JPH02251568A - Resin composition and electric part using same composition - Google Patents

Abstract

PURPOSE:To obtain a composition for sealing electronic parts having low anisotropy of dimensional change and excellent adhesivity to metals by blending a polyarylene sulfide ketone or a mixture of the polyarylene sulfide ketone and a polyarylene sulfide with glass flake. CONSTITUTION:(A) A polyarylene sulfide ketone (preferably polyphenylene sulfide ketone having 1 to 30,000g/10 minutes melt flow rate) or a mixture of the polyarylene sulfide ketone and a polyarylene sulfide (preferably polyphenylene sulfide having 2 to 60,000g/10 minutes melt flow rate) is blended with (B) <=30wt.%, especially <=15wt.% based on a resin composition of glass flake having preferably <=100mum thickness and not passing 48 mesh sieve and optionally (C) 1 to 50 pts.wt. fibrous reinforcing agent to give the resin composition. Electric parts comprising the composition as a package material.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a resin composition that has little anisotropy in dimensional change and has excellent adhesion to metals, 7-recontact resins, etc. The present invention relates to electronic components with excellent reliability using a product as a packaging material.

(Prior art) Polyphenylene sulfide resin and/or polyphenylene sulfide ketone resin are known as engineering glasstics with excellent chemical resistance, heat resistance, flame retardance, and electrical properties, and are widely used in various fields. These resins are attracting attention as encapsulating materials for electronic components.

However, these resins have drawbacks such as poor adhesion to metals, poor ductility, and brittleness, so they are generally blended with fibrous reinforcing materials such as glass fiber to improve strength, rigidity, and toughness. However, as a result, the smoothness of the interface between the resin and metal, etc. is lost, anisotropy occurs, and phenomena such as warping and twisting occur in the molded product. A gap is formed at the interface with the lead, etc., and the lead is deformed, further deteriorating the reliability of the electronic component.

(Problems to be Solved by the Invention) The present invention relates to warping of a molded product of polyarylene sulfide ketone or a mixture thereof and polyarylene sulfide.
Provided are a resin composition that is less deformed such as twisting and has improved adhesion to metal, and an electronic component using the composition.

(Means for Solving the Problems) The present inventors have discovered that a resin composition comprising polyarylene sulfide and/or polyarylene sulfide ketone and glass flakes has a smooth surface and reduces warpage, twisting, etc. Therefore, the inventors discovered that the adhesiveness with metals, silicon chips, etc. is increased, and that electronic components using the composition as a package material have excellent reliability, leading to the present invention.

That is, the present invention relates to a polyarylene sulfide ketone or a resin composition comprising the resin and the polyarylene sulfide ketone and glass flakes.

Polyarylene sulfide (hereinafter referred to as PA) used in the present invention
S) refers to uncrosslinked or partially crosslinked polyarylene sulfide and mixtures or modified products thereof,
Preferably the melt flow rate is ASTM D1238.
-74 (360℃, 5Kf load) 2 to 60.0OO
L? /10 minutes is preferred since it provides a composition with specific properties containing more than 1 mole of polyphenylene sulfide.

PAS polymerization methods include, for example, polymerization of p-sochlorpe/zene in the presence of sulfur and sodium carbonate, sulfurization in a polar solvent), sodium hydrogen sulfide and sodium hydroxide, or hydrogen sulfide and sodium hydroxide. A method of polymerization in the presence of p-chlorothiophenol, a method of self-condensation of p-chlorothiophenol, a method of polymerizing sodium sulfide and p-dichlorpe/ze/in an amide solvent such as N-methylpyrrolidone or dimederacetamide, or a sulfonic solvent such as sulfolano. A method of reaction is suitable. At this time, in order to adjust the degree of polymerization, it is a preferable method to add an alkali metal salt of carbo/acid or sulfo/acid, and to add alkali hydroxide. The copolymerization component may include 30 moenyl, alkokene, carboxylic acid, or a metal base of carbo/acid), or trifunctional phenylsulfide as long as it does not significantly affect the crystallinity of the polymer, but preferably the copolymerization component is It is preferably 10 mol% or less. In particular, when trifunctional or higher functional phenyl, piphenyl, naphthyl sulfide bonds, etc. are selected for copolymerization, 3 mol% or less, more preferably 1 mol%
The following is good.

Such PAS can be produced by common manufacturing methods, such as (1) reaction of a rhodane-substituted aromatic compound with an alkali sulfide (U.S. Pat. No. 2,513,188, Japanese Patent Publication No. 44-27671).
(2) Condensation reaction of thiophenols in the presence of an alkali catalyst or copper salt (US Pat. No. 3,274,165, British Patent No. 11)
60660] (3) Condensation reaction of aromatic compounds with sulfur chloride in the presence of a Lewis acid catalyst (Special Publication No. 46-2
No. 7255, Belgian Patent No. 29437), and can be arbitrarily selected depending on the purpose.

It has a polyarylene sulfide ketone polymerization component or a random copolymerization component used in the present invention, and preferably conforms to ASTM D1238-74 (360°C).

1 to 30 in melt flow rate measured under 5-load).
000y-/10 min.

The I realine/sulfide ketone can be obtained, for example, by a method in which dihalobenzophenone is reacted with an alkali metal sulfide or the like in a polar solvent (US Pat. No. 4,716,212).

Such a resin contains 30 moles of unfinished alkoxy, cal-heta-acid or carbanoic acid metal base as a copolymerization component),
It may be contained as a trifunctional phenyl sulfide bond component or as a random copolymerization component as long as it does not significantly affect the crystallinity of the polymer, but preferably the copolymerization component is 100 mol% or less. In particular, when trifunctional or higher functional phenyl, biphenyl, naphthyl sulfide bonds, etc. are selected for non-polymerization, the amount is preferably 3 mol % or less, more preferably 1 mol or less.

The glass flakes used in the present invention are, for example, b/l≧3 (where b and t are each H@
Known and commonly used scale-like glass having a short axis and thickness according to the definition of yvood can be used, and there is no limit to the percentage, but E glass is preferably used for electronic component applications. In general, it is preferable that the composition has a thickness of 100 μm or less and a particle size distribution that does not pass through a 48-mesh sieve (Tyler standard sieve) and accounts for 30% by weight or less in the composition. Particularly in electronic component applications, it is preferable that the weight be less than 15% by weight. On the other hand, extremely large flakes are undesirable because they cause loss of surface smoothness and impair adhesion to metals, silicon chips, etc.

Furthermore, various known silicone oils and modified products thereof can be used as unmodified and/or modified silicone oils used as necessary in the present invention. Typical unmodified silicone oils are polydimethylsiloxane and polymethylphenylsiloxane, the latter of which is, for example, a polynomethyl-diphenylsiloxane copolymer. Lydimethyl-phenylmethylsiloxane? Limer polymethylphenyl/
/phenylsiloxa/copolymer. On the other hand, the faecal silicone oil is obtained by modifying a part of the above-mentioned unmodified silicone oil with a functional group, and the preferred functional groups are hydroxyl group, amino group, carxyl group, epoxy group, methacryloxy group, mercapto group. These are the basics. Specific examples of these include terminal silanol polydimethyl siloxane, terminal 7 lanol nomethylsophenyl siloxane, terminal carbinol polydimethyl siloxane, terminal hydroxyl polydimethyl siloxane, polymethyl hydroxyalkylene ox 7 domethyk siloxane, Terminal acetoxypolydimethylsiloxane, terminal dimethylaminopolydimethylsiloxane, terminal ethoxypolydimethylsiloxane, terminal stearoxypolytsumethylsiloxane/, terminal aminopropyl polydimethylsiloxane, aminoalkyl-containing T-structure polydimethylsiloxane/, terminal caldex Siglovir? lydimethylronroxane,
Caldexyglobil-containing T-structure polymethylsiloxane, terminal glycidoxyglobil borodimethylsiloxane/,
Glycidoxyglopyl-containing T-structure polydimethylsiloxane, polyglycidoxyglopylmethylsiloxane, polyglycidoxyglopylmethyl-no-methylsiloxane copolymer, methacryloxypropyl-terminated polydimethylsiloxane, methacryloxyglobil-containing T-structure polydimethylsiloxane , polydimethyl-methacryloxyglopylmethylsiloxane/, mercagutoglobil-containing T-structure polymethylsiloxane, ? Examples include rimerkagutopropylmethylsiloxane.

The unmodified and/or modified silicone oil that can be used in the present invention is 0.01 to 20 parts by weight per 100 parts by weight of polyphenin/sulfide ketone or a mixture thereof with pps.
If the amount is less than 0.01 part by weight, the moisture resistance and fluidity during sealing of the composition of the present invention will decrease, and the adhesion to the leads of electronic components will be impaired, so it is not preferable. The above is undesirable because it causes problems such as an increase in volatile components during sealing and bleeding onto the surface of the molded product.

Copolymerization, jt' IJ, which can be used as necessary in the present invention
Amide is nylon 6.66.610, 612.10.1
1.12, preferably having a melting point of 170°C or lower. The amount of such copolyamide added is 10% of the amount of polyarylene sulfide ketone or a mixture of this and PAS and glass flakes.
It is used in an amount of 0.05 to 30 parts by weight. If the amount added is less than 0.05 parts by weight, the effect of the present invention will be small, and if it exceeds 30 parts by weight, the absorbency of the composition itself will increase.

The hydrogenated polymer of conjugated diene used as necessary in the present invention refers to a polymer derived from one or more types of conjugated diene/monomer, that is, a homopolymer of a single conjugated diene, for example, 1,3-butadiene. Alternatively, two or more conjugated dienes such as 1,3-ptadiene/, inbre/(2-methyl-1
. Refers to something that has been returned.

Hydrogenated copolymers of conjugated diene and aromatic vinyl hydrocarbons are block copolymers or block copolymers with varying ratios of conjugated diene and aromatic vinyl hydrocarbons, or block copolymers with varying amounts of unsaturated bonds. At least 80% of the amount has been reduced by hydrogenation. In this case, a block copolymer of a conjugated diene and an aromatic vinyl hydrocarbon is preferably used.

Note that the double bond of the aromatic nucleus is excluded from the unsaturated bonds that are reduced by hydrogenation.

Conjugated dienes used as raw materials for hydrogenated polymers and hydrogenated copolymers include 1,3-butanoene, isogrene (2
, 3-methyl-1,3-butadiene), 1,3-pebutadiene, etc., and 1,3-butanoene and isogren are preferably used.

Examples of the aromatic vinyl hydrocarbon used as a raw material for the hydrogenated copolymer include styrene, α-methylstyrene, 0-methylstyrene/, p-methylstyrene, 1,3-methylstyrene, and vinylnaphthalene, with styrene being preferred. Can be used.

Preferred specific examples of the hydrogenated polymers and hydrogenated copolymers are hydrogenated polybutadiene/, styrene/putadier//styrene triblock hydrogenated copolymers, and styrene/isogre/.
/ styrene Tripcock hydrogenated copolymer, etc.

The hydrogenation polymerizability of these conjugated dienes and/or the hydrogenated polymers of conjugated dienes and aromatic vinyl hydrocarbons can be modified by grafting 0.01 to 10% by weight of unsaturated carboxylic acids or derivatives thereof. In the present invention, an amide compound selected from bis fatty acid amides, bis aromatic amides, substituted amides, and substituted ureas may be added in order to further improve the adhesion to metals. Examples of bis-aliphatic silane amides include ethylene bis-oleic acid amide, ethylene bispehe/acid amide, ethylene bis-stearic acid amide, ethylene bis-lauric acid amide, hexamethine/bis-oleic acid amide, butylene bis-stearic acid amide, N,N'-dio Raylsebacic acid amide, N, N'-tholeyl adipic acid amide, N, N
Examples include '-distearyl sepacic acid amide, N,N'-distearyl adipic acid amide, and the like. Examples of the bisaromatic acid amide include m-xylylene bisstearic acid amide, N,N'-sostearyl isoheptalic acid amide, N,
Substituted amides such as N'-distearyl terephthalic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl rumitic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, Examples include N-stearyl stearic acid amide and the like. Substituted ureas include N-butyl-N'-stearylurea, N-propyl-N'-stearylurea,
N-allyl + N/-stearyl IU, N-phenyl-N'-stearylurea, N-stearyl-N'-stearylurea, etc. or RNHCONHR'NHCONH
R (R= C12~C18゜R'=XDI, TDI
, MDI).

The amount of the amide compound in the composition of the present invention is preferably 0.01 to 0.4% by weight, particularly preferably 0.02 to 0.3% by weight.

In the present invention, fatty acid lower alcohol esters (simple esters), fatty acid polyhydric alcohol esters (glycerides), fatty acid polyglycol esters fatty acid fatty alcohol esters (ester waxes), and hiester waxes are used in order to further improve adhesion to metals, etc. An ester selected from the saponified products of can be added.

Examples of fatty acid lower alcohol esters include butyl stearate, octyl stearate, and examples of fatty acid polyhydric alcohol esters include glycerol tripalmitate, glycerol tristearate, and polyglycol esters of fatty acids. Examples of dilaurate of lyethylene glycol, aliphatic alcohol esters of fatty acids such as beeswax, ihota wax, carnauba wax, cetyl palmitate, ethylene glycol ester of montanic acid, saponified calcium hydroxide of partial ethylene glycol ester of montanic acid, etc. I can do it.

The ester contains 0.01 to 1.0 weight'jk in the composition of the present invention.
%, preferably 0.02 to 0.8% by weight
is within the range of

In the present invention, a fibrous reinforcing material can be optionally blended to improve strength and physical properties, and the amount of such reinforcing material added is preferably 1 to 50% by weight, more preferably 1 to 30% by weight.
It is outside the weight range. If it is less than 1% by weight, the strength improvement effect will be weak, and if it exceeds 50% by weight, the adhesion to metal will decrease, which is not preferable. Examples of fibrous reinforcement include glass fiber,
Potassium titanate fiber, aramid fiber, silica fiber, alumina fiber, silica/alumina fiber, zirconia fiber,
Examples include, but are not limited to, boron nitride fibers, silicon nitride fibers, boron fibers, gypsum fibers, polyester fibers, polyethylene fibers, polyacrylic fibers, fluorine fibers, phenol fibers, and processed mineral fibers.

In the present invention, fillers other than those described above can be added within a range that does not impair the effects of the present invention.

Specific examples of such fillers include the following:
They may be used alone or in combination, but are not necessarily limited to this.

Examples include silica, diatomaceous earth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, antimonic acid, anotimo/barium ferrite, stro/thium ferrite, beryllium oxide, pumice, pumice balloon, lead oxide, bismuth oxide. , zirconium oxide, manganese dioxide,
Oxides such as tin dioxide, barium oxide, mini iron oxide,
Hydroxides such as aluminum hydroxide, magnesium hydroxide, and basic magnesium carbonate; carbonates such as calcium carbonate, magnesium carbonate, dolomite, and dawsonite;
Sulfuric acid or sulfites such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, zinc sulfide, calcium sulfide, strontium sulfide, cadmium sulfide,
Sulfides such as barium sulfide, Merck, clay mica, glass balloons, raspies, calcium silicate, mo/
Silicates such as morillonite, pet/tonite, etc.
Granular, spherical, and hollow inorganic fillers such as Cargen black, graphite, molybdenum sulfide, poron, silicon carbide, lead zirconate titanate, zinc borate, barium metaborate, calcium borate, and sodium borate, and fragrance. Liquid crystal polymers such as family polyamides or polyesters
These include organic fillers such as polytetrafluoroethylene and silicone rubber.

jl! K, in the composition of the present invention, 7 run, titanate, zirconate,
Additives commonly called coupling agents such as zircoaluminate type and aluminum chelate compound type can be added, and particularly preferred are silane coupling agents such as Ashi, vinyl silane, acrylic silane, amino 7-lane, epoxy silane, and Mercagto silane. , halosilane, etc.

The amount of the silane coupling agent added is 0.01 to 1 part by weight per 7100 parts by weight of polyarylene sulfide or polyarylene sulfide keto.

The composition of the present invention may also contain other polymers such as polysulfo/, polyallylsulfone, etc., to the extent that the object of the present invention is not impaired.
Polyether sulfone, polyester, polyolefin, polystyrene, I-lymethylpentene, polycarbonate, polyphenylene oxide, polyarylate, phenoxy resin, epoxy resin, liquid crystal polymer, etc. may also be added.

Furthermore, suitable amounts of known additives such as heat stabilizers, antioxidants, corrosion inhibitors, fluidity improvers, lubricants, mold release agents, colorants, and epoxy compounds can be added. As corrosion inhibitors, alkali metal carbonates, hydroxides such as sodium carbonate, lithium carbonate, lithium hydroxide, zinc oxide, lead oxide, magnesium oxide, barium oxide, dolomite, γ-alumina, hydrotalcites, etc. .1
It is preferable to add up to 10% by weight. Especially zinc oxide,
γ-alumina, dolomite t! This is preferable in terms of increasing the reliability of the cage material.

The polyarylene sulfide resin composition of the present invention can be used to seal electronic components mainly by injection molding, transfer molding, compression molding, dipping, or other methods. Examples of the electronic components include IC, hybrid IC,
Transistor Diode, Capacitor Resistor Thyristor, +Illumination, Varistor Connector
transferer, crystal oscillator, fuse, rectifier,
These include power supplies, switches, various sensors, relays, surge absorbers, and composite parts of these. These electronic components sealed with the composition of the present invention have excellent adhesion to metal and silicon chips, and have increased reliability because water intrusion from the interface between the leads and the resin is reduced.

Furthermore, since the resin composition of the present invention has extremely small warp and twist, it can be suitably applied to hollow cavity packages, pin grid arrays, leadless chip carriers, leaded chip carriers, and other applications where devices are not hermetically sealed. Ru.

(Example) The present invention will be further explained by examples.

<Examples 1 to 14, Comparative Examples 1 to 5> Polyphenylene sulfide and/or polyphenylene sulfide ketone having a melt flow rate of 400,054/10 minutes as measured by ASTM D1238-74 (360, 5 to 4 loads) On the other hand, glass flakes and glass fibers are blended in the proportions shown in Table 1, and after mixing, 651
18 extruder at 355°C (Examples 1 to 14, Comparative Example 5
) or at 320°C (Comparative Examples 1 to 4) and pelletized, using a 1-ounce injection molding machine at the same cylinder temperature as extrusion pelletizing and at a mold temperature of 150°C as shown in Figure 11C. A metal (4270I) insert molded product was prepared and subjected to a red ink penetration test. In this test, the insert molded product shown in Figure IK was left in red ink at 60° C. for 1 hour, and the rate of penetration of the red ink into the resin-sealed portion (indicated by diagonal lines) was evaluated. In addition, the evaluation is 0% for no red ink intrusion, and 1 for intrusion in the central part of the molded product.
It was set as 00%.

Since the composition of the present invention has small warpage, it is difficult to form gaps after molding, and the intrusion of red ink is also small.

! <Examples 15 to 29, Comparative Examples 6 to 7> IJ phenylene sulfide m fat and U having a melt flow rate of 5000%/10 minutes measured by ASTM D1238-74 (360°C, 5 to 4 loads) 300
0? Glass flakes, glass fibers, and fillers were blended and mixed with polyphenylene sulfide ketone having a temperature of /10 minutes in the proportions shown in the second coating, and melted and mixed at 350°C using a 65U extruder. A high voltage diode element was sealed using a 1 oz injection molding machine at a cylinder temperature of 350°C and a mold temperature of 150°C.
Leakage current (IR) was measured after a 500-hour Glenn 7 Jaegtsker test at 2 atm at .degree.

The lower the leakage current value, the less water enters between the resin and the lead or element, indicating that the reliability of the electronic component is high.

(Effects of the Invention) By blending glass flakes into polyarylene sulfide ketone or a mixture thereof and PAS, the present invention reduces deformation such as warping and twisting of the molded product, and improves adhesion to metal. Provide what you have.

[Brief explanation of drawings]

FIG. 1 is a plan view (IL) and a side view (b) of a molded product in which a metal lead having a thickness of Q and 15 mm is inserted into a resin composition. A: Red ink penetration part 100%, B: Red ink penetration part 0%
, X: resin composition, Y: metal lead. Agent Patent Attorney Katsutoshi Takahashi (α) 1.5□□

Claims (5)

[Claims] (1) A resin composition comprising a polyarylene sulfide ketone and glass flakes. (2) A resin composition comprising polyarylene sulfide, polyarylene sulfide ketone, and glass flakes. (3) A resin composition comprising polyarylene sulfide and/or polyarylene sulfide ketone, glass flakes, and fibrous reinforcement. (4) Claim 1, wherein the glass flakes have a thickness of 100 μm or less, of which 30% by weight or less of the composition does not pass through a 48 mesh (Tyler standard sieve).
2. The resin composition of item 2 or item 3. (5) An electronic component using the resin composition according to claim 1 or 2 as a packaging material.