JP2003305780A - Method for manufacturing heat-resistant molded resin article and soldering method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a heat-resistant molded resin product which shows a modulus of elasticity and a heat resistance in a high temperature area and reduces strength and appearance changes in a molded article on a base after a soldering step, even when the base to be soldered is exposed to a high temperature. <P>SOLUTION: A resin composition contains a polyarylenesulfide resin (A) and an aromatic polyester (B) having a specific polyester structural unit, and further, if necessary, a silane compound. This composition is molded in a molten state to form a molten molded article which is, in turn, heat-treated to manufacture a heat-resistant resin molded product. Also the soldering method is provided. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a heat-resistant resin molded article, which comprises melt-molding and heat-treating a resin composition containing a polyarylene sulfide resin and an aromatic polyester resin having a specific structure. Since the obtained heat-resistant molded article is excellent in heat resistance, rigidity and the like, it is suitably used for precision parts, various electric / electronic parts, mechanical parts, automobile parts and the like.

[0002]

2. Description of the Related Art Polyarylene sulfide resins typified by polyphenylene sulfide resins have a high melting point, excellent flame retardancy and chemical resistance, and have good flowability during molding. It is widely used as an engineering plastic in various electronic parts, mechanical parts, and automobile parts.

In recent years, in the field of electric and electronic industries,
With the miniaturization of products and the improvement of productivity, surface mounting method for resin-based electronic parts (surface mounting method) (hereinafter SMT
Method), a method of soldering on a printed circuit board has been adopted. 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.
Both of them have higher melting points than tin-lead eutectic solder (for example, melting point 220 ° C. in the case of tin-silver eutectic solder), and therefore the temperature of the heating furnace (reflow furnace) must be further increased during surface mounting. As a result, when the SMT method is used for soldering, when the resin-based molded article such as the connector is passed through the soldering heating furnace (reflow furnace), the molded article may melt or deform. There is a strong demand in this field for molded articles having higher heat resistance.

In order to improve the heat resistance of polyarylene sulfide resins, for example, Japanese Patent No. 3194385 discloses various polymers, namely polyphenylene ether,
A technique of heat-treating a molded product obtained by melt-kneading polysulfone, polycarbonate, polyarylate, polyetherimide and the like and a polyarylene sulfide resin has been reported. However, although these methods can slightly improve the decrease in heat resistance and elastic modulus at high temperatures,
The degree thereof is extremely small, and for example, it does not satisfy the level required for the above-mentioned surface mounting compatible parts.

Further, a technique of blending a polyarylene sulfide resin with an aromatic polyester is disclosed in JP-A-53-53.
It is described in Japanese Patent Publication No. 57255. However, this publication does not describe the heat treatment as described in the present invention. Further, this technique can improve impact resistance and heat resistance, but the degree thereof is still insufficient, and it has not reached the level required for surface mountable components and the like.

[0006]

DISCLOSURE OF THE INVENTION The problem to be solved by the present invention is to provide a heat resistance containing a polyarylene sulfide resin in which the elastic modulus and heat resistance of the polyarylene sulfide resin in a high temperature range are drastically improved. To provide a resin molded article, a method for producing a heat resistant molded article having excellent heat resistance even under high temperature conditions in a heating furnace (reflow furnace) during surface mounting, and a soldering method for the heat resistant molded article. It is in.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a composition containing a polyarylene sulfide resin and an aromatic polyester having a polyester structural unit having a specific structure is heat treated. By doing so, it is possible to obtain a heat-resistant resin molded article that has better heat resistance and higher elastic modulus in the high temperature range than before, and has excellent heat resistance even during surface mounting and under high temperature conditions in a heating furnace (reflow furnace). Found that a molded article having properties is obtained,
The present invention has been completed.

That is, the present invention relates to a polyarylene sulfide resin (A) and a compound represented by the general formula (1)

[Chemical 3] (In the formula, Ar is an aromatic ring or a heterocycle. Y is an alkylene group having 1 to 8 carbon atoms, an oxygen atom, a sulfur atom,
A linking group in which a nitrogen atom or a hetero atom thereof and a carbon atom are bonded. Further, n is a repeating unit and is an integer. R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, and may be the same or different, and at least one of them has 1 to 8 carbon atoms. Is an alkyl group. ) And / or general formula (2)

[Chemical 4] (In the formula, Ar is an aromatic ring or a heterocycle. N is a repeating unit and is an integer. R ¹ , R ² , R ³ and R ⁴ are
A hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
They may be the same as or different from each other. ), A resin composition comprising an aromatic polyester (B) having a polyester structural unit represented by the formula (1) is melt-molded, and the resulting melt-molded product is heat-treated, which is a method for producing a heat-resistant resin molded article. Is provided. The present invention also provides the above heat-resistant resin molded article, wherein the surface temperature of the substrate is 2
The present invention provides a method for soldering a heat-resistant molded article, which comprises soldering to the substrate under conditions of 80 ° C or higher.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION First, a method for producing a heat-resistant resin molded article according to the present invention is a polyarylene sulfide resin (A).
And the aromatic polyester (B) having a specific structure are melt-molded, and the resulting melt-molded product is heat-treated.

The polyarylene sulfide resin (A) [hereinafter referred to as PAS resin (A)] used in the present invention contains a repeating unit having a structure in which an aromatic ring which may have a substituent and a sulfur atom are bonded. A random copolymer,
It is a block copolymer, and a mixture thereof or a mixture with a homopolymer. Typical examples of the above random copolymers and block copolymers include polyphenylene sulfide (hereinafter referred to as PPS), polyphenylene sulfide ketone, polyphenylene sulfide sulfone,
Examples thereof include polyphenylene sulfide ketone sulfone. Among the PAS resins (A), it is preferable that the bond of the sulfur atom to the aromatic ring in the repeating unit be a structure bonded to the para position of the aromatic ring in terms of heat resistance and crystallinity.

The PAS resin (A) used in the present invention is P
PS is preferred, and in particular, the following general formula (3)

[0012]

[Chemical 5] PPS containing 70 mol% or more of the structural unit represented by (not containing a substituent in the aromatic ring) is preferable from the viewpoints of physical properties and economical efficiency of the obtained molded article. If the amount is 70 mol% or more, a molded article having excellent properties can be obtained.

As a method of manufacturing PPS, for example, N
-A method of reacting sodium sulfide with p-dichlorobenzene in an amide solvent such as methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane, p
-A method of polymerizing 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-chlorothio. Examples include a method by self-condensation of phenol. In the present invention, among these methods, sodium sulfide and p are added in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane.
-The method of reacting dichlorobenzene is preferred. At this time, it is preferable 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.

The PPS used in the present invention may contain a bonding structural unit as shown below as a copolymerization component as long as the crystallinity of the polymer is not significantly affected. Examples of such a bond structural unit include those represented by the general formula (4)

[0015]

[Chemical 6] The meta-bond structural unit represented by the general formula (5)

[0016]

[Chemical 7] An ether bond structural unit represented by the general formula (6)

[0017]

[Chemical 8] A sulfone bond structural unit represented by the general formula (7)

[0018]

[Chemical 9] A ketone bond structural unit represented by the general formula (8)

[0019]

[Chemical 10] A biphenyl bond structural unit represented by the general formula (9)

[0020]

[Chemical 11] (In the formula, R represents an alkyl group, a nitro group, a phenyl group or an alkoxy group.), A substituted phenyl sulfide bond structural unit represented by the general formula (10).

[0021]

[Chemical 12] A trifunctional phenyl sulfide bond structural unit represented by the general formula (11)

[0022]

[Chemical 13] And a naphthyl bond structural unit represented by. If these bond structural units are less than 30 mol%, PPS
However, the content of these structural units is preferably 10 mol% or less. In particular, when a phenyl bond or a naphthyl sulfide bond having three or more functional groups is selected as the copolymerization component, it is preferably 3 mol% or less, and particularly preferably 1 mol% or less.

The PAS resin (A) used in the present invention preferably has a substantially linear structure in terms of mechanical strength of a molded product, compatibility with an aromatic polyester resin, and the like. “Substantially having a linear structure” means that the linear structure is the main component, but it may have a partially crosslinked structure as long as the performance such as the mechanical strength is not impaired. This PAS resin having a substantially linear structure can be produced by the production method described in JP-B-52-12240. That is, p-dihalogenbenzene is reacted with a mixture in contact with a sulfur source such as an alkali metal sulfide or an alkali metal persulfide, an alkali metal carboxylic acid, or an organic amide.

The above-mentioned PAS resin having a substantially linear structure, which is washed after the acid treatment, can reduce the amount of residual metal ions, improve the moisture resistance property, and by-product during the polymerization. It is particularly preferable in that the amount of remaining low molecular weight impurities can be reduced. The acid used for this acid treatment is not particularly limited as long as it has no action of decomposing the PAS resin, and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. Of these, acetic acid and hydrochloric acid are preferred. As the method of acid treatment,
Although there is a method of immersing the PAS resin in an acid or an acid aqueous solution, it can be further stirred or heated if necessary.

Acetic acid was used as the acid and P was used as the PAS resin.
The method using PS will be described more specifically. First pH
The acetic acid aqueous solution of No. 4 was heated to 80 to 90 ° C.
Immerse S and stir for 30 minutes. By performing this operation, the effect of reducing the amount of residual metal ions and the amount of low-molecular weight impurities remaining can be obtained. The acid-treated PPS is washed several times with water or warm water in order to physically remove the remaining acid or salt. The water used at this time is preferably distilled water or deionized water.

As PPS used for the above acid treatment, P
It is also possible to use PS particles. The PPS powder may be in the form of pellets, or may be in a slurry state after polymerization.

P used in the heat-resistant resin molded article of the present invention
As PS, especially under a load of 316 ° C./5000 g according to ASTM D1238-86 (orifice: 0.082
(5 ± 0.002 inch diameter × 0.315 ± 0.001 inch length) preferably has a melt flow rate of 300.
It is preferably 0 g / 10 minutes or less, more preferably 1500 g / 10 minutes or less.

Next, the aromatic polyester (B) used in the present invention has the general formula (1)

[0029]

[Chemical 14] And / or general formula (2)

[0030]

[Chemical 15] Is an aromatic polyester having a polyester structural unit represented by:

In the general formula (1), Ar is an aromatic ring or a heterocycle. Specific examples of this Ar include a benzene ring, naphthalene ring, 9-oxofluorene ring, anthracene ring, anthraquinone ring, biphenylene group, terphenyl group, quaterphenyl group, azobenzene group, furan ring, thiophene ring, 4H-pyran ring, 4-oxo-
4H-pyran ring, dibenzofuran ring, dibenzothiophene ring, xanthene ring, dibenzodioxin ring, phenoxathiine ring, thianthrene ring, pyrrole ring, indole ring, carbazole ring, pyrazole ring, imidazole ring,
Examples thereof include those having an aromatic ring or a heterocyclic structure such as a pyridine ring, a quinoline ring, a bipyridine ring and a pyrimidine ring.

Y is an alkylene group having 1 to 8 carbon atoms, an oxygen atom, a sulfur atom, a nitrogen atom or a connecting group in which a hetero atom of these is bonded to a carbon atom, and the mechanical strength of the molded article, PAS From the viewpoint of compatibility with resins and the like, an alkylene group having 1 to 8 carbon atoms is preferable. Also,
n is the number of repeating units and is an integer, but n is 20
It is preferably ˜2000.

R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms and may be the same or different, and at least one of them has a carbon atom number. It is an alkyl group having 1 to 8 carbon atoms, but from the viewpoint of improving mechanical properties and heat resistance, all are preferably alkyl groups having 1 to 8 carbon atoms, and among them, a methyl group having 1 carbon atom. Is particularly preferable.

In the general formula (2), Ar and n are general formulas.
Same as (1). R¹, R^Two, R ^ThreeAnd R^FourIs water
An elementary group or an alkyl group having 1 to 8 carbon atoms,
They may be the same or different, but mechanical properties and heat resistance
All of them are alkyl groups having 1 to 8 carbon atoms in order to improve the property.
Is preferred, of which the number of carbon atoms is 1.
A methyl group is particularly preferred.

The aromatic polyester (B) used in the present invention is generally obtained from an aromatic dicarboxylic acid and an aromatic diol, and has a polyester structure in the general formula (1) and the general formula (2) in the molecule. It has a unit.
The aromatic polyester (B) of the present invention only needs to have the polyester structural unit having the above structure, and may have other structural units as long as the effects of the present invention are not impaired. The aromatic polyester (B) used in the present invention preferably has a weight average molecular weight of 10,000 to 1,
, 000,000.

Examples of the aromatic dicarboxylic acid component constituting the above aromatic polyester structural unit include phthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 9-oxofluorenedicarboxylic acid, anthracene dicarboxylic acid, anthraquinone dicarboxylic acid, biphenylenedicarboxylic acid. Acid, terphenyldicarboxylic acid, quaterphenyldicarboxylic acid, azobenzenedicarboxylic acid, furandicarboxylic acid, thiophenedicarboxylic acid, 4H-pyrandicarboxylic acid, 4-oxo-4H-pyrandicarboxylic acid, dibenzofurandicarboxylic acid, dibenzothiophenedicarboxylic acid, Xanthene dicarboxylic acid, dibenzodioxin dicarboxylic acid, phenoxathiine dicarboxylic acid, thianthrene dicarboxylic acid, pyrrole dicarboxylic acid, indole dicarboxylic acid, carboxylic acid Ba tetrazole dicarboxylic acid, pyrazole dicarboxylic acids, imidazole dicarboxylic acid, pyridine-dicarboxylic acid, quinoline dicarboxylic acid, bipyridine dicarboxylic acids include dicarboxylic acids such as pyrimidine dicarboxylic acid. The carboxylic acids also include acid ester derivatives, acid anhydrides, acid halides and the like.

Of these carboxylic acid components, isophthalic acid, terephthalic acid and their derivatives, acid anhydrides, acid halides and the like are preferable, and these carboxylic acids can be used alone or in combination. The compounding ratio of these is preferably 5 to 100: 95 to 0 and more preferably 60 to 100: 40 to 0 in terms of molar ratio of isophthalic acids and terephthalic acids (isophthalic acids: terephthalic acids). .

On the other hand, as the aromatic diol component constituting the aromatic polyester structural unit of the present invention, for example, 4,
4'-biphenol, 3,3 ', 5,5'-tetraalkyl- (1,1'-biphenyl) -4,4'-diol
(Alkyl group has 1 to 8 carbon atoms), 3,3'-dialkyl- (1,1'-biphenyl) -4,4'-diol (alkyl group has 1 to 8 carbon atoms), 3- Alkyl-
(1,1'-biphenyl) -4,4'-diol (alkyl group has 1 to 8 carbon atoms), 2,2'-bis (4-
Hydroxy-3-methylphenyl) propane, 2,2 '
-Bis (4-hydroxy-3-ethylphenyl) propane, α, α'-bis (4-hydroxy-3,5-dimethylphenyl) -1,4-diisopropylbenzene, bis (4-hydroxy-3-methylphenyl) ) Methane, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) sulfide, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, 4, 4'-dihydroxy-
3,3′-dimethylazobenzene, 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylbenzophenone and the like can be mentioned.

Of these, 3,3 ', 5,5'-tetraalkyl- (1,1'-biphenyl) -4,4'-diol (wherein the alkyl group has 1 to 8 carbon atoms) is preferable,
3,3 ', 5,5'-Tetramethyl- (1,1'-biphenyl) -4,4'-diol is particularly preferred.

The aromatic polyester (B) used in the present invention can be produced by a conventionally known polymerization method.
For example, (1) after dissolving an aromatic dicarboxylic acid dihalide and an aromatic diol in two types of solvents that are incompatible with each other,
An interfacial polymerization method in which two liquids are mixed and stirred in the presence of an alkali and a catalytic amount of a quaternary ammonium salt to carry out a polycondensation reaction, (2) an aromatic dicarboxylic acid dihalide and an aromatic diol are used as a tertiary amine, etc. Solution polymerization method of reacting in an organic solvent in the presence of an alkaline compound which accepts the acid of
(3) Aromatic dicarboxylic acid and aromatic diester, or
Examples of the method include a melt polymerization method in which an aromatic dicarboxylic acid diester and an aromatic diol are used as raw materials, and a transesterification reaction is performed in a molten state. An aromatic polyester obtained by any of the above methods can also be used.

The heat-resistant resin molded article obtained by the production method of the present invention is melt-molded by mixing the above-mentioned PAS resin (A) and aromatic polyester (B) by a conventionally known method (resin composition). Then, it is obtained by heat treatment.

The mixing ratio of the PAS resin (A) and the aromatic polyester (B) at the time of the above mixing is PAS resin (A) 9
Aromatic polyester (B) based on 9.9 to 20 parts by weight
It is preferably 0.1 to 80 parts by weight, and 5 to 50 parts by weight of the PAS resin (A) aromatic aromatic polyester 5 to
Particularly preferred is 50 parts by weight. When the blending amount of the aromatic polyester (B) is within the above range, the heat resistance of the heat resistant resin molded article of the present invention is further improved.

The resin composition obtained by mixing the PAS resin (A) and the aromatic polyester (B) may contain a silane compound (C). Examples of the silane compound (C) include aminoalkoxysilane, epoxyalkoxysilane, and vinylalkoxysilane, and one or more of these can be used. Of these, aminoalkoxysilanes are particularly preferable from the viewpoint of improving mechanical properties and heat resistance.

As such an aminoalkoxysilane,
Have one or more amino groups in one molecule and two alkoxy groups
Any silane compound having at least one can be used, and specifically, 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,
Examples thereof include N-phenyl-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 can be used. Specifically, for example, , Γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and the like.

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

The amount of the silane compound (C) used in the present invention is 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of the PAS resin (A) and the aromatic polyester (B). It is preferably 0.1 to 2 parts by weight, and particularly preferably 0.1 to 2 parts by weight.

As the resin composition used in the present invention, in addition to the above PAS resin (A), aromatic polyester (B), silane compound (C), fibrous reinforcing material (D-1) and / or inorganic substance. You may contain a filler (D-2). Examples of the fibrous reinforcing material (D-1) include glass fiber, PAN-based or pitch-based carbon fiber, silica fiber,
Inorganic fibrous material of silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, aluminum borate fiber, potassium titanate fiber, and fibrous metal such as stainless steel, aluminum, titanium, copper and brass. Examples thereof include substances and organic fibrous substances such as aramid fibers. Examples of the inorganic filler (D-2) include silicates such as mica, talc, wollastonite, sericite, kaolin, clay, bentonite, asbestos, alumina silicate, zeolite, pyrophyllite, calcium carbonate, and magnesium carbonate. ,
Carbonates such as dolomite, sulfates such as calcium sulfate and barium sulfate, metal oxides such as alumina, magnesium oxide, silica, zirconia, titania and iron oxide,
Examples thereof include glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate and the like. These fibrous reinforcing materials (D-1) and inorganic fillers (D-2) may be used alone or in combination of two or more kinds.

Fibrous reinforcing material (D-1) used in the present invention
The amount of the inorganic filler (D-2) and / or the inorganic filler (D-2) can be used within a range that does not impair the performance of the heat-resistant resin molded article of the present invention, and the PAS resin (A) and the aromatic polyester (B) are mixed. Preferably 3 per 100 parts by weight of total
To 400 parts by weight. In addition, fibrous reinforcement (D-
1) and / or the inorganic filler (D-2) is surface-treated with a surface treatment agent such as a silane coupling agent or a titanium coupling agent within a range that does not impair the performance of the heat-resistant resin molded article of the present invention. It may be one.

The resin composition used in the present invention includes
An appropriate amount of a plasticizer, a mold release agent, a colorant, a lubricant, a heat resistance stabilizer, a weather resistance stabilizer, a foaming agent, an anticorrosive agent, a flame retardant, a wax, etc. may be added without departing from the object of the present invention. .

Further, the resin composition used in the present invention may be mixed with the following polymers in a range not impairing the object of the present invention. Such polymers include ethylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester,
(Meth) homopolymers or copolymers of monomers such as acrylonitrile, polyurethanes, polyamides, polyesters such as polybutylene terephthalate / polyethylene terephthalate, polyacetals, polycarbonates, polysulfones, Polyallyl sulfone, polyethylene tersulfone, polyphenylene ether, polyether ether ketone, polyether ether ketone, polyimide, polyamide imide, polyether imide, silicone resin, epoxy resin, phenoxy resin, liquid crystal polymer, polyaryl ether Examples thereof include homopolymers such as ter, random copolymers or block copolymers, and graft copolymers.

The melt molding of the above resin composition can be carried out by various known methods. For example, PAS resin, aromatic polyester, fiber reinforcing material and / or inorganic filler, silane compound, etc., which are optionally added, are uniformly mixed in a tumbler or a Henschel mixer, and then mixed into a uniaxial or biaxial extruder. A method of supplying and melt-kneading, pelletizing, and then subjecting this to a molding machine and melt-molding this, is preferable, and this method is preferable.

Examples of the melt molding method include injection molding, extrusion molding, compression molding and the like. Of these, injection molding is particularly preferable.

The method for producing a heat-resistant molded article of the present invention is characterized by heat-treating the melt-molded article obtained above. The conditions of the heat treatment cannot be unconditionally specified because they vary depending on the compounding ratio of the resin, etc., but the heat treatment temperature is usually from the melting point of the polyarylene sulfide resin (A) minus 5 to the melting point minus 100 ° C., preferably the melting point minus It is 10 to minus 85 ° C. The melting point here is a differential scanning calorimeter (DSC7 manufactured by Perkin Elmer).
Is measured according to JIS K 7121. Although the heat treatment time varies relatively depending on the heat treatment temperature, it is usually preferably 1 minute or more and 100 hours or less. There is no particular upper limit for the heat treatment time, but 1
000 hours or less is preferable.

The heat treatment method for the heat-resistant resin molded article is not particularly limited, but for example, a method of heating for a predetermined time in a heating device kept at a predetermined temperature is suitable.
The heating device is not particularly limited, and examples thereof include a heat circulation type electric oven.

The heat-resistant resin molded article obtained by the production method of the present invention is excellent in heat resistance and elastic modulus in a high temperature range.

The heat-resistant resin molded article obtained by the present invention is
Since it has the above-mentioned performance, it can be preferably used for a soldered molded product. In this soldering method, the surface temperature of the substrate is 2
It is to be soldered to the substrate under the condition of 80 ° C. or higher. Conventionally, molded articles made of PAS resin have been melted or deformed under the condition that the surface temperature of the substrate to be soldered is 280 ° C. or higher. However, the heat-resistant resin molded article used in the present invention is soldered. Even under the condition that the surface temperature of the substrate is 280 ° C. or higher, the molded article can be soldered to the substrate without melting or deformation.

The above-mentioned surface temperature of the substrate to be soldered means the temperature on the surface of the substrate actually measured in the soldering step in the SMT method. Specific examples of the base include a printed circuit board and a circuit board in the SMT method.

Examples of the soldering step for obtaining the heat-resistant resin molded article of the present invention include the SMT method described above. This SMT heating furnace (reflow furnace)
The heating method in the inside is a heat conduction method in which a substrate is placed on a heat-resistant belt moving on a heater and heated, about 220
Vapor phase soldering (VPS) method that uses latent heat at the time of coagulation of a fluorine-based liquid having a boiling point of ℃, hot air convection heat transfer method that allows hot air to be circulated forcibly, and infrared rays above or below the substrate There are an infrared method of heating from both sides, a method of using heating by hot air and a heating of infrared rays in combination, and any heating method may be used in the present invention, but the heating method by infrared rays is particularly preferable. The advantages of using the heating method using infrared rays include excellent running cost, excellent maintainability, and short soldering processing time.

The heat-resistant resin molded article obtained by the production method of the present invention can be used in a wide variety of fields such as electric / electronics, vehicles, home appliances, construction, sanitary, sports and sundries. Specific applications include connectors, switches,
Sensor, socket, condenser, jack, fuse holder, relay, coil bobbin, resistor, IC and L
ED housing, gear, bearing retainer, spring holder, chain tensioner, washer,
Worm wheels, belts, filters, various housings, auto tensioners and weight rollers, breaker parts, clutch parts and the like. Among these, surface mount compatible connectors, switches,
Sensors, resistors, relays, capacitors, sockets,
Jack, fuse holder, coil bobbin, IC and L
It is useful for ED housings and the like.

[0061]

The present invention will be described in more detail with reference to the following examples.

Various measuring methods and evaluation criteria in Examples and Comparative Examples are as follows. (1) [Dynamic Viscoelasticity] The pellets obtained in the examples described later were molded by using an injection molding machine to obtain a test piece having a length of 20 mm × a width of 10 mm and a thickness of 2 mm. Then, for this test piece, Table-1, Table-2,
After performing heat treatment under the conditions shown in Table 3 and Table 4, a dynamic viscoelasticity measuring device (DM manufactured by Seiko Instruments Inc.
S6100) at a frequency of 1 Hz and a temperature rising rate of 4 ° C / min, and is measured in a temperature range of 20 ° C to 250 ° C.
Temperature dependence of storage elastic modulus (E ') (30 ° C, 80 ° C, 1
30 ° C, 180 ° C) was determined.

(2) [Flexural strength and flexural elongation at break after solder reflow heating] The pellets obtained in the examples described below were molded using an injection molding machine to obtain test pieces having a thickness of 1.6 mm. Next, after subjecting this test piece to a heat treatment under the conditions shown in Table-1, Table-2, Table-3 and Table-4, the bending strength and bending rupture elongation after solder reflow heating were measured according to ASTM D790. did. Reflow heating was performed with an infrared reflow device (TPF-2 manufactured by Asahi Engineering Co., Ltd.). As heating conditions at this time, after preheating at 180 ° C. for 100 seconds, heating and holding were performed until the surface of the substrate reached 280 ° C. That is, the temperature profile (temperature curve) is reflowed so that the temperature is 100 seconds at 200 ° C. or higher, 90 seconds at 220 ° C. or higher, 80 seconds at 240 ° C. or higher, and 60 seconds at 260 ° C. or higher. The settings were made by, and heating and holding were performed.

(3) [Appearance of molded article at the time of soldering] The pellets obtained in the examples described below were molded using an injection molding machine, and the shape was 70 mm in length × 10 mm in width × 8 mm in height.
A 0.8 mm thick box connector was created. Next, after heat-treating this box-shaped connector, it was placed on a printed board and heated under the same conditions as in (2) above. The appearance was evaluated by visually observing the box-shaped connector after heating and evaluating it according to the following two-stage criteria. A: No change in appearance is seen. B: Surface roughening or melting is observed.

(4) [Melt Flow Rate] The PPS used in the examples described below was used as it was according to ASTM D1.
According to 238-86, under 316 ° C / 5000g load (orifice: 0.0825 ± 0.002 inch diameter x
The melt flow rate was measured using a melt indexer (ASTM-C manufactured by Toyo Seiki Co., Ltd.) of 0.315 ± 0.001 inch).

[Synthesis 1] (Synthesis of Aromatic Polyester) 3,3 ′, 5, was added to a polymerization apparatus equipped with a stirring blade and a nitrogen inlet.
5'-tetramethyl-1,1'-biphenyl-4,4 '
-Lol containing 2.42 Kg of diol (10.0 mol) and 50 g of metacresol, 1.0 Kg of sodium hydroxide
Was dissolved in deoxygenated water to obtain an aqueous solution. Separately, 64 g of tetrabutylammonium bromide, 1.62 Kg of isophthalic acid chloride (8.0 mol) and 0.41 Kg of terephthalic acid chloride (2.0 mol) were dissolved in 5 L of dichloromethane to obtain an organic solution. The organic solution was added while stirring the aqueous solution under a nitrogen stream, the stirring was continued at 25 ° C. for 30 minutes, and then the aqueous phase was removed. The organic solution phase containing the product was repeatedly washed with distilled water, poured into an acetone bath to obtain a precipitate, and further washed with acetone to obtain an aromatic polyester. Then, in a vacuum dryer at 200 ° C for 3 hours, about 10
It was vacuum dried under a reduced pressure condition of Pa to obtain 3.2 kg of aromatic polyester. This aromatic polyester is hereinafter referred to as PA
Called R-1.

[Synthesis Example 2] (Synthesis of Aromatic Polyester) 3,3 ′, 5,5′-tetramethyl-in Synthesis Example 1
Instead of 1,1′-biphenyl-4,4′-diol,
4,4'-biphenol 1.86 Kg (10.0 mol)
Was used to perform an operation similar to that in Synthesis Example 1 to obtain an aromatic polyester. This aromatic polyester is hereinafter referred to as PAR-2.
Say.

[Synthesis Example 3] (Synthesis of Aromatic Polyester) 3,3 ′, 5,5′-tetramethyl-in Synthesis Example 1
Instead of 1,1′-biphenyl-4,4′-diol, 4,4′-isopropylidene bis (2,6-dimethylphenol) 2.84 kg (10.0 mol) was used, and Synthesis Example 1 was used. The same operation as above was performed to obtain an aromatic polyester. This aromatic polyester is hereinafter referred to as PAR-3.

[Examples 1 to 16] and [Comparative Examples 1 to 8] First, PPS and the aromatic polyester were uniformly tumbled in the ratios shown in Table-1, Table-2, Table-3 and Table-4. Mixed in. Then, using a twin-screw extruder with a vent made by Toshiba Machine Co., Ltd. "TEM-35B", 40 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 with respect to 60 parts by weight of the above mixture. While being supplied, the mixture was melt-kneaded at 310 ° C. to obtain pellets of the composition. Then, using the pellets obtained from the composition, test pieces for dynamic viscoelasticity measurement and bending strength measurement were produced, and after heat treatment, storage elastic modulus (E ′) on the PPS side after solder reflow heating was produced. 2) temperature dependence (30 ° C., 80 ° C., 130 ° C., 180 ° C.) and bending strength were measured. In addition, after the box-shaped connector was molded and heat-treated, the appearance of the box-shaped connector after solder reflow heating was evaluated. The evaluation results were as shown in Table-1, Table-2, Table-3 and Table-4.

All of Examples 1 to 4 are linear type PPS.
(Melt flow rate: 1000 g / 10 minutes) and an example of heat-treating a melt-molded product composed of the aromatic polyester synthesized in Synthesis Example 1, but no decrease in bending strength or surface roughness is observed even after infrared reflow heating. . On the other hand, as compared with Comparative Example 1, the storage elastic modulus (E ′) at each temperature was improved.

All of Examples 5 to 8 are linear type PPS.
(Melt flow rate: 1000 g / 10 minutes) and an example of heat treatment of a melt-molded product composed of the aromatic polyester synthesized in Synthesis Example 2, but no decrease in bending strength and surface roughness are observed even after infrared reflow heating. . On the other hand, the storage elastic modulus (E ′) at each temperature was improved in comparison with Comparative Example 2.

All of Examples 9 to 12 were crosslinked PPS.
(Melt flow rate: 700 g / 10 minutes) and Synthesis Example 2
This is an example of heat-treating a melt-molded product composed of the aromatic polyester synthesized in 1., but no decrease in bending strength and surface roughness are observed even after infrared reflow heating. On the other hand, the storage elastic modulus (E ′) at each temperature was improved in comparison with Comparative Example 3.

All of Examples 13 to 16 are linear type P
This is an example of heat-treating a melt-molded product composed of PS (melt flow rate; 1000 g / 10 minutes) and the aromatic polyester resin synthesized in Synthesis Example 3. However, there is a decrease in bending strength and surface roughness after infrared reflow heating. Not observed. On the other hand, as compared with Comparative Example 4, the storage elastic modulus (E ′) at each temperature was improved.

Comparative Example 1 is an example in which a heat treatment is not applied to a melt-molded product composed of linear type PPS (melt flow rate; 1000 g / 10 min) and PAR-1, but the bending strength after infrared reflow heating is lowered, Roughness is also observed in the appearance.

Comparative Example 2 is an example in which a melt-molded product composed of linear PPS (melt flow rate; 1000 g / 10 min) and PAR-2 was not subjected to heat treatment, but the bending strength after infrared reflow heating decreased, Roughness is also observed in the appearance.

Comparative Example 3 is an example in which a melt-molded product composed of crosslinked PPS (melt flow rate; 700 g / 10 min) and PAR-2 was not heat-treated, but the bending strength after infrared reflow heating was lowered, Roughness is also observed in the appearance.

Comparative Example 4 is an example in which a melt-molded product composed of linear PPS (melt flow rate; 1000 g / 10 min) and PAR-3 was not heat-treated, but the bending strength after infrared reflow heating was lowered, Roughness is also observed in the appearance.

Comparative Example 5 is an example in which a heat treatment is not applied to a melt-molded product made of a linear type PPS (melt flow rate; 1000 g / 10 minutes), but the bending strength after infrared reflow heating is lowered and the surface is rough even in appearance. Is observed.

Comparative Example 6 is an example in which a melt-molded product made of linear type PPS (melt flow rate; 1000 g / 10 min) was heat-treated, but the bending strength after infrared reflow heating was lowered and the surface was rough even in appearance. Is observed.

Comparative Example 7 is a linear PPS (melt flow rate; 1000 g / 10 min) and a commercially available polyarylate U-100 (an aromatic polyester manufactured by Unitika Ltd.), which is 4,4'-isopropylidene bisphenol. And consists of isophthalic acid and terephthalic acid.)
This is an example in which the heat-treated melt-formed product made of is not subjected to heat treatment, but the bending strength after infrared reflow heating is reduced, and surface roughness is observed in appearance.

Comparative Example 8 is a linear type PPS (melt flow rate; 1000 g / 10 minutes) and a commercially available polyarylate U-100 (an aromatic polyester manufactured by Unitika Ltd.), which is 4,4'-isopropylidene bisphenol. And consists of isophthalic acid and terephthalic acid.)
This is an example of heat-treating a melt-molded product consisting of, but the bending strength after infrared reflow heating is reduced, and surface roughness is observed in appearance.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

[0085]

[Table 4] 1) Linear type PPS "DSP LR-03G" manufactured by Dainippon Ink and Chemicals, Inc.
(Melt flow rate; 1000 g / 10 minutes) 2) Cross-linked PPS "DSP C-106G" manufactured by Dainippon Ink and Chemicals, Inc. (Melt flow rate; 700 g / 10 minutes) 3) Aromatic polyester manufactured by Unitika Ltd. "U Polymer U-100"

The thermoplastic resin molded article obtained by the production method of the present invention has excellent elastic modulus and heat resistance in a high temperature range, and even if the substrate to be soldered is exposed to a high temperature, Since the strength change and the appearance change of the molded article on the substrate after the soldering process are very small, soldering of electronic parts such as connectors, switches, relays, coil bobbins, etc. onto the printed circuit board in the SMT method is performed especially in the electric and electronic fields. It is useful as an attachment method.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 3/00 C08K 3/00 5/541 7/02 7/02 C08L 67/02 C08L 67/02 81 / 02 81/02 B23K 1/00 330E // B23K 1/00 330 101: 42 B23K 101: 42 B29K 67:00 B29K 67:00 81:00 81:00 C08K 5/54 F term (reference) 4F071 AA45 AA62 AA88 AB26 AB28 AC16 AD01 AE17 AF20 AF45 AH12 AH17 BA01 BB05 BC06 4F073 AA12 BA24 BA25 BA32 BB02 GA01 4F201 AA27K AA34K AB11 AB16 AB22 AD16 AK04 AR06 BA07 BR05 BR10 BR0 BR0 BR0 4X070 DE148 DE187 DE238 DG048 DG058 DH048 DJ008 DJ017 DJ038 DJ048 DJ058 DK007 DL007 EX016 EX036 EX066 EX076 FA047

Claims (10)

[Claims] 1. A polyarylene sulfide resin (A) and a compound represented by the general formula (1): (In the formula, Ar is an aromatic ring or a heterocycle. Y is an alkylene group having 1 to 8 carbon atoms, an oxygen atom, a sulfur atom,
A linking group in which a nitrogen atom or a hetero atom thereof and a carbon atom are bonded. Further, n is a repeating unit and is an integer. R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, and may be the same or different, and at least one of them has 1 to 8 carbon atoms. Is an alkyl group. ) And / or general formula (2) (In the formula, Ar is an aromatic ring or a heterocycle. N is a repeating unit and is an integer. R ¹ , R ² , R ³ and R ⁴ are
A hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
They may be the same as or different from each other. ), A resin composition comprising an aromatic polyester (B) having a polyester structural unit represented by the formula (1) is melt-molded, and the resulting melt-molded product is heat treated, and a method for producing a heat-resistant resin molded article, . 2. The polyarylene sulfide resin (A)
The method for producing a heat-resistant resin molded article according to claim 1, wherein has a substantially linear structure. 3. The polyarylene sulfide resin (A)
Is a polyphenylene sulfide resin, The method for producing a heat-resistant resin molded article according to claim 1 or 2. 4. The general formula (1) and the general formula (2)
And R¹, R^Two, R ^ThreeAnd R^FourBut has 1 to 8 carbon atoms
The alkyl group according to any one of claims 1 to 3.
Of the above heat-resistant resin molded article. 5. The method for producing a heat resistant resin molded article according to claim 1, wherein the resin composition further contains a silane compound (C). 6. The heat resistance according to claim 1, wherein the resin composition further contains a fibrous reinforcing material (D-1) and / or an inorganic filler (D-2). A method for producing a resin molded article. 7. The production of a heat-resistant resin molded article according to claim 1, wherein the dicarboxylic acid unit in the polyester structural unit in the general formula (1) is isophthalic acid and / or terephthalic acid. Method. 8. The temperature of the heat treatment is a melting point of the polyarylene sulfide resin (A) minus 5 ° C. to a melting point minus 1.
It is 00 degreeC, The manufacturing method of the heat resistant resin molded article as described in any one of Claims 1-7 characterized by the above-mentioned. 9. The heat-resistant resin molded article according to any one of claims 1 to 8 is soldered to a substrate under the condition that the surface temperature of the substrate is 280 ° C. or higher. Soldering method for heat-resistant molded articles. 10. The method for soldering a heat-resistant molded article according to claim 9, wherein the heating method uses infrared rays.