WO2003082955A1 - Polyarylene sulfide resin and sealing agent for electronic parts - Google Patents

Polyarylene sulfide resin and sealing agent for electronic parts Download PDF

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Publication number
WO2003082955A1
WO2003082955A1 PCT/JP2003/003676 JP0303676W WO03082955A1 WO 2003082955 A1 WO2003082955 A1 WO 2003082955A1 JP 0303676 W JP0303676 W JP 0303676W WO 03082955 A1 WO03082955 A1 WO 03082955A1
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Prior art keywords
polyarylene sulfide
sulfide resin
less
amount
ppm
Prior art date
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PCT/JP2003/003676
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French (fr)
Japanese (ja)
Inventor
Satoru Kinouchi
Minoru Senga
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Idemitsu Petrochemical Co., Ltd.
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Publication of WO2003082955A1 publication Critical patent/WO2003082955A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
    • C08G75/0254—Preparatory processes using metal sulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
    • C08G75/0213—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0277—Post-polymerisation treatment
    • C08G75/0281—Recovery or purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/14—Polysulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a polyarylene sulfide resin and a sealing material for electronic components comprising the same. More specifically, the present invention relates to a polystyrene sulfide resin used for a structural material such as an electronic component or an automobile electric component, and a sealing material for an electronic component made of the resin.
  • the present invention has been made in view of the above-mentioned problems, and is a polyarylene sulfide resin which does not cause degradation of electronic device performance due to elution of ionic impurities, reduction in adhesion, contamination of internal parts or gas burning. And a sealing material for electronic components comprising the same.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, the above-mentioned problems were solved by reducing the total amount of metal ions and the amount of oligomer contained in the polyarylene sulfide resin to a certain amount or less. We have found that we can do this and completed the present invention. Disclosure of the invention
  • a polyarylene sulfide resin having an oligomer amount of 30 mg / g or less that is extracted into a black form.
  • the polyarylene sulfide resin of the present invention preferably has a total content of metal ions of 100 ppm or less, and preferably has a total amount of metal ions extracted with hot water of 100 ppm or less.
  • polyarylene sulfide resin of the present invention is preferably produced using lithium sulfide as a raw material.
  • a polyarylene sulfide resin composition containing the above polyarylene sulfide resin and silicic acid.
  • the polyarylene sulfide resin composition of the present invention can further contain an elastomer, and can further contain a silane coupling agent and a Z or epoxy resin.
  • an electronic component sealing material comprising the above-mentioned polyarylene sulfide resin or polyarylene sulfide resin composition.
  • an electronic component including the above electronic component sealing material.
  • FIG. 1 is a schematic diagram showing an apparatus for producing a polyarylene sulfide resin.
  • BEST MODE FOR CARRYING OUT THE INVENTION the polyarylene sulfide resin of the present invention will be described.
  • the polyarylene sulfide resin of the present invention is a polymer based on the structural formula [1 Ar—S—] (where Ar is an arylene group and S is iodide). It is a polymer containing preferably at least 70 mol%, more preferably at least 80 mol%, of the repeating unit represented by the general formula (1). When the content of the repeating unit is less than 70 mol%, the original crystalline component, which is a characteristic of the crystalline polymer, is small, and the mechanical strength may be insufficient.
  • R 1 is a substituent selected from an alkyl group having 6 or less carbon atoms, an alkoxy group, a phenyl group, a carbonyl group or a metal salt thereof, a nitro group, and a halogen atom such as fluorine, chlorine, and bromine.
  • m is an integer of 0 to 4.
  • n represents the average degree of polymerization and ranges from 20 to: L00.
  • a copolymer other than a homopolymer can be used as the polyarylene sulfide resin.
  • the copolymerizable structural unit include metaphenylene sulfide unit, orthophenylene sulfide unit, p, p 'diphenylene sulfone sulfide unit, ⁇ ,' diphenylene sulfone sulfide unit, ⁇ , ⁇ '—biphenylene sulfide Unit, ⁇ , ⁇ '—diphenylene methylene sulfide unit, ⁇ , ⁇ ′—diphenylene cumenyl sulfide unit, naphthyl sulfide unit and the like.
  • polyarylene sulfide resin is generally known to have a molecular structure such as a linear type, a semi-linear type, or a cross-linked type depending on its production method.
  • the structure is not particularly limited.
  • the amount of the oligomer extracted into the pore form is 30 mg or less.
  • the amount of the oligomer is preferably 25 mgZg or less, more preferably 12 mgZg or less.
  • the oligomer means a low-molecular-weight polyarylene sulfide resin that elutes when subjected to Soxhlet extraction with a black hole form.
  • the polyarylene sulfide resin preferably has a total amount of contained metal ions and a total amount of Z or hot water-extracted metal ions of 100 ppm or less. If the total amount of these metal ions exceeds 100 ppm, the amount of metal ions eluted to the electrodes and wiring of the electronic components will increase, and they will corrode and cause disconnection. It can be difficult.
  • the metal ion species contained in the polyarylene sulfide resin varies depending on the type of the raw material, the type of the material used for the post-treatment, the production conditions, and the like, and examples thereof include Na, Li, K, and Fe.
  • the total amount of the metal ions contained and / or the total amount of the metal ions extracted with hot water is more preferably 50 ppm or less, and particularly preferably 30 ppm or less.
  • Na and Li are preferably 30 ppm or less
  • K is preferably 50 ppm or less
  • 6 is preferably 10 13 111 or less.
  • Such a polyarylene sulfide resin can be produced by a production method using lithium sulfate as a raw material.
  • the polymerization conditions are not particularly limited, and for example, a production method of a batch method or a continuous method can be used.
  • FIG. 1 is a schematic view of an apparatus for producing a polyarylene sulfide resin.
  • This equipment consists of a main polymerization tank 1, a transfer process pipe 2 and a stationary tank 3, and a mixer 4 is installed in the middle of the pipe.
  • the reaction liquid containing the polyarylene sulfide resin is continuously discharged from the main polymerization tank 1 consisting of a single-stage CSTR (continuous stirred tank reactor), and then mixed with the washing liquid in the mixer 4 to form the first stationary tank. Within 3, it is settled using the density difference.
  • CSTR continuous stirred tank reactor
  • the polyarylene sulfide resin is present on the lower phase side in the stationary tank 3 and is detected by a liquid level gauge.
  • this mixer Z settler type washing operation is performed about 3 to 4 stages, and the injection amount of the washing target is set to about 4 to 5 times the amount of the liquid discharged from the main polymerization tank 1.
  • the pipe 2 for transferring the polyarylene sulfide resin and the stationary tank 3 need a jacket structure in order to keep them at a high temperature.
  • a double pipe having an inner diameter of ⁇ / 2 ⁇ and an outer diameter of 1 ⁇ 1 / 2 ⁇ is used.
  • the washing solution contains a small amount of a low-molecular-weight polyarylene sulfide resin, that is, an oligomer, it is preferable to use a double pipe or the like for the piping structure. Can also drive. , ⁇
  • polyarylene sulfide is preferably produced by a continuous polymerization method using lithium sulfide as a raw material.
  • Manufacture resin At this time, prior to the continuous polymerization, a prepolymer of a polyarylene sulfide resin may be synthesized, and the continuous polymerization may be performed using the prepolymer.
  • the polyarylene sulfide resin composition of the present invention contains the above polyarylene sulfide resin and silica.
  • silica is added to improve dimensional stability, mechanical properties, thermal conductivity and the like of electronic components and the like.
  • examples of the silica include fused silica, crystalline silica, and synthetic silica. Of these, fused silica is preferred.
  • Silica is preferably added in an amount of 100 to 500 parts by weight based on 100 parts by weight of the polyarylene sulfide resin.
  • these silicas may be used after pre-treatment with a silane coupling agent described later.
  • elastomers rubber-like elastic material
  • elastomers include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiochol rubber, acryl rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer (SBR) , Hydrogenated styrene-butadiene block copolymer (SEB, SEBC), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isopre
  • SBR SBR
  • SEB SBS
  • SEBS SEBS
  • SIR SEP
  • SIS SEPS
  • core shell rubber EPM
  • EPDM EPDM
  • a rubber modified from these is preferably used.
  • elastomers can be used alone or in combination of two or more.
  • the elastomer is preferably added in an amount of 5 to 25 parts by weight based on 100 parts by weight of the polyarylene sulfide resin.
  • a silane coupling agent can be added to the polyarylene sulfide resin composition in order to further improve the adhesiveness of electronic parts and the like.
  • the silane coupling agent include epoxy group-containing compounds such as aglycidoxypropyltrimethoxysilane, aglycidoxypropyltriethoxysilane, and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • Alkoxy silane compounds such as 7-mercaptopropyltrimethoxysilane, 7 "-mercaptopropyltriethoxysilane, peridopropylpropyltrimethoxysilane, peridopropylpropylethoxysilane, and -(2-Peridoethyl) peridopropyl-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, -isocyanatopropyltrimethoxysilane, perisocyanatopropyltriethoxysilane, r-isosia Isocyanato group-containing alkoxysilane compounds such as natopropylmethyldimethoxysilane, artoxysilane, T-isocyanatopropylethyldimethoxysilane, isocyanatopropylethylethoxysilane,
  • vinyl group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane hydrochloride.
  • methacryloxypropyltrimethoxysilane (3 methacryloxypropyltrimethoxysilane) and acrylaminopropyltrimethoxysilane (3-aminopropyltrimethoxysilane).
  • the silane coupling agent is preferably added in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the polyarylene sulfide resin.
  • an epoxy resin can be added to the polyarylene sulfide resin composition in order to further improve the compatibility.
  • the epoxy resin contains two or more epoxy groups and can be used in liquid or solid form.
  • Epoxy resins include, for example, bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-1-diphenyldimethylmethane, 4 Glycidyl ethers of bisphenols such as, 4'-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashphenol, 2,2,5,51-tetrakis (4-hydroxyphenyl) hexane, Instead of bisphenol, glycidyl ethers such as halogenated bisphenols, diglycidyl ether of butanediol, etc .; glycidyl esters such as daricidyl phthalate; and daricidyl such as N-daricidylaniline etc.
  • Epoxy resin, resin, epoxidized soybean oil, etc. The to linear systems and vinylcyclohexane Examples include cyclic non-glycidyl epoxy resins such as sendoxides and epoxides, type epoxy resins, and halogen-substituted products thereof. Of these, a nopolak type epoxy resin is preferred.
  • the evoquisi resin is preferably added in an amount of 1 to 10 parts by weight based on 100 parts by weight of the polyarylene sulfide resin.
  • the polyarylene sulfide resin composition of the present invention contains a polyarylene sulfide resin having a small amount of oligomers, a total amount of contained metal ions, or a small amount of metal ions extracted with hot water, the content of these impurities is small. This has the effect of not deteriorating the performance of the electronic component as described above.
  • the composition has an oligomer amount of 3 O mg / g or less, a total amount of contained metal ions of 100 ppm or less, or a total amount of hot water extracted metal ions of 50 ppm or less.
  • the polyarylene sulfide resin and the composition thereof of the present invention include a plasticizer, a crystal nucleating agent, a release agent, a coloring inhibitor, an antioxidant, and a heat stabilizer as long as the effects of the present invention are not impaired.
  • Additives such as lubricants, UV inhibitors, coloring agents, flame retardants, foaming agents or other resins can be added.
  • the polyarylene sulfide resin and the composition thereof of the present invention can be produced, for example, by melt-kneading the above-mentioned components using an apparatus such as a Brabender-mixer, an extruder, particularly a twin-screw extruder.
  • an apparatus such as a Brabender-mixer, an extruder, particularly a twin-screw extruder.
  • any molding method such as injection molding, extrusion molding, professional molding, tube molding, transfer molding, compression molding, injection compression molding, etc., injection molded products, sheets, films, pipes Extruded products such as fibers, rods and rods, transfer molded products and compression molded products can be obtained.
  • the polyarylene sulfide resin and the composition thereof of the present invention may be used as a sealing material for electronic components, for example, a sealing material or a case material for casing, covering or sealing electronic devices and automotive electrical components. It can be used as a structural material in contact with metal members such as electronic devices and lead frames.
  • Such electronic components include, for example, transistors, FETs, diodes, thyristors, triacs, diacs, IGBTs, ICs, semiconductors such as intelligent power modules, light-emitting diodes, photodiodes, phototransistors, laser diodes, and photo diodes.
  • Optical semiconductors such as cyris, photo bra, CCD, C-MOS, etc., substrates, connectors, resistors, capacitors, coils, relays, Examples include sensors and automotive electrical components such as module cases and coil cases.
  • a polymerization reaction (260 ° C.) was carried out in the main polymerization tank 1 of the above-described production apparatus of FIG. 1 to synthesize a polyarylene sulfide resin.
  • the charge amount of the prepolymer was 15.O kgZhr, and the average residence time was 3 hours.
  • the reaction liquid discharged from the main polymerization tank 1 was led to the stationary tank 3 (260 ° C) to separate the reaction liquid from the polyarylene sulfide resin phase.
  • washing solution H 2 0 / NM P mixture, 'neutralizing agent such as NH 4 C 1 optionally
  • the washing liquid was also injected at 17 kg / hr into the high molecular weight polyarylene sulfide resin phase extracted from the bottom of the stationary tank 3 and again contact-mixed with the washing liquid and separated in the stationary separation tank.
  • the intrinsic viscosity of the obtained polymer was 77 inh, and was 0.16, and the amount of Li contained in the polymer was 60 ppm. At this time, no metal ions other than Li were detected.
  • the form-form soluble component contained in this polymer was 23 mg Zg. Further, the amount of metal ions extracted with hot water in this polymer was 30 ppm. In addition, these test methods followed the following method.
  • Sample 04g ⁇ 0. OO lg is dissolved in 10 cc of ⁇ -cloth Naphylene in 235 for 15 minutes, and the viscosity and polymer obtained in a thermostat at 206 ° C are not dissolved.
  • the relative viscosity to the viscosity of; -chloronaphthalene was measured, and the intrinsic viscosity? 7 inh was obtained from the following equation.
  • the pellets discharged from the extruder outlet were cooled with liquid nitrogen, then powdered, sieved with a 9-mesh sieve, and 9 g of the obtained sample was subjected to Soxhlet extraction for 8 hours using a black hole form as a solvent.
  • the extract of the formal form was filtered at 40 ° C or higher using a cylindrical filter paper (ADVANTE C84 (28 ⁇ 100 mm)), and the solvent was removed.
  • the obtained solid was used as a chloroform-soluble component.
  • the amount of soluble components in the mouth was determined by liquid mouth chromatography and expressed as the weight (mg) per gram of the sample before Soxhlet extraction.
  • particles having a mesh of 100 mesh and a mesh of 200 mesh were selected. 1 g of the particles were poured into 100 ml of pure water, extracted with hot water at 121 ° C. for 2 hours, and the amount of hot water oil-extracted metal ions was measured by ion chromatography.
  • the polyarylene sulfide resin composition was prepared by blending PPS 1, silica (manufactured by Denki Kagaku Kogyo) and elastomer (Bondane AX8390, manufactured by Sumitomo Chemical) in the proportions shown in Table 1 obtained in Example 1.
  • Table 1 the unit of the amount of each component is parts by weight.
  • the prepared resin composition was evaluated by the following method. Table 1 shows the results.
  • the TO-3P transistor package (10A, withstand voltage 500V) was continuously energized in a 60 X 95% Rh environment, and the time until failure occurred was measured to evaluate the electrical characteristics. The time until the occurrence of a failure was the time until leakage current ⁇ 100 mA.
  • the polyarylene sulfide resin composition was prepared by blending PPS 1, obtained in Example 1, PPS 2 described later, and silica at a ratio shown in Table 1, and evaluated. Table 1 shows the results. Comparative Examples 1-4
  • Example 2 the same method as in Example 1 was used to reduce the injection amount of the cleaning solution to 16 kg / hr at the outlet of the main polymerization tank 1 and to 3 kgZhr in the stationary tank 3. Except that polyarylene sulfide resin (PPS 2) (content of metal ion: 1,300 Ppm, amount of extracted metal ion: 600 ppm, amount of oligomer: 5 OmgZg) was used in the same manner as in Examples 2 to 5 A polyarylene sulfide resin composition was prepared and evaluated. Table 1 shows the mixing ratio and the evaluation results.
  • PPS 2 polyarylene sulfide resin
  • a polyarylene sulfide resin which does not cause a decrease in the performance of an electronic device due to elution of ionic impurities, decrease in adhesion, contamination of internal components or gas burning, and an electronic component sealing made therefrom. Material can be provided.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

A polyarylene sulfide resin having a content of an oligomer which may be extracted by chloroform of 30 mg/g or less and having a total content of metal ions of 100 ppm or less. The polyarylene sulfide resin and a polyarylene sulfide resin composition containing the polyarylene sulfide resin and silica can be advantageously used as a sealing agent for electronic parts.

Description

明 細 書 ポリアリ一レンスルフィド樹脂及びこれからなる電子部品用封止材 技術分野  Description Polyarylene sulfide resin and encapsulant for electronic components made of it
本発明は、 ポリアリ—レンスルフィド樹脂及びこれからなる電子部品用封止材 に関する。 より詳細には、 電子部品や自動車電装部品等の構造材料に用いるポリ ァリ一レンスルフィド樹脂及びこれからなる電子部品用封止材に関する。 背景技術  The present invention relates to a polyarylene sulfide resin and a sealing material for electronic components comprising the same. More specifically, the present invention relates to a polystyrene sulfide resin used for a structural material such as an electronic component or an automobile electric component, and a sealing material for an electronic component made of the resin. Background art
ポリアリーレンスルフィド樹脂組成物において、 ベースレジンとして繁用され ているポリフエ二レンスルフィド樹脂中の N a量や C 1量を規定することで、 樹 脂組成物の電子部品への適用を試みた例が知られている。 例えば、 特開昭 6 2— 1 5 0 7 5 2号公報では、 全 N a含有量が 8 0 0 p p m以下、 水溶性 C 1含有量 が 5 0 p p m以下のポリフエ二レンスルフィド樹脂からなる封止材が開示されて いる。  An example of an attempt to apply a resin composition to electronic components by specifying the Na content and C1 content in polyphenylene sulfide resin, which is frequently used as a base resin in a polyarylene sulfide resin composition It has been known. For example, Japanese Patent Application Laid-Open No. 62-150725 discloses a seal made of a polyphenylene sulfide resin having a total Na content of 800 ppm or less and a water-soluble C 1 content of 50 ppm or less. Stoppers are disclosed.
しかし、 上記の封止材を用いた電子部品では、 実際には、 連続通電試験を行う と、 電極や導線等の金属部材の腐食が起こり、 断線や漏れ電流の増大等の不良が 発生することがあった。 これは、 金属部材の表面に付着した水分に、 N aや C 1 以外のイオン性物質が溶け出して、 電気伝導性を生じることが原因である。 従つ て、 ポリフエ二レンスルフィド樹脂の N a含有量と C 1含有量を規定するだけで は、 このような不良を防止するには不足であり、 これらだけでなく、 ポリフエ二 レンスルフィド樹脂中のイオン性不純物、 特に金属イオンの総量を規定する必要 がある。  However, in the case of electronic components using the above-mentioned sealing materials, in practice, when a continuous conduction test is performed, corrosion of metal members such as electrodes and conductive wires occurs, and defects such as disconnection and increase in leakage current occur. was there. This is due to the fact that ionic substances other than Na and C 1 are dissolved out into the water attached to the surface of the metal member, thereby generating electrical conductivity. Therefore, it is not sufficient to prevent such defects only by specifying the Na content and the C1 content of the polyphenylene sulfide resin. It is necessary to specify the total amount of ionic impurities, especially metal ions.
また、 ポリフエ二レンスルフイド樹脂の製造過程で生成するオリゴマーも、 そ の含有量が増加すると、 これからなる封止材と、 電子デバイスや金属部材との密 着性の低下や、 これらの汚染を招く可能性がある。 さらに、 オリゴマー量が増加 すると、 加熱時に揮発性のガスが発生し易くなるため、 射出成形時にガス焼けを 招く場合がある。 従って、 このような不具合を防止するには、 ポリフエ二レンス ルフィド樹脂中のオリゴマー量を規定する必要がある。 本発明は、 以上の様な不具合を鑑みなされたもので、 イオン性不純物の溶出、 密着性の低下、 内部部品の汚染又はガス焼け等による電子デバイスの性能の低下 を起こさないポリアリ一レンスルフィド樹脂及びこれからなる電子部品用封止材 を提供す ことを目的とする。 In addition, when the content of oligomers produced in the production process of polyphenylene sulfide resin increases, the adhesion between the encapsulant and the electronic device or metal member may be reduced, or these contaminations may be caused. There is. Further, when the amount of the oligomer is increased, volatile gas is easily generated at the time of heating, which may cause gas burning at the time of injection molding. Therefore, in order to prevent such a problem, it is necessary to regulate the amount of oligomer in the polyphenylene sulfide resin. SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and is a polyarylene sulfide resin which does not cause degradation of electronic device performance due to elution of ionic impurities, reduction in adhesion, contamination of internal parts or gas burning. And a sealing material for electronic components comprising the same.
本発明者等は、 上記目的を達成するために鋭意研究を重ねた結果、 ポリアリー レンスルフィド樹脂中の含有金属イオン総量及びオリゴマ一量を一定量以下に低 減することにより、 上記の課題が解決できることを見出し本発明を完成させた。 発明の開示  The present inventors have conducted intensive studies to achieve the above object, and as a result, the above-mentioned problems were solved by reducing the total amount of metal ions and the amount of oligomer contained in the polyarylene sulfide resin to a certain amount or less. We have found that we can do this and completed the present invention. Disclosure of the invention
本発明の第一の態様によれば、 クロ口ホルムに抽出されるオリゴマー量が 3 0 m g / g以下のポリアリーレンスルフィド樹脂が提供される。  According to a first aspect of the present invention, there is provided a polyarylene sulfide resin having an oligomer amount of 30 mg / g or less that is extracted into a black form.
本発明のポリアリーレンスルフィド樹脂は、 好ましくは、 含有金属イオンの総 量が 1 0 0 p p m以下であり、 また、 好ましくは、 熱水抽出金属イオンの総量が l O O p p m以下である。  The polyarylene sulfide resin of the present invention preferably has a total content of metal ions of 100 ppm or less, and preferably has a total amount of metal ions extracted with hot water of 100 ppm or less.
また、 本発明のポリアリ一レンスルフィド樹脂は、 好ましくは、 硫化リチウム を原料として製造される。  In addition, the polyarylene sulfide resin of the present invention is preferably produced using lithium sulfide as a raw material.
本発明の第二の態様によれば、 上記のポリアリーレンスルフィド樹脂及びシリ 力を含むポリアリーレンスルフィド樹脂組成物が提供される。  According to a second aspect of the present invention, there is provided a polyarylene sulfide resin composition containing the above polyarylene sulfide resin and silicic acid.
本発明のポリアリーレンスルフイド樹脂組成物は、 さらに、 エラストマ一を含 むことができ、 さらに、 シランカップリング剤及び Z又はエポキシ樹脂を含むこ とができる。  The polyarylene sulfide resin composition of the present invention can further contain an elastomer, and can further contain a silane coupling agent and a Z or epoxy resin.
本発明の第三の態様によれば、 上記のポリアリーレンスルフィド樹脂又はポリ ァリーレンスルフィド樹脂組成物からなる電子部品用封止材が提供される。 本発明の第四の態様によれば、 上記の電子部品用封止材を含む電子部品が提供 される。 図面の簡単な説明  According to a third aspect of the present invention, there is provided an electronic component sealing material comprising the above-mentioned polyarylene sulfide resin or polyarylene sulfide resin composition. According to a fourth aspect of the present invention, there is provided an electronic component including the above electronic component sealing material. BRIEF DESCRIPTION OF THE FIGURES
図 1は、 ポリアリ一レンスルフィド樹脂の製造装置を示す模式図である。 発明を実施するための最良の形態 以下、 本発明のポリアリーレンスルフィド樹脂について説明する。 FIG. 1 is a schematic diagram showing an apparatus for producing a polyarylene sulfide resin. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the polyarylene sulfide resin of the present invention will be described.
本発明のポリアリーレンスルフィド樹脂は、 構造式 〔一 A r— S—〕 （ただし、 A rはァリーレン基、 Sはィォゥである） を基本とする重合体で、 その代表的例 は、 下記ニ般式 （1 ) で示される繰り返し単位を、 好ましくは 7 0モル％以上、 より好ましくは 8 0モル％以上含有する重合体である。 当該繰り返し単位が 7 0 モル％未満だと、 結晶性ポリマ一としての特徴である本来の結晶成分が少なく、 機械的強度が不充分となる場合がある。  The polyarylene sulfide resin of the present invention is a polymer based on the structural formula [1 Ar—S—] (where Ar is an arylene group and S is iodide). It is a polymer containing preferably at least 70 mol%, more preferably at least 80 mol%, of the repeating unit represented by the general formula (1). When the content of the repeating unit is less than 70 mol%, the original crystalline component, which is a characteristic of the crystalline polymer, is small, and the mechanical strength may be insufficient.
Figure imgf000005_0001
Figure imgf000005_0001
(式中、 R1は炭素数 6以下のアルキル基、 アルコキシ基、 フエニル基、 力ルポ キシル基もしくはその金属塩、 ニトロ基、 及びフッ素、 塩素、 臭素等のハロゲン 原子から選ばれる置換基であり、 mは 0〜4の整数である。 nは平均重合度を示 し、 2 0〜： L 0 0の範囲である。 ） (Wherein, R 1 is a substituent selected from an alkyl group having 6 or less carbon atoms, an alkoxy group, a phenyl group, a carbonyl group or a metal salt thereof, a nitro group, and a halogen atom such as fluorine, chlorine, and bromine. And m is an integer of 0 to 4. n represents the average degree of polymerization and ranges from 20 to: L00.
本発明では、 ポリアリ一レンスルフイド樹脂として、 単独重合体以外に共重合 体も用いることができる。 共重合構成単位としては、 例えば、 メタフエ二レンス ルフィド単位、 オルソフエ二レンスルフイド単位、 p , p ' ージフエ二レンゲ トンスルフイド単位、 Ρ， ' ージフエ二レンスルホンスルフイド単位、 ρ , ρ ' —ビフエ二レンスルフイド単位、 ρ , ρ ' —ジフエ二レンメチレンスルフ イド単位、 ρ， ρ ' —ジフエ二レンクメニルスルフイド単位、 ナフチルスルフ ィド単位等が挙げられる。  In the present invention, a copolymer other than a homopolymer can be used as the polyarylene sulfide resin. Examples of the copolymerizable structural unit include metaphenylene sulfide unit, orthophenylene sulfide unit, p, p 'diphenylene sulfone sulfide unit, Ρ,' diphenylene sulfone sulfide unit, ρ, ρ'—biphenylene sulfide Unit, ρ, ρ'—diphenylene methylene sulfide unit, ρ, ρ′—diphenylene cumenyl sulfide unit, naphthyl sulfide unit and the like.
尚、 ポリアリーレンスルフイド樹脂は、 一般にその製法により、 リニアタイプ、 セミリニアタイプ、 架橋タイプ等の分子構造を有するものが知られているが、 本 発明では、 ポリアリーレンスルフイド樹脂の分子構造は、 特に制限されない。 本発明のポリアリーレンスルフィド樹脂は、 クロ口ホルムに抽出されるオリゴ マー量が 3 O mg Z g以下である。 オリゴマー量が 3 O m gを超えると、 電子部 品等に使用したときに、 デバイスや金属部材等との密着性が低下したり、 これら が汚染される場合や、 樹脂組成物の射出成形時にガス焼けを起こす場合がある。 オリゴマー量は、 好ましくは 2 5 m gZ g以下であり、 より好ましくは 1 2 mg Zg以下である。 ここで、 オリゴマーとは、 クロ口ホルムでソックスレー抽出し たときに溶出する低分子量のポリアリーレンスルフィド樹脂を意味する。 Incidentally, polyarylene sulfide resin is generally known to have a molecular structure such as a linear type, a semi-linear type, or a cross-linked type depending on its production method. The structure is not particularly limited. In the polyarylene sulfide resin of the present invention, the amount of the oligomer extracted into the pore form is 30 mg or less. When the amount of the oligomer exceeds 3 Omg, when used in electronic components, the adhesion to devices and metal members is reduced, May be contaminated, or gas burning may occur during injection molding of the resin composition. The amount of the oligomer is preferably 25 mgZg or less, more preferably 12 mgZg or less. Here, the oligomer means a low-molecular-weight polyarylene sulfide resin that elutes when subjected to Soxhlet extraction with a black hole form.
また、 ポリアリ一レンスルフイド樹脂は、 好ましくは、 含有金属イオンの総量 及び Z又は熱水抽出金属イオンの総量が 1 0 0 p p m以下である。 これらの金属 イオンの総量が 1 0 0 p pmを超えると、 電子部品の電極や配線等に溶出する金 属イオン量が多くなり、 これらが腐食して断線等を起こすため、 長時間の通電が 困難になる場合がある。 ポリアリーレンスルフィド樹脂中に含まれる金属イオン 種は、 原料の種類、 後処理に用いる材料の種類及び製造条件等により異なるが、 例えば、 N a、 L i、 K、 F e等が挙げられる。 含有金属イオンの総量及び/又 は熱水抽出金属イオンの総量は、 より好ましくは 5 0 p p m以下であり、 特に好 ましくは 3 0 p p m以下である。 特に、 上記金属イオンのうち、 N a及び L iは 3 0 p p m以下が好ましく、 Kは 5 0 p p m以下が好ましく、 6は1 0 13 111 以下が好ましい。  Further, the polyarylene sulfide resin preferably has a total amount of contained metal ions and a total amount of Z or hot water-extracted metal ions of 100 ppm or less. If the total amount of these metal ions exceeds 100 ppm, the amount of metal ions eluted to the electrodes and wiring of the electronic components will increase, and they will corrode and cause disconnection. It can be difficult. The metal ion species contained in the polyarylene sulfide resin varies depending on the type of the raw material, the type of the material used for the post-treatment, the production conditions, and the like, and examples thereof include Na, Li, K, and Fe. The total amount of the metal ions contained and / or the total amount of the metal ions extracted with hot water is more preferably 50 ppm or less, and particularly preferably 30 ppm or less. In particular, among the above metal ions, Na and Li are preferably 30 ppm or less, K is preferably 50 ppm or less, and 6 is preferably 10 13 111 or less.
このようなポリアリ一レンスルフィド樹脂は、 硫ィ匕リチウムを原料とする製造 方法により製造することができる。 硫化リチウムを原料とする製造方法では、 重 合条件に特に制限はなく、 例えば、 バッチ法、 連続法の製造方法を用いることが できる。  Such a polyarylene sulfide resin can be produced by a production method using lithium sulfate as a raw material. In the production method using lithium sulfide as a raw material, the polymerization conditions are not particularly limited, and for example, a production method of a batch method or a continuous method can be used.
例えば、 連続重合法では、 図 1の製造装置により重合を行うことができる。 図 1は、 ポリアリ一レンスルフイド樹脂の製造装置の模式図である。 この装置は、 本重合槽 1、 移送プロセスの配管 2及び静置槽 3よりなつており、 さらに配管途 中にミキサー 4を設置している。 ポリアリーレンスルフィド樹脂を含む反応液は、 1段 C S T R (連続攪拌槽型反応器） カ^なる本重合槽 1より連続的に排出され た後、 洗浄液とともにミキサー 4で混合され、 第 1静置槽 3内で、 密度差を利用 して静置される。 このとき、 ポリアリーレンスルフイド樹脂は、 静置槽 3内の下 相側に存在し、 液面計で検出される。 連続重合法では、 このミキサー Zセトラー 型洗浄操作を 3〜 4段程実施し、 さらに洗浄被の注入量を、 本重合槽 1より排出 される液量の 4〜5倍程度にすることにより、 ポリアリ一レンスルフィド樹脂を 含む槽内の含有金属イオン濃度を 1 0 0 p p m以下に、 また、 クロ口ホルムに抽 出されるオリゴマー量を 3 0 p pm以下まで低減することが可能となる。 For example, in the continuous polymerization method, polymerization can be performed by the production apparatus shown in FIG. FIG. 1 is a schematic view of an apparatus for producing a polyarylene sulfide resin. This equipment consists of a main polymerization tank 1, a transfer process pipe 2 and a stationary tank 3, and a mixer 4 is installed in the middle of the pipe. The reaction liquid containing the polyarylene sulfide resin is continuously discharged from the main polymerization tank 1 consisting of a single-stage CSTR (continuous stirred tank reactor), and then mixed with the washing liquid in the mixer 4 to form the first stationary tank. Within 3, it is settled using the density difference. At this time, the polyarylene sulfide resin is present on the lower phase side in the stationary tank 3 and is detected by a liquid level gauge. In the continuous polymerization method, this mixer Z settler type washing operation is performed about 3 to 4 stages, and the injection amount of the washing target is set to about 4 to 5 times the amount of the liquid discharged from the main polymerization tank 1. Reduce the metal ion concentration in the tank containing the polyarylene sulfide resin to 100 ppm or less, and extract it to the It is possible to reduce the amount of the oligomer to be output to 30 ppm or less.
このとき、 ポリアリーレンスルフィド樹脂を移送する配管 2及び静置槽 3は、 高温に保持しておくために、 ジャケット構造を必要とする。 例えば、 配管 2の場 合、 内径 Γ / 2 Β、 外径 1 · 1 / 2 Βの二重管等を用いる。 また、 洗浄溶液側には 低分子量ポリアリーレンスルフイド樹脂、 即ち、 オリゴマーがわずかに含まれて いるため、 配管構造は二重管等を用いる方が好ましいが、 二重管構造を用いなく ても運転できる。 ，ノ  At this time, the pipe 2 for transferring the polyarylene sulfide resin and the stationary tank 3 need a jacket structure in order to keep them at a high temperature. For example, in the case of the pipe 2, a double pipe having an inner diameter of Γ / 2Β and an outer diameter of 1 · 1 / 2Β is used. In addition, since the washing solution contains a small amount of a low-molecular-weight polyarylene sulfide resin, that is, an oligomer, it is preferable to use a double pipe or the like for the piping structure. Can also drive. , ノ
本発明では、 反応が容易に進行して、^高分子量のポリアリ一レンスルフィド樹 脂を効率的に得られる点から、 好ましくは、 硫化.リチウムを原料にした連続重合 法でポリアリーレンスルフイド樹脂を製造する。 このとき、 連続重合に先立って、 ポリアリ一レンスルフィド樹脂のプレボリマ一を合成し、 このプレボリマーを用 いて連続重合を行ってもよい。  In the present invention, from the viewpoint that the reaction proceeds easily and a high-molecular-weight polyarylene sulfide resin can be efficiently obtained, polyarylene sulfide is preferably produced by a continuous polymerization method using lithium sulfide as a raw material. Manufacture resin. At this time, prior to the continuous polymerization, a prepolymer of a polyarylene sulfide resin may be synthesized, and the continuous polymerization may be performed using the prepolymer.
次に、 本発明のポリアリーレンスルフィド樹脂組成物について説明する。  Next, the polyarylene sulfide resin composition of the present invention will be described.
本発明のポリアリーレンスルフィド樹脂組成物では、 上記のポリアリーレンス ルフィド樹脂及びシリカを含む。  The polyarylene sulfide resin composition of the present invention contains the above polyarylene sulfide resin and silica.
本発明では、 シリカは、 電子部品等の寸法安定性、 機械特性、 熱導電性等を向 上させるために添加される。 シリカとしては、 例えば、 溶融シリカ、 結晶性シリ 力、 合成シリカ等が挙げられる。 このうち、 溶融シリカが好ましい。  In the present invention, silica is added to improve dimensional stability, mechanical properties, thermal conductivity and the like of electronic components and the like. Examples of the silica include fused silica, crystalline silica, and synthetic silica. Of these, fused silica is preferred.
シリカは、 ポリアリ一レンスルフイド樹脂 1 0 0重量部に対して、 好ましくは 1 0 0〜 5 0 0重量部添加する。  Silica is preferably added in an amount of 100 to 500 parts by weight based on 100 parts by weight of the polyarylene sulfide resin.
尚、 これらのシリカは、 後述するシランカップリング剤で予備処理してから使 用してもよい。  Incidentally, these silicas may be used after pre-treatment with a silane coupling agent described later.
'ポリアリーレンスルフィド樹脂組成物には、 さらに、 電子部品等の耐衝撃性を 向上させるために、 エラストマ一 （ゴム状弾性体） を添加することができる。 エラストマ一としては、 例えば、 天然ゴム、 ポリブタジエン、 ポリイソプレン、 ポリイソブチレン、 ネオプレン、 ポリスルフィドゴム、 チォコールゴム、 ァクリ ルゴム、 ウレタンゴム、 シリコーンゴム、 ェピクロロヒドリンゴム、 スチレン一 ブタジエンブロック共重合体 ( S B R) 、 水素添加スチレン一ブタジエンブロッ ク共重合体 ( S E B , S E B C) 、 スチレン一ブタジエン一スチレンブロック共 重合体 ( S B S ) 、 水素添加スチレン—ブタジエン一スチレンブロック共重合体 (SEBS) 、 スチレン—イソプレンブロック共重合体 （S I R) 、 水素添加ス チレン一イソプレンブロック共重合体 (SEP) 、 スチレン一イソプレン一スチ レンプロック共重合体 (S I S) , 水素添加スチレン一イソプレン一スチレンブ ロック共重合体 (SEPS) 、 又はエチレンプロピレンゴム （EPM) 、 ェチレ ンプロピレンジェンゴム （EPDM) 、 あるいはブタジエン一アクリロニトリル —スチレン—コアシェルゴム （ABS) 、 メテルメタクリレートーブタジエン一 スチレン一コアシェルゴム (MBS) 、 メチルメ夕クリレ一トープチルァクリレ 一卜一スチレン一コアシェルゴム （MAS) 、 ォクチルァクリレ一トーブ夕ジェ ン一スチレン一コアシェルゴム (MABS) 、 アルキルァクリレ一ト一ブ夕ジェ ンーァクリロ二トリ レ一スチレン一コアシェルゴム （AABS) 、 ブタジエン一 スチレン一コアシェルゴム (SBR) 、 メチルメタクリレート一プチルァクリレ —トーシロキサンをはじめとするシロキサン含有コアシェルゴム等のコアシェル タイプの粒子状エラストマ一、 又はこれらを変性したゴム等が挙げられる。 'An elastomer (rubber-like elastic material) can be further added to the polyarylene sulfide resin composition in order to improve the impact resistance of electronic components and the like. Examples of elastomers include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiochol rubber, acryl rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer (SBR) , Hydrogenated styrene-butadiene block copolymer (SEB, SEBC), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block Copolymer (SEPS), or ethylene propylene rubber (EPM), ethylene propylene rubber (EPDM), or butadiene-acrylonitrile-styrene-core-shell rubber (ABS), meter methacrylate butadiene-styrene-core-shell rubber (MBS), Methyl methyl terephthalate styrene core styrene core rubber (MAS), octyl acrylone styrene rubber core styrene-core shell rubber (MABS), alkyl acrylate rubber styrene core styrene core shell Rubber (AABS), Butadier One styrene first core shell rubber (SBR), methyl methacrylate one Puchiruakurire - include rubber such as core-shell type particulate elastomer one or these were modified such as a siloxane-containing core shell rubber including a toe siloxane.
このうち、 特に、 SBR、 SEB、 SBS、 SEBS, S I R、 SEP, S I S、 SEPS、 コアシェルゴム、 EPM、 EPDM, 又はこれらを変性したゴム が好ましく用いられる。 これらのエラストマ一は 1種単独で、 又は 2種以上配合 して用いることができる。  Among them, SBR, SEB, SBS, SEBS, SIR, SEP, SIS, SEPS, core shell rubber, EPM, EPDM, or a rubber modified from these is preferably used. These elastomers can be used alone or in combination of two or more.
エラストマ一は、 ポリアリ一レンスルフイ ド樹脂 100重量部に対して、 好ま しくは 5〜 25重量部添加する。  The elastomer is preferably added in an amount of 5 to 25 parts by weight based on 100 parts by weight of the polyarylene sulfide resin.
また、 ポリアリーレンスルフイド樹脂組成物には、 さらに、 電子部品等の密着 性をより向上させるために、 シランカツプリング剤を添加することができる。 シランカップリング剤としては、 例えば、 ァーグリシドキシプロピル卜リメ トキシシラン、 ァ―グリシドキシプロピルトリエトキシシラン、 β— (3,4 - エポキシシクロへキシル) エヂルトリメトキシシラン等のエポキシ基含有アルコ キシシラン化合物、 Τ—メルカプトプロピルトリメトキシシラン、 7"—メルカ ブトプロピルトリエトキシシラン等のメルカプト基含有アルコキシシラン化合物、 Τーゥレイドプロビルトリメトキシシラン、 ァ一ゥレイドプロピルトリエトキ シシラン、 ァー （2—ゥレイドエチル） ァミノプロピルトリメトキシシラン等 のゥレイド基含有アルコキシシラン化合物、 Τ—イソシアナトプロピルトリメ トキシシラン、 ァーイソシアナトプロピルトリエトキシシラン、 r一イソシァ ナトプロピルメチルジメトキシシラン、 アー- トキシシラン、 T一イソシアナトプロピルェチルジメトキシシラン、 ァーイソ シアナトプロピルェチルジェトキシシラン、 ァ一ィソシアナトプロピルトリク ロロシラ 等のイソシアナト基含有アルコキシシラン化合物、 r - ( 2—アミ ノエチル） ァミノプロピルメチルジメトキシシラン、 Ύ一 ( 2—アミノエチ ル） ァミノプロピルトリメトキシシラン、 T—アミノプロピルトリメトキシシ ラン等のアミノ基含有アルコキシシラン化合物、 ァーヒドロキシプロピルトリ メトキシシラン、 ァーヒドロキシプロピルトリエトキシシラン等の水酸基含有 アルコキシシラン化合物、 r - ビニルトリメトキシシラン、 N
Figure imgf000009_0001
Further, a silane coupling agent can be added to the polyarylene sulfide resin composition in order to further improve the adhesiveness of electronic parts and the like. Examples of the silane coupling agent include epoxy group-containing compounds such as aglycidoxypropyltrimethoxysilane, aglycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Alkoxy silane compounds, mercapto group-containing alkoxysilane compounds such as 7-mercaptopropyltrimethoxysilane, 7 "-mercaptopropyltriethoxysilane, peridopropylpropyltrimethoxysilane, peridopropylpropylethoxysilane, and -(2-Peridoethyl) peridopropyl-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, -isocyanatopropyltrimethoxysilane, perisocyanatopropyltriethoxysilane, r-isosia Isocyanato group-containing alkoxysilane compounds such as natopropylmethyldimethoxysilane, artoxysilane, T-isocyanatopropylethyldimethoxysilane, isocyanatopropylethylethoxysilane, and isocyanatopropyltrichlorosila, r- ( 2-aminopropyl) aminopropylmethyldimethoxysilane, amino (2-aminoethyl) aminopropyltrimethoxysilane, amino-containing alkoxysilane compounds such as T-aminopropyltrimethoxysilane, and hydroxypropyltrimethoxysilane Hydroxyl-containing alkoxysilane compounds such as silane and hydroxypropyltriethoxysilane, r-vinyltrimethoxysilane, N
Figure imgf000009_0001
ァーァミノプロピルトリメトキシシラン ·塩酸塩等のビニル基含有アルコキシ シラン化合物等が挙げられる。 And vinyl group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane hydrochloride.
これらのうち、 ァ一メタクリロキシプロプルトリメトキシシラン ( 3 メタ クリロキシプロプルトリメトキシシラン) 、 ァ一ァミノプロプルトリメトキシ シラン ( 3—ァミノプロプルトリメ キシシラン) が好ましい。  Of these, preferred are methacryloxypropyltrimethoxysilane (3 methacryloxypropyltrimethoxysilane) and acrylaminopropyltrimethoxysilane (3-aminopropyltrimethoxysilane).
シランカップリング剤は、 ポリアリーレンスルフィド樹脂 1 0 0重量部に対し て、 好ましくは 0 . 5〜 5重量部添加する。  The silane coupling agent is preferably added in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the polyarylene sulfide resin.
また、 ポリアリーレンスルフイド樹脂組成物には、 さらに、 相溶性を向上させ るために、 エポキシ樹脂を添加することができる。 エポキシ樹脂は、 二個以上の エポキシ基を含んでおり、 液体状又は固体状のものが使用できる。  Further, an epoxy resin can be added to the polyarylene sulfide resin composition in order to further improve the compatibility. The epoxy resin contains two or more epoxy groups and can be used in liquid or solid form.
エポキシ樹脂としては、 例えば、 ビスフエノール A、 レゾルシノ一ル、 ハイド ロキノン、 ピロカテコール、 ビスフエノール F、 サリゲニン、 1 , 3 , 5—トリ ヒドロキシベンゼン、 ビスフエノール S、 トリヒドロキシ一ジフエニルジメチル メタン、 4， 4 ' —ジヒドロキシビフエニル、 1 , 5—ジヒドロキシナフタレ ン、 カシュ一フエノール、 2 , 2 , 5 , 5一テ卜ラキス ( 4ーヒドロキシフエ二 ル） へキサン等のビスフエノ一ルのグリシジルェ一テル、 ビスフエノールの代わ りにハロゲン化ビスフエノール、 ブタンジオールのジグリシジルエーテル等のグ リシジルエーテル系、 フタル酸ダリシジルエステル等のグリシジルエステル系、 N—ダリシジルァニリン等のダリシジルァミン系等のダリシジルエポキシ樹脂、 ン、 エポキシ化大豆油等の線状系及びビニルシクロへキ センジオキサイド、 ド等の環状系の非グリシジ ルエポキシ樹脂、 型ェポキシ樹脂及びこれらのハロゲン置換物等が挙 げられる。 このうち、 ノポラック型エポキシ樹脂が好ましい。 Epoxy resins include, for example, bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-1-diphenyldimethylmethane, 4 Glycidyl ethers of bisphenols such as, 4'-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashphenol, 2,2,5,51-tetrakis (4-hydroxyphenyl) hexane, Instead of bisphenol, glycidyl ethers such as halogenated bisphenols, diglycidyl ether of butanediol, etc .; glycidyl esters such as daricidyl phthalate; and daricidyl such as N-daricidylaniline etc. Epoxy resin, resin, epoxidized soybean oil, etc. · The to linear systems and vinylcyclohexane Examples include cyclic non-glycidyl epoxy resins such as sendoxides and epoxides, type epoxy resins, and halogen-substituted products thereof. Of these, a nopolak type epoxy resin is preferred.
ェボキジ樹脂は、 ポリアリーレンスルフイド樹脂 1 0 0重量部に対して、 好ま しくは 1〜1 0重量部添加する。  The evoquisi resin is preferably added in an amount of 1 to 10 parts by weight based on 100 parts by weight of the polyarylene sulfide resin.
本発明のポリアリ一レンスルフイド樹脂組成物は、 オリゴマー量、 含有金属ィ オンの総量又は熱水抽出金属イオンの総量の少ないポリアリ一レンスルフィド樹 脂を含んでいるので、 これら不純物の含有量が少なく、 上述したような電子部品 の性能を低下させない効果を有する。 好ましくは、 この組成物のオリゴマー量は 3 O m g / g以下、 含有金属イオンの総量は 1 0 0 p p m以下、 又は熱水抽出金 属イオンの総量は 5 0 p p m以下である。  Since the polyarylene sulfide resin composition of the present invention contains a polyarylene sulfide resin having a small amount of oligomers, a total amount of contained metal ions, or a small amount of metal ions extracted with hot water, the content of these impurities is small. This has the effect of not deteriorating the performance of the electronic component as described above. Preferably, the composition has an oligomer amount of 3 O mg / g or less, a total amount of contained metal ions of 100 ppm or less, or a total amount of hot water extracted metal ions of 50 ppm or less.
また、 本発明のポリアリーレンスルフイド樹脂及びその組成物には、 本発明の 効果を損なわない範囲で、 可塑剤、 結晶核剤、 離型剤、 着色防止剤、 酸化防止剤、 熱安定剤、 滑剤、 紫外線防止剤、 着色剤、 難燃剤、 発泡剤又は他の樹脂等の添加 剤を加えることができる。  In addition, the polyarylene sulfide resin and the composition thereof of the present invention include a plasticizer, a crystal nucleating agent, a release agent, a coloring inhibitor, an antioxidant, and a heat stabilizer as long as the effects of the present invention are not impaired. Additives such as lubricants, UV inhibitors, coloring agents, flame retardants, foaming agents or other resins can be added.
本発明のポリアリーレンスルフイド樹脂及びその組成物は、 例えば、 上記の各 成分を、 ブラベンダ一ミキサ一、 押出機、 特に二軸押出機等の装置を用い、 溶融 混練して製造することができ、 さらに、 射出成形、 押出成形、 プロ一成形、 チュ ーブ成形、 トランスファ一成形、 圧縮成形、 射出圧縮成形等の任意の成形法に供 することにより、 射出成形品、 シート、 フィルム、 パイプ、 繊維、 棒状体等の押 出成形品、 トランスファー成形品、 圧縮成形品とすることができる。  The polyarylene sulfide resin and the composition thereof of the present invention can be produced, for example, by melt-kneading the above-mentioned components using an apparatus such as a Brabender-mixer, an extruder, particularly a twin-screw extruder. In addition, by subjecting it to any molding method such as injection molding, extrusion molding, professional molding, tube molding, transfer molding, compression molding, injection compression molding, etc., injection molded products, sheets, films, pipes Extruded products such as fibers, rods and rods, transfer molded products and compression molded products can be obtained.
本発明のポリアリ一レンスルフィド樹脂及びその組成物は、 電子部品用封止部 材、 例えば、 電子デバイスや自動車電装部品のケ一シング、 被覆又は封止のため の封止材又はケース材等、 電子デバイスゃリードフレーム等の金属部材と接する 構造材料として使用できる。  The polyarylene sulfide resin and the composition thereof of the present invention may be used as a sealing material for electronic components, for example, a sealing material or a case material for casing, covering or sealing electronic devices and automotive electrical components. It can be used as a structural material in contact with metal members such as electronic devices and lead frames.
このような電子部品としては、 例えば、 トランジスタ、 F E T、 ダイオード、 サイリス夕、 トライアツク、 ダイアック、 I G B T、 I C類、 インテリジェント パワーモジュール等の半導体類、 発光ダイオード、 フォトダイオード、 フォトト ランジス夕、 レーザーダイオード、 フォトサイリス夕、 フォト力ブラ、 C C D , C一 MO S等の光半導体、 基板、 コネクタ、 抵抗、 コンデンサ、 コイル、 リレー、 センサ、 及びモジュールケース、 コイルケース等の自動車電装部品等が挙げられ る。 実施例 Such electronic components include, for example, transistors, FETs, diodes, thyristors, triacs, diacs, IGBTs, ICs, semiconductors such as intelligent power modules, light-emitting diodes, photodiodes, phototransistors, laser diodes, and photo diodes. Optical semiconductors such as cyris, photo bra, CCD, C-MOS, etc., substrates, connectors, resistors, capacitors, coils, relays, Examples include sensors and automotive electrical components such as module cases and coil cases. Example
次に、 本発明を実施例によりさらに詳細に説明するが、 本発明はこれらの実施 例に制限されない。  Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
実施例 1 Example 1
ポリアリーレンスルフィド樹脂の合成 Synthesis of polyarylene sulfide resin
攪拌翼のついた原料合成槽 （lm3) に、 N—メチルー 2_ピロリドン （NM P) 554 kg, 及び水酸化リチウム （L i OH . 1H20) 100 k gを仕込 み、 昇温し 140°Cに保ち、 原料 L i OH中に含まれる水を回分蒸留し、 除去 した。 この操作終了後、 130°Cに保ったまま、 気体状の硫化水素 （H2S) を 6 5 Nk L吹き込んだ。 この操作により水硫化リチウム （L i SH) を下記 (1) 式により合成した。 The raw synthesis vessel equipped with a stirring blade (lm 3), N-methyl-2_ pyrrolidone (NM P) 554 kg, and lithium hydroxide (L i OH. 1H 2 0 ) to 100 kg viewed charged, the temperature was raised 140 While maintaining the temperature at ° C, water contained in the raw material LIOH was removed by batch distillation. After the completion of this operation, 65 Nk L of gaseous hydrogen sulfide (H 2 S) was blown while maintaining the temperature at 130 ° C. By this operation, lithium hydrosulfide (L i SH) was synthesized by the following equation (1).
L i OH + H2S → L i SH + H20 (1) L i OH + H 2 S → L i SH + H 2 0 (1)
その後、 硫化水素の吹き込みを停止し、 再び合成槽を 205°Cまで昇温した。 昇温に伴い、 硫化水素を吹き込んだ際に副生する水を回分蒸留により除去すると 共に、 下記 （2) 式の反応を進行させ、 硫化リチウム （L i 2S) を 49. 62 kg (1. 08 kmo 1) と N—メチルァミノ酪酸リチウム （LMAB) の混合 物を得た。 After that, the injection of hydrogen sulfide was stopped, and the temperature of the synthesis tank was raised to 205 ° C again. As the temperature rises, water produced as a by-product when hydrogen sulfide is blown in is removed by batch distillation, and the reaction of the following formula (2) is allowed to proceed to convert lithium sulfide (L i 2 S) to 49.62 kg (1 A mixture of .8 kmo1) and lithium N-methylaminobutyrate (LMAB) was obtained.
2L i SH → L i 2S + LMAB + H2S† (2) 上記 （2) 式の反応終了後、 パラジクロロベンゼン （PDCB) 154 kg (1. 05 kmo 1 ) を投入し、 さらに純水 29. 2kgを投入し、 210 °C X 3時間のプレ縮合操作を実施した後、 90°Cまで冷却した。 さらに、 PDC B 15 kg (0. 102 kmo 1 ) と NMP 80 k gをこれに加えて、 プレポリ マーを合成した。 2L i SH → L i 2 S + LMAB + H 2 S † (2) After the completion of the reaction of the above equation (2), pour 154 kg (1.05 kmo 1) of paradichlorobenzene (PDCB) and further add pure water 29 2 kg was charged, and a pre-condensation operation was performed at 210 ° C for 3 hours, and then cooled to 90 ° C. Furthermore, a prepolymer was synthesized by adding 15 kg (0.102 kmo 1) of PDC B and 80 kg of NMP.
上記操作で合成したプレボリマ一を用い、 上述した図 1の製造装置の本重合槽 1で重合反応 (260°C) を行い、 ポリアリーレンスルフイド樹脂を合成した。 このとき、 プレポリマーのチャージ量を 15. O kgZh rとし、 また、 平均滞 留時間て = 3時間とした。 本重合槽 1から排出される反応液を静置槽 3 (260°C) に導き、 反応液と ポリアリーレンスルフイド樹脂相を分離した。 本重合槽 1の出口には、 ポリマー 相中に含まれるハロゲン化リチウムを洗浄除去する目的で、 洗浄液 （H20/NM P混合液、'場合により NH4C 1等の中和剤） を 16 kgZh rで注入した。 静 置槽 3の底部より抜き出した、 高分子量ポリアリーレンスルフイド樹脂相にも洗 浄液を 17 kg/h rで注入し、 再度洗浄液と接触混合し、 静置分離槽で分離し た。 このポリアリーレンスルフイド樹脂の洗浄操作を 3段繰り返し、 洗浄を終了 したポリアリーレンスルフィド樹脂相を脱揮機能付押出機に導き、 揮発性溶媒 (主に NMP) を除去した後、 水冷してペレ夕イジングを行ない、 製品 （PPS 1) を得た。 製品の生産量は約 2 k g/h rであった。 Using the prepolymer synthesized by the above operation, a polymerization reaction (260 ° C.) was carried out in the main polymerization tank 1 of the above-described production apparatus of FIG. 1 to synthesize a polyarylene sulfide resin. At this time, the charge amount of the prepolymer was 15.O kgZhr, and the average residence time was 3 hours. The reaction liquid discharged from the main polymerization tank 1 was led to the stationary tank 3 (260 ° C) to separate the reaction liquid from the polyarylene sulfide resin phase. The outlet of the polymerization vessel 1, for the purpose of washing away lithium halide contained in the polymer phase, washing solution (H 2 0 / NM P mixture, 'neutralizing agent such as NH 4 C 1 optionally) Injected at 16 kgZhr. The washing liquid was also injected at 17 kg / hr into the high molecular weight polyarylene sulfide resin phase extracted from the bottom of the stationary tank 3 and again contact-mixed with the washing liquid and separated in the stationary separation tank. This washing operation of the polyarylene sulfide resin was repeated in three steps, and the washed polyarylene sulfide resin phase was led to an extruder with a devolatilization function to remove volatile solvents (mainly NMP) and then cooled with water. Pelleting was performed to obtain a product (PPS 1). Product output was about 2 kg / hr.
得られたポリマーの固有粘度 ?7 inhは、 0. 16であり、 ポリマ一中に含まれ る L i量は、 60 ppmであった。 このとき、 L i以外の金属イオンは検出され なかった。 また、 このポリマー中に含まれるクロ口ホルム可溶成分は、 23mg Zgであった。 さらに、 このポリマー中の熱水抽出金属イオン量は、 30 p pm であった。 尚、 これらの試験方法は、 以下の方法に従った。  The intrinsic viscosity of the obtained polymer was 77 inh, and was 0.16, and the amount of Li contained in the polymer was 60 ppm. At this time, no metal ions other than Li were detected. The form-form soluble component contained in this polymer was 23 mg Zg. Further, the amount of metal ions extracted with hot water in this polymer was 30 ppm. In addition, these test methods followed the following method.
[固有粘度の測定]  [Measurement of intrinsic viscosity]
サンプル 04g±0. O O l gを、 α—クロ口ナフ夕レン 10 c c中に 235 、 15分間内で溶解させ、 206 °Cの恒温槽内で得られる粘度とポリ マ一を溶解させていない α;—クロロナフタレンの粘度との相対粘度を測定し、 固有粘度 ?7inhを、 次式から求めた。  Sample 04g ± 0. OO lg is dissolved in 10 cc of α-cloth Naphylene in 235 for 15 minutes, and the viscosity and polymer obtained in a thermostat at 206 ° C are not dissolved. The relative viscosity to the viscosity of; -chloronaphthalene was measured, and the intrinsic viscosity? 7 inh was obtained from the following equation.
?7inh= 1 n (相対粘度） /ポリマー濃度 [d 1/g]  ? 7inh = 1 n (relative viscosity) / polymer concentration [d 1 / g]
[ポリマー中の L i量の定量]  [Quantitative determination of Li in polymer]
l〜3 gのポリマ一を、 マツフル炉で 600°C、 10時間焼成灰化した。 こ れを、 I CP-AES装置 （誘導結合高周波プラズマ発光分光分析装置） を用い て分析した。  1 to 3 g of the polymer was baked and incinerated at 600 ° C. for 10 hours in a Matsufur furnace. This was analyzed using an ICP-AES device (inductively coupled high frequency plasma emission spectrometer).
[クロロホルム可溶成分の測定]  [Measurement of soluble components in chloroform]
押出機出口より排出されるペレットを液体窒素で冷却した後、 粉枠し、 9メッ シュの篩にかけ、 得られたサンプル 9 gを、 クロ口ホルムを溶媒として 8時間ソ ックスレー抽出した。 次に、 クロ口ホルム抽出液を、 円筒ろ紙 （ADVANTE C 84 (28 X 100 mm) ) を用いて 40 °C以上でろ過し、 溶媒を除き、 得 られた固形物をクロロホルム可溶成分とした。 ク口口ホルム可溶成分を液体ク口 マトグラフィ一で定量し、 ソックスレー抽出前のサンプル 1 g当たりの重量 （m g) で表した。 The pellets discharged from the extruder outlet were cooled with liquid nitrogen, then powdered, sieved with a 9-mesh sieve, and 9 g of the obtained sample was subjected to Soxhlet extraction for 8 hours using a black hole form as a solvent. Next, the extract of the formal form was filtered at 40 ° C or higher using a cylindrical filter paper (ADVANTE C84 (28 × 100 mm)), and the solvent was removed. The obtained solid was used as a chloroform-soluble component. The amount of soluble components in the mouth was determined by liquid mouth chromatography and expressed as the weight (mg) per gram of the sample before Soxhlet extraction.
[熱水抽出金属ィオン量の測定]  [Measurement of hot water extracted metal ion amount]
ペレツトサンプルを凍結粉碎法により粉碎した後、 100メッシュ p a s s、 200メッシュ保持の粒子を選別した。 この粒子 1 gを 100 m 1の純水中に投 入し、 121°Cで 2時間熱水抽出した後、 イオンクロマトグラフィーで熱水油 出金属イオン量を測定した。  After the pellet sample was pulverized by a freeze-pulverization method, particles having a mesh of 100 mesh and a mesh of 200 mesh were selected. 1 g of the particles were poured into 100 ml of pure water, extracted with hot water at 121 ° C. for 2 hours, and the amount of hot water oil-extracted metal ions was measured by ion chromatography.
実施例 2〜 5 Examples 2 to 5
実施例 1で得られた PPS 1、 シリカ （電気化学工業製） 及びエラストマ一 (ボンダイン AX8390、 住友化学製） を、 表 1に示す割合で配合してポリア リ一レンスルフイド樹脂組成物を調製した。 尚、 表 1中、 各成分の配合量の単位 は、 重量部である。 調製した樹脂組成物を、 以下の方法で評価した。 結果を表 1 に示す。  The polyarylene sulfide resin composition was prepared by blending PPS 1, silica (manufactured by Denki Kagaku Kogyo) and elastomer (Bondane AX8390, manufactured by Sumitomo Chemical) in the proportions shown in Table 1 obtained in Example 1. In Table 1, the unit of the amount of each component is parts by weight. The prepared resin composition was evaluated by the following method. Table 1 shows the results.
密着性 Adhesion
住友重機製 50 t竪型成形機 SV— 50を用い、 成形条件設定を、 シリンダ温 度： 350°C、 金型温度： 15 O 、 射出速度： 10mmZS、 保圧： 100 kg f /cm2として、 TO— 3 P形状のサンプルを採取し、 レッドインク試験 を実施して、 赤インクの浸入状態を、 以下の基準で目視により評価した。 Using a 50 t vertical molding machine SV-50 manufactured by Sumitomo Heavy Industries, the molding conditions were set as follows: cylinder temperature: 350 ° C, mold temperature: 15 O, injection speed: 10 mmZS, holding pressure: 100 kgf / cm 2 , TO-3P-shaped samples were collected and subjected to a red ink test, and the infiltration state of the red ink was visually evaluated according to the following criteria.
〇：赤ィンクが侵入していない。 〇: Red ink has not entered.
X ：赤インクが侵入している。 X: Red ink has penetrated.
TO— 3 Pトランジスタパッケージ （10A、 耐電圧 500 V) を、 60 X 95 %Rh環境下で連続通電処理し、 不良発生までの時間を測定して電機特性を 評価した。 尚、 不良発生までの時間は、 漏れ電流≥ 100mAとなるまでの時 間とした。 The TO-3P transistor package (10A, withstand voltage 500V) was continuously energized in a 60 X 95% Rh environment, and the time until failure occurred was measured to evaluate the electrical characteristics. The time until the occurrence of a failure was the time until leakage current ≥ 100 mA.
実施例 6 Example 6
実施例 1で得られた P P S 1、 後述する P P S 2及びシリカを、 表 1に示す割 合で配合してポリアリーレンスルフイド樹脂組成物を調製し、 評価した。 結果を 表 1に示す。 比較例 1〜 4 The polyarylene sulfide resin composition was prepared by blending PPS 1, obtained in Example 1, PPS 2 described later, and silica at a ratio shown in Table 1, and evaluated. Table 1 shows the results. Comparative Examples 1-4
PP S Iの代わりに、 実施例 1と同様の方法で、 洗浄液の注入量を、 本重合槽 1の出口では 16 kg/h rとし、 静置槽 3では 3 k gZh rに低減して製造し たポリアリ一レンスルフイド樹脂 （PPS 2) (含有金属イオン量： 1， 300 P pm、 抽出金属イオン量： 600 p pm、 オリゴマー量： 5 OmgZg) を用 いた以外は、 実施例 2〜5と同様にして、 ポリアリ一レンスルフイド樹脂組成物 を調製し、 評価した。 配合割合及び評価結果を表 1に示す。 Instead of PP SI, the same method as in Example 1 was used to reduce the injection amount of the cleaning solution to 16 kg / hr at the outlet of the main polymerization tank 1 and to 3 kgZhr in the stationary tank 3. Except that polyarylene sulfide resin (PPS 2) (content of metal ion: 1,300 Ppm, amount of extracted metal ion: 600 ppm, amount of oligomer: 5 OmgZg) was used in the same manner as in Examples 2 to 5 A polyarylene sulfide resin composition was prepared and evaluated. Table 1 shows the mixing ratio and the evaluation results.
表 1 table 1
実施例 実施例 実施例 実施例 実施例 比較例 比較例 比較例 比較例  Example Example Example Example Example Example Comparative example Comparative example Comparative example Comparative example
2 3 4 5 6 1 2 3 4  2 3 4 5 6 1 2 3 4
PPS 1 50 45 30 27 45  PPS 1 50 45 30 27 45
PPS 2 5 50 45 30 27  PPS 2 5 50 45 30 27
組成 Composition
シリカ 50 50 70 70 50 50 50 70 70  Silica 50 50 70 70 50 50 50 70 70
エラストマ一 5 3 5 3  Elastomer 5 3 5 3
含有金属イオン量 30 28 18 17 90 >100 >100 >100 >100 Metal ion content 30 28 18 17 90> 100> 100> 100> 100
(p pm;  (p pm;
抽出金属イオン量 18 16 10 10 40 >100 >100 >100 >100 Extracted metal ion amount 18 16 10 10 40> 100> 100> 100> 100
(p pm)  (p pm)
抽出オリゴマー量 Extracted oligomer amount
17 16 10 10 18 44 40 34 32 C 17 16 10 10 18 44 40 34 32 C
(m g Z g ) (m g Z g)
密着性 〇 〇 〇 〇 〇 X X 〇 〇 Adhesion 〇 〇 〇 〇 〇 X X 〇 〇
連続通電試験 (h r) >1000 >1000 >1000 >1000 〉1000124 98 200 500 Continuous conduction test (hr)>1000>1000>1000> 1000〉 1000 124 98 200 500
産業上の利用可能性 Industrial applicability
本発明によれば、 イオン性不純物の溶出、 密着性の低下、 内部部品の汚染又は ガス焼け等による電子デバイスの性能の低下を起こさないポリアリーレンスルフ ィド樹脂及びこれからなる電子部品用封止材を提供できる。  According to the present invention, there is provided a polyarylene sulfide resin which does not cause a decrease in the performance of an electronic device due to elution of ionic impurities, decrease in adhesion, contamination of internal components or gas burning, and an electronic component sealing made therefrom. Material can be provided.

Claims

請 求 の 範 囲 クロ口ホルムに抽出されるオリゴマ一量が 3 0 m g / g以下のポリアリ ド樹脂。 Scope of Claim Polyalidide resin whose amount of oligomer extracted into black-mouthed form is 30 mg / g or less.
2 . 含有金属イオンの総量が 1 0 0 p pm以下である請求の範囲第 1項記載の ポリアリーレンスルフィド樹月' 2. The polyarylene sulfide as described in claim 1, wherein the total amount of the contained metal ions is 100 ppm or less.
3 . 熱水抽出金属イオンの総量が 1 0 0 p m以下である請求の範囲第 1項記 載のポリアリ一レンスルフイド樹脂。 3. The polyarylene sulfide resin according to claim 1, wherein the total amount of the metal ions extracted with hot water is 100 ppm or less.
4. 硫ィヒリチウムを原料として製造される請求の範囲第 1項記載のポリアリー ド樹脂。 4. The polyaryl resin according to claim 1, which is produced using lithium sulfide.
5 . 請求の範囲第 1項に記載のポリアリーレンスルフィド樹脂及びシリカを含 むポリアリーレンスルフィド樹脂組成物。 5. A polyarylene sulfide resin composition comprising the polyarylene sulfide resin according to claim 1 and silica.
6 . さらに、 エラストマ一を含む請求の範囲第 5項記載のポリアリーレンスル フィド樹脂組成物。 6. The polyarylene sulfide resin composition according to claim 5, further comprising an elastomer.
7 . さらに、 シラン力ップリング剤及び Z又はエポキシ樹脂を含む請求の範囲 第 5項記載のポリアリーレンスルフィド樹脂組成物。 7. The polyarylene sulfide resin composition according to claim 5, further comprising a silane coupling agent and a Z or epoxy resin.
8 . 請求の範囲第 1項〜第 4項のいずれか一項に記載のポリアリ一レンスルフ ィド樹脂又は請求の範囲第 5項〜第 7項のいずれか一項に記載のポリアリーレン スルフィド樹脂組成物からなる電子部品用封止材。 8. The polyarylene sulfide resin according to any one of claims 1 to 4 or the polyarylene sulfide resin composition according to any one of claims 5 to 7. Sealing material for electronic components.
9 . 請求の範囲第 8項に記載の電子部品用封止材を含む電子部品。 9. An electronic component comprising the electronic component sealing material according to claim 8.
PCT/JP2003/003676 2002-03-29 2003-03-26 Polyarylene sulfide resin and sealing agent for electronic parts WO2003082955A1 (en)

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