc. The polyamide resin composition of the present invention is all of these electric / electronic components. Can be manufactured by injection molding.

The copolymerized polyamide resin (A) is blended to realize excellent moldability in addition to high heat resistance, fluidity and low water absorption, and the component (a) corresponding to polyamide 6T and polyamide 11 And a conventional 6T polyamide (for example, polyamide 6T6I composed of terephthalic acid / isophthalic acid / hexamethylenediamine, polyamide composed of terephthalic acid / adipic acid / terephthalic acid) 6T66, polyamide 6T6I66 composed of terephthalic acid / isophthalic acid / adipic acid / hexamethylenediamine, polyamide 6T / M-5T composed of terephthalic acid / hexamethylenediamine / 2-methyl-1,5-pentamethylenediamine, terephthalic acid / hexa From methylenediamine / ε-caprolactam It has the feature that the superabsorbent has been greatly improved, which is a disadvantage of that polyamide 6T6). Furthermore, since it has a flexible long-chain fatty skeleton derived from the polyamide 11 component, it also has a feature that it is easy to ensure fluidity.

The component (a) corresponds to 6T polyamide obtained by co-condensation polymerization of hexamethylenediamine (6) and terephthalic acid (T) in an equimolar amount, and specifically, the following formula (I) It is represented by

The component (a) is a main component of the copolymerized polyamide resin (A) and has a role of imparting excellent heat resistance, mechanical properties, slidability and the like to the copolymerized polyamide resin (A). The blending ratio of the component (a) in the copolymerized polyamide resin (A) is 55 to 75 mol%, preferably 60 to 70 mol%, more preferably 62 to 68 mol%. When the blending ratio of the component (a) is less than the above lower limit, the 6T polyamide that is a crystal component is subject to crystal inhibition by the copolymer component, which may lead to a decrease in moldability and high-temperature characteristics. Since melting | fusing point becomes high too much and there exists a possibility of decomposing | disassembling at the time of processing, it is not preferable.

The component (b) corresponds to 11 polyamide obtained by polycondensation of 11-aminoundecanoic acid or undecane lactam, and is specifically represented by the following formula (II).

The component (b) is for improving water absorption and fluidity, which is a drawback of the component (a). The moldability is adjusted by adjusting the melting point and the temperature rising crystallization temperature of the copolymerized polyamide resin (A). It has the role of improving, the role of reducing the water absorption rate to improve the trouble caused by changes in physical properties and dimensional changes at the time of water absorption, and the role of improving the fluidity at the time of melting by introducing a flexible skeleton. The blending ratio of the component (b) in the copolymerized polyamide resin (A) is 45 to 25 mol%, preferably 40 to 30 mol%, more preferably 38 to 32 mol%. When the blending ratio of the component (b) is less than the above lower limit, the melting point of the copolymerized polyamide resin (A) is not sufficiently lowered, the moldability may be insufficient, and the water absorption rate of the obtained resin is reduced. The effect is insufficient, and there is a risk of instability of physical properties such as deterioration of mechanical properties upon water absorption. When the above upper limit is exceeded, the melting point of the copolymerized polyamide resin (A) is too low, the crystallization speed is slow, the moldability may be adversely affected, and the amount of the component (a) corresponding to 6T polyamide This is not preferable because there is a risk that mechanical properties and heat resistance may be insufficient.

In addition to the components (a) and (b), the copolymerized polyamide resin (A) is (c) a structural unit obtained from an equivalent molar salt of diamine and dicarboxylic acid other than the structural unit of (a) above, or You may copolymerize the structural unit obtained from aminocarboxylic acid or lactam other than the structural unit of said (b) at maximum 20 mol%. The component (c) has a role to give the copolymer polyamide resin (A) other characteristics that cannot be obtained by 6T polyamide or 11 polyamide, or to further improve the characteristics obtained by 6T polyamide or 11 polyamide. Specific examples include the following copolymerization components. Examples of the diamine component include 1,2-ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 5-pentamethylenediamine, 2-methyl-1,5-pentamethylenediamine, 1,6-hexa Methylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 2-methyl-1,8-octamethylenediamine, 1,10-decamethylenediamine, 1,11 Undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,16-hexadecamethylenediamine, 1,18-octadecamethylenediamine, 2,2,4 (or 2, 4,4) -aliphatic diamines such as trimethylhexamethylenediamine, piperazine, Cyclohexanediamine, bis (3-methyl-4-aminohexyl) methane, bis- (4,4'-aminocyclohexyl) methane, cycloaliphatic diamines such as isophoronediamine, metaxylylenediamine, paraxylylenediamine, Examples thereof include aromatic diamines such as paraphenylenediamine and metaphenylenediamine, and hydrogenated products thereof. As the dicarboxylic acid component, the following dicarboxylic acids or acid anhydrides can be used. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and 2,2′-diphenyldicarboxylic acid. 4,4'-diphenyl ether dicarboxylic acid, 5-sulfonic acid sodium isophthalic acid, 5-hydroxyisophthalic acid and other aromatic dicarboxylic acids, fumaric acid, maleic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, , 2-Cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexa Dicarboxylic acids, such as aliphatic or alicyclic dicarboxylic acids such as dimer acid. Further, lactams such as ε-caprolactam and 12-lauryl lactam, and aminocarboxylic acids having a structure in which they are ring-opened can be used.

Specific examples of the component (c) include polycaproamide (polyamide 6), polydodecanamide (polyamide 12), polytetramethylene adipamide (polyamide 46), polyhexamethylene adipamide (polyamide 66), polyun Decamethylene adipamide (polyamide 116), polymetaxylylene adipamide (polyamide MXD6), polyparaxylylene adipamide (polyamide PXD6), polytetramethylene sebamide (polyamide 410), polyhexamethylene sebacamide (Polyamide 610), polydecamethylene adipamide (polyamide 106), polydecamethylene sebamide (polyamide 1010), polyhexamethylene dodecamide (polyamide 612), polydecamethylene dodecamide (polyamide 1012), polyhexamethy Isophthalamide (polyamide 6I), polytetramethylene terephthalamide (polyamide 4T), polypentamethylene terephthalamide (polyamide 5T), poly-2-methylpentamethylene terephthalamide (polyamide M-5T), polyhexamethylene hexahydroterephthalate Amides (Polyamide 6T (H)), Polynonamethylene terephthalamide (Polyamide 9T), Polydecamethylene terephthalamide (Polyamide 10T), Polyundecamethylene terephthalamide (Polyamide 11T), Polydodecamethylene terephthalamide (Polyamide 12T), Polybis (3-methyl-4-aminohexyl) methane terephthalamide (polyamide PACMT), polybis (3-methyl-4-aminohexyl) methane isophthalamide ( Polyamide PACMI), polybis (3-methyl-4-amino-hexyl) methane dodecamide (polyamide PACM12), and the like polybis (3-methyl-4-amino-hexyl) methane tetradecanoyl bromide (polyamide PACM14). These may be copolymerized alone or in combination of multiple components. Any copolymerization technique such as random copolymerization, block copolymerization, and graft copolymerization may be used.

Among the structural units, examples of a preferable component (c) include polyhexamethylene adipamide for imparting high crystallinity to the copolymerized polyamide resin (A), and poly (polyethylene) for imparting further low water absorption. Examples include decamethylene terephthalamide and polydodecanamide. The blending ratio of the component (c) in the copolymerized polyamide resin (A) is preferably up to 20 mol%, more preferably 10 to 20 mol%. When the proportion of the component (c) is less than the above lower limit, the effect of the component (c) may not be sufficiently exhibited. When the proportion exceeds the above upper limit, the amount of the essential component (a) or component (b) is small. Therefore, the originally intended effect of the copolymerized polyamide resin (A) may not be sufficiently exhibited, which is not preferable.

Examples of the catalyst used for producing the copolymerized polyamide resin (A) include phosphoric acid, phosphorous acid, hypophosphorous acid or a metal salt, ammonium salt and ester thereof. Specific examples of the metal species of the metal salt include potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony. Examples of the ester include ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, and phenyl ester. Moreover, it is preferable to add alkali compounds, such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide, from a viewpoint of melt retention stability improvement.

The relative viscosity (RV) of the copolymerized polyamide resin (A) measured at 20 ° C. in 96% concentrated sulfuric acid is 0.4 to 4.0, preferably 1.0 to 3.0, more preferably 1.5. ~ 2.5. Examples of a method for setting the relative viscosity of the polyamide within a certain range include a means for adjusting the molecular weight.

The copolymerized polyamide resin (A) can adjust the end group amount and the molecular weight of the polyamide by adjusting the molar ratio between the amino group amount and the carboxyl group to carry out polycondensation or adding a terminal blocking agent. it can. When polycondensation is performed at a constant ratio of the molar ratio of the amino group and the carboxyl group, the molar ratio of all diamines to all dicarboxylic acids used is diamine / dicarboxylic acid = 1.00 / 1.05 to 1.10 / It is preferable to adjust to the range of 1.00.

Examples of the timing for adding the end-capping agent include starting raw materials, starting polymerization, late polymerization, or finishing polymerization. The end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide, but acid anhydrides such as monocarboxylic acid or monoamine, phthalic anhydride, Monoisocyanates, monoacid halides, monoesters, monoalcohols and the like can be used. Examples of the end capping agent include aliphatic monoacids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid. Alicyclic monocarboxylic acids such as carboxylic acid and cyclohexanecarboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, aromatic monocarboxylic acid such as phenylacetic acid, maleic anhydride Acid, phthalic anhydride, acid anhydrides such as hexahydrophthalic anhydride, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, etc. Aliphatic monoamines, Examples thereof include alicyclic monoamines such as cyclohexylamine and dicyclohexylamine, and aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine.

The acid value and amine value of the copolymerized polyamide resin (A) are preferably 0 to 200 eq / ton and 0 to 100 eq / ton, respectively. When the terminal functional group exceeds 200 eq / ton, not only gelation and deterioration are promoted during the melt residence, but also problems such as coloring and hydrolysis are caused even in the use environment. On the other hand, when a reactive compound such as glass fiber or maleic acid-modified polyolefin is compounded, the acid value and / or amine value is preferably 5 to 100 eq / ton in accordance with the reactivity and the reactive group.

The copolymerized polyamide resin (A) can be produced by a conventionally known method. For example, hexamethylene diamine, terephthalic acid, which is a raw material monomer of the component (a), and 11 a raw material monomer of the component (b). -Aminoundecanoic acid or undecanactactam, and if necessary (c) a structural unit obtained from an equimolar salt of a diamine other than the structural unit of (a) and a dicarboxylic acid, an aminocarboxylic acid other than the structural unit of (b) Alternatively, it can be easily synthesized by co-condensation of lactam. The order of the copolycondensation reaction is not particularly limited, and all the raw material monomers may be reacted at once, or a part of the raw material monomers may be reacted first, followed by the remaining raw material monomers. The polymerization method is not particularly limited, but from raw material charging to polymer production may proceed in a continuous process, and after producing an oligomer once, the polymerization is advanced by an extruder or the like in another process, or the oligomer is solidified. A method of increasing the molecular weight by phase polymerization may be used. By adjusting the charging ratio of the raw material monomer, the proportion of each structural unit in the copolymerized polyamide to be synthesized can be controlled.

The copolymerized polyamide resin (A) is preferably present in a proportion of 20 to 70% by mass, preferably 25 to 55% by mass in the polyamide resin composition of the present invention. When the proportion of the copolymerized polyamide resin (A) is less than the above lower limit, the mechanical strength is lowered, and when it exceeds the upper limit, the blending amount of the flame retardant (B), (C) or the reinforcing material (D) is insufficient. In addition, the desired effect is difficult to obtain.

The flame retardant (B) is blended for imparting flame retardancy to the electric / electronic component, and examples thereof include phosphinates and / or diphosphinates and / or polymers thereof. Specific examples include aluminum salts, calcium salts, and zinc salts of methylethylphosphinic acid, aluminum salts, calcium salts, and zinc salts of diethylphosphinic acid, and aluminum salts, calcium salts, and zinc salts of methylpropylphosphinic acid. . In particular, an aluminum salt is preferable from the viewpoint of stability.

The flame retardant (C) is a nitrogen-containing phosphoric acid compound, and is combined with the flame retardant (B) in order to impart high flame retardancy to electrical and electronic parts. Specific examples include melamine phosphate, melamine pyrophosphate, melamine polyphosphate, and the like, and these nitrogen-containing phosphate compounds and / or metal salts thereof may be mentioned. The nitrogen-containing phosphate compounds and / or metal salts thereof listed here are examples, and are not limited thereto.

The ratio of the total amount of the flame retardants (B) and (C) is 30 to 80 parts by mass, preferably 40 to 70 parts by mass with respect to 100 parts by mass of the copolymerized polyamide resin (A). If the total blending amount of the flame retardants (B) and (C) is less than the above lower limit, the target high flame retardancy cannot be obtained, and if it exceeds the above upper limit, the physical properties are significantly lowered and the fluidity is lowered. There is a risk that the molding processability will decrease.

The blending mass ratio (B) / (C) of the flame retardants (B) and (C) is important for coexisting high flame retardancy, mechanical properties, and fluidity. As (B) / (C) Is from 5 to 50, preferably from 5 to 40.

The reinforcing material (D) is blended to improve the moldability of the polyamide resin composition and the strength of the molded product, and uses at least one selected from a fibrous reinforcing material and a needle-shaped reinforcing material. . Examples of the fibrous reinforcing material include glass fiber, carbon fiber, boron fiber, ceramic fiber, and metal fiber. Examples of the acicular reinforcing material include potassium titanate whisker, aluminum borate whisker, zinc oxide whisker, and carbonic acid. Calcium whiskers, magnesium sulfate whiskers, wollastonite and the like can be mentioned. As glass fibers, chopped strands or continuous filament fibers having a length of 0.1 mm to 100 mm can be used. As the cross-sectional shape of the glass fiber, a glass fiber having a circular cross section and a non-circular cross section can be used. The diameter of the circular cross-section glass fiber is 20 μm or less, preferably 15 μm or less, more preferably 10 μm or less. Further, a glass fiber having a non-circular cross section is preferred from the viewpoint of physical properties and fluidity. Non-circular cross-section glass fibers include those that are substantially oval, substantially oval, or substantially bowl-shaped in a cross section perpendicular to the length direction of the fiber length, and have a flatness of 1.5 to 8. It is preferable. Here, the flatness is assumed to be a rectangle with the smallest area circumscribing a cross section perpendicular to the longitudinal direction of the glass fiber, the length of the long side of the rectangle is the major axis, and the length of the short side is the minor axis. It is the ratio of major axis / minor axis. The thickness of the glass fiber is not particularly limited, but the minor axis is about 1 to 20 μm and the major axis is about 2 to 100 μm. Further, glass fibers are preferably used in the form of chopped strands which are formed into fiber bundles and cut to a fiber length of about 1 to 20 mm.

The ratio of the reinforcing material (D) is 30 to 200 parts by mass, preferably 50 to 160 parts by mass with respect to 100 parts by mass of the copolymerized polyamide resin (A). When the ratio of the reinforcing material (D) is less than the above lower limit, the mechanical strength of the molded product is lowered, and when it exceeds the upper limit, the extrudability and the moldability tend to be lowered.

Examples of the non-fibrous or non-needle filler (E) include reinforcing fillers, conductive fillers, magnetic fillers, flame retardant fillers, thermal conductive fillers, thermal yellowing suppression fillers, etc. Glass beads, glass flakes, glass balloons, silica, talc, kaolin, mica, alumina, hydrotalcite, montmorillonite, graphite, carbon nanotubes, fullerene, indium oxide, tin oxide, iron oxide, magnesium oxide, aluminum hydroxide, Magnesium hydroxide, calcium hydroxide, red phosphorus, calcium carbonate, lead zirconate titanate, barium titanate, aluminum nitride, boron nitride, zinc borate, barium sulfate, and non-acicular wollastonite, potassium titanate, Aluminum borate, magnesium sulfate, Zinc, and calcium carbonate. These fillers may be used not only alone but also in combination of several kinds. Among these, talc is preferable because Tc1 is lowered and moldability is improved.

The addition of filler is not essential, but when blended, the optimum amount of filler may be selected, but a maximum of 5 parts by mass is added to 100 parts by mass of copolymerized polyamide resin (A). However, from the viewpoint of the mechanical strength of the resin composition, the content is preferably 0.1 to 5 parts by mass, more preferably 1 to 2 parts by mass. When the filler is talc, the amount is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, and further preferably 1 to 2 parts by mass with respect to 100 parts by mass of the copolymerized polyamide resin (A).
In addition, in order to improve the affinity with the polyamide resin, the fibrous reinforcing material and the filler are preferably used in combination with a coupling agent at the time of organic treatment or a coupling agent treatment or melt compound. Any of silane coupling agents, titanate coupling agents, and aluminum coupling agents may be used, and among them, aminosilane coupling agents and epoxysilane coupling agents are particularly preferable.

In the polyamide resin composition of the present invention, various additives of conventional polyamide resin compositions for electric and electronic parts can be used. Additives include stabilizers, impact modifiers, mold release agents, slidability improvers, colorants, plasticizers, crystal nucleating agents, polyamide resins different from copolymerized polyamide resins (A), and thermoplastic resins other than polyamides Etc. The possible blending amounts of these components in the polyamide resin composition are as described below, but the total of these components is preferably 30% by mass or less, more preferably 20% by mass or less in the polyamide resin composition. 10 mass% or less is further more preferable, and 5 mass% or less is especially preferable.

Stabilizers include organic antioxidants such as hindered phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, heat stabilizers, light stabilizers such as hindered amines, benzophenones, and imidazoles. Examples include ultraviolet absorbers, metal deactivators, and copper compounds. Copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, cupric iodide, cupric phosphate, cupric pyrophosphate, Copper salts of organic carboxylic acids such as copper sulfide, copper nitrate, and copper acetate can be used. Further, as a component other than the copper compound, an alkali metal halide compound is preferably contained. Examples of the alkali metal halide compound include lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, bromide. Examples thereof include sodium, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide and the like. These additives may be used alone or in combination of several kinds. The addition amount of the stabilizer may be an optimal amount, but it is possible to add a maximum of 5 parts by mass with respect to 100 parts by mass of the copolymerized polyamide resin (A).

The polyamide resin composition of the present invention may be polymer blended with a polyamide having a composition different from that of the copolymerized polyamide resin (A). The polyamide having a composition different from that of the copolymerized polyamide of the present invention is not particularly limited, but polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polytetramethylene adipamide (Polyamide 46), polyhexamethylene adipamide (polyamide 66), polymetaxylylene adipamide (polyamide MXD6), polyparaxylylene adipamide (polyamide PXD6), polytetramethylene sebacamide (polyamide 410), Polyhexamethylene sebamide (polyamide 610), polydecamethylene adipamide (polyamide 106), polydecamethylene sebamide (polyamide 1010), polyhexamethylene dodecamide (polyamide 612), polydecamethylene dodecamide (polyamide) Amide 1012), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polytetramethylene terephthalamide (polyamide 4T), polypentamethylene terephthalamide (polyamide 5T), poly-2-methylpenta Methylene terephthalamide (polyamide M-5T), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), poly-2-methyl-octamethylene terephthalamide, polynonamethylene terephthalamide (polyamide 9T), polydecamethylene terephthalamide (Polyamide 10T), polyundecamethylene terephthalamide (polyamide 11T), polydodecamethylene terephthalamide (polyamide 12T), polybis (3-methyl) 4-aminohexyl) methane terephthalamide (polyamide PACMT), polybis (3-methyl-4-aminohexyl) methane isophthalamide (polyamide PACMI), polybis (3-methyl-4-aminohexyl) methane dodecamide (polyamide PACM12) Polybis (3-methyl-4-aminohexyl) methane tetradecamide (polyamide PACM14), a polyalkyl ether copolymerized polyamide or the like, or these copolymerized polyamides may be used alone or in combination. Of these, polyamide 66, polyamide 6T66, and the like may be blended with polyamide 10T derivative for imparting further low water absorption, etc., in order to increase the crystallization speed and improve the moldability. The addition amount of polyamide having a composition different from that of the copolymerized polyamide resin (A) may be selected, but a maximum of 50 parts by mass can be added to 100 parts by mass of the copolymerized polyamide resin (A). It is.

A thermoplastic resin other than polyamide having a composition different from that of the copolymerized polyamide resin (A) may be added to the polyamide resin composition of the present invention. Polymers other than polyamide include polyphenylene sulfide (PPS), liquid crystal polymer (LCP), aramid resin, polyetheretherketone (PEEK), polyetherketone (PEK), polyetherimide (PEI), thermoplastic polyimide, polyamideimide (PAI), polyether ketone ketone (PEKK), polyphenylene ether (PPE), polyether sulfone (PES), polysulfone (PSU), polyarylate (PAR), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene Phthalate, polycarbonate (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polymethylpentene (TPX), polystyrene ( S), polymethyl methacrylate, acrylonitrile - styrene copolymer (AS), acrylonitrile - butadiene - styrene copolymer (ABS) and the like. These thermoplastic resins can be blended in a molten state by melt kneading. However, the thermoplastic resin may be made into a fiber or particle and dispersed in the polyamide resin composition of the present invention. An optimum amount of the thermoplastic resin may be selected, but a maximum of 50 parts by mass can be added to 100 parts by mass of the copolymerized polyamide resin (A).

Impact modifiers include ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene- Polyolefin resins such as methacrylic acid ester copolymer, ethylene vinyl acetate copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene -Styrene copolymer (SIS), vinyl polymer resin such as acrylate copolymer, polybutylene terephthalate or polybutylene naphthalate as hard segment, polytetramethylene glycol or polycaprolactone or poly Polyester block copolymer in which the turbo sulfonate diol as a soft segment, a polyamide elastomer, urethane elastomer, acrylic elastomer, silicone rubber, fluorinated rubber, and the like polymer particles having a core-shell structure constituted from two different polymers. An optimum amount of the impact modifier may be selected, but a maximum of 30 parts by mass can be added to 100 parts by mass of the copolymerized polyamide resin (A).

When a thermoplastic resin other than the copolymerized polyamide resin (A) and an impact resistance improving material are added to the polyamide resin composition of the present invention, a reactive group capable of reacting with the polyamide is copolymerized. Preferably, the reactive group is a group capable of reacting with an amino group, a carboxyl group and a main chain amide group which are terminal groups of the polyamide resin. Specific examples include a carboxylic acid group, an acid anhydride group, an epoxy group, an oxazoline group, an amino group, an isocyanate group, etc. Among them, an acid anhydride group is most excellent in reactivity. There is also a report that the thermoplastic resin having a reactive group that reacts with the polyamide resin is finely dispersed in the polyamide and is finely dispersed, so that the distance between the particles is shortened and the impact resistance is greatly improved [ S, Wu: Polymer 26, 1855 (1985)].

Examples of the release agent include long chain fatty acids or esters thereof, metal salts, amide compounds, polyethylene wax, silicone, polyethylene oxide, and the like. The long chain fatty acid preferably has 12 or more carbon atoms, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid, and montanic acid. Partial or total carboxylic acid is esterified with monoglycol or polyglycol. Or a metal salt may be formed. Examples of the amide compound include ethylene bisterephthalamide and methylene bisstearyl amide. These release agents may be used alone or as a mixture. The addition amount of the release material may be selected as an optimum amount, but it is possible to add up to 5 parts by mass with respect to 100 parts by mass of the copolymerized polyamide resin (A).

The polyamide resin composition of the present invention preferably has an underwater equilibrium water absorption of 3.0% or less as measured by the method described in the Examples section below. In order to make the equilibrium water absorption in water within this range, it is important to select the copolymerized polyamide resin (A) described above. The underwater equilibrium water absorption is more preferably 2.5% or less. The lower limit of the equilibrium water absorption rate in water is preferably 0%, but is about 1.5% from the characteristics of the copolymerized polyamide resin (A) used.
It is preferable to have.

The polyamide resin composition preferably has a melting point (Tm) of 300 to 330 ° C. and a temperature rising crystallization temperature (Tc1) of 90 to 120 ° C. When the melting point exceeds the above upper limit, the processing temperature required for injection molding of the polyamide resin composition of the present invention becomes extremely high, so that it may be decomposed during processing and the desired physical properties and appearance may not be obtained. On the other hand, when Tm is less than the above lower limit, the crystallization rate is slow, and in some cases, molding may be difficult, and further, solder heat resistance may be reduced. The temperature rise crystallization temperature Tc1 is a temperature at which crystallization starts when the temperature is raised from room temperature. If the ambient temperature of the resin composition at the time of molding is lower than Tc1, crystallization hardly proceeds. On the other hand, when the temperature of the resin composition becomes higher than Tc1, crystallization proceeds easily, and dimensional stability, physical properties, etc. can be sufficiently exhibited. Since the shape of the electric / electronic parts is thin and fine, it is considered that the resin temperature after injection molding almost coincides with the mold temperature. Therefore, if the Tc1 of the resin composition is high, it is necessary to increase the mold temperature accordingly, leading to a decrease in workability. When Tc1 exceeds the upper limit, not only the mold temperature required for injection molding of the polyamide resin composition of the present invention becomes high and molding becomes difficult, but also in a short cycle of injection molding. In some cases, crystallization does not proceed, causing molding difficulties such as insufficient mold release, or insufficient crystallization, resulting in insufficient product strength and lack of reliability. Conversely, when Tc1 is less than the above lower limit, it is necessary to inevitably lower the glass transition temperature as a resin composition. Since Tc1 is generally a temperature higher than the glass transition temperature, when Tc1 is less than 90 ° C., a lower value is required as the glass transition temperature. In that case, the physical properties greatly decrease or the physical properties after water absorption. Problems that cannot be maintained. Since it is necessary to keep Tg relatively high, it is desirable that Tc1 be at least 90 ° C. or higher.

In the copolymerized polyamide resin (A), since a specific amount of the polyamide 11 component is copolymerized with the polyamide 6T, a resin having an excellent balance of low water absorption and fluidity in addition to a high melting point and moldability can be obtained. In the molding of surface-mounted electrical and electronic parts, in addition to a high melting point of 300 ° C. or higher and low water absorption, thin-walled, high-cycle molding is required. In the hexamethylene terephthalamide / polyhexamethylene adipamide copolymer (polyamide 6T / 66), although the moldability is good, the water absorption is extremely high. Therefore, in the reflow soldering process performed by surface mounting or the like, there is a problem that blisters are generated in a molded product. On the other hand, polynonamethylene terephthalamide (polyamide 9T) has low water absorption, but since Tg is 125 ° C., Tc1 is inevitably 125 ° C. or higher, and the mold temperature during molding is 140 ° C. or higher. Therefore, there is a difficulty in moldability. Even when trying to mold with a low-temperature mold, problems such as insufficient fluidity and secondary shrinkage and deformation due to crystallization during post-processing and use. From the background as described above, a resin having a high melting point of 300 ° C. or higher, low water absorption, easy moldability, and high fluidity is required. In the copolymerized polyamide resin (A), a specific amount of polyamide is added to polyamide 6T. By copolymerizing 11, in addition to imparting a high melting point, low water absorption and fluidity, Tc1 can be kept low, and the processability of injection molding can be greatly improved.

The polyamide resin composition of the present invention can be produced by blending the above-described constituent components by a conventionally known method. For example, each component is added during the polycondensation reaction of the copolymerized polyamide resin (A), the blended polyamide resin (A) and other components are dry blended, or a twin screw type extruder is used. The method of melt-kneading each structural component can be mentioned.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the measured value described in the Example is measured by the following method.

(1) Relative viscosity 0.25 g of polyamide resin was dissolved in 25 ml of 96% sulfuric acid and measured at 20 ° C. using an Ostwald viscometer.

(2) Amount of terminal amino groups 0.2 g of polyamide resin was dissolved in 20 ml of m-cresol and titrated with a 0.1 mol / l hydrochloric acid ethanol solution. Cresol red was used as the indicator. Expressed as equivalents (eq / ton) in 1 ton of resin.

(3) Melting point (Tm) and temperature rising crystallization temperature (Tc1)
Using a Toshiba Machine injection molding machine EC-100, the cylinder temperature is set to the melting point of the resin + 20 ° C, the mold temperature is set to 35 ° C, the length is 127 mm, the width is 12.6 mm, and the thickness is 0.8 mm. A piece was injection molded to produce a test piece. In order to measure the melting point (Tm) and temperature rising crystallization temperature (Tc1) of the obtained molded product, 5 mg of a part of the molded product was weighed into an aluminum pan, sealed with an aluminum lid, and a measurement sample. Then, using a differential scanning calorimeter (SSC / 5200 manufactured by SEIKO INSTRUMENTS), the temperature was raised from room temperature to 20 ° C./min in a nitrogen atmosphere, and the measurement was carried out to 350 ° C. At that time, the peak top temperature of the highest temperature peak among the exothermic peaks obtained was defined as the temperature raising crystallization temperature (Tc1). The temperature was further raised, and the peak top temperature of endotherm due to melting was defined as the melting point (Tm).

(4) Solder heat resistance Using Toshiba Machine's injection molding machine EC-100, the cylinder temperature is set to the melting point of the resin + 20 ° C., the mold temperature is set to 140 ° C., the length is 127 mm, the width is 12.6 mm, and the thickness is 0.8 mm. The test piece for the UL combustion test was injection molded to produce a test piece. The test piece was left in an atmosphere of 85 ° C. and 85% RH (relative humidity) for 72 hours. The specimen was heated in an air reflow furnace (AIS-20-82C manufactured by ATEC) from room temperature to 150 ° C over 60 seconds, preheated, and then heated to 190 ° C at a rate of 0.5 ° C / min. Preheating was performed. Thereafter, the temperature was raised to a predetermined set temperature at a rate of 100 ° C./min, held at the predetermined temperature for 10 seconds, and then cooled. The set temperature was increased from 240 ° C. every 5 ° C., and the highest set temperature at which the surface did not swell or deformed was defined as the reflow heat resistant temperature, which was used as an index of solder heat resistance.
○: Reflow heat-resistant temperature is 260 ° C or higher ×: Reflow heat-resistant temperature is less than 260 ° C

(6) Underwater equilibrium water absorption rate Using Toshiba Machine's injection molding machine EC-100, the cylinder temperature is set to the melting point of the resin + 20 ° C, the mold temperature is set to 140 ° C, and a flat plate 100mm long, 100mm wide and 1mm thick is injected. Molded to prepare a test piece for evaluation. This test piece was immersed in hot water at 80 ° C. for 50 hours, and the saturated water absorption was determined from the following equation from the weight at the time of saturated water absorption and drying.
Saturated water absorption (%) = {(weight at saturated water absorption−weight at drying) / weight at drying} × 100

(7) Flame retardance Using Toshiba Machine's injection molding machine EC-100, the cylinder temperature is set to the melting point of the resin + 20 ° C., the mold temperature is set to 140 ° C., the length is 127 mm, the width is 12.7 mm, and the thickness is 1.6 mm. Test specimens for evaluation were produced by injection molding. Using this test piece, flame retardancy evaluation was performed according to the UL-94 vertical combustion test.

(8) Bending strength and flexural modulus Using Toshiba Machine's injection molding machine EC-100, the cylinder temperature is set to the melting point of the resin + 20 ° C, the mold temperature is set to 140 ° C, and a test piece for evaluation according to JIS K7161 Was created and physical properties were evaluated.

This example was carried out using a copolymerized polyamide resin (A) synthesized as exemplified below.

<Synthesis Example 1>
7.56 kg of 1,6-hexamethylenediamine, 10.79 kg of terephthalic acid, 7.04 kg of 11-aminoundecanoic acid, 9 g of sodium diphosphite, 40 g of acetic acid as a terminal conditioner and 17.52 kg of ion-exchanged water The mixture was charged into a liter autoclave, pressurized with N ₂ from normal pressure to 0.05 MPa, released, and returned to normal pressure. This operation was performed 3 times, N ₂ substitution was performed, and then uniform dissolution was performed at 135 ° C. and 0.3 MPa with stirring. Thereafter, the solution was continuously supplied by a liquid feed pump, heated to 240 ° C. with a heating pipe, and heated for 1 hour. Thereafter, the reaction mixture was supplied to a pressure reaction can, heated to 290 ° C., and a part of water was distilled off so as to maintain the internal pressure of the can at 3 MPa to obtain a low-order condensate. Thereafter, this low-order condensate is directly supplied to a twin-screw extruder (screw diameter: 37 mm, L / D = 60) while maintaining the molten state, and the resin temperature is 335 ° C. while water is removed from three vents. The polycondensation proceeded under melting to obtain a copolymerized polyamide resin (A). The obtained copolymerized polyamide resin (A) had a relative viscosity of 2.1, a terminal amino group amount of 16 eq / ton, and a melting point of 314 ° C. Table 1 shows the charging ratio of the raw material monomers of the copolymerized polyamide resin (A) of Synthesis Example 1.

<Synthesis Example 2>
Example 1 except that the amount of 1,6-hexamethylenediamine was changed to 8.12 kg, the amount of terephthalic acid was changed to 11.62, and the amount of 11-aminoundecanoic acid was changed to 6.03 kg. Thus, a copolymerized polyamide resin (A) was synthesized. The obtained copolymer polyamide resin (A) had a relative viscosity of 2.1, a terminal amino group amount of 28 eq / ton, and a melting point of 328 ° C. Table 1 shows the charging ratio of the raw material monomers of the copolymerized polyamide resin (A) of Synthesis Example 2.

<Synthesis Example 3>
The amount of 1,6-hexamethylenediamine was changed to 8.12 kg, the amount of terephthalic acid was changed to 9.96 kg, the amount of 11-aminoundecanoic acid was changed to 6.03 kg, adipic acid (other than terephthalic acid) The copolymerized polyamide resin (A) was synthesized in the same manner as in Example 1 except that 1.46 kg of (dicarboxylic acid) was charged. The obtained copolymerized polyamide resin (A) had a relative viscosity of 2.1, a terminal amino group amount of 35 eq / ton, and a melting point of 310 ° C. Table 1 shows the charging ratio of the raw material monomers of the copolymerized polyamide resin (A) of Synthesis Example 3.

<Synthesis Example 4>
A copolymerized polyamide resin (A) was synthesized in the same manner as in Example 1 except that 7.04 kg of 11-aminoundecanoic acid was changed to 6.41 kg of undecane lactam. The obtained copolymerized polyamide resin (A) had a relative viscosity of 2.1, a terminal amino group amount of 13 eq / ton, and a melting point of 315 ° C. Table 1 shows the charging ratio of the raw material monomers of the copolymerized polyamide resin (A) of Synthesis Example 4.

<Synthesis Example 5>
A copolymerized polyamide resin (A) was synthesized in the same manner as in Synthesis Example 1 except that 5.80 kg of 1,6-hexamethylenediamine, 8.30 kg of terephthalic acid, and 6.70 kg of 11-aminoundecanoic acid were used. . The obtained copolymerized polyamide resin (A) had a relative viscosity of 2.0, a terminal amino group amount of 15 eq / ton, and a melting point of 280 ° C. Table 1 shows the charging ratio of raw material monomers of the copolymerized polyamide resin (A) of Synthesis Example 5.

Examples 1-8, Comparative Examples 1-5
The components and mass ratios shown in Table 2 were melt-kneaded at a melting point of each polyamide raw material + 20 ° C. using a twin screw extruder STS-35 manufactured by Coperion Co., Ltd., and Examples 1 to 8 and Comparative Examples 1 to 5 A polyamide resin composition was obtained. The raw materials used in the preparation of the polyamide resin composition are as follows.
Polyamide raw materials: Copolyamide (A) prepared on the basis of Synthesis Examples 1 to 5, PA6T / 6 (Ultramide (R) KR4351 manufactured by BASF), PA66 (GLAMIDE (R) T-662 manufactured by Toyobo Co., Ltd.) Relative viscosity 2 .8 Terminal carboxyl group amount 40 equivalent / ton)
Flame retardant (B): diethylphosphinic acid aluminum salt (EXOLIT (R) OP1230 manufactured by Clariant Japan)
Flame retardant (C-1): Melamine polyphosphate (MELAPUR (R) 200/70 manufactured by BASF)
Flame retardant (C-2): Melamine polyphosphate, melam, melem condensate (PHOSMEL-200 manufactured by Nissan Chemical Co., Ltd.)
Reinforcing material (D): Glass fiber (manufactured by Nitto Boseki Co., Ltd., CS-3J-459)
Filler (E): Talc (Micron White 5000A, Hayashi Kasei Co., Ltd.)
Mold release agent: Magnesium stearate Stabilizer: Pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by Chiba Specialty Chemicals)

As is apparent from Table 2, Examples 1 to 8 not only satisfy flame retardancy, low water absorption, and solder heat resistance, but also exhibit mechanical properties that can withstand use as surface mount type electric and electronic parts. I understand. On the other hand, in Comparative Example 1, the flame retardant (C) is not included, and sufficient flame retardancy cannot be obtained. In Comparative Example 2, the balance of the flame retardant blending amount is poor, and sufficient mechanical properties cannot be obtained because the flame retardant (C) is excessive. In Comparative Example 3, although flame retardancy and low water absorption were sufficiently obtained, the melting point is low, so that the solder heat resistance is poor. In Comparative Example 4, flame retardancy and mechanical properties are satisfactory, but low heat absorption is difficult, so solder heat resistance is poor. Comparative Example 5 is inferior in solder heat resistance and low water absorption due to the influence of the resin skeleton.

The flame retardant polyamide resin composition of the present invention uses a specific copolymerized polyamide resin excellent in heat resistance, moldability, fluidity and low water absorption, so that the surface has a high level of satisfaction while satisfying the required properties. The mounting type electric / electronic component can be advantageously produced industrially.

Claims

A flame-retardant polyamide resin composition for use in surface-mount electric and electronic parts, comprising: (a) 55 to 75 mol% of a structural unit obtained from an equimolar molar salt of hexamethylenediamine and terephthalic acid; and (b) Copolymerized polyamide resin (A) composed of 45 to 25 mol% of structural units obtained from 11-aminoundecanoic acid or undecane lactam, flame retardant (B) composed of metal salt of phosphinic acid, and nitrogen-containing phosphoric acid compound Containing at least one reinforcing material (D) selected from the group consisting of a flame retardant (C), a fibrous reinforcing material and an acicular reinforcing material, and a non-fibrous or non-acicular filling material (E); The total of the flame retardants (B) and (C) is 30 to 80 parts by mass, the reinforcing material (D) is 30 to 200 parts by mass, and the filler (E) is 0 with respect to 100 parts by mass of the polymerized polyamide resin (A). Contains up to 5 parts by weight It is, and the mass ratio of the flame retardant (B) / (C) is a flame-retardant polyamide resin composition, wherein the 5 to 50.
The flame retardant polyamide resin composition according to claim 1, wherein the polyamide resin composition has an equilibrium water absorption rate of 3.0% or less.
3. The flame-retardant polyamide resin according to claim 1, wherein the polyamide resin composition has a melting point (Tm) of 300 to 330 ° C. and a temperature-rising crystallization temperature (Tc1) of 90 to 120 ° C. Composition.
The non-fibrous or non-needle filler (E) is talc, and is contained in a proportion of 0.1 to 5 parts by mass of talc with respect to 100 parts by mass of the copolymerized polyamide resin (A). 4. The flame retardant polyamide resin composition according to any one of 1 to 3.
The copolymerized polyamide resin (A) is (c) a structural unit obtained from an equivalent molar salt of a diamine other than the structural unit of (a) and a dicarboxylic acid, or an aminocarboxylic acid other than the structural unit of (b) or The flame-retardant polyamide resin composition according to any one of claims 1 to 4, which comprises up to 20 mol% of a structural unit obtained from lactam.