JP2003231731A - Polyarylene sulfide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which comprises a polyarylene sulfide, a thermotropic liquid crystal resin and a polyisocyanate compound and is excellent in moldability and heat resistance. <P>SOLUTION: This polyarylene sulfide resin composition is characterized in that it comprises the polyarylene sulfide (A), the thermotropic liquid crystal resin (B) and the polyisocyanate compound (C), and if necessary, a reinforcing material and/or a filler. The use of the polyisocyanate compound (C) can realize improvement in compatibility of the polyarylene sulfide (A) with the thermotropic liquid crystal resin (B) and improvement in heat resistance of the resin composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applied to electric / electronic parts, automobile parts, etc., which are required to have moldability and heat resistance in addition to chemical resistance, flame retardancy and excellent mechanical properties. It relates to an arylene sulfide resin composition. In particular, conventional polyarylene sulfide (hereinafter referred to as PAS)
The present invention relates to a resin composition that withstands a high temperature environment in which heat resistance is insufficient for a resin. INDUSTRIAL APPLICABILITY The resin composition of the present invention is useful, for example, as a material for electronic components to be soldered with lead-free solder.

[0002]

2. Description of the Related Art PAS resins have excellent heat resistance,
It has chemical resistance, flame retardancy, and mechanical properties, and among other things, the molding material reinforced with a reinforcing material such as glass fiber is used as a metal substitute in the fields of electric / electronic parts and automobile parts. In recent years, demand has increased significantly.

[0003] However, even in the parts which have conventionally used the PAS resin, due to changes in the assembly process and the like, further improvement in heat resistance is indispensable, and there are cases in which the conventional PAS resin cannot be used. For example, in the environment where consideration for environmental protection is emphasized and lead-free solder used for joining electrical and electronic parts is required, the temperature to which parts are exposed during the soldering process becomes high. In some cases, conventional PAS resins have insufficient heat resistance.

On the other hand, the thermotropic liquid crystal resin is a copolymer of para-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, para-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl and terephthalic acid, isophthalic acid. As typified by liquid crystal polyester resins such as polymers, due to their excellent physical properties such as fluidity, heat resistance, rigidity, and dimensional accuracy, their importance is expanding in recent years, especially for electrical and electronic parts. In particular, because it has better heat resistance than PAS resin,
Application to applications requiring higher heat resistance than PAS resin is also under consideration.

However, the thermotropic liquid crystal resin has the drawback that it is generally more expensive and has a lower weld strength than the PAS resin, and therefore its application is currently limited.

Therefore, a method of compensating for each other's defects and making the best use of the advantages thereof by using a composition of a PAS resin and a thermotropic liquid crystal resin has been studied.

For example, JP-A-3-70773, JP-A-4-353561 and the like disclose a composition in which burrs are reduced and crystallinity is improved by blending a PAS resin and a thermotropic liquid crystal resin. ing.

In addition, Japanese Patent Laid-Open No. 5-230371,
JP-A-7-166056 and JP-A-7-22420
No. 8 discloses the use of a third component such as a polyalkylene ether, an alkoxysilane, or an epoxy compound in a blend of a PAS resin and a thermotropic liquid crystal resin.
A composition having improved compatibility between a resin and a thermotropic liquid crystal resin is disclosed.

However, in the resin composition comprising these PAS resin and thermotropic liquid crystal resin,
It is hard to say that the compatibility between the PAS resin and the thermotropic liquid crystal resin is still at a sufficient level, and due to this insufficient compatibility, the excellent heat resistance of the thermotropic liquid crystal resin cannot be expressed and the application is limited. It is in the present situation.

[0010]

The problem to be solved by the present invention is to improve the compatibility between the PAS resin and the thermotropic liquid crystal resin so as to obtain chemical resistance, flame retardancy, excellent mechanical properties and molding. PA with workability and especially improved heat resistance
It is to provide an S resin composition.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in view of such circumstances, and as a result, by incorporating a polyisocyanate compound into a composition comprising a PAS resin and a thermotropic liquid crystal resin, The inventors have found that a resin composition having excellent compatibility between the PAS resin and the thermotropic liquid crystal resin can be obtained, and completed the present invention.

That is, the present invention provides a polyarylene sulfide resin composition comprising a polyarylene sulfide resin (A), a thermotropic liquid crystal resin (B) and a polyisocyanate compound (C). is there. Further, the present invention provides a molded article obtained by molding the above polyarylene sulfide resin composition, further characterized in that the molded article is soldered by a surface mounting method using lead-free solder. The present invention provides a method of fixing to a wiring board.

The type of the PAS resin (A) used in the present invention is not particularly limited, but for example, a random copolymer containing a repeating unit having a structure in which an aromatic ring which may have a substituent and a sulfur atom are bonded. , Block copolymers, and their mixtures or mixtures with homopolymers. Typical examples of these PAS resins include polyphenylene sulfide (hereinafter referred to as PPS), polyphenylene sulfide ketone, polyphenylene sulfide sulfone, and polyphenylene sulfide ketone sulfone. Among these PAS resins, a structure in which the bond of the aromatic ring of the repeating unit is in the para position is preferable in terms of heat resistance and crystallinity.

Particularly, a PPS resin containing 70 mol% or more of a repeating constitutional unit represented by the following general formula (in the formula, the aromatic ring does not include a substituent) is preferable in terms of physical properties and economy.

[0015]

[Chemical 4]

The method for producing the PPS resin is not particularly limited, but for example, 1) p-dichlorobenzene and
If necessary, other copolymerization component is polymerized in the presence of sulfur and sodium carbonate, 2) p-dichlorobenzene and, if necessary, other copolymerization component are sulfurized in a polar solvent. A method of polymerizing in the presence of sodium or sodium hydrosulfide and sodium hydroxide, or in the presence of hydrogen sulfide and sodium hydroxide, 3) p-chlorothiophenol and, if necessary, other copolymerization components. Condensation method, 4) reacting sodium sulfide with p-dichlorobenzene and, if necessary, other copolymerization components in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane. And the like. Among these methods, the method of 4) is suitable. At this time, an alkali metal salt of carboxylic acid or sulfonic acid or an alkali hydroxide may be added to control the degree of polymerization.

As the copolymerization component contained in the PPS resin, for example, a meta bond represented by the following structural formula,

[0018]

[Chemical 5]

An ether bond represented by the following structural formula,

[Chemical 6]

A sulfone bond represented by the following structural formula,

[Chemical 7]

A sulfide ketone bond represented by the following structural formula,

[Chemical 8]

A biphenyl bond represented by the following structural formula,

[Chemical 9]

A substituted phenyl sulfide bond represented by the following structural formula,

[Chemical 10] (In the formula, R represents an alkyl machine, a nitro group, a phenyl group or an alkoxy group.)

A trifunctional phenyl sulfide bond represented by the following structural formula,

[Chemical 11]

Naphthyl bond represented by the following structural formula

[Chemical 12] Ingredients including The content of these components is
Although not particularly limited, it is preferably less than 30 mol%. However, in the case of containing a trifunctional or higher bond,
It is usually 5 mol% or less, preferably 3 mol% or less.

The melt viscosity of the PAS resin (A) used in the present invention is not particularly limited, but the viscosity measured at 300 ° C. at a shear rate of 500 sec ⁻¹ and using a capillary rheometer is 10. ~ 3000Pa
・ S is preferable in terms of the balance between mechanical properties and fluidity.

The PAS resin (A) used in the present invention can be manufactured by the manufacturing method described in JP-B-52-12240, but is not limited to this method.

The PAS resin (A) has a metal content, especially N
It is preferable that the PAS resin has a low a content. Particularly, the Na content is preferably 500 ppm or less.
The lower the Na content, the higher the compatibility of the PAS resin and the thermotropic liquid crystal resin tends to be.

As a method for obtaining a PAS resin having a low Na content, Japanese Patent Laid-Open No. 223232/1987 and Japanese Patent Laid-Open No. 10-232 / 1987
-45911, JP-A-10-45912,
As described in JP-B-10-60113 and the like, a method of washing after acid treatment can be mentioned. 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 preferably used. As a method of the acid treatment, there is a method of immersing the PAS resin in an acid or an acid aqueous solution. At this time, stirring or heating can be carried out if necessary.

For the acid treatment of the PAS resin used in the present invention,
It is also possible to use a PAS resin powder or a PAS resin in a slurry state after polymerization.

Further, as the PAS resin, a PAS resin having a terminal thiol group concentration of 5 μmol / g or more and 50 μmol / g or less can also be suitably used.

Further, as the PAS resin used in the present invention, a polyarylene sulfide resin modified with a carboxyl group, that is, a carboxyl group-containing resin (hereinafter referred to as CPA).
S-based resin) can be used. Examples of CPAS-based resins include the following general formula

[0033]

[Chemical 13] The following general formula

[0034]

[Chemical 14] (In the formula, Y represents O, SO ₂ , CH ₂ , C (CH ₃ ) ₂ , CO or C (CF ₃ ) _2. )

Or the following general formula

[Chemical 15] CPAS having a repeating structural unit represented by

[0036]

[Chemical 16] A copolymer with PAS having a repeating unit represented by

The content of the repeating structural unit in the CPAS cannot be unconditionally specified because it varies depending on the purpose of use and the like, but it is 0.5 to 30 mol% in the CPAS resin,
Preferably, it is 0.8 to 20 mol%. The CPAS-based resin obtained by such copolymerization may be a random type, a block type, or a graft type. Most typically, the PAS part is PPS and the CPAS part is the following general formula.

[Chemical 17] And a copolymer which is a carboxyl group-containing polyphenylene sulfide resin (CPPS) represented by.

As a method for producing a CPAS resin by copolymerization, the following method can be mentioned. That is, for example, in the case of the random type, a method using a dihalogeno aromatic compound, an alkali metal sulfide, a dihalogeno aromatic carboxylic acid and / or an alkali metal salt thereof, as described in JP-A-63-305131, Examples thereof include a method of using an alkali metal hydrosulfide compound and an alkali metal hydroxide instead of the alkali sulfide used in the production method.
In the case of block type, (1) dihalogenoaromatic carboxylic acid and / or its alkali metal salt and sulfidizing agent (alkali sulfide; hydrosulfide alkali metal compound and hydroxylation) in a polar solvent in which a PAS prepolymer is present. (2) CP method of reacting with alkali metal)
A method of reacting a dihalogeno aromatic compound and a sulfidizing agent in a polar solvent in which an AS prepolymer is present,
(3) There is a method of reacting the PAS prepolymer and the CPAS prepolymer in a polar solvent.

Further, as the PAS resin of the present invention, a polyarylene sulfide resin having an amino group, that is, an amino group-containing polyarylene sulfide resin (hereinafter referred to as APAS resin) can be used. The amino group content in the APAS resin is
0.1 to 30 mol% is preferable. This APAS resin can be obtained by polymerizing coexistence of an amino group-containing aromatic halide when an alkali metal sulfide and dihalobenzene are reacted in an amide solvent such as N-methylpyrrolidone. However, the method is not limited to this.

Amino group-containing aromatic halides that can be used in the copolymerization of the APAS resin are represented by the following general formula:

[0041]

[Chemical 18] (In the formula, X represents a halogen atom, Z is a hydrogen atom, -N
H ₂ or a halogen atom, R ₁ represents a hydrocarbon group having 1 to 12 carbon atoms, m is an integer of 0-4. The compound represented by these can be mentioned.

Specific examples of the compound include m-fluoroaniline, m-chloroaniline, 3,5-dichloroaniline, 2-amino-4-chlorotoluene, 2-amino-6-chlorotoluene and 4-amino. 2-chlorotoluene, 3-chloro-m-phenylenediamine, m-bromoaniline, 3,5-dibromoaniline, m-iodoaniline and the like are used, and one kind or a mixture of two or more kinds thereof is used. can do.

The thermotropic liquid crystal resin (B) used in the present invention is not particularly limited, but a typical example thereof is a liquid crystal polyester resin. Less than,
The liquid crystal polyester resin will be described.

The liquid crystal polyester resin is a resin which forms an anisotropic molten phase at a temperature of 400 ° C. or lower. Specifically, for example, an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid are reacted with each other. Obtained by reacting different aromatic hydroxycarboxylic acids, obtained by reacting an aromatic dicarboxylic acid with a nuclear-substituted aromatic diol, and polyesters such as polyethylene terephthalate with an aromatic hydroxycarboxylic acid. The thing obtained by making it react is mentioned. Further, instead of the above aromatic dicarboxylic acid, aromatic diol, and aromatic hydroxycarboxylic acid, their ester-forming derivatives may be used.

As the repeating structural unit of the liquid crystal polyester resin used in the present invention, the repeating structural unit derived from the following aromatic dicarboxylic acid, the repeating structural unit derived from an aromatic diol, the repeating structural unit derived from an aromatic hydroxycarboxylic acid. Structural units and the like can be exemplified, but the present invention is not limited thereto.

Examples of the repeating structural unit derived from the aromatic dicarboxylic acid include the following structures.

[0047]

[Chemical 19] (In the formula, X1 represents a halogen atom, an alkyl group or an aryl group)

[0048]

[Chemical 20] Further, examples of the repeating structural unit derived from the aromatic diol include the following structures.

[0049]

[Chemical 21] (In the formula, X1 represents a halogen atom, an alkyl group or an aryl group)

[0050]

[Chemical formula 22] (In the formula, X2 represents a halogen atom or an alkyl group)

[0051]

[Chemical formula 23]

Further, examples of the repeating structural unit derived from the aromatic hydroxycarboxylic acid include the following structures.

[0053]

[Chemical formula 24] (In the formula, X2 represents a halogen atom or an alkyl group)

[0054]

[Chemical 25]

The thermotropic liquid crystal resin (B) used in the present invention is a liquid crystal polyester resin containing a repeating structural unit represented by the following structural formula [1] in view of the balance of heat resistance, mechanical properties, processability and the like. preferable.

[0056]

[Chemical formula 26]

Examples of the liquid crystal polyester resin containing the repeating unit [1] include liquid crystal polyester resins containing the following combinations of repeating units. Note that the present invention is not limited to these examples.

[0058]

[Chemical 27]

[0059]

[Chemical 28]

[0060]

[Chemical 29]

[0061]

[Chemical 30]

[0062]

[Chemical 31]

[0063]

[Chemical 32]

[0064]

[Chemical 33]

The method for producing the liquid crystal polyester resins used in the present invention is described in, for example, JP-B-47-47.
870, Japanese Patent Publication 63-3888, Japanese Patent Publication 6
No. 3-3891, Japanese Patent Publication No. 56-18016,
It is described in Japanese Examined Patent Publication No. 2-51523 and Japanese Examined Patent Publication No. 7-47625. Among these, a combination of is preferable, and a combination of is more preferable.

The above liquid crystal polyester resin preferably further has the following (group a) and / or (group b) repeating units. (Group a) is the following structural formula [2] and / or structural formula [3]

[0067]

[Chemical 34]

(Group b) is a repeating unit consisting of the following structural formula [4], structural formula [5], structural formula [6]
And structural formula [7]

[0069]

[Chemical 35] It is a repeating unit consisting of one or more structural formulas selected from the group consisting of

For group a, the structural formula [2]
The repeating unit consisting of and the repeating unit consisting of the structural formula [3] have a molar ratio of structural formula [3] / structural formula [2] = 0 to 1.5 in terms of fluidity during processing. It is preferable. Regarding the above group b, the repeating unit consisting of the structural formula [4], the repeating unit consisting of the structural formula [5], the repeating unit consisting of the structural formula [6] and the repeating unit consisting of the structural formula [7] are From the viewpoint of fluidity, it is preferable that the molar ratio of [Structural formula [4] + Structural formula [5]] / [Structural formula [6] + Structural formula [7]] is in the range of 1-10.

The total number of moles of the (group a) to the total number of moles of the (group b) is substantially 1:
1, the structural formula [5] / the structural formula [4] is in the range of 0 to 2 molar ratio, and the structural formula [7] / the structural formula [6] is preferably in the range of 0 to 2 molar ratio. Furthermore, it is preferable that the above structural formula [1] / (group a) has a molar ratio of 1 to 6. As used herein, "the total number of moles of the (group a) to the total number of moles of the (group b) is substantially 1: 1" means that the polyester is hydrolyzed using, for example, an alkali represented by NaOH. And / or solvolysis, and when the constituent components are analyzed by the NMR (nuclear magnetic resonance) method or the GC (gas chromatography) method, the amount of the terminal group depending on the molecular weight is set as an error range, It means that it can be concluded that the total number of moles of the (group a) with respect to the total number of moles of the group b) is 1: 1. When the molar ratio is within the above range, the balance between mechanical properties and fluidity becomes particularly good.

As the liquid crystal polyester resin used in the present invention, a wholly aromatic polyester resin having a melting point of 300 ° C. or higher is particularly preferable. The wholly aromatic polyester referred to here is a repeating structural unit used (a repeating structural unit derived from an aromatic dicarboxylic acid, a repeating structural unit derived from an aromatic diol, a repeating structural unit derived from an aromatic hydroxycarboxylic acid). All of) are polyesters having an aromatic group in the main chain. Such melting point is 300 ° C
When the above-mentioned wholly aromatic polyester resin is used, the heat resistance level with the PAS resin (A) is highly balanced in addition to the mechanical properties and fluidity.

The melt viscosity of the thermotropic liquid crystal resin (B) is not particularly limited, but the PAS resin (A) when measured at the same temperature and the same shear rate.
Where η (A) is the viscosity of thermotropic liquid crystal resin (B) and η (B) is the melt viscosity of the thermotropic liquid crystal resin (B), η (A) / η (B)
Is in the range of 0.1 to 10, PAS resin (A)
Is preferable for improving the compatibility of the thermotropic liquid crystal resin (B).

The composition ratio of the PAS resin (A) and the thermotropic liquid crystal resin (B) is not particularly limited, but it is preferable that P
From the viewpoint of increasing the heat resistance level of AS resin,
It is preferable to use 0.1 to 100 parts by weight of the thermotropic liquid crystal resin (B) with respect to 100 parts by weight of the PAS resin (A).

Next, the polyisocyanate compound (C) used in the present invention will be described.

The polyisocyanate compound (C) used in the present invention refers to an organic compound having two or more isocyanate groups and / or isothiocyanate groups in one molecule.

Specific examples of the polyisocyanate compound (C) include, for example, m-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and 4,4. ′ -Diphenylpropane diisocyanate, 1,5-naphthalene diisocyanate,
Aromatic polyisocyanates such as 3,3′-dimethyl-4,4′-biphenylene diisocyanate, dimethylphenylmethane diisocyanate diphenyl ether-4,4′-diisocyanate, diphenylsulfone-4,4′-diisocyanate and triphenylmethane triisocyanate Araliphatic polyisocyanates of xylene diisocyanates; 4,4'-cyclohexane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, 1,1
Examples thereof include aliphatic polyisocyanates such as 2-dodecane diisocyanate, hexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate, mixtures thereof, and compounds having an isothiocyanate group corresponding thereto. .

Further, a block type polyisocyanate modified product in which an isocyanate group is masked with a dimer, a trimer or the like of these isocyanate compounds; a carbodiimide modified type; a phenol; a lactam or the like is also a polyisocyanate compound (C). include. These block-type isocyanates are generally excellent in storage stability because they do not react at room temperature, but the isocyanate groups are usually regenerated by heating at 140 to 200 ° C. and exhibit excellent reactivity. Among the blocked polyisocyanate modified products, a multimer type block polyisocyanate modified product is particularly preferable because it does not generate a compound that easily volatilizes when the isocyanate group is regenerated.

The polyisocyanate compound (C) used in the present invention preferably has a molecular weight of 200 or more. The molecular weight as used herein means a molecular weight calculated based on a molecular formula for a low molecular weight polyisocyanate compound, and means a numerical value at a number average molecular weight for a high molecular weight polyisocyanate compound. When the molecular weight is 200 or more, the PAS resin composition of the present invention hardly volatilizes during the production process,
The effect of improving the compatibility between the PAS resin and the thermotropic liquid crystal resin is great.

The flash point of the polyisocyanate compound (C) used in the present invention is preferably 150 ° C. or higher. Here, the flash point can be measured by a Cleveland open flash point measurement test based on ISO2592, a setter closed-type flash point measurement test that is a test method for flammable solids that are the second category of dangerous substances under the Fire Service Act, and the like. it can. As in the case of classifying dangerous substances under the Fire Service Act, a measuring method according to the type of polyisocyanate compound can be used.

Since the higher the flash point is, the less likely it is to volatilize during the manufacturing process of the composition, the greater the effect of improving the compatibility between the PAS resin and the thermotropic liquid crystal resin and the smaller the thermal decomposability tend to be. When the PAS resin composition of the invention is molded by injection molding or the like, the moldability tends to be good.

To the PAS resin composition of the present invention, various reinforcing materials and / or fillers are preferably added for the purpose of improving mechanical properties and molding processability. Examples of the reinforcing material and the filler that can be used in the present invention include glass fiber, carbon fiber, calcium titanate, potassium titanate, silicon carbide, aramid fiber, ceramic fiber, metal fiber, silicon nitride, barium sulfate and sulfuric acid. Calcium, kaolin, clay, bentonite, sericite, zeolite, mica, mica, talc, wollastonite, PMF, ferrite, aluminum silicate, calcium silicate, calcium carbonate, dolomite, magnesium oxide, magnesium hydroxide, antimony trioxide, oxidation Examples include titanium, iron oxide, milled glass, glass beads and glass balloons.

Further, the PAS resin composition of the present invention may contain a lubricant such as graphite, molybdenum disulfide, polytetrafluoroethylene and the like, and a stabilizer thereof. Further, an antioxidant, a heat stabilizer, an ultraviolet absorber, a release agent, a rust preventive, a lubricant, a crystal nucleating agent, a coloring agent, a silane coupling agent, etc. are added within a range not impairing the object of the present invention. be able to.

Further, to the PAS resin composition of the present invention, a thermosetting resin and a thermoplastic resin other than the PAS resin and liquid crystal polyester resin used in the present invention are added within a range not impairing the object of the present invention. can do. As these thermosetting resins and other thermoplastic resins, for example, epoxy resin, silicone resin, polyimide, polyethylene, polypropylene, polystyrene, styrene butadiene copolymer, polyamide, polycarbonate, polysulfone, polyether sulfone, polyarylate. , Polyacetal, polyether ketone, polyether ether ketone, polybutylene terephthalate, polyethylene terephthalate, liquid crystal polymer, polyamide imide, polyether imide and the like.

Particularly, diglycidyl ether of 1,6-dihydroxynaphthalene and / or triglycidyl ether or tetraglycidyl ether of naphthalene ring-containing hydroxy compound as described in JP-A-7-82485. A naphthalene type polyfunctional epoxy resin is preferably used.

The PAS resin composition of the present invention can be prepared by various known methods. As a preparation method, for example, PAS, thermotropic liquid crystal resin, polyisocyanate, if necessary, fillers and the like are mixed in advance with a Henschel mixer or a tumbler, and then supplied to a uniaxial or biaxial extrusion kneader, etc. Examples thereof include a method of kneading at 360 ° C., granulating and pelletizing.

In addition, other reinforcing materials, fillers and various additives may be added if necessary during the above mixing.

In addition, other reinforcing materials, fillers and various additives may be added as required during the above mixing.

After pelletizing, annealing, UV irradiation, plasma irradiation or the like may be performed.

A molded article can be obtained by molding the PAS resin composition of the present invention obtained above. A typical molding method is injection molding, but press molding, extrusion molding, blow molding or the like may be used. Further, these molding methods may be combined.

Since the molded article of the present invention has good heat resistance, it can be used in a field requiring heat resistance. Examples thereof include peripheral parts of automobile engines, industrial parts exposed to high-temperature heat medium, and electronic parts fixed to a wiring board. Of these, especially, lead-free solder is used for surface mounting (surface mounting;
It is particularly preferably applied to molded parts that are soldered by the MT method).

Here, the SMT method generally means that an electronic component is placed on a printed printed circuit board via cream-like solder and then the printed circuit board is passed through a heating furnace (reflow furnace). To melt the solder,
A method of fixing electronic components on a wiring board. This SM
The T method is a conventional insertion mounting in which 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. This method is different from the method (read-through method).

The SMT method can increase the mounting density and can mount both front and back surfaces.
It has advantages such as reduction in manufacturing cost due to efficiency improvement, and is currently becoming the mainstream of the soldering method. 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.

A so-called lead-free solder in which several kinds of metals are added to tin as a base has been proposed as an alternative material, but all have higher melting points than tin-lead eutectic solder (for example, tin-silver eutectic solder). The melting point is 220 ° C. in the case of solder), and the temperature in the heating furnace (reflow furnace) must be further raised during surface mounting. As a result, when soldering is performed using the SMT 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 in this field for a molded article of a thermoplastic resin having higher heat resistance.

Examples of such molded articles 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, the PAS resin composition of the present invention is a connector, switch, sensor, resistor, relay, condenser, socket, jack, fuse holder, coil bobbin, IC and LED for SMT method.
It is useful as a material for housings and the like.

[0096]

EXAMPLES The present invention will be further described below with reference to examples. Parts in the examples indicate parts by weight. The present invention is not limited to the scope of these examples.

The measured values and evaluation criteria in the examples described below were measured and evaluated as follows. <Measurement Method and Evaluation Criteria> Melting Point: Thermotropic liquid crystal resin obtained in the Reference Example described later was used as a sample and was measured according to JIS K 7121 using DSC7 which is a differential scanning calorimeter manufactured by Perkin Elmer. -Weighted deflection temperature: Measured according to ASTM D648 using the thermotropic liquid crystal resin obtained in the reference example described later as a sample. Melt viscosity; PAS resin obtained in the reference example described below is used as a sample and the shear rate is 500 sec ^{−1 at} 300 ° C.
It was measured by using a capillary rheometer.

Flash point: The polyisocyanate compound used in the later examples was determined by a Ceta closed flash point measuring device. -Bending strength; using the test pieces obtained in the examples described below, AS
The initial bending strength and the bending strength after heating were measured according to TM D790. The heating was carried out through an infrared reflow device with the test piece placed on the substrate. At this time, the heating condition is 18
After preheating at 0 ° C for 100 seconds, the substrate surface is 280 ° C
Was set. -Bending strength retention rate: Calculated as bending strength after heating / initial bending strength (%).

Reference Example 1 Synthesis of thermotropic liquid crystal 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-naphthalenedicarboxylic acid 64.9 g (0.3 mol), 4-hydroxybenzoic acid 621.5 g ( 4.5 mol) and 612.5 g (6 mol) of acetic anhydride were placed in a reaction vessel equipped with a condenser and a stirrer and heated to 170 ° C. while stirring under a nitrogen gas atmosphere for 60 minutes at this temperature. It was refluxed. Next, the reaction vessel was gradually raised to 370 ° C. over 4 hours while removing by-product acetic acid, and the reaction system was further depressurized to 25 kPa at 370 ° C. At that temperature, the pressure was adjusted to 0.5 to 2 over 2 hours while removing the by-product acetic acid.
Polymerization was carried out under reduced pressure to 1 kPa.

Then, polymerization was carried out at 370 ° C. for 1 hour. During this polymerization, strong agitation was performed while removing by-product acetic acid, then the system was gradually cooled, and the thermotropic liquid crystal resin obtained at 200 ° C. was taken out of the system. The melting point of this resin was 350 ° C. This thermotropic liquid crystal resin is hereinafter referred to as LCP-1.

Reference Example 2 Synthesis of thermotropic liquid crystal 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-naphthalenedicarboxylic acid 43.3 g (0.2 mol), 4,
With the above LCP-1 except that 24.2 g (0.1 mol) of 4'-biphenyldicarboxylic acid, 621.5 g (4.5 mol) of 4-hydroxybenzoic acid and 612.5 g (6 mol) of acetic anhydride were used. Polymerization was performed by performing the same operation.
The obtained thermotropic liquid crystal resin is hereinafter referred to as LCP-2. This resin has a melting point of 365 ° C and a deflection temperature under load of 2
It was 70 ° C. (Reference Example 3) Synthesis of thermotropic liquid crystal resin 110.1 g (1 mol) of hydroquinone, 58.1 g (0.35 mol) of terephthalic acid, 58.1 g of isophthalic acid
(0.35 mol), 2,6-naphthalenedicarboxylic acid 6
4.9 g (0.3 mol), 4-hydroxybenzoic acid 62
Polymerization was performed in the same manner as in LCP-1 except that 1.5 g (4.5 mol) and acetic anhydride 612.5 g (6 mol) were used. The thermotropic liquid crystal resin thus obtained is hereinafter referred to as LCP.
-3. The melting point and the deflection temperature under load of this resin measured in the same manner as above were 328 ° C. and 238 ° C., respectively.

Examples 1 to 9 and Comparative Examples 1 to 8 The various raw materials produced in Reference Example and other raw materials were uniformly mixed in the proportions shown in the following table, and then 330 to 350 mm in a 35 mmφ twin-screw extruder. Kneading was performed at 370 ° C. to obtain pellets. Using this pellet, a cylinder temperature of 330 to 370 ° C. and a mold temperature of 130 by an in-line screw type injection molding machine.
A test piece having a thickness of 1.6 mm was molded at a temperature of C, an injection pressure of 80 to 100 MPa, and an injection speed of medium speed.

Other components used in Examples and Comparative Examples are as follows. PPS-1: Dainippon Ink and Chemicals PPS "C-11"
5 ”Crosslinking type, melt viscosity 120 Pa · s. PPS-2: Dainippon Ink and Chemicals PPS "LR-3"
G ”linear type, melt viscosity 110 Pa · s. ISO-1: 4,4'-diphenylmethane diisocyanate molecular weight 250.3 flash point 218 ° C ISO-2: isophorone diisocyanate molecular weight 222.3 flash point 163 ° C ISO-3: isophorone diisocyanate adduct
Uretdione-bonded block (“VES” manufactured by Daicel Hüls Ltd.)
TAGON BF 1540 ") Flash point 182 ° C EPO-1: Bisphenol type polyepoxy compound (Dainippon Ink and Chemicals" EPICLON 850 ") GF-1: Glass fiber (chopped strand, average fiber diameter 10 μm)

With respect to the above molded article, the initial bending strength, the bending strength after heating and the bending strength retention rate were measured. The results are shown in Table-1 and Table-2.

[0105]

[Table 1]

[0106]

[Table 2]

Example 10 Using the pellets of the composition of Example 1, an injection molding machine was used to obtain a shape of 70 mm in length × 10 mm in width × 8 mm in height, and
A box-shaped connector having a thickness of 8 mm was molded. Insert a metal terminal into the molded product and use lead-free solder Sn-3.0Ag-
The printed circuit board and the metal terminal portion were soldered using 0.5 Cu. The soldering conditions were set such that the surface of the printed board was 280 ° C. after preheating at 180 ° C. for 100 seconds by an infrared reflow device. The resulting molded article to which the printed circuit board and the box-shaped connector were soldered had a good shape with no deformation.

Comparative Example 9 A molded article was prepared in the same manner as in Example 10 except that the composition of Comparative Example 3 was used. The resulting molded article, to which the printed circuit board and the box-shaped connector were soldered, was observed to have blister formation and had a poor shape.

[0109]

EFFECT OF THE INVENTION The polyarylene sulfide resin composition of the present invention has excellent heat resistance, and particularly when it is used for parts to be soldered or peripheral parts of parts to be soldered, It is very useful in molded articles such as connectors, switches, relays, coil bobbins and the like in the electric and electronic fields, since the strength thereof is extremely small even when exposed to high temperatures.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J002 CK051 CL062 DA016 DA066                       DE076 DE116 DE126 DE136                       DE186 DE236 DF016 DG046                       DG056 DJ006 DJ036 DJ046                       DJ056 DL006 FA042 FA046                       FA086 FA096 FD016 FD170                       GN00 GQ00                 4J034 BA07 DA01 DA03 DA05 DB03                       DB07 DC02 DC03 DD03 DF01                       DF17 DF21 DR01 HA01 HA07                       HA08 HB03 HB06 HC11 HC12                       HC13 HC17 HC22 HC33 HC46                       HC52 HC61 HC64 HC65 HC67                       HC70 HC71 HC73 HD03 HD04                       HD07 MA01 MA21 QB14 QD01                       QD04 RA14

Claims (12)

[Claims] 1. A polyarylene sulfide resin composition comprising a polyarylene sulfide resin (A) and a thermotropic liquid crystal resin (B) and a polyisocyanate compound (C). 2. The polyarylene sulfide resin composition according to claim 1, wherein the thermotropic liquid crystal resin (B) has a melting point of 300 ° C. or higher. 3. The polyarylene sulfide resin composition according to claim 1, wherein the thermotropic liquid crystal resin (B) is a liquid crystal polyester resin having a repeating structural unit represented by the following structural formula. [Chemical 1] 4. The thermotropic liquid crystal resin (B) is a liquid crystal polyester resin further having a repeating unit consisting of (group a) and / or (group b),
(Group a) is structural formula [2] and / or structural formula [3]
It is a repeating unit represented by (Group b) is a repeating unit represented by one or more structural formulas selected from the group consisting of structural formula [4], structural formula [5], structural formula [6] and structural formula [7], Chemical 3] The polyarylene sulfide resin composition according to claim 3. 5. The repeating unit of the structural formula has a molar ratio of structural formula [3] / structural formula [2] = 0 to 1.5, wherein [structural formula [4] + structural formula [5] ] / [Structural formula [6]
The polyarylene sulfide resin composition according to claim 4, wherein + structure [7]] is in the range of 1 to 10. 6. The total number of moles of the (group a) to the total number of moles of the (group b) is substantially 1: 1 and further, the (group c) / the (group a).
= 1 to 6 molar ratio, and structural formula [5] / structural formula [4] = 0 to 2 molar ratio, structural formula [7] /
The polyarylene sulfide resin composition according to claim 4 or 5, wherein the structural formula [6] is in the range of 0 to 2 molar ratio. 7. The polyarylene sulfide resin composition according to claim 1, wherein the polyisocyanate compound (C) has a molecular weight of 200 or more. 8. The polyarylene sulfide resin composition according to claim 1, wherein the flash point of the polyisocyanate compound (C) is 150 ° C. or higher. 9. The content of the polyisocyanate compound (C) is 100 parts by weight based on 100 parts by weight of the polyarylene sulfide resin (A) and the thermotropic liquid crystal resin (B).
The polyarylene sulfide resin composition according to any one of claims 1 to 8, which is 01 to 10 parts by weight. 10. Reinforcing material and / or filler (D)
The polyarylene sulfide resin composition according to claim 1, which comprises: 11. A molded article obtained by molding the polyarylene sulfide resin composition according to any one of claims 1 to 10. 12. A method of fixing to a wiring board, which comprises soldering the molded article according to claim 11 by surface mounting using lead-free solder.