JP2001115048A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which does not blister (swell) on soldering works in a reflowing oven by a surface-loading method. SOLUTION: This thermoplastic resin composition comprises (A) 90 to 99.99 pts.wt. of a thermoplastic resin having a crystal-melting temperature of >=200 deg.C, (B) 10 to 0.01 pts.wt. of hydrophobic zeolite [provided that the total amount of the components (A) and (B) is 100 pts.wt.], and, if necessary, (C) a flame retardant, (D) a flame retardant auxiliary, and/or (E) an inorganic filler [excluding the component (B)].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition which does not generate blisters when soldering in a reflow furnace.

[0002]

2. Description of the Related Art Polyamide resins having an aromatic group such as polyamide 4,6 resin (nylon 4,6) and terephthalic acid are known.
Because of its excellent mechanical properties, physical properties, electrical properties, moldability, and the like, it is used in a wide range of fields such as electric / electronic parts, vehicle parts, various devices, and miscellaneous goods.

[0003] In recent years, in the field of the electric and electronic industries, connectors, switches,
A method of soldering resin-based electronic components such as relays and coil bobbins on a printed circuit board by a surface mounting method (surface mounting method; SMT method) has been adopted. Here, the surface mounting method refers to a method in which electronic components are placed on a printed wiring board via a creamy solder, and then the wiring board is passed through a heating furnace (reflow furnace) to remove the solder. A method of melting and fixing an electronic component on a wiring board. The surface mounting method is
The conventional insertion mounting method (lead-through) in which the lead wire of the electronic component is passed through the through hole on the wiring board and soldered (free soldering or wave soldering) directly to the surface opposite to the surface on which the electronic component is mounted method)
And different.

[0004] The surface mounting method has the advantages that the mounting density can be increased, mounting on both sides is possible, and the manufacturing cost can be reduced by improving efficiency. It is becoming.

[0005]

When soldering is performed by using the above surface mounting method, when a resin component such as a connector is passed through a soldering reflow furnace, a blister (blister) is formed on the surface of the resin component. Blistering may occur. The cause of this blister has not yet been fully elucidated. When blisters are generated, the commercial value may be significantly reduced. Therefore, a material that does not generate blisters even by the surface mounting method is desired. In view of the above circumstances, an object of the present invention is to obtain a thermoplastic resin having excellent blister resistance.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that blending a hydrophobic zeolite with a thermoplastic resin significantly improves blister resistance. The present invention has been completed.
That is, the thermoplastic resin composition of the present invention comprises (A) 90 to 99.99 parts by weight of a thermoplastic resin having a crystal melting temperature of 200 ° C. or higher, and (B) 10 to 0.01 parts by weight of a hydrophobic zeolite (provided that (A) The total amount of the component (B) and the component (B) is 100 parts by weight.).

The hydrophobic zeolite of the component (B) usually has a SiO ₂ / Al ₂ O ₃ molar ratio of 30 or more (claim 2). The thermoplastic resin composition of the present invention comprises (C) a total of 100 parts by weight of the components (A) and (B).
The composition may further comprise 5 to 70 parts by weight of a flame retardant and (D) 0 to 50 parts by weight of a flame retardant aid (Claim 3). The thermoplastic resin composition of the present invention comprises (E) an inorganic filler (excluding the component (B)) based on 100 parts by weight of the total of the components (A) and (B). It may further contain 300 parts by weight (claim 4). The crystal melting temperature of the thermoplastic resin is preferably 270 ° C. or higher in order to support the surface mounting method (SMT method).

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As the thermoplastic resin (A) used in the present invention, polyamide resin, polyester resin, polyarylene sulfide resin, liquid crystal polymer and the like are preferably used, and polyamide resin is particularly preferable. These resins can be used alone or in combination of two or more.

The polyamide resin has an amide bond (—NHC)
Examples of the polymer having O-) include a polymer obtained from polycondensation of diamine and dicarboxylic acid, a polymer obtained from polycondensation of aminocarboxylic acid, and a polymer obtained from ring-opening polymerization of lactams. One type of polyamide resin may be used alone, or two or more types may be used in combination. Here, examples of the diamine include aliphatic diamines, aromatic diamines, and alicyclic diamines.

Examples of the aliphatic diamines include carbon numbers
Diamines having 3 to 18 linear or side chains are included. Specific examples include 1,3-trimethylenediamine, 1,4
-Tetramethylene diamine, 1,5-pentamethylene diamine, 1,6-hexamethylene diamine, 1,7-heptamethylene diamine, 1,8-octamethylene diamine, 2-methyl-1,8-octane diamine, 1, 9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecanemethylenediamine, 1,12-dodecamethylenediamine, 1,13
-Tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,15-pentadecamethylenediamine, 1,16
-Hexadecamethylenediamine, 1,17-heptadecamethylenediamine, 1,18-octadecamethylenediamine, 2,
Examples thereof include 2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine. These may be used alone or in combination of two or more.

As the aromatic diamines, diamines having 6 to 27 carbon atoms having at least one phenylene group in the molecule are used. Specific examples include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 3,4-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 4,4 '-Diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4,4'-di (m-aminophenoxy) diphenylsulfone, 4,4 '-Di (p-aminophenoxy)
Diphenylsulfone, benzidine, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-
Bis (4-aminophenyl) propane, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 4,4′-bis (4-
Aminophenoxy) biphenyl, 2,2-bis [4- (4-
Aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3
-Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4'-diamino-3,3'-diethyl- 5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylmethane, 2,4
-Diaminotoluene, 2,2'-dimethylbenzidine and the like, and these may be used alone or in combination of two or more.

The alicyclic diamines include at least one cyclohexylene group having 4 to 1 carbon atoms in the molecule.
5 diamines are used. Specific examples include 4,4'-diamino-dicyclohexylenemethane, 4,4'-diamino-
Dicyclohexylene propane, 4,4'-diamino-3,3'-
Dimethyl-dicyclohexylenemethane, 1,4-diaminocyclohexane, piperazine, etc.
One type may be used alone, or two or more types may be used in combination.

Examples of the dicarboxylic acids include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids.

The aliphatic dicarboxylic acids include those having carbon atoms
2-18 saturated or unsaturated dicarboxylic acids are used.
Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, prasillic acid, tetradecandioic acid, pentadecandioic acid, Octadecandioic acid, maleic acid, fumaric acid and the like can be mentioned, and these may be used alone or in combination of two or more.

The aromatic dicarboxylic acids include at least one phenylene group having 8 to 15 carbon atoms in the molecule.
The dicarboxylic acid of, for example, isophthalic acid, terephthalic acid, methyl terephthalic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenylmethane-4,4'- Dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and the like. These may be used alone or in combination of two or more. Furthermore, polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used as long as they can be melt-molded.

The aminocarboxylic acids include those having 4 to 18 carbon atoms.
Are used. As a specific example, 4
-Aminobutyric acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-
Aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 14-aminotetradecanoic acid, 16-aminohexadecanoic acid, 18-aminooctadecanoic acid and the like. More than one species may be used in combination.

Specific examples of lactams include ε-caprolactam, ω-laurolactam, ζ-enantholactam, η-caprylactam and the like.
The seeds may be used alone or in combination of two or more.

As a preferable raw material of the polyamide resin, ε
-Caprolactam (nylon 6), 1,6-hexamethylenediamine / adipic acid (nylon 6,6), 1,4-tetramethylenediamine / adipic acid (nylon 4,6), 1,6-hexamethylenediamine / terephthal Acid, 1,6-hexamethylenediamine / terephthalic acid / ε-caprolactam,
1,6-hexamethylenediamine / terephthalic acid / adipic acid, 1,9-nonamethylenediamine / terephthalic acid, 1,9
-Nonamethylenediamine / terephthalic acid / ε-caprolactam, 1,9-nonamethylenediamine / 1,6-hexamethylenediamine / terephthalic acid / adipic acid, m-xylylenediamine / adipic acid, and more preferably, 1,4-tetramethylenediamine / adipic acid (nylon 4,6), 1,6-hexamethylenediamine / terephthalic acid / ε-caprolactam, 1,6-hexamethylenediamine / terephthalic acid / adipic acid, 1,9- Nonamethylenediamine / terephthalic acid, 1,9-nonamethylenediamine /
Terephthalic acid / ε-caprolactam, polyamide resin composed of 1,9-nonamethylenediamine / 1,6-hexamethylenediamine / terephthalic acid / adipic acid,
Particularly preferred is 1,4-tetramethylenediamine / adipic acid (nylon 4,6).

Examples of the polyester resin used in the present invention include those obtained from a diol component having 2 to 6 carbon atoms and an aromatic dicarboxylic acid. Preferred examples of the diol component include ethylene glycol and butanediol. As the aromatic dicarboxylic acids, those described as the components of the polyamide resin can all be used, and preferred are terephthalic acid and isophthalic acid.

Preferred raw materials for the polyester resin used in the present invention are butanediol / terephthalic acid and ethylene glycol / terephthalic acid, and more preferably ethylene glycol / terephthalic acid.

The polyarylene sulfide resin used in the present invention is mainly composed of components represented by the following general formula.

Embedded image (In the formula, Ar represents an aromatic group having 6 or more carbon atoms.) Here, as Ar (aromatic group) in the formula, p-phenylene, m-phenylene, 2,6-naphthalene, 4,4 '-Biphenylene, p, p'-bibenzyl, and their nuclear substituents are representative examples.

A typical example of the polyarylene sulfide resin is polyphenylene sulfide, and among them, poly-p-phenylene sulfide is preferable. Here, polyphenylene sulfide has the following structural formula (1)

Embedded image The main component is a structural unit represented by

As poly-p-phenylene sulfide, at least 70 mol% of a structural unit of a p-phenylene nucleus is used.
More preferably, it contains 90 mol% or more. As poly-p-phenylene sulfide, those obtained by a known method can be used.
A relatively low molecular weight polymer obtained by the production method represented by JP-3368, an essentially linear high molecular weight polymer obtained by the production method represented by JP-B-52-12240, etc. Used. The polymer obtained by the method described in JP-B No. 45-3368 is heated by heating under an oxygen atmosphere after polymerization, or by adding a crosslinking agent such as peroxide and heating. It can also be used after increasing the degree of polymerization.

Among the poly-p-phenylene sulfides, an essentially linear polymer having a relatively high molecular weight or a linear polymer partially crosslinked is preferably used.
In addition, poly-p-phenylene sulfide contains less than 30 mol% of the repeating units in the following structural formulas (2) to (2).
It can be composed of a repeating unit having (8) or the like.

Embedded image

The preferred melt viscosity of the polyarylene sulfide resin is usually 100 to 10,000 poise (310 ° C., shear rate 1,000 sec ⁻¹ ).

The liquid crystal polymer used in the present invention is p-
Hydroxybenzoic acid as an essential component, if necessary,
The diol represented by the following structural formula (9),
Under the nitrogen atmosphere using a dicarboxylic acid represented by 0), an aromatic oxycarboxylic acid such as m-oxybenzoic acid, 2-hydroxy-6-naphthoic acid, p-aminophenol, p-aminobenzoic acid, etc. It is a copolymer obtained by heating and melting and performing polycondensation. One type of liquid crystal polymer may be used alone, or two or more types may be used in combination.

When the diol represented by the structural formula (9) and the dicarboxylic acid represented by the structural formula (10) are used in combination,
In the polymer, structural units derived from diol and dicarboxylic acid are present at random. Structural formula (1
Even if the compound represented by 1) is added as one of the components, the basic performance is not changed and there is no problem.

[0028]

Embedded image (Where X and X ′ may be the same or different from each other,

Embedded image (Wherein, n is an integer of 1 to 6). )

The thermoplastic resin as the component (A) of the present invention is a crystalline polymer and has a crystal melting temperature (Tm) of 20.
0 ° C or higher. The crystal melting temperature is preferably 250 ° C. or higher, more preferably 270 ° C. or higher, in order to easily cope with the surface mounting method (SMT method). If the crystal melting temperature is lower than 200 ° C., there is a possibility that the thermoplastic resin may be melted when soldering by the surface mounting method, which is not preferable.

The hydrophobic zeolite which is the component (B) of the present invention
Usually, SiO₂/ Al ₂O₃Molar ratio of 30 or more
Above, preferably 35 or more, particularly preferably 40 or more
Used. As a kind of hydrophobic zeolite,
High-silica zeolite, which is a synthetic zeolite,
Can be The high silica zeolite is SiO₂/ Al₂O
₃Unlike hydrophilic zeolite with a molar ratio of about 1 to 10,
SiO₂Subtle crystal composition and structure due to many components
Cavities inside the crystal become hydrophobic
You. High silica zeolite has an MFI crystal type
, SiO₂/ Al₂O₃Those with a molar ratio of 35 to 600 are preferred
It is used well. Can be used other than high silica zeolite
As hydrophobic zeolites, chabazite and natural mol
Denite, clinoptilolite, erionite, four
Natural zeolites such as jasite, or type A zeolite
Light, X-type zeolite, Y-type zeolite, L-type zeolite
G, P-type zeolite, ZSM-5, synthetic mordenite,
Synthesize zeolite such as zeolite omega, if necessary
Examples include those subjected to dealumination.

The hydrophobic zeolite is SiO ₂ / Al ₂ O
The Al atom in ₃ may be at least partially substituted with an atom of another metal such as Ga, In, or Ti. The particle size of the hydrophobic zeolite is usually about 0.1 to 10 μm.
The effective pore diameter of the hydrophobic zeolite is not particularly limited,
Usually, it is in the range of 1 to 30 mm. Commercially available hydrophobic zeolites include "Absentz" (trade name) manufactured by UOP,
"ZSM-5" (trade name) manufactured by Eka Nobel, BASF-J
"VAA-ATS" (trade name) manufactured by Apan, "Zeostar" (trade name) manufactured by Nippon Chemical Industry Co., Ltd., and the like.

The mixing ratio (weight ratio) of the components (A) and (B) used in the present invention is (A) / (B) = 90 to 99.99 / 1.
0 to 0.01, preferably 95 to 99.99 / 5 to 0.01, more preferably 97 to 99.98 / 3 to 0.02, and particularly preferably 99.55 to 99.98.
/0.45 to 0.02. If the amount of the component (A) is less than 90 parts by weight and the amount of the component (B) is more than 10 parts by weight, the mechanical strength is poor. If the amount of the component (A) exceeds 99.99 parts by weight and the amount of the component (B) is less than 0.01 part by weight, the blister resistance is poor.

As the flame retardant of the component (C) of the present invention, known flame retardants are used. Known flame retardants include halogen-based flame retardants, phosphorus-based flame retardants, and the like.
One type may be used alone, or two or more types may be used in combination. Preferred flame retardants are halogen-based flame retardants. Among the halogen-based flame retardants, bromo-based flame retardants are particularly preferred.

Preferred among the bromo flame retardants are at least one flame retardant selected from the group consisting of brominated polystyrene, brominated polyphenylene ether, and brominated epoxy oligomer, and brominated polystyrene is particularly preferred.

The brominated polystyrene used in the present invention is represented by the following general formula:

Embedded image (P is an integer of 1 to 5 and n is an integer of 2 or more).

[0036] Brominated polystyrene is produced by polymerizing brominated styrene or by brominating polystyrene. The bromine content in the brominated polystyrene is preferably from 40 to 75% by weight, particularly preferably from 50 to 75% by weight. The brominated polystyrene may optionally contain other copolymerizable monomers.

Other copolymerizable monomers include ethylene, propylene, butadiene, butene, hexene, pentene, methylbutene, methylpentene, styrene, acrylonitrile, vinyl chloride, vinyl acetate and the like.
Among them, ethylene, propylene, butadiene, styrene and acrylonitrile are preferred.

In producing brominated polystyrene,
A functional group-containing vinyl monomer may be copolymerized.
Examples of the functional group include one or more functional groups selected from a carboxyl group, an acid anhydride group, an oxazoline group, and an epoxy group. Specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic anhydride, vinyl oxazoline, glycidyl methacrylate,
Allyl glycidyl ether and the like can be mentioned. The functional group-containing vinyl monomer may be copolymerized with brominated styrene, or may be used to modify the terminal or the like of brominated polystyrene.

The weight average molecular weight of the brominated polystyrene (M
w) is a gel permeation chromatography (G
PC), using tetrahydrofuran (THF) as a solvent, diluting the flame retardant to a concentration of 1 mg / ml, and a flow rate of 1.0 ml.
Per minute at a temperature of 36 to 40 ° C. to obtain a weight average molecular weight in terms of polystyrene.
The weight average molecular weight of the brominated polystyrene is not particularly limited, but is preferably 5,000 to 500,000, and particularly preferably 10,000.
00-300,000.

Table 1 shows specific examples of the flame retardant.

[Table 1] Preferred flame retardants are the above-mentioned polybrominated styrenes such as D-1, D-2 and D-3 obtained by polymerizing brominated styrene. By using polybrominated styrene, the effect of the present invention can be further improved.

The amount of the flame retardant of component (C) is 5 to 70 parts by weight, preferably 10 to 60 parts by weight, based on 100 parts by weight of the total of components (A) and (B). When the amount of the component (C) is less than 5 parts by weight, the effect of adding the flame retardant to the flame retardancy cannot be sufficiently obtained.

As the flame retardant auxiliary of the component (D) of the present invention,
Examples thereof include metal compounds of Group Va of the periodic table and metal compounds such as boron oxide, zirconium oxide, iron oxide, and zinc oxide. Among them, an antimony compound which is a metal compound belonging to Group Va of the periodic table is particularly preferable.

Examples of the antimony compound include antimony trioxide, antimony pentoxide, sodium antimonate and the like, and antimony trioxide is particularly preferably used. These flame retardant aids may be used alone or in combination of two or more.

The amount of the flame-retardant auxiliary component (D) used is (A)
The amount is 0 to 50 parts by weight, preferably 1 to 30 parts by weight based on 100 parts by weight of the total amount of the component and the component (B). If the amount of the component (D) exceeds 50 parts by weight, the mechanical strength decreases.

As the inorganic filler of the component (E), (B)
Any inorganic filler other than the components is used, and examples thereof include various fillers such as fibrous, powdery, granular, plate-like, needle-like, cloth-like, and mat-like fillers. Typical specific examples include glass fiber, asbestos fiber, carbon fiber, graphite fiber, calcium carbonate, talc, catalbo, walasteinite, silica, alumina, silica alumina, diatomaceous earth, clay, calcined clay, kaolin, mica (fine Synthetic and natural mineral whiskers such as mica), granular glass, glass flakes, glass balloons (hollow glass), gypsum, redwood, metal fibers, titanium dioxide, potassium titanate whiskers, aluminum borate whiskers,
Examples include magnesium oxide, calcium silicate, asbestos, sodium aluminate, calcium aluminate, aluminum, aluminum oxide, aluminum hydroxide, copper, stainless steel, zinc oxide, and metal whiskers.

Among these, glass fibers, carbon fibers, kaolin, mica, talc and various whiskers are preferred in terms of mechanical strength and the like, and glass fibers, kaolin and talc are particularly preferred in terms of economy. The inorganic filler may be surface-treated as long as the moldability and physical properties of the resin composition of the present invention are not impaired. Among them, an inorganic filler subjected to a surface treatment with a compound (a sizing agent or the like) represented by aminosilane, acrylic silane, vinyl, urethane, acrylic urethane or the like is preferably used.

The amount of the inorganic filler used as the component (E) is
5 to 100 parts by weight of the total amount of the components (A) and (B)
It is 300 parts by weight, preferably 5 to 200 parts by weight, particularly preferably 5 to 150 parts by weight. If the amount of the component (E) is less than 5 parts by weight, sufficient effects on rigidity and dimensional stability cannot be obtained, and if it exceeds 300 parts by weight, moldability is poor.

The composition of the present invention contains a copper compound such as copper iodide, an aromatic amine compound,
An antioxidant such as a hindered phenol compound, an organic phosphorus compound, a sulfur compound, or a heat stabilizer can also be added.

Further, if necessary, other components such as a pigment, as long as the moldability and physical properties are not impaired.
Dyes, ultraviolet absorbers, weathering agents, lubricants, crystal nucleating agents, release agents, plasticizers, antistatic agents and the like may be added.

Further, ABS is used as another thermoplastic resin.
Resin, HIPS, AS resin, PS, PTFE, polyvinylidene fluoride, aramid fiber, polyethylene, polypropylene and the like can also be blended. These thermoplastic resins may be modified with a functional group such as a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, an oxazoline group, an amino group, and an amide group.

The thermoplastic resin composition of the present invention can be obtained by melt-kneading using a kneader. Examples of the kneading machine include an extruder, a kneader, a roll, a Brabender, a Banbury mixer, a continuous kneader, a combination thereof, and the like, and preferably an extruder. Among the extruders, a twin-screw extruder is particularly preferred.

As a method for charging each component of the present invention into the kneading machine, a method of charging all the components in a lump, or a method of kneading some components and then charging the remaining components in one or more portions. There are a kneading method, a method in which a part of each component is charged, and a method in which the remaining component is divided into arbitrary numbers and charged.

The thermoplastic resin composition of the present invention can be molded by any molding method. For example, it can be formed by injection molding, compression molding, vacuum molding, sheet molding, film molding, injection press molding, blow molding, profile extrusion molding, two-color molding, thermo-ejection molding, insert molding, outsert molding, or the like.

Since the thermoplastic resin composition of the present invention has excellent performance, it can be used for electric and electronic devices, vehicles, home appliances, buildings,
It can be used in a wide range of fields such as sanitary, sports, and miscellaneous goods. Specific examples include connectors, switches, sensors, sockets, capacitors, jacks, fuse holders, relays, coil bobbins, resistors, and ICs.
And LED housing, gear, bearing retainer,
Examples include spring holders, chain tensioners, washers, worm wheels, belts, filters, various housings, auto tensioners and weight rollers, breaker parts, clutch parts, and the like. Among them, the thermoplastic resin composition of the present invention is particularly suitable for a connector, a switch, a sensor, a resistor, a relay, a capacitor, a socket, a jack, a fuse holder, a coil bobbin, a housing for an IC or an LED for a surface mounting method (SMT method). Useful for etc.

[0055]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following examples. Note that “%” and “parts” in Examples and Comparative Examples mean “% by weight” and “parts by weight” unless otherwise specified.

Examples 1 to 16 and Comparative Examples 1 to 4 [Materials] Materials used in Examples and Comparative Examples are as follows. [Preparation of (A) Component] The following A-1 to A-5 were prepared as the thermoplastic resin of the (A) component of the present invention. [A-1] Nylon 4,6 comprising 1,4-tetramethylenediamine and adipic acid, having a relative viscosity of 3.5 measured with 96% sulfuric acid 1 g / dl (25 ° C.) and a crystal melting temperature of 300 ° C.
(Polyamide 4,6 resin) was used. [A-2] obtained by polymerizing 192.14 g of terephthalic acid, 230.56 g of hexamethylenediamine, and 121.26 g of adipic acid,
A polyamide resin having a relative viscosity of 2.6 measured at 1 g / dl (25 ° C.) of 96% sulfuric acid and a crystal melting temperature of 325 ° C. was used. [A-3] The relative viscosity measured with 96% sulfuric acid 1 g / dl (25 ° C.) obtained by polymerizing 162.76 g of terephthalic acid, 113.73 g of hexamethylenediamine, and 107.76 g of ε-caprolactam was obtained.
In 2.7, a polyamide resin having a crystal melting temperature of 326 ° C. was used. [A-4] 257.4 g of terephthalic acid, 1,9-nonadiamine 31
A polyamide resin obtained by polymerizing 0.28 g and 60.32 g of adipic acid, having a relative viscosity of 2.8 measured with 96% sulfuric acid of 1 g / dl (25 ° C.), and having a crystal melting temperature of 290 ° C. was used. [A-5] A polyphenylene sulfide resin (M2588, manufactured by Toray Industries, Ltd.) having a crystal melting temperature of 285 ° C. was used. [A-6] 299 g of terephthalic acid, 284.8 g of 1,9-nonadiamine
A polyamide resin having a relative viscosity of 2.8 measured with 96% sulfuric acid of 1 g / dl (25 ° C.) and a crystal melting temperature of 310 ° C. was used.

[Preparation of Component (B)] The following hydrophobic zeolite was used as the component (B) of the present invention. [B-1] A hydrophobic zeolite having an SiO ₂ / Al ₂ O ₃ molar ratio of 40, an average particle diameter of 4 μm, and an effective pore diameter of 6 ° was used. [B-2] A hydrophobic zeolite having an SiO ₂ / Al ₂ O ₃ molar ratio of 450, an average particle diameter of 4 μm, and an effective pore diameter of 6 ° was used.

[Preparation of Component (C)] As the flame retardant of the component (C) of the present invention, polybrominated styrene (PDBS-80, manufactured by Great Lake Chemical Co., Ltd., bromine content: 59%) was used. [Preparation of Component (D)] Antimony trioxide was used as a flame retardant aid. [Preparation of (E) component] Fiber diameter 10μ as inorganic filler
m, a glass fiber chopped strand having a cut length of 3 mm (surface treatment agent: aminosilane, sizing agent: urethane) was used.

[Preparation and Evaluation of Composition] Of the components shown in Table 2, components other than component (E) were uniformly mixed by a tumbler, and the screw had a two-stage kneading block.
Using a 44 mmφ twin-screw extruder having a feed port in the middle between the first and second kneading blocks, the above mixture is supplied from the root of the extruder, and the component (E) is supplied from the feed port in the middle, and a vacuum vent While kneading, and pelletized. After the obtained pellets were sufficiently dried by a dehumidifying dryer, predetermined test pieces were prepared by an injection molding machine. Table 2 shows the mixing ratio of each component in each test piece (Examples 1 to 11 and Comparative Examples 1 to 8).

[0060]

[Table 2]

These test pieces were evaluated by the following methods. [Mechanical strength] The tensile strength was measured according to ASTM D638. Table 4 shows the results. [Blister property] Evaluation was performed using AIS-260 manufactured by Atec Techtron Co., Ltd. as a reflow device. Test piece A 0.8 mm thick flat plate obtained by injection molding was allowed to absorb water at 30 ° C. and 90% RH for 10 hours to obtain a blister evaluation test piece. Reflow test conditions Table 3 shows the set temperatures of the reflow apparatus. In Table 3, “PH1,” “PH2,” and “PH3” mean the set temperature of the reflow preheating zone, and “RE” means the set temperature of the reflow zone.

[0062]

[Table 3]

Evaluation The number of blisters generated on the test piece was counted. Table 4 shows the evaluation results.

[Table 4]

Table 4 shows the following. Example 1
No. 16 is an example in which a hydrophobic zeolite in an amount within the range of the present invention is blended with a thermoplastic resin, and is excellent in blister resistance. Comparative Examples 1 to 4 are examples in which the blending amount of the hydrophobic zeolite is smaller than the range of the present invention, and the blister resistance is inferior.

[0065]

The thermoplastic resin composition of the present invention is excellent in blister resistance during soldering in a reflow furnace. Further, by blending the inorganic filler in a specific amount, mechanical strength and dimensional stability can be improved.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G073 BA57 BA63 BB71 CN03 CZ01 DZ05 FA02 GA01 UB01 4J002 AA011 CF031 CF161 CF181 CL001 CN011 DJ006 FD019 FD137 FD138 GC00 GL00 GN00 GQ00

Claims (5)

[Claims] (A) 90 to 99.99 parts by weight of a thermoplastic resin having a crystal melting temperature of 200 ° C. or more; (B) 10 to 0.01 parts by weight of a hydrophobic zeolite (provided that the components (A) and (B) Is a total amount of 100 parts by weight.). 2. The hydrophobic zeolite as the component (B),
SiO₂/ Al₂O ₃The method according to claim 1, wherein the molar ratio is 30 or more.
The thermoplastic resin composition according to the above. 3. A flame retardant (C) in an amount of 5 to 70 parts by weight, based on 100 parts by weight of the total of the components (A) and (B).
3. The thermoplastic resin composition according to claim 1, further comprising (D) 0 to 50 parts by weight of a flame retardant aid. 4. An inorganic filler (E) excluding the component (B) in an amount of 5 to 300 parts by weight based on 100 parts by weight of the total of the component (A) and the component (B). The thermoplastic resin composition according to claim 1, comprising: 5. The thermoplastic resin having a crystal melting temperature of 270.
The thermoplastic resin composition according to any one of claims 1 to 4, which has a temperature of at least 0C.