JP2003221511A - Thermoplastic resin molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin molded article having excellent heat resistance in surface mounting even under a high temperature condition in a heating furnace (reflow furnace). <P>SOLUTION: This thermoplastic resin molded article is prepared by using a composition comprising at least a component (A) and a component (B), wherein the component (A) is at least one kind of thermoplastic resins having ≥220°C melting temperature or glass transition temperature and the component (B) is a metal borate, and soldered to a base body in a condition in which the base body to be soldered with the composition has ≥220°C surface temperature. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a high temperature condition such as a melting point or a glass transition point of a thermoplastic resin,
The present invention relates to a soldered thermoplastic resin molded article having excellent heat resistance. More specifically, electrical and electronic components such as connectors, switches, capacitors, integrated circuits (ICs), relays, resistors, light emitting diodes (LEDs),
The present invention relates to a thermoplastic resin molded article such as an underhood part around an automobile engine, various automotive parts such as an automotive connector, precision machine parts, pump parts and the like.

[0002]

2. Description of the Related Art In recent years, in the fields of electric and electronic industries, resin-based electronic components such as connectors, switches, relays and coil bobbins have been subjected to surface mounting (surface mounting or By the SMT method), a method of soldering on a printed circuit board has been adopted. Here, the surface mounting method is generally a method in which an electronic component is placed on a printed and printed wiring board via cream-like solder and then the wiring board is passed through a heating furnace (reflow furnace). This is a method of melting the solder and fixing the electronic components on the wiring board. In this surface mounting method, the lead wires of electronic components are passed through through holes on the wiring board, and soldering (free soldering or wave soldering) is performed directly on the surface opposite to the surface on which the electronic components are mounted. It is different from the insertion mounting method (read-through method).

The surface mounting method has the advantages that the mounting density can be increased, both front and back surfaces can be mounted, and that manufacturing cost can be reduced by improving efficiency. Is becoming. Conventionally, tin-lead eutectic solder (melting point 184 ° C) was generally used as the solder used in this surface mounting technology, but in recent years, due to environmental pollution, the use of lead has been reduced, and further abolition has been promoted. Has been done. As an alternative material, so-called lead-free solder in which several kinds of metals are added based on tin has been proposed, but both have higher melting points than tin-lead eutectic solder (for example, in the case of tin-silver eutectic solder) Has a melting point of 220 ° C), and a heating furnace (reflow furnace) for surface mounting
The temperature of must be raised further. As a result, when soldering is performed using the surface mount method, when a thermoplastic resin molded article such as a connector is passed through a soldering heating furnace (reflow furnace), the molded article may melt or deform. There is a strong demand for thermoplastic molded articles having higher heat resistance in this field.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic resin molded article having excellent heat resistance under high temperature conditions in a heating furnace (reflow furnace) during surface mounting.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that at least one heat selected from the group consisting of a melting point or a glass transition point of 220 ° C. or higher. A composition comprising a plastic resin and a metal borate, the thermoplastic resin molded article being soldered under high temperature conditions in which the surface temperature of a substrate to be soldered is 220 ° C. or higher using the composition. This has led to the completion of the present invention.

That is, the present invention is a thermoplastic resin molded article using a composition comprising at least component (A) and component (B), wherein component (A) has a melting point or glass transition point of 2
At least one thermoplastic resin having a temperature of 20 ° C. or higher, the component (B) is a metal borate, and the composition is soldered under the condition that the surface temperature of the substrate is 220 ° C. or higher, It is a thermoplastic resin molded article characterized by being soldered to a substrate. The present invention is also a thermoplastic resin molded article using a composition comprising at least component (A) and component (B), wherein component (A) has a melting point or a glass transition point of 220 ° C or higher. A kind of thermoplastic resin, the component (B) is a metal borate, and the composition is soldered to the substrate under the condition that the surface temperature of the substrate to be soldered is 240 ° C. or higher. Is a thermoplastic resin molded article. Further, the present invention is
A thermoplastic resin molded article comprising a composition comprising at least component (A) and component (B), wherein component (A) has a melting point or a glass transition point of 220 ° C. or higher.
A thermoplastic resin, the component (B) is a metal borate, and the composition has a surface temperature of 2 to be soldered.
A thermoplastic resin molded article, which is soldered to the substrate under conditions of 60 ° C. or higher. Also,
The present invention is a thermoplastic resin molded article comprising a composition comprising at least component (A) and component (B), wherein component (A) has at least one melting point or glass transition point of 220 ° C. or higher. A thermoplastic resin, the component (B) is a metal borate, and the composition is soldered to a substrate under the condition that the surface temperature of the substrate to be soldered is 280 ° C. or higher. And a thermoplastic resin molded article.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Next, necessary items for carrying out the present invention will be specifically described below.

The thermoplastic resin molded article of the present invention is a thermoplastic resin molded article comprising a composition comprising at least the component (A) and the component (B), and the component (A) has a melting point or a glass transition point. At least one thermoplastic resin having a temperature of 220 ° C. or higher, wherein the component (B) is a metal borate,
The surface temperature of the substrate to which the composition is soldered is 220 ° C.
It is soldered to the base under the above conditions.

The thermoplastic resin (A) used in the present invention is
It is a thermoplastic resin having a melting point or a glass transition point of 220 ° C. or higher. The melting point or glass transition point of the thermoplastic resin (A) is 2
When the temperature is 20 ° C. or higher, a thermoplastic resin molded article can be obtained without melting or deformation even under high temperature conditions in the soldering step, which is preferable.

Examples of the thermoplastic resin (A) include:
Polyarylene sulfide resin, thermotropic liquid crystal polyester resin, polyalkylene terephthalate resin, polyamide resin, aromatic polysulfone resin and the like are preferable, and polyarylene sulfide resin is more preferable. These resins may be used alone or in combination of two or more.

The polyarylene sulfide (hereinafter referred to as PAS) resin which is one of the thermoplastic resins (A) used in the present invention is represented by the general formula -Ar-S- (Ar is an arylene group). It is a PAS resin. Here, Ar of the arylene group is p-phenylene group, m-phenylene group,
o-phenylene group, and structural formulas [1] to
A divalent aromatic residue selected from the group consisting of [4], wherein each aromatic ring has a halogen such as F, Cl or Br,
A substituent such as an alkyl group (which may be linear or branched) with or without a substituent such as a CH ₃ group may be introduced. This may be a homopolymer, a random copolymer, a block copolymer, linear, branched,
Alternatively, cross-linked types and mixtures thereof are used.

[0012]

[Chemical 1]

[0013]

[Chemical 2]

[0014]

[Chemical 3]

[0015]

[Chemical 4]

The PAS resin used in the present invention is preferably a polyphenylene sulfide (hereinafter referred to as PPS) resin.

The PPS resin used in the present invention is preferably one containing a structural unit represented by the following general formula [5] in an amount of 70 mol% or more because it gives a molded article having excellent properties.

[0018]

[Chemical 5]

The PPS resin can be polymerized by, for example,
A method of polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, a method of polymerizing in a polar solvent in the presence of sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide, p-chloro. Examples include self-condensation of ruthiophenol.
A suitable method is to react sodium sulfide with p-dichlorobenzene in an amide solvent such as methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane. At this time, it is a preferable method to add an alkali metal salt of carboxylic acid or an alkali metal salt of sulfonic acid or to add an alkali hydroxide in order to adjust the degree of polymerization.

If the amount of the copolymerization component is less than 30 mol%, the following meta-bond structural unit [6], ether-bond structural unit [7], sulfone-bond structural unit [8], and ketone-bond structural unit will be shown below.

[9], biphenyl bond structural unit [10], substituted phenyl sulfide bond structural unit [11], trifunctional phenyl sulfide bond structural unit [12], naphthyl bond structural unit [13], etc. The content of the copolymerization component is preferably 10 mol% or less, though it may be in a range that does not significantly affect the properties. Particularly when phenyl, biphenyl, naphthyl sulfide bonds having three or more functional groups are selected for copolymerization, the content is preferably 3 mol% or less, more preferably 1 mol% or less.

[0021]

[Chemical 6]

[0022]

[Chemical 7]

[0023]

[Chemical 8]

[0024]

[Chemical 9]

[0025]

[Chemical 10]

[0026]

[Chemical 11]

In the formula, R represents an alkyl group, a nitro group, a phenyl group or an alkoxy group.

[0028]

[Chemical 12]

[0029]

[Chemical 13]

Such a PPS resin is produced by a general method, for example, (1) reaction of a halogen-substituted aromatic compound with an alkali sulfide (US Pat. No. 2,513,188, JP-B-44-2).
7671, JP-B-45-3368), (2) Condensation reaction in the presence of an alkali catalyst or copper salt of thiophenols (US Pat. No. 3,274,165, British Patent No. 1160660), (3) aromatic compound Of sulfur and sulfur chloride in the presence of Lewis acid catalyst (Japanese Patent Publication No. 46-
No. 27255, Belgian Patent No. 29437), etc., and can be arbitrarily selected according to the purpose.

The PPS resin used in the thermoplastic resin molded article of the present invention may be a crosslinked PPS resin or a non-crosslinked (linear) PPS resin. Among these PPS resins, particularly under a load of 316 ° C./5000 g according to ASTM D1238-86 (orifice: 0.0
825 ± 0.002 inch diameter × 0.315 ± 0.001
Melt flow rate in inches length) is preferably 3
000 g / 10 minutes or less, more preferably 1500 g / 1
It is 0 minutes or less. Furthermore, the form of the PPS resin used is not particularly limited, and may be granular such as pellets or powder.

As the thermotropic liquid crystal polyester resin which is one of the thermoplastic resins (A), known ones can be used, for example, those containing aromatic hydroxycarboxylic acid, aromatic diol and aromatic dicarboxylic acid as main constituent units. An aromatic hydroxycarboxylic acid, a polyalkylene diol and an aromatic dicarboxylic acid as main constituent units,
Those having different aromatic hydroxycarboxylic acids as main constituent units, those having aromatic dicarboxylic acids and nucleus-substituted aromatic diols as main constituent units, those having aromatic hydroxycarboxylic acids and hydroxynaphthoic acid as main constituent units, Examples thereof include those having an aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid and dihydroxybiphenyl as main constituent units, those having polyphosphazene as a main chain and polyalkylene diols and aromatic carboxylic acids as side chains.
Instead of these aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxycarboxylic acids, their ester-forming derivatives can be used.

Among these, those containing p-hydroxybenzoic acid and polyethylene terephthalate as main constituent units, those containing p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid as main constituent units, dihydroxy compounds and A polycondensation product of a dicarboxy compound or the like is preferable. Examples of the dihydroxy compound include ethylene glycol, hydroquinone, 2,6-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl and bisphenol-A. Among these, ethylene glycol, hydroquinone,
4,4'-dihydroxybiphenyl and the like are preferable, and ethylene glycol, hydroquinone and the like are more preferable. Examples of dicarboxy compounds include terephthalic acid, isophthalic acid, and 2,6-dicarboxynaphthalene. Among these, terephthalic acid and isophthalic acid are preferable, and terephthalic acid is more preferable. Dihydroxy compound and dicarboxy compound,
Each of them can be used alone or in combination of two or more.

As the polyalkylene terephthalate resin which is one of the thermoplastic resins (A) used in the present invention, a polyester resin having an aromatic ring as a chain unit is an aromatic dicarboxylic acid or its ester derivative and a di-
Is a polymer or copolymer obtained by a condensation reaction containing, as a main component, a vinyl alcohol or its ester derivative.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid and 2,6-
Naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 1,
2-bis (p-carboxyphenoxy) ethane, ester derivatives thereof, etc. may be mentioned. If the acid component is 30 mol% or less, for example, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid,
It may be substituted with a dicarboxylic acid other than the aromatic dicarboxylic acid such as an alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid and an ester derivative thereof.

The diol component has 2 to 2 carbon atoms.
10 aliphatic diols are preferred, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 3-methyl-1,3-propanediol, neopentyl glycol, 1 , 5-pentanediol, 1,6
-Hexanediol, decamethylene glycol, cyclohexanediol, cyclohexanedimethanol, etc. may be mentioned, and if it is a small amount, it is a long chain glycol having a molecular weight of 400 to 6000, that is, polyethylene glycol, polyglycol. 1,
You may copolymerize 3-propylene glycol, polytetramethylene glycol, etc.

Examples of the polyalkylene terephthalate resin used in the present invention include polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexyne dimethylene terephthalate and polyethylene-2. , 6-naphthalate,
Examples thereof include polybutylene-2,6-naphthalate, and among them, polybutylene terephthalate is preferable.

In addition, one of the thermoplastic resins (A) used in the present invention is a polyamide resin, which has an amide bond (--NH
Examples of the polymer having CO-) include polymers obtained by polycondensation of diamine and dicarboxylic acid, polymers obtained by polycondensation of aminocarboxylic acid, and polymers obtained by ring-opening polymerization of lactams. The polyamide resins may be used alone or in combination of two or more.

Here, examples of the diamine include aliphatic diamines, aromatic diamines, and alicyclic diamines. The aliphatic diamines preferably include diamines having a straight chain or a side chain having 3 to 18 carbon atoms, such as 1,3-trimethylene diamine.
1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,
7-heptamethylenediamine, 1,8-octamethylenediamine, 2-methyl-1,8-octanediamine,
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, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, and the like. These may be used alone or in combination of two or more.

The aromatic diamines preferably include diamines having at least one phenylene group in the molecule and having 6 to 27 carbon atoms, and examples thereof include o-phenylenediamine, m-phenylenediamine and p-phenylene. Diamine, m-xylylenediamine, p-xylylenediamine, 3,4-diaminodiphenyl ether,
4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4,4 '
-Di (m-aminophenoxy) diphenyl sulfone,
4,4'-di (p-aminophenoxy) diphenyl sulfone, 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, etc. may be mentioned, and these may be used alone or in combination of two or more kinds.

The alicyclic diamines preferably include diamines having 4 to 15 carbon atoms and having at least one cyclohexylene group in the molecule.
4,4'-diamino-dicyclohexylene methane, 4,
4'-diamino-dicyclohexylene propane, 4,4 '
-Diamino-3,3'-dimethyl-dicyclohexylene methane, 1,4-diaminocyclohexane, piperazine and the like can be mentioned, and these may be used alone or in combination of two or more kinds.

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

Examples of the aliphatic dicarboxylic acids include saturated or unsaturated dicarboxylic acids having 2 to 18 carbon atoms, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and the like. Suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid,
Prasiric acid, tetradecanedioic acid, pentadecanedioic acid,
Examples thereof include octadecanedioic acid, maleic acid and fumaric acid, and these may be used alone or in combination of two or more kinds.

The aromatic dicarboxylic acids are preferably dicarboxylic acids having 8 to 15 carbon atoms and having at least one phenylene group in the molecule. Examples thereof include isophthalic acid, terephthalic acid, methylterephthalic acid and biphenyl- 2,2'-dicarboxylic acid, biphenyl-4,4 '
-Dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid,
Examples thereof include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,4-naphthalenedicarboxylic acid. 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 within the range in which they can be melt-molded.

The aminocarboxylic acid is preferably
An aminocarboxylic acid having 4 to 18 carbon atoms, for example, 4
-Aminobutyric acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid,
10-aminodecanoic acid, 11-aminoundecanoic acid, 1
2-aminododecanoic acid, 14-aminotetradecanoic acid,
Examples thereof include 16-aminohexadecanoic acid and 18-aminooctadecanoic acid, which may be used alone or in combination of two or more kinds.

Examples of lactams include ε-caprolactam, ω-laurolactam, ζ-enanthlactam, η-capryllactam and the like, and these may be used alone or in combination of two or more kinds.

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 / terephthalic acid, 1,6-hexamethylenediamine / terephthalic acid / ε-caprolactam, 1,6-hexamethylenediamine / terephthalate 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 may be mentioned, 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, 1,9-nonamethylenediamine / A polyamide resin composed of 1,6-hexamethylenediamine / terephthalic acid / adipic acid can be mentioned.

Next, one aromatic polysulfone resin of the thermoplastic resin (A) used in the present invention usually has the following structural unit [14].

[0049]

[Chemical 14]

(In the formula [14], R ¹ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, a phenyl group or a halogen atom, and p is independently a number of 0 to 4 Each R ¹ on the same or different nucleus may be different from each other.)

The ratio of the above structural unit [14] to all structural units is usually preferably 30 mol% or more, more preferably 50 mol% or more, and particularly preferably 80 mol% from the viewpoint of heat resistance, mechanical properties and the like. It is more preferable that substantially all the structural units are the structural unit [14].

The structural unit [14] has a heat resistance of
From the viewpoint of mechanical properties and the like, p is preferably 0, that is, the following structural unit [14a] is preferable.

[0053]

[Chemical 15]

The aromatic polysulfone resin used in the present invention may have the following structural unit [15] or [16].

[0055]

[Chemical 16]

(In the formula [15], R ¹ and p are defined by the formula [1
4], and X represents an organic group having 1 to 20 carbon atoms, a carbonyl group, a divalent sulfur atom or an oxygen atom).

[0057]

[Chemical 17]

(In the formula [16], the definitions of R ¹ and p are the same as those in the formula [14], and q represents a number of 1 to 3.)

When the aromatic polysulfone resin has the above structural units [14] and [15], [14] / [1]
The molar ratio of [5] is usually preferably in the range of 0.5 to 50 mol%.

Further, the above structural units [14] and [16]
In the case of the above, the molar ratio [14] / [16] is usually preferably in the range of 1.0 to 20 mol%.

Examples of the structural unit [15] include the following structural units [15a] to [15d].

[0062]

[Chemical 18]

Examples of the structural unit [16] include the following structural units [16a] and [16b].

[0064]

[Chemical 19]

The molecular terminal structure of the aromatic polysulfone resin, which is one of the thermoplastic resins (A) used in the present invention, is, for example, halogen such as --Cl, --OH or --OM.
(M is a metal atom such as an alkali metal), -OR (R is an alkyl group) and the like. The kind and ratio of the molecular terminal structure can be appropriately adjusted depending on the production conditions of the aromatic polysulfone resin and the like.

The metal borate salt (B) used in the present invention is a salt having a valence of one to three valent metal elements, and examples thereof include magnesium borate, calcium borate, and borate. Chromic acid, manganese borate, iron borate, cobalt borate, nickel borate, copper borate, zinc borate, aluminum borate, gallium borate, strontium borate, yttrium borate, zirconium borate, niobium borate , Molybdenum borate, lead borate, barium borate, tungsten borate, lithium borate and the like, but preferably aluminum borate, magnesium borate, nickel borate, more preferably aluminum borate. .

The form of the metal borate salt (B) used in the present invention is not particularly limited and may be granular such as pellets, powdery or fibrous.

Examples of the fibrous metal borate salt (B) include, for example, aluminum borate fibers, and commercially available products include, for example, "Arborex Y" (Shikoku Chemical Industry Co., Ltd.).
Manufactured).

The boric acid metal salt (B) used in the present invention may be surface-treated with a surface treatment agent such as a silane coupling agent or a titanium coupling agent.

The compounding ratio of the metal borate salt (B) in the present invention can be used within a range that does not impair the performance of the thermoplastic resin molded article of the present invention.
The amount of the metal borate (B) is preferably 70 to 1 part by weight based on 99 parts by weight.

Further, the thermoplastic resin molded article of the present invention comprises
The composition may contain a fibrous reinforcing material (C-1) and / or an inorganic filler (C-2). Examples of the fibrous reinforcing material (C-1) used in the present invention include glass fiber, PAN-based or pitch-based carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, Examples include boron fibers, potassium titanate fibers, inorganic fibrous substances such as stainless steel, aluminum, titanium, copper, brass and other metallic fibrous substances, and aramid fibers and other organic fibrous substances. Fibers are particularly preferred. Examples of the inorganic filler (C-2) include mica, talc, wollastonite, sericite, kaolin, clay, bentonite, asbestos, alumina silicate, zeolite, pyrophyllite, and other silicates and calcium carbonate,
Magnesium carbonate, carbonates such as dolomite, calcium sulfate, sulfates such as barium sulfate, alumina, magnesium oxide, silica, zirconia, titania, metal oxides such as iron oxide, glass beads, ceramic beads, boron nitride, silicon carbide, Examples include calcium phosphate. These fibrous reinforcing materials (C-1) and / or inorganic fillers (C-2) may be used alone or in combination of two or more kinds.

The fibrous reinforcing material (C-
The compounding amount of 1) and / or the inorganic filler (C-2) is
It can be used within a range that does not impair the performance of the thermoplastic resin molded article of the present invention, and the above fibrous material is added to 100 parts by weight of the total amount of the above-mentioned thermoplastic resin (A) and metal borate salt (B). The reinforcing material (C-1) and / or the inorganic filler (C-2) are preferably in the range of 1 to 200 parts by weight. Further, the fiber reinforcing material (C-1) and / or the inorganic filler (C-2) may be used as a silane coupling agent or a titanium coupling agent as long as the performance of the thermoplastic resin molded article of the present invention is not impaired. It may be one that has been surface-treated with a surface-treating agent.

Further, the thermoplastic resin molded article of the present invention comprises
The composition may contain a silane compound (D). The silane compound (D) is, for example, one kind or two or more kinds of aminoalkoxysilane, epoxyalkoxysilane, vinylalkoxysilane and the like.

The above aminoalkoxysilane is 1
Any silane compound having one or more amino groups and two or more alkoxy groups in the molecule is effective, and for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl)
-Γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl)- γ-aminopropylmethyldimethoxysilane, N-phenyl-
Examples include γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane.

As the epoxyalkoxysilane, any silane compound having one or more epoxy groups and two or more alkoxy groups in one molecule is effective. For example, γ-glycid Examples include xypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane.

Further, as vinylalkoxysilane,
Have 1 or more vinyl groups in one molecule and 2 alkoxy groups
Any silane compound having at least one silane compound is effective, and examples thereof include vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris (β-methoxyethoxy) silane.

The compounding amount of the silane compound usable in the present invention is such that the above-mentioned thermoplastic resin (A) and boric acid metal salt (B) are used.
With respect to the total amount of 100 parts by weight of
It is 5 parts by weight, more preferably 0.1 to 2 parts by weight.

The surface temperature of the substrate to be soldered in the present invention means the temperature on the surface of the substrate actually measured in the soldering step in the surface mounting method. Specific examples of the substrate include a printed circuit board and a circuit board in a surface mounting method.

The thermoplastic resin molded article of the present invention comprises a composition comprising at least component (A) and component (B), wherein component (A) has a melting point or a glass transition point of 220 ° C. or higher. A kind of thermoplastic resin, the component (B) is a metal borate, and the composition is soldered to the substrate under the condition that the surface temperature of the substrate to be soldered is 220 ° C. or higher. Is characterized by. Further, the molded thermoplastic resin article of the present invention may be a molded article soldered to the substrate under the condition that the surface temperature of the substrate to which the composition is soldered is 240 ° C or higher. Also,
The thermoplastic resin molded article of the present invention may be a molded article soldered to the substrate under the condition that the surface temperature of the substrate to which the composition is soldered is 260 ° C or higher. Further, the thermoplastic resin molded article of the present invention may be a molded article soldered to the substrate under the condition that the surface temperature of the substrate to which the composition is soldered is 280 ° C or higher. Here, under the condition that the surface temperature of the substrate to which the composition is soldered is 220 ° C. or higher, the composition can be soldered to the substrate without melting or deformation. On the other hand, even under the condition that the surface temperature of the substrate to which the composition is soldered is 240 ° C. or higher, or under the condition that the surface temperature of the substrate to which the composition is soldered is 260 ° C. or higher, and further, the composition is Even when the surface temperature of the substrate to which the product is soldered is 280 ° C. or higher, the composition can be soldered to the substrate without melting or deformation.

The soldering process for obtaining the thermoplastic resin molded article of the present invention includes, for example, a surface mounting method. The heating method in the heating furnace (reflow furnace) in this surface mounting method is as follows. Heat conduction method of heating by placing the substrate on a heat resistant belt that moves on the heater, about 220 ° C
Vapor phase soldering (VPS) method that uses latent heat when a fluorinated liquid with a boiling point of 5 is agglomerated, hot air convection heat transfer method that allows hot air to be forcedly circulated, and upper or lower surfaces of the substrate by infrared rays There are an infrared method of heating from above, a method of using heating by hot air and heating by infrared rays in combination, and any heating method may be used in the present invention. Particularly preferred is a thermoplastic resin molded article obtained by a heating method using infrared rays in the soldering step. The advantages of using the infrared heating method in the soldering process include excellent running cost, maintainability, and short soldering processing time.

By adding polyphenylene ether to the thermoplastic resin (A) used in the present invention, the heat resistance of the molded article is further improved, and the thermoplastic resin molded article of the present invention can be more easily soldered by a soldering step. Can be formed by.

The polyphenylene ether (hereinafter referred to as PPE) used in the present invention can be obtained by polycondensing one or more monocyclic phenols represented by the following general formula [17].

[0083]

[Chemical 20]

(However, R ₁ is an alkyl group having 1 to 3 carbon atoms, R ₂ and R ₃ are hydrogen or an alkyl group having 1 to 3 carbon atoms.) The PPE is a homopolymer. May be a copolymer.

Examples of the monocyclic phenol represented by the above general formula [17] include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol and 2-methyl-6-ethyl. Phenol, 2-
Methyl-6-propylphenol, 2-ethyl-6-propylphenol, m-cresol, 2,3-dimethylphenol, 2,3-diethylphenol, 2,3-dipropylphenol, 2-methyl-3-ethylphenol , 2-methyl-3-propylphenol, 2-ethyl-3-methylphenol, 2-ethyl-3-propylphenol, 2-propyl-3-methylphenol, 2-
Propyl-3-ethylphenol, 2,3,6-trimethylphenol, 2,3,6-triethylphenol,
2,3,6-tripropylphenol, 2,6-dimethyl-3-ethylphenol, 2,6-dimethyl-3-propylphenol and the like can be mentioned.

Examples of the PPE used in the present invention include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,2). 6-dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-
1,4-phenylene) ether, poly (2-methyl-6)
-Propyl-1,4-phenylene) ether, poly (2
-Ethyl-6-propyl-1,4-phenylene) ether, 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol / 2,3,6-triethylphenol copolymer Polymer, 2,6
-Diethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dipropylphenol / 2,
Styrene is added to 3,6-trimethylphenol copolymer, poly (2,6-dimethyl-1,4-phenylene) ether, 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, and the like. Examples thereof include graft-polymerized copolymers. Particularly preferred PPE is poly (2,6-dimethyl-1,4-phenylene) ether or 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer.

The amount of PPE added according to need in the present invention is preferably 0.5 to 50 parts by weight, more preferably 1 part by weight, relative to 100 parts by weight of the thermoplastic resin (A).
~ 30 parts by weight.

As the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride for modifying the PPE used in the present invention, those having a total carbon number of 3 to 10 can be mentioned. Here, the total number of carbons means the number including the carbons derived from the carboxylic acid. Examples of such compounds include maleic acid, fumaric acid, chloromaleic acid, citraconic acid, itaconic acid, and other α, β-unsaturated dicarboxylic acids; acrylic acid, crotonic acid, vinylacetic acid, methacrylic acid, and pentenoic acid. Unsaturated monocarboxylic acids exemplified by Angelica acid; and anhydrides of these α, β-unsaturated dicarboxylic acids and unsaturated monocarboxylic acids. Among these, maleic acid, fumaric acid, acrylic acid, methacrylic acid and maleic anhydride are preferable, and maleic anhydride is the most preferable. Modified PPE
Can be produced, for example, by previously adding a modifier to PPE and melt-kneading.

The amount of the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride used for modifying the PPE in the present invention is PP
It is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of E.

The composition used in the molded article of the present invention includes a plasticizer, a release agent, a colorant, a lubricant, a heat resistance stabilizer, a weather resistance stabilizer, a foaming agent, a rust inhibitor, a flame retardant, An appropriate amount of wax or the like may be added within a range that does not impair the object of the present invention.

The molded article of the present invention is used in electric / electronic, vehicles,
It can be used in a wide range of fields such as home appliances, construction, sanitary, sports and sundries. Specific applications include connectors, switches, sensors, sockets, capacitors, jacks, fuse holders, relays, coil bobbins, resistors, IC and LED housings, gears, bearing retainers, spring holders, chain tensioners, washers, worm wheels. , Belts, filters, various housings, auto tensioners and weight rollers, breaker parts, clutch parts and the like. Among these, it is useful for connectors, switches, sensors, resistors, relays, capacitors, sockets, jacks, fuse holders, coil bobbins, IC and LED housings, etc. for surface mounting systems.

[0092]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the scope of these examples.

[Reference Example 1] Synthesis of thermotropic liquid crystal polyester resin 55.1 g (0.5 mol) of hydroquinone, 4,4'-
Dihydroxybiphenyl 93.1 g (0.5 mol), terephthalic acid 116.3 g (0.7 mol), 2,6-dicarboxynaphthalene 64.9 g (0.3 mol), p-hydroxybenzoic acid 621.5 g ( (4.5 mol) and 612.5 g (6 mol) of acetic anhydride were charged into a reaction vessel equipped with a condenser and a stirrer, the temperature was raised with stirring under a nitrogen gas atmosphere, and the mixture was refluxed at 170 ° C. for 60 minutes. Then, the reaction vessel was gradually raised to 370 ° C. over 4 hours while removing the by-product acetic acid, and the reaction system was further heated to 370 ° C. at 25 kPa.
The pressure was reduced to. Further, the pressure was reduced to 0.5 to 1 kPa over 2 hours while removing acetic acid as a by-product at that temperature to carry out polymerization. Then, polymerization was carried out at 370 ° C. for 1 hour. During this time, while removing acetic acid by-produced, polymerization was performed under strong stirring, and then the system was gradually cooled to 200 ° C.
The polymer obtained in 1. was taken out of the system. The melting point was measured using a differential scanning calorimeter (DSC7 manufactured by Perkin Elmer Co., Ltd.) (in accordance with JIS K 7121), and the melting point was 350.
It was ℃.

[Reference Example 2] Synthesis of maleic anhydride-modified PPE 97 parts by weight of PPE and 3 parts by weight of maleic anhydride were uniformly mixed in a tumbler, and then a twin-screw extruder "TEM-" manufactured by Toshiba Machine Co., Ltd. with a vent was used. 35B "was melt-kneaded to obtain maleic anhydride-modified PPE pellets. Incidentally, PPE
Was poly (2,6-dimethyl-1,4-phenylene) ether, and the intrinsic viscosity of PPE used (measured value at 30 ° C. in chloroform) was 0.45 dl / g.

[Example 1] and [Example 16] PPS (manufactured by Dainippon Ink and Chemicals, Inc., product name: DSP)
60 parts by weight of LR-03G) and 40 parts by weight of aluminum borate powder were uniformly mixed with a tumbler. Next, a twin-screw extruder with a vent made by Toshiba Machine Co., Ltd. "TEM-35B"
Was melt-kneaded to obtain pellets of the composition.

[Example 2] and [Example 17] PPS (manufactured by Dainippon Ink and Chemicals, Inc., product name: DSP)
60 parts by weight of LR-03G) and 40 parts by weight of magnesium borate powder were uniformly mixed with a tumbler. Next, a twin-screw extruder with a vent made by Toshiba Machine Co., Ltd. "TEM-35B"
Was melt-kneaded to obtain pellets of the composition.

[Example 3] and [Example 18] PPS (manufactured by Dainippon Ink and Chemicals, Inc., product name: DSP)
LR-03G) 60 parts by weight and nickel borate powder 40
Parts by weight were uniformly mixed with a tumbler. Then Toshiba Machine
Melt-kneading was performed using a vented twin-screw extruder "TEM-35B" to obtain pellets of the composition.

[Example 4] and [Example 19] PPS (manufactured by Dainippon Ink and Chemicals, Inc., product name: DSP)
60 parts by weight of LR-03G) and 40 parts by weight of aluminum borate fiber were uniformly mixed with a tumbler. Next, a twin-screw extruder with a vent made by Toshiba Machine Co., Ltd. "TEM-35B"
Was melt-kneaded to obtain pellets of the composition.

Example 5 60 parts by weight of PPS (manufactured by Dainippon Ink and Chemicals, Inc., product name: DSP LR-03G)
20 parts by weight of aluminum borate fibers were uniformly mixed with a tumbler. Next, using a twin-screw extruder with a vent made by Toshiba Machine Co., Ltd. "TEM-35B", melt kneading while supplying 20 parts by weight of glass fiber chopped strands having a fiber diameter of 10 µm and a length of 3 mm from the side feeder, A pellet of the composition was obtained.

Example 6 50 parts by weight of PPS (manufactured by Dainippon Ink and Chemicals, Inc., product name: DSP LR-03G)
40 parts by weight of aluminum borate fiber and 10 parts by weight of maleic anhydride-modified PPE extruded in Reference Example 2 were uniformly mixed with a tumbler. Then, the mixture was melt-kneaded using a twin-screw extruder "TEM-35B" manufactured by Toshiba Machine Co., Ltd. to obtain pellets of the composition.

[Example 7] 50 parts by weight of PPS (manufactured by Dainippon Ink and Chemicals, Inc., product name: DSP LR-03G)
30 parts by weight of aluminum borate fiber and 10 parts by weight of maleic anhydride-modified PPE extruded in Reference Example 2 were uniformly mixed with a tumbler. Then, using a twin-screw extruder with a vent manufactured by Toshiba Machine Co., Ltd. "TEM-35B", 10 parts by weight of glass fiber chopped strands having a fiber diameter of 10 µm and a length of 3 mm were melt-kneaded while being supplied from the side feeder. A pellet of the composition was obtained.

[Example 8] 50 parts by weight of PPS (manufactured by Dainippon Ink and Chemicals, Inc., product name: DSP LR-03G)
20 parts by weight of aluminum borate fiber and 10 parts by weight of maleic anhydride-modified PPE extruded in Reference Example 2 were uniformly mixed with a tumbler. Next, using a twin-screw extruder with a vent made by Toshiba Machine Co., Ltd. "TEM-35B", melt kneading while supplying 20 parts by weight of glass fiber chopped strands having a fiber diameter of 10 µm and a length of 3 mm from the side feeder, A pellet of the composition was obtained.

Example 9 50 parts by weight of PPS (manufactured by Dainippon Ink and Chemicals, Inc., product name: DSP LR-03G)
20 parts by weight of aluminum borate fiber and 10 parts by weight of PPE were uniformly mixed with a tumbler. Then Toshiba Machine
Using a vented twin-screw extruder "TEM-35B", a fiber diameter of 10 µm and a length of 3 m from a side feeder.
The glass fiber chopped strand of m was melt-kneaded while supplying 20 parts by weight to obtain pellets of the composition.

Example 10 35 parts by weight of PPS (manufactured by Dainippon Ink and Chemicals, Inc., product name: DSP LR-03G), 20 parts by weight of aluminum borate fiber, maleic anhydride-modified PPE5 extruded in Reference Example 2 20 parts by weight of calcium carbonate powder (produced by Maruo Calcium Co., Ltd.) were uniformly mixed with a tumbler. Next, using a twin-screw extruder with a vent made by Toshiba Machine Co., Ltd. "TEM-35B", melt kneading while supplying 20 parts by weight of glass fiber chopped strands having a fiber diameter of 10 µm and a length of 3 mm from the side feeder, A pellet of the composition was obtained.

[Example 11] 40 parts by weight of PPS (manufactured by Dainippon Ink and Chemicals, Inc., product name: DSP LR-03G), 20 parts by weight of aluminum borate fiber, maleic anhydride-modified PPE20 extruded in Reference Example 2 Parts by weight were uniformly mixed with a tumbler. Next, using a twin-screw extruder with a vent made by Toshiba Machine Co., Ltd. "TEM-35B", melt kneading while supplying 20 parts by weight of glass fiber chopped strands having a fiber diameter of 10 µm and a length of 3 mm from the side feeder, A pellet of the composition was obtained.

[Example 12] and [Example 20] 60 parts by weight of the thermotropic liquid crystal polyester resin synthesized in Reference Example 1 and 40 parts by weight of aluminum borate fiber were uniformly mixed in a tumbler. Then, the mixture was melt-kneaded using a twin-screw extruder "TEM-35B" manufactured by Toshiba Machine Co., Ltd. to obtain pellets of the composition.

[Example 13] and [Example 21] 60 parts by weight of polybutylene terephthalate resin (synthetic product) having a relative viscosity of 0.9, aluminum borate fiber 40
Parts by weight were uniformly mixed with a tumbler. Then Toshiba Machine
Melt-kneading was performed using a vented twin-screw extruder "TEM-35B" to obtain pellets of the composition.

Example 14 Relative viscosity of 2.6 obtained by polymerizing terephthalic acid, hexamethylenediamine, and adipic acid (measurement solvent: 96% sulfuric acid, sample concentration 1 g / d
60 parts by weight of a polyamide resin (synthetic product) having a melting point of 325 ° C. and 40 parts by weight of aluminum borate fibers were uniformly mixed with a tumbler. Next, a twin-screw extruder with a vent made by Toshiba Machine Co., Ltd. "TEM-3
5B ”was melt-kneaded to obtain pellets of the composition.

[Example 15] Aromatic polysulfone resin (manufactured by Sumitomo Chemical Co., Ltd., product name: Sumika Excel PES4)
60 parts by weight of 100P) and 40 parts by weight of aluminum borate fibers were uniformly mixed with a tumbler. Then, the mixture was melt-kneaded using a twin-screw extruder with a vent manufactured by Toshiba Machine Co., Ltd. "TEM-35B" to obtain pellets of the composition.

[Comparative Example 1] and [Comparative Example 7] PPS (manufactured by Dainippon Ink and Chemicals, Inc., product name: DSP)
60 parts by weight of LR-03G) were uniformly mixed with a tumbler. Next, a twin-screw extruder with a vent made by Toshiba Machine Co., Ltd. "T
"EM-35B" was melt-kneaded while supplying 40 parts by weight of glass fiber chopped strands having a fiber diameter of 10 μm and a length of 3 mm from a side feeder to obtain pellets of the composition.

[Comparative Example 2] 50 parts by weight of PPS (manufactured by Dainippon Ink and Chemicals, Inc., product name: DSP LR-03G)
And maleic anhydride-modified PPE1 extruded in Reference Example 2
0 part by weight was uniformly mixed with a tumbler. Next, using a twin-screw extruder “TEM-35B” manufactured by Toshiba Machine Co., Ltd. with a vent, a fiber diameter of 10 μm and a length of 3 from a side feeder.
40 parts by weight of glass fiber chopped strands were melt-kneaded to obtain pellets of the composition.

[Comparative Example 3] and [Comparative Example 8] 60 parts by weight of the thermotropic liquid crystal polyester resin synthesized in Reference Example 1 was used in a twin-screw extruder with a vent manufactured by Toshiba Machine Co., Ltd. "TEM-35B". Then, 40 parts by weight of a glass fiber chopped strand having a fiber diameter of 10 μm and a length of 3 mm was melt-kneaded from a side feeder to obtain pellets of the composition.

[Comparative Example 4] 60 parts by weight of a polybutylene terephthalate resin (synthetic product) having a relative viscosity of 0.9 was mixed with a ventilated twin-screw extruder "TEM-35" manufactured by Toshiba Machine Co., Ltd.
B ”using a side feeder with a fiber diameter of 10 μm,
While supplying 40 parts by weight of glass fiber chopped strands having a length of 3 mm, the mixture was melt-kneaded to obtain pellets of the composition.

[Comparative Example 5] Relative viscosity obtained by polymerizing terephthalic acid, hexamethylenediamine and adipic acid was 2.6 (measurement solvent: 96% sulfuric acid, sample concentration 1 g / d).
1, a measuring temperature of 25 ° C.), and 60 parts by weight of a polyamide resin (synthetic product) having a melting point of 325 ° C. using a vented twin-screw extruder “TEM-35B” manufactured by Toshiba Machine Co., Ltd. Was melt-kneaded while supplying 40 parts by weight of glass fiber chopped strands having a fiber diameter of 10 μm and a length of 3 mm to obtain pellets of the composition.

[Comparative Example 6] Aromatic polysulfone resin (Sumitomo Chemical Co., Ltd., trade name: SUMIKAEXCEL PES41)
00P) 60 parts by weight using a twin-screw extruder with a vent made by Toshiba Machine Co., Ltd. “TEM-35B” while supplying 40 parts by weight of glass fiber chopped strands having a fiber diameter of 10 μm and a length of 3 mm from a side feeder. Melt kneading was performed to obtain pellets of the composition.

Various properties in Examples and Comparative Examples were measured by the following methods. (1) [Method of measuring flexural strength after solder reflow heating] A pellet having a thickness of 1.6 mm was molded by an injection molding machine using the pellet obtained from the composition, and ASTM D7
According to 90, the bending strength after heating was measured. Heating was performed by an infrared reflow device for Examples 1 to 15 and Comparative Examples 1 to 6, and Examples 16 to 21, Comparative Example 7 and Comparative Example 8 were performed.
Was conducted by a hot air convection heat transfer reflow device. As the heating conditions, after preheating at 180 ° C. for 100 seconds, heating and holding were performed under the conditions shown in Table 1 until the surface of the substrate reached the target temperature. For example, if the substrate surface is 280 ° C
In order to reach up to
The temperature profile (temperature curve) is set by the reflow device so that it will be 90 seconds in the area of 220 ° C or more, 80 seconds in the area of 240 ° C or more, and 60 seconds in the area of 260 ° C or more for 2 seconds. To do.

(2) [Appearance evaluation method for molded articles during soldering] Using pellets obtained from the composition, an injection molding machine was used to obtain a shape of 70 mm in length × 10 mm in width × 8 mm in height and 0.
A box-shaped connector having a thickness of 8 mm was molded, and this molded article was placed on a substrate and heated under the same conditions as in the above (1).
The appearance was evaluated by visually observing the box-shaped connector after heating and evaluating it according to the following three-stage criteria. A: No change in appearance is seen. B: Surface roughness is observed. C: Melting and / or deformation is observed.

The results of evaluating the pellets of the compositions obtained in Examples 1 to 21 and Comparative Examples 1 to 8 by the above method are shown in Table 2.
Shown in.

Example 1 is an example in which the PPS resin is used as the thermoplastic resin (A) and the aluminum borate powder is used as the metal borate salt (B) by the infrared heating method. Even if the temperature rises to 280 ° C., the bending strength does not decrease, and no change in appearance is observed.

Example 2 is an example in which the PPS resin is used as the thermoplastic resin (A) and the magnesium borate powder is used as the metal borate salt (B) by the infrared heating method. Even if the temperature rises to 280 ° C., the bending strength does not decrease, and no change in appearance is observed.

Example 3 is an example in which the PPS resin is used as the thermoplastic resin (A) and the nickel borate powder is used as the metal borate salt (B) by the infrared heating method. Even if the temperature rises to 280 ° C., the bending strength does not decrease, and no change in appearance is observed.

In Examples 4 to 11, the PPS resin was used as the thermoplastic resin (A) by the infrared heating method,
This is an example of using aluminum borate fibers as the boric acid metal salt (B), but the bending strength did not decrease even when the surface temperature of the substrate increased to 280 ° C., and no change in appearance was observed.

Example 12 is an example in which an infrared heating system is used, a thermotropic liquid crystal polyester resin is used as the thermoplastic resin (A), and aluminum borate fibers are used as the metal borate salt (B). The bending strength did not decrease even when the surface temperature of the product increased to 280 ° C., and no change in appearance was observed.

Example 13 is an example in which a polybutylene terephthalate resin was used as the thermoplastic resin (A) and aluminum borate fiber was used as the boric acid metal salt (B) in the infrared heating method. Surface temperature is 2
It did not melt even at 60 ° C.

Example 14 is an example in which a polyamide resin is used as the thermoplastic resin (A) and aluminum borate fibers are used as the metal borate salt (B) by the infrared heating method. Even if the temperature rises to 280 ° C., the bending strength does not decrease, and no change in appearance is observed.

Example 15 is an example in which an aromatic polysulfone resin is used as the thermoplastic resin (A) and aluminum borate fibers are used as the metal borate salt (B) by the infrared heating method. Even when the surface temperature was 260 ° C., the phenomenon of softening was not recognized.

Example 16 uses the hot air convection heating method.
Further, this is an example in which a PPS resin is used as the thermoplastic resin (A) and an aluminum borate powder is used as the metal borate salt (B). However, even if the surface temperature of the substrate rises to 280 ° C., the bending strength does not decrease. There was no change in appearance.

Example 17 uses the hot air convection heating method.
Further, this is an example in which a PPS resin is used as the thermoplastic resin (A) and magnesium borate powder is used as the metal borate salt (B). However, even if the surface temperature of the substrate rises to 280 ° C., the bending strength does not decrease. There was no change in appearance.

Example 18 uses the hot air convection heating method.
Further, this is an example in which a PPS resin is used as the thermoplastic resin (A) and nickel borate powder is used as the metal borate salt (B). However, even if the surface temperature of the substrate rises to 280 ° C., the bending strength does not decrease. There was no change in appearance.

Example 19 uses the hot air convection heating method.
Further, this is an example in which a PPS resin is used as the thermoplastic resin (A) and aluminum borate fibers are used as the metal borate salt (B). However, even if the surface temperature of the substrate rises to 280 ° C., the bending strength does not decrease. There was no change in appearance.

Example 20 uses the hot air convection heating method,
In addition, thermotropic liquid crystal polyester resin is used as the thermoplastic resin (A) and aluminum borate fiber is used as the metal borate salt (B), but the bending strength is high even if the surface temperature of the substrate rises to 280 ° C. There is no decrease in
No change in appearance was observed.

Example 21 uses the hot air convection heating method.
Further, in this example, a polybutylene terephthalate resin was used as the thermoplastic resin (A) and aluminum borate fibers were used as the metal borate salt (B), but the substrate did not melt even at a surface temperature of 260 ° C.

Comparative Examples 1 and 2 are examples in which the PPS resin is used as the thermoplastic resin (A) and the boric acid metal salt (B) is not used by the infrared heating method, but the surface temperature of the substrate is In particular, the bending strength was lowered at 220 ° C. or higher, and the surface roughness was observed in appearance especially at 260 ° C. or higher.

Comparative Example 3 is an example in which an infrared heating method is used and a thermotropic liquid crystal polyester resin is used as the thermoplastic resin (A) and the metal borate salt (B) is not used. The bending strength decreased at 220 ° C. or higher, and the surface was observed to be rough especially at 280 ° C. in appearance.

Comparative Example 4 is an example in which the polybutylene terephthalate resin is used as the thermoplastic resin (A) and the metal borate salt (B) is not used by the infrared heating method, but the surface temperature of the substrate is 220 ° C. It was observed that the bending strength was significantly lowered below and the surface temperature of the substrate melted at 220 ° C.

Comparative Example 5 is an example in which the polyamide resin is used as the thermoplastic resin (A) and the metal borate salt (B) is not used by the infrared heating method, but the surface temperature of the substrate is particularly 220 ° C. or more. The bending strength was decreased, and the surface was observed to have surface roughness especially at 280 ° C.

Comparative Example 6 is an example in which the aromatic polysulfone resin is used as the thermoplastic resin (A) and the metal borate salt (B) is not used by the infrared heating method, but the surface temperature of the substrate is 220 ° C. A phenomenon of softening and fluidization was observed at.

Comparative Example 7 is an example in which the PPS resin is used as the thermoplastic resin (A) and the boric acid metal salt (B) is not used by the hot air convection heating method, but the surface temperature of the substrate is particularly 220 ° C. In the above, the bending strength decreased, and the surface was observed to have a rough surface, particularly at 260 ° C or higher.

Comparative Example 8 is an example in which the hot air convection heating method is used and the thermotropic liquid crystal polyester resin is used as the thermoplastic resin (A) and the metal borate salt (B) is not used. In particular, the bending strength was lowered at 220 ° C. or higher, and the surface was observed to be rough at 280 ° C. in appearance.

[0140]

[Table 1]

[0141]

[Table 2]

[0142]

[Table 3]

[0143]

[Table 4]

[0144]

[Table 5]

[0145]

INDUSTRIAL APPLICABILITY The thermoplastic resin molded article of the present invention has excellent heat resistance, and changes in strength of the molded article on the substrate after the soldering process even if the substrate to be soldered is exposed to high temperatures. , And the change in appearance is very small, and it is particularly effective for soldering method on the printed circuit board in the surface mounting method (surface mounting method; SMT method) of electronic parts such as connectors, switches, relays, coil bobbins in the electric and electronic fields. is there.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4F071 AA43 AA51 AA54 AA62 AA64                       AB27 AF17 AF21 AH07 AH12                       BA01 BB05 BC03 BC07                 4J002 CF031 CF041 CF051 CF061                       CF071 CF181 CL001 CL011                       CL031 CN011 CN031 DK006                       FA046 FA086 FD010 FD016                       GN00 GQ00

Claims (14)

[Claims] 1. A thermoplastic resin molded article comprising a composition comprising at least component (A) and component (B),
The component (A) is at least one thermoplastic resin having a melting point or a glass transition point of 220 ° C. or higher, the component (B) is a metal borate, and the surface temperature of the substrate to which the composition is soldered. A thermoplastic resin molded article, which is soldered to the substrate under the condition that the temperature is 220 ° C. or higher. 2. A thermoplastic resin molded article comprising a composition comprising at least component (A) and component (B).
The component (A) is at least one thermoplastic resin having a melting point or a glass transition point of 220 ° C. or higher, the component (B) is a metal borate, and the surface temperature of the substrate to which the composition is soldered. A thermoplastic resin molded article, which is soldered to the substrate under the condition that the temperature is 240 ° C. or higher. 3. A thermoplastic resin molded article comprising a composition comprising at least component (A) and component (B),
The component (A) is at least one thermoplastic resin having a melting point or a glass transition point of 220 ° C. or higher, the component (B) is a metal borate, and the surface temperature of the substrate to which the composition is soldered. A thermoplastic resin molded article, which is soldered to the substrate under the condition that the temperature is 260 ° C. or higher. 4. A thermoplastic resin molded article comprising a composition comprising at least component (A) and component (B).
The component (A) is at least one thermoplastic resin having a melting point or a glass transition point of 220 ° C. or higher, the component (B) is a metal borate, and the surface temperature of the substrate to which the composition is soldered. A thermoplastic resin molded article, which is soldered to the substrate under the condition that the temperature is 280 ° C. or higher. 5. The thermoplastic resin (A) is at least one selected from the group consisting of polyarylene sulfide resin, thermotropic liquid crystal polyester resin, polyalkylene terephthalate resin, polyamide resin, and aromatic polysulfone resin. 5. The thermoplastic resin molded article according to any one of items 4 to 4. 6. The thermoplastic resin molded article according to any one of claims 1 to 4, wherein the thermoplastic resin (A) is a polyphenylene sulfide resin. 7. The thermoplastic resin molded article according to claim 1, wherein the metal element contained in the metal borate salt (B) has a valence of 1 to 3. 8. The thermoplastic resin molded article according to any one of claims 1 to 6, wherein the boric acid metal salt (B) is aluminum borate. 9. The composition containing at least the component (A) and the component (B) further containing a fibrous reinforcing material (C-1) and / or an inorganic filler (C-2). 8
The thermoplastic resin molded article according to any one of 1. 10. The thermoplastic resin molded article according to claim 1, further comprising a silane compound (D) in the composition containing at least the component (A) and the component (B). . 11. A heating method according to at least one selected from the group consisting of an infrared method, a hot air method, a heat conduction method, and a vapor phase soldering (VPS) method, as a heating method in the soldering step. 10. The thermoplastic resin molded article according to any one of 10. 12. The thermoplastic resin molded article according to any one of claims 1 to 10, wherein an infrared method is used as a heating method in the soldering step. 13. The thermoplastic resin molded article according to claim 1, which comprises a polyphenylene ether. 14. The polyphenylene ether is a polyphenylene ether modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride having a total carbon number of 3 to 10 (the total carbon number includes a carbon number derived from a carboxylic acid). The thermoplastic resin molded article according to claim 13.