JPH083327A - Connector - Google Patents

Abstract

PURPOSE:To obtain a connector consisting of a high-fluid thermoplastic resin excellent in mechanical properties, significantly suppressed in dimensional change and mechanical strength drop due to its moisture absorption and in blistering in its reflow oven soldering, and excellent in injection moldability and fluidity. CONSTITUTION:This connector consists of a high-fluid thermoplastic resin comprising (1) 10-90wt.% of nylon 46 resin, (2) 5-89wt.% of polyphenylene sulfide resin and (3) 1-20wt.% of an olefin polymer With an unsaturated carboxylic acid (derivative) as a comonomer, with >=55mm in the flow length in a spiral- flow with a width of 10mm and thickness of 0.5mm.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention has excellent mechanical properties, greatly suppresses dimensional change and strength reduction due to moisture absorption, and blister (blister) generation during soldering in a reflow furnace, which results in fluidity and molding. The present invention relates to a connector made of a highly fluid thermoplastic resin having excellent workability.

2. Description of the Related Art In the field of electronic parts, various resin-based electronic parts materials are soldered onto a printed circuit board by a surface mounting method (SMT method) in accordance with the recent miniaturization and productivity improvement of electric and electronic products. Is increasing. When connecting the parts on the printed circuit board by surface mounting method, usually,
Soldering is carried out in a hot-air / far-infrared reflow furnace, and not only heat resistance but also blister resistance (molded products such as connectors are reflowable against resin materials for electronic parts.
Blisters on the surface of parts when passing through a furnace], near-infrared, far-infrared or hot-air reflow furnace (a temperature of 240 to 260 ° C is reached during peaking)
It is required that the electronic parts do not deform, burn (discolor), or the like when passing through and soldering. In addition, with the fine pitch of connectors and the like, it is required that the fluidity, especially the fluidity of the thin portion, be good, that there be little dimensional change due to moisture absorption rate / moisture absorption, and that there is little decrease in strength after moisture absorption. There is a case where it will be done. As an evaluation method showing the fluidity associated with the fine pitch, particularly the fluidity of a thin portion, a spiral flow having a width of 10 mm and a thickness of 0.5 mm can be mentioned, but the injection pressure is 500 k.
A resin material having a flow length of more than 50 mm in a spiral flow having a width of 10 mm and a thickness of 0.5 mm under the condition of g / cm ² was extremely rare. Generally, polyamide resin has excellent mechanical properties such as strength, impact resistance, and abrasion resistance, high heat resistance and high chemical resistance, and good injection moldability. It is used in various applications such as electrical parts and general mechanical parts. In particular, nylon 4,6 resin has the highest melting point among aliphatic nylons and is known to have excellent heat resistance as an engineering plastic. In addition, it also has excellent mechanical properties such as tensile strength and bending strength, and has a short crystallization cycle because of its high crystallization rate, and has good meltability and injection moldability due to its low melt viscosity. It is a resin that has characteristics and is expected to be used in various fields. In particular, in the field of electronic parts such as connectors, the adoption of nylon 4,6 is increasing due to its excellent heat resistance (high deflection temperature under load), moldability (fluidity) and good toughness. are doing. However, surface mounting electronic components made of nylon 4,6 are used in near-infrared, far-infrared,
Alternatively, when passing through a hot air (air) type reflow furnace, there is a problem that blisters (blisters) occur on the surface, and the dimension of the molded product after reflow also changes due to moisture absorption or mechanical There is a problem that the strength decreases, and improvement has been demanded. Nylon 4,6
As a method for improving blister resistance of electronic parts made of resin, dimensional change before and after moisture absorption, and strength reduction after moisture absorption, a method of blending an aromatic polyester resin with nylon 4 and 6 (Japanese Patent Laid-Open Nos. 3-190962 and 3) No. 263461, etc.) has been proposed, but the decrease in strength and dimensional change due to moisture absorption and the blister property are improved, but there is a problem that burning occurs when retained during molding. In addition, JP-A-3-13
In 1655, 4-202361, and 4-2096553, a method of blending a modified polyphenylene ether with a nylon 4,6 resin is proposed, but although dimensional change and strength reduction due to moisture absorption are improved, Blisterability was not improved. Furthermore, JP-A-4-20
2358, 2-255564, nylon 4,
A method has been proposed in which an amorphous copolyamide is blended with 6 resin, but the dimensional change and strength reduction due to moisture absorption are improved, but the blister resistance is not sufficiently improved.

[0002]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to maintain the mechanical properties of nylons 4 and 6, while maintaining blister resistance and dimensional change due to moisture absorption. -An object of the present invention is to obtain a connector made of a high-fluidity thermoplastic resin having improved strength reduction and excellent fluidity and molding processability.

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a nylon 4,6 resin is blended with a polyphenylene sulfide resin and, if necessary, an amorphous polyamide resin to absorb moisture. Accordingly, they have found that a connector in which dimensional change and strength reduction are remarkably improved can be obtained, and the present invention has been completed. That is, the present invention is a connector having a thermoplastic resin portion, wherein the thermoplastic resin is (A) nylon 4,6 resin 6 to 90% by weight,
(B) Polyphenylene sulfide resin 5 to 89% by weight, (C) Amorphous polyamide resin 0 to 30% by weight,
(D) Olefin-based polymer having unsaturated carboxylic acid or its derivative as a copolymerization component 0.1 to 20% by weight,
(E) Fibrous filler 0 to 50% by weight, (F) Flame retardant
0 to 30% by weight, (G) flame retardant aid 0 to 15% by weight, cylinder of injection molding machine-temperature 310 ° C, mold temperature 100 ° C, injection pressure 500 kg / cm ² , width 10 mm, Provided is a connector made of a high-fluidity thermoplastic resin, which has a flow length of 55 mm or more in a spiral flow having a thickness of 0.5 mm.

The present invention will be described below for each component. (A) Nylon 4,6 Resin Nylon 4,6 resin used in the present invention comprises a polytetramethylene adipamide obtained from tetramethylene diamine and adipic acid and a polytetramethylene adipamide unit as main constituent components. A copolyamide is included. Further, other polyamide may be contained as a mixed component within a range not impairing the properties of nylons 4 and 6. The copolymerization component is not particularly limited, and a known amide-forming component can be used. As a typical example of the copolymerization component, 6-
Aminocaproic acid, 11-aminoundecanoic acid, 12-
Amino acids such as aminoundecanoic acid and para-aminomethylbenzoic acid; lactams such as ε-caprolactam and ω-lauryllactam; ethylenediamine, tetremethylenediamine, hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4- / 2 , 4,
4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (p- Aminocyclohexyl) methane, 1-
Amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (aminoprosyl) Diamines represented by piperazine, aminoethylpiperazine, m-xylylenediamine, p-xylylenediamine and the like, and adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid , 2-chloroterephthalic acid,
2-methylterephthalic acid, 5-methylisophthalic acid, 5
-Sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, dicarboxylic acids represented by diglycolic acid, etc. can be mentioned,
Further, other polyamides used as a mixed component may include those composed of these components. Further, the method of manufacturing nylons 4 and 6 used in the present invention is arbitrary. For example, JP-A-56-149430 and JP-A-56-
149431, JP-A-58-83029, JP-A-61-43631, and the like, that is, first, a prepolymer having a small amount of cyclic end groups is produced under specific conditions, and then steam is produced. Method for preparing high-viscosity nylon 4,6 by solid-state polymerization in atmosphere or 2
-There is a method of obtaining it by heating in a polar organic solvent such as -pyrrolidone or N-methylpyrrolidone. Nylon 4,
The degree of polymerization of 6 is not particularly limited, but may be 96 at 25 ° C.
% Sulfuric acid, relative viscosity at 1 g / dl is 1.5-6.
Nylon 4,6 within the range of 0 is preferably used. The amount of nylon 4,6 used in the present invention is 6 to 90.
%, Preferably 7-80% by weight, more preferably 10-75% by weight, particularly preferably 12-70%.
% By weight. If the amount of nylon 4,6 added is less than 6% by weight, flowability and molding processability will be problematic, and if it exceeds 90% by weight, blister resistance will be poor.

(B) Polyphenylene sulfide The polyphenylene sulfide resin used in the present invention preferably contains a structural unit represented by the following general formula (1) as a main component.

[0005]

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Specifically, poly-p-phenylene sulfide and poly-m-phenylene sulfide are preferable,
Poly-p-phenylene sulfide is preferably used because of its heat resistance and moldability. In this case, the poly-p-phenylene sulfide is preferably a heavy one containing at least 70 mol% or more, more preferably 90 mol% or more of the constituent unit of the p-phenylene nucleus. This structural unit is 70
When it is less than mol%, the crystallinity and heat resistance of the polyphenylene sulfide resin tend to be low, which is not preferable. Polyphenylene sulfide is generally used in Japanese Patent Publication No.
A polymer having a relatively small molecular weight obtained by the production method represented by JP-A-5-3368, and JP-B-52-1224.
There is an essentially linear polymer having a high molecular weight obtained by the production method represented by JP-A No.
The polymer obtained by the method described in Japanese Patent No. 68 may be used after being polymerized to have a high degree of polymerization by heating in an oxygen atmosphere after polymerization or by adding a crosslinking agent such as peroxide and heating. It is possible, and it is possible to use polyphenylene sulfide obtained by any method in the present invention, but an essentially linear and relatively high molecular weight polymer or a partially cross-linked linear one Are more preferably used. Further, polyphenylene sulfide can comprise less than 30 mol% of its repeating unit with a repeating unit having the following structural formula.

[0007]

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[Chemical 4]

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[0008]

[Chemical 6]

[Chemical 7]

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The melt viscosity of the polyphenylene sulfide used in the present invention is not particularly limited as long as it can be kneaded with a nylon 4,6 resin or an amorphous polyamide resin and a composite material can be produced, but it is usually 100 to 10, 000 poise (310 ° C., shear rate 1000 sec ⁻¹ ) is used. Further, the polyphenylene sulfide used in the present invention is a deionization treatment with hot water, an acid such as acetic acid, an epoxy compound, an amino group-containing compound for the purpose of improving compatibility with nylon 4,6 resin and amorphous polyamide resin. It is also possible to process them by using the above method. The content of these polyphenylene sulfide resins is 5 to 90% by weight, preferably 5 to 60% by weight, more preferably 6 to 50% by weight, and particularly preferably 7 to 45% by weight. When this blending amount is less than 5% by weight, the effect of reducing the moisture absorption rate of the connector is not sufficient, and the blistering resistance is low.
If the amount exceeds 90% by weight, the excellent fluidity, molding processability and mechanical properties of nylon 4,6 are impaired, which is not preferable.

(C) Amorphous Polyamide Resin The amorphous polyamide resin used in the present invention is obtained by polycondensation of a lactam having three or more membered rings, a polymerizable ω-aminocarboxylic acid, a diamine and a dicarboxylic acid. Polyamide can be used. Specific examples of the monomer constituting the amorphous polyamide resin include lactams such as ε-caprolactam and ω-laurolactam, 6-
Aminocaproic acid, 11-aminoundecanoic acid, 12-
Aminocarboxylic acids such as aminododecanoic acid and p-aminobenzoic acid, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4 / 2,4,4-trimethylhexamethylenediamine, 5 -Methylnonamethylenediamine, m
-Xylylenediamine, p-Xylenediamine, 1.3-
Bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (aminocyclohexyl) methane, 1-amino-3-aminomethyl-
3,5,5-trimethylcyclohexane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, etc. There are diamines, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and nadonodicarboxylic acid. The amorphous polyamide used in the present invention may have any monomer composition as long as it has a glass transition temperature of 130 ° C. or higher. Specific examples of the amorphous polyamide include hexamethylenediamine and bis (3 -Methyl-4-aminocyclohexyl) methane and terephthalic acid and / or isophthalic acid heavy compound, ε-caprolactam and hexamethylenediamine and 1
-Amino-3-aminomethyl-3,5,5-trimethylcyclohexane and a heavy compound of terephthalic acid and the like can be mentioned. The molecular weight of the amorphous polyamide used in the present invention is also not particularly limited, but the relative viscosity when measured using m-cresol at a concentration of 1 g / dl and 25 ° C. is 1.2.
˜5.0, more preferably 1.3 to 4.0. If the relative viscosity exceeds 5.0, not only the flowability deteriorates, but also the toughness represented by Izod impact strength decreases, which is not preferable. If the relative viscosity is less than 1.2, the mechanical strength decreases. Occurs. The amount of the amorphous polyamide used in the present invention is 0 to 30% by weight, preferably 1 to 30% by weight, more preferably 3 to 28% by weight, and particularly preferably 4 to 25% by weight. By adding the amorphous polyamide, the dimensional change of the resin forming the connector before and after moisture absorption is reduced, but if the blending amount exceeds 30% by weight, the blister resistance is deteriorated, which is not preferable.

(D) Unsaturated carboxylic acid or its derivative
The examples of the unsaturated carboxylic acid or its derivative used in the olefin polymer present invention that the copolymer component, maleic acid, maleic acid esters, maleic acid amides, maleic acid, methyl maleic anhydride, chlorophthalic anhydride Maleic acid, citraconic anhydride, butynyl succinic anhydride, tetrahydrophthalic anhydride, fumaric acid, fumaric acid ester, fumaric acid amide, fumaric acid imide, phthalic acid, itaconic acid, itaconic anhydride, itaconic acid ester, itaconic acid amide, Itaconic acid imide, halogenated maleic acid, crotonic acid, acrylic acid, ethyl acrylate, butyl acrylate, methoxyethyl acrylate, 2-ethylhexyl acrylate, 2-acrylic acid acrylate
Hydroxyethyl, glycidyl acrylate, methyl methacrylate, methyl methacrylate, butyl methacrylate,
Examples thereof include 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, and the like, with maleic anhydride and glycidyl methacrylate being particularly preferable. Examples of the olefinic unsaturated monomer which is a copolymer component of an olefinic polymer having an unsaturated carboxylic acid or a derivative thereof as a copolymerization component used in the present invention include the following. Ethylene, propylene,
Examples thereof include olefins such as butene-1, decene-1, octacene-1, styrene, vinyl esters such as vinyl acetate and vinyl propionate, and ethylene is particularly preferable. These monomers and unsaturated carboxylic acids or derivatives may be used alone or in the form of a copolymer. Specific examples of the olefin polymer having an unsaturated carboxylic acid or its derivative as a copolymer component used in the present invention include ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, and ethylene. -Ethyl acrylate-glycidyl methacrylate copolymer, ethylene-propylene-methyl acrylate-glycidyl methacrylate copolymer, ethylene-propylene-ethyl acrylate-glycidyl methacrylate copolymer, ethylene-
Vinyl acetate / glycidyl methacrylate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid / maleic anhydride copolymer, ethylene / maleic acid copolymer, ethylene / ethyl acrylate / acrylic acid copolymer, styrene -Maleic anhydride copolymer, ethylene-g
-Maleic anhydride copolymer (g represents a graft), ethylene / propylene-g-maleic anhydride copolymer, and the like. The content of the unsaturated carboxylic acid or its derivative in the olefin-based polymer having an unsaturated carboxylic acid or its derivative as a copolymer component used in the present invention is preferably 0.1 to 30% by weight, more preferably It is 0.5 to 25% by weight. The amount of the olefin polymer containing the unsaturated carboxylic acid or its derivative as the component (D) as a copolymer component is 0.1 to 20% by weight, preferably 0.5 to 18% by weight, It is more preferably 1 to 15% by weight, and particularly preferably 2 to 13% by weight. If the blending amount is less than 0.1% by weight, the compatibilization of a plurality of blended resin components is insufficient, so the blister resistance is poor, and if it exceeds 20% by weight, the heat resistance is poor.

(D) Fibrous Filler The fibrous filler used in the present invention includes what are called rod-shaped fillers, needle-shaped fillers, columnar fillers, short fibrous fillers, etc., and preferably, The filler has an aspect ratio represented by the ratio of the length in the longitudinal direction to the average diameter of the cross section of 16 to 1500 and an average diameter of the cross section of 0.1 to 100 μm. The aspect ratio of the fibrous filler can be calculated, for example, by a value measured by a micrograph. Specifically, from its material, a filler called glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker. Is. For the purposes of the present invention,
Glass fiber and carbon fiber are preferable, and glass fiber is particularly preferable because of its economical efficiency. Those treated with a sizing agent (polyvinyl acetate, polyurethane, acrylic urethane, polyester, etc.) and a coupling agent (aminosilane, acrylic silane, vinyl silane, epoxy silane, etc.) are preferable as long as the moldability and physical properties of the present invention are not impaired. .
The composition of the present invention has a composition of (D) a fibrous filler,
Mechanical strength is improved, water absorption can be reduced, and blister resistance can be improved. The blending amount of fibrous filler is 0 to 5
0% by weight, preferably 1 to 50% by weight, more preferably 2 to 48% by weight, particularly preferably 5 to 45%.
% By weight. If the amount of the fibrous filler compounded exceeds 50% by weight, the fluidity and moldability will be poor.

(E) Flame Retardant The flame retardant used in the present invention is not limited, but particularly preferably brominated polystyrene and brominated polyphenylene ether.
One or two flame retardants selected from tellurium and brominated epoxy oligomers, and brominated polystyrene is particularly preferable. The brominated polystyrene used in the present invention can be represented by the following general formula (9).

[0014]

[Chemical 9]

(P is an integer of 1 to 5 and n is an integer of 2 or more) Brominated polystyrene, which is produced by polymerizing brominated styrene or brominating polystyrene. Further, it can be used even if other vinyl compound is copolymerized in the general formula (9). The molecular weight of the brominated polystyrene represented by the general formula (9) is not particularly limited, but those having a weight average molecular weight of 5,000 to 1,000,000 are preferably used. The blending amount of the flame retardant is 0 to 30% by weight, preferably 1 to 30% by weight, more preferably 2 to 28% by weight, particularly preferably 5 to 25% by weight.
Is. When the blending amount of the flame retardant of the present invention exceeds 30% by weight, mechanical properties and thermal properties are impaired, which is not preferable.

(F) Flame Retardant Auxiliary Agent The flame retardant auxiliary agent used in the present invention functions to increase the flame retardancy of nylon 4,6 resin by a synergistic effect with the flame retardant. Examples of such compounds include metal compounds of Group Va of the periodic table, boron oxide, zirconium oxide, iron oxide,
Examples thereof include metal compounds such as zinc oxide, and especially V of the periodic table.
Antimony compounds are preferable as the metal compound of group a.
Examples of the antimony compound include antimony trioxide, antimony pentoxide, sodium antimonate and the like, but antimony trioxide is particularly preferably used. Further, even if only one kind of these flame retardant aids is blended, 2
It may be a combination of two or more species. The addition amount of the flame retardant aid in the present invention is 0 to 15% by weight, preferably 0.5 to
It is 12% by weight, more preferably 1 to 10% by weight.
The amount of the flame retardant aid compounded is preferably 1 metal atom such as antimony to 2 to 5 bromine atoms in the brominated polystyrene as the component (F). If the blending amount exceeds 15% by weight, mechanical properties are impaired, which is not preferable.

The resin composition used in the connector of the present invention contains a copper compound such as copper iodide, an aromatic amine compound, a hindered phenol compound, an organic phosphorus compound and a sulfur compound for the purpose of improving heat resistance. It is also possible to add an antioxidant or a heat stabilizer. In addition, if necessary, other components, such as pigments, dyes, ultraviolet absorbers, weathering agents, and lubricants, as long as the moldability and physical properties are not impaired.
A crystal nucleating agent, a release agent, a plasticizer, an antistatic agent, etc. may be added. Furthermore, small amounts of other thermoplastic resins such as other polyamide resins, polyester resins, polyphenylene ether resins, polycarbonate resins, phenoxy resins, polyethylene and its copolymers, polypropylene and its copolymers, styrene and Its copolymer,
You may mix | blend polystyrene and its copolymer, an acrylic resin and an acrylic polymer, a polyamide elastomer, etc.

Any method can be used to obtain the resin composition used in the connector of the present invention. For example, a batch type mixer such as a kneader, a Brabender, a Banbury mixer or a single-screw or twin-screw extruder is used to simultaneously or separately prepare, for example, 2 to 5 components in advance with each blender. It is possible to use a method of pre-blending with a mixer or the like, pre-mixing with a kneader or an extruder, and further mixing and homogenizing the remaining components. The flowability of the composition of the present invention depends on the cylinder temperature of the injection molding machine, the temperature of 310.
° C., mold temperature 100 ° C., under the conditions of injection pressure 500 kg / cm ^2, width 10 mm, spiral flow thickness 0.5 mm - are those flow length in the above 55 mm, preferably 55～100Mm, more preferably Is 57 to 90 mm,
Particularly preferably, it is 58 to 80 mm. This fluidity can be adjusted by the composition ratio of the components (A) to (G),
The more components (A) and (C) there are, the more components (B), (D),
The smaller the amount of the component (E) and the smaller the molecular weight of the components (A) to (C), the larger the amount can be made.

In the present invention, what is called a connector may be any of a wire-to-wire (relay) connector-, a wire-to-board connector-, a board-to-board connector, and the like, and an FFC / FPC connector. -, SIMM socket, ROM socket, interface connector-, card edge connector-, disk drive power
Examples of connectors include connectors, board-in connectors, jumpers, wires, and the like. The form may be any of straight type, right angle type, multi-harness type, eject lever type, clip mounting type, bottom entry type, strain relief, etc., and the connection form is stack connection or horizontal connection. , Or vertical connection. The connector of the present invention is a main body of the above various connectors, or mainly a housing (case, case,
Body, cover), frame, electrical insulator, slide (slider), base, wafer, lens cam, spool, cover
It is a material used as a cord, yoke, eject pin, eject lever, and the like. According to the present invention, the mechanical strength is high enough to withstand the press-fitting of metal pins, the specific gravity is low, the dimensional change due to moisture absorption during storage and the decrease in strength are small, and the reflow furnace is used when assembling the substrate. It is possible to provide a connector which can suppress the occurrence of blister (swelling) during soldering due to, and can be produced at a relatively low cost because it has excellent injection moldability.

[0020]

EXAMPLES AND COMPARATIVE EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Examples 1 to 8 and Comparative Examples 1 to 9 Table 1 shows the composition and characteristic evaluation results of each Example and Comparative Example.
~ Shown in Table 3. The resin composition had a cylinder temperature of 3
Twin-screw extruder set to 00-320 ° C (Ikegai Tekko PCM
45) was melt-kneaded into pellets with the compositions shown in Tables 1 and 2. A predetermined test piece was prepared from the obtained pellets by an injection molding machine (cylinder-temperature: 290 to 320 ° C.) and used for the test. However, the respective raw materials used for the sample preparation shown in Examples and Comparative Examples are as follows. Component (A) : Nylon 4,6 resin: "STANYL" manufactured by DSM, Netherlands, relative viscosity 3.0 at 96% sulfuric acid 1 g / dl. Component (B) : Polyphenylene sulfide resin: Linear polyphenylene sulfide resin (hereinafter abbreviated as L-PPS), 310 ° C., melt viscosity of 500 poises at a shear rate of 1000 / sec. Semi-crosslinked polyphenylene sulfide resin (hereinafter, abbreviated as SL-PPS, melt viscosity 400 poise at 310 ° C., shear rate 1200 / sec. (C) component : amorphous polyamide resin: “GR” manufactured by Ems Co., Ltd.
IVORY XE3038 " (D) component : olefin polymer: ethylene / ethyl acrylate / glycidyl methacrylate copolymer (ethylene / ethyl acrylate / glycidyl methacrylate weight ratio = 97/3), ethylene / ethyl acrylate / glycidyl methacrylate Polymer (ethylene / ethyl acrylate / glycidyl methacrylate weight ratio = 94 /
6), ethylene / glycidyl methacrylate copolymer (ethylene / glycidyl methacrylate weight ratio = 85 /
15) Component (E) : fibrous filler: glass fiber (fiber diameter 10
(F) component : flame retardant: brominated polystyrene (bromine content 58% by weight) (G) component : flame retardant aid: antimony trioxide

The extrudability, tensile strength, water absorption rate, water absorption tensile strength retention rate, moisture absorption dimension change rate, deflection temperature under load, blister resistance, and flow length in the examples and comparative examples were measured by the following measuring methods. Yes Extrudability : The take-off property of the strand when the resin composition is melt-kneaded and pelletized by a twin-screw extruder, the pellet shape is "○: good, △: problematic, x: strand cannot be taken"
It was evaluated. Tensile strength : According to ASTM D638. Water absorption rate : Calculated from the increase in weight of a sample in an absolutely dry state, which was molded into a diameter of 50 mm and a thickness of 3.2 mm, after being immersed in 23 ° C. water for 24 hours. Water absorption tensile strength retention rate : The humidity was adjusted to a saturated moisture absorption state in a constant temperature and humidity chamber with a temperature of 70 ° C and a relative humidity of 62%, and ASTM D63
It was measured according to 8, and expressed as the retention rate with respect to the strength during absolute drying. Hygroscopic dimensional change rate : 127 mm in length, 12.7 mm in width, and 3.2 mm in thickness are molded into test pieces, and the temperature is 70 ° C and the relative humidity is 62
% Humidity was adjusted to a saturated water absorption state in a constant temperature and humidity tank, and the dimensional change in the vertical direction was expressed by the rate of change from the dimension immediately after molding. Deflection Temperature Under Load : ASTM D648 (264 psi)
Was measured according to. Blister resistance : A sample molded to have a length of 127 mm, a width of 12.7 mm, and a thickness of 0.8 mm is immersed in water at 23 ° C. for 24 hours, and the test piece after immersion is fixed to a glass epoxy substrate having a thickness of 1.6 mm. Then, the preheating part 180 ° C. and the main heating part are passed through a far-infrared reflow furnace (temperature-time profile is illustrated in FIG. 1) in which various temperatures are set at intervals of 10 ° C., and a blister ( It was observed with the naked eye whether or not blistering) occurred. The maximum temperature on the surface of the glass epoxy substrate where no blister was observed was defined as the blister resistance temperature of the sample. Flow length : The flow length was measured in a spiral flow having a width of 10 mm and a thickness of 0.5 mm under the conditions of a cylinder of an injection molding machine, a temperature of 310 ° C., a mold temperature of 100 ° C., and an injection pressure of 500 kg / cm ² .

[0022]

[Figure 1]

[0023]

[Table 1]

[0024]

[Table 2]

As shown in Examples 1 to 8, the connector made of the high-fluidity thermoplastic resin of the present invention has excellent extrudability,
It has excellent moldability such as fluidity, good mechanical properties such as tensile strength and good heat resistance such as deflection temperature under load, and not only has a low water absorption rate, it also poses no problem in the normal soldering process even after water absorption and moisture absorption. It exhibits excellent blister resistance to the extent that it does not exist, and has extremely good performance such as reduced water absorption strength and small changes in moisture absorption dimension. Comparative Example 1
Is the case where the compounding amount of (A) nylon 4, 6 is less than the scope of claims of the present invention and the content of (B) polyphenylene sulfide exceeds the scope of claims of the present invention, and extrudability is poor. No sample could be made. Comparative Example 2
(A) Nylon 4,6 content exceeds the claimed range of the present invention, and (B) polyphenylene sulfide compounded amount is below the claimed range of the present invention, not only high water absorption but also water absorption・ Lower water absorption strength after moisture absorption, large change in moisture absorption, and poor blister resistance. Comparative Example 3
In the case where (B) the polyphenylene sulfide resin is not blended and the blending amount of the (C) amorphous polyamide exceeds the scope of the claims of the present invention, not only the water absorption rate is high, but also after water absorption / moisture absorption. The water absorption strength and the moisture absorption dimensional change are large, and the blister resistance is poor. Comparative Example 4 is a case where (A) nylons 4 and 6 are not blended, and has a problem in extrusion processability, poor fluidity, and poor blister resistance. Comparative Example 5 is a case where the (D) olefin polymer is not blended, has a problem in extrusion processability, and is inferior in blister resistance. Comparative Example 6 is a case where the blending amount of the (D) olefin polymer exceeds the scope of the claims of the present invention, mechanical properties such as tensile strength and heat resistance such as deflection temperature under load are poor, and there is a problem in extrusion processability. And the fluidity and blister resistance are inferior. Comparative Example 7 is a case where the compounding amount of the (E) fibrous filler exceeds the scope of the claims of the present invention, there is a problem in extrusion processability, and the fluidity is poor. Comparative Example 8 is a case where the blending amount of the flame retardant exceeds the scope of the claims of the present invention, the heat resistance such as the deflection temperature under load is poor, the extrusion processability is problematic, and the water absorption strength after water absorption / moisture absorption is low. The deterioration is large and the blister resistance is poor. Comparative Example 9
When the compounding amount of the flame retardant aid is beyond the scope of the claims of the present invention, mechanical properties such as tensile strength are inferior, there is a problem in extrusion processability, and the decrease in water absorption strength after water absorption / moisture absorption is large. , Inferior in blister resistance.

[0026]

EFFECTS OF THE INVENTION According to the present invention, mechanical properties are excellent, dimensional changes due to moisture absorption and strength reduction, and blister generation during soldering in a reflow furnace are significantly suppressed, and injection moldability and fluidity are improved. It is possible to obtain a connector made of a highly fluid thermoplastic resin having excellent properties.

[0027]

[Brief description of drawings]

FIG. 1 illustrates a temperature-time profile of a far-infrared reflow furnace for measuring blister resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location B29L 31:36

Claims (1)

[Claims] 1. A connector having a thermoplastic resin portion, wherein the thermoplastic resin is (A) nylon 4,6 resin 6.
~ 90 wt%, (B) polyphenylene sulfide resin 5 to 89 wt%, (C) amorphous polyamide resin 0
30% by weight, (D) Olefin-based polymer having unsaturated carboxylic acid or its derivative as a copolymerization component 0.1-2
0% by weight, (E) fibrous filler 0 to 50% by weight,
(F) 0 to 30% by weight of flame retardant, (G) flame retardant aid 0
-15% by weight, cylinder of injection molding machine-temperature 3
10 ℃, mold temperature 100 ℃, injection pressure 500kg / cm
^A connector made of a high-fluidity thermoplastic resin, which has a flow length of 55 mm or more in a spiral flow having a width of 10 mm and a thickness of 0.5 mm under the condition of ² .