JPH0381367A - Polyarylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition which is excellent in adhesion to metal or element and resistance to adhesion to solder and is useful as electronic component sealing material, coating material, etc., by dispersing specified nylon particles in a polyarylene sulfide resin. CONSTITUTION:A polyarylene sulfide resin composition for electronic component sealing or coating is prepared by dispersing 0.1-30 pts.wt., preferably 0.2-20 pts.wt., minute particles (with a mean particle diameter of 1.0mum or less) of nylon 11 and/or nylon 12 in 100 pts.wt. polyarylene sulfide resin with a melt flow rate of at least 1,000g/10min.

Description

Detailed Description of the Invention (Field of Industrial Application) The polyarylene sulfide resin composition of the present invention has excellent adhesion to lead metals and elements of electronic components and non-solder adhesion properties, so it can be used in various electronic components. Can be used for sealing or coating. The resulting electronic components have increased reliability.

(Prior art and problems to be solved by the invention) Polyarylene sulfide resin has excellent performance in heat resistance, chemical resistance, electrical properties, flame retardance, etc., and has low melt viscosity. In recent years, it has attracted attention as a material for encapsulating electronic components in place of epoxy resin because of its small performance degradation. However, unlike epoxy resin, polyarylene sulfide does not have suitable functional groups, so it has the disadvantage of poor adhesion to lead metals or elements used in electronic components. The current situation is that the reliability of coated electronic components deteriorates.

Furthermore, when electronic components sealed or coated with polyarylene sulfide are soldered, there is a problem in that the solder tends to adhere not only to the lead metal but also to the polyarylene sulfide portion.

Previously, the present inventors discovered that when a low melting point copolymerized polyamide is added to polyarylene sulfide, the adhesion with metals and elements is greatly improved (Japanese Patent Laid-Open No. 63-18
No. 9458), but it was found that the composition did not have sufficient thermal stability and there was a limit to the injection molding temperature of polyarylene sulfide. On the other hand, if nylon 6 or nylon 12 is used instead of the copolymerized boria, it has the advantage of improving thermal stability, but as disclosed in the comparative example in the above-mentioned published patent application, it is difficult to adhere to the lead frame. I wasn't sexual enough.

Incidentally, even before the above-mentioned prior art document, there was an example in which nylon 12 was added to polyarylene sulfide with a considerably high melt viscosity to improve impact resistance (Japanese Patent Laid-Open No. 53-69).
No. 255), the relationship between the particle size of nylon 120 and the adhesion to metal and solderability in electronic component sealing or coating compositions using polyarylene sulfide with a low melt viscosity such as the present invention is not clear. Ta.

(Means for Solving the Problems) In view of the above circumstances, the present inventors have made extensive studies and found that in a polyarylene sulfide composition containing nylon 11 and/or nylon 12, the nylon has an average particle diameter of 1.0 μm. The present invention was developed based on the discovery that excellent adhesion to metals and elements and non-solder adhesion can be obtained by dispersing it in the following.

That is, the present invention provides: (1) a polyarylene sulfide resin a-acid characterized by comprising nylon 11 and/or nylon 12 with an average particle diameter of 1.0 μ or less; (2) a polyarylene sulfide (3) The polyarylene sulfide resin composition according to claim 1, characterized in that it has a melt flow rate of 1000 g/10 minutes or more; The present invention relates to the polyarylene sulfide resin composition according to claim 2; (4) the resin aTy according to claim 3; and an electronic component sealed or coated with the resin aTy according to claim 3.

The polyarylene sulfide of the present invention is a polymer containing a sulfide bond and an aromatic ring, and its production method uses an aromatic compound or thiophene having one or more nuclear-substituted halogens as described in Japanese Patent Publication No. 45-3368, for example. It can be obtained by reacting with an alkali metal monosulfide in a polar solvent at high temperature. An example of a preferred polyarylene sulfide is polynylene sulfide.

The polyarylene sulfide can have any flowability when melted depending on the purpose of sealing or coating electronic parts, and is usually prepared by 437M method D-1238-74 (315,5
5 at the melt flow rate measured at °C, 5 kg load)
00 to 30,000 g/10 minutes, more preferably t, ooo to 3G, QOOg/I0
It's a minute.

If the melt flow rate is low, it is not preferable because it puts stress on the elements and leads of electronic components. These polyarylene sulfides having a melt-to-roll rate are mainly of a linear type that is not substantially crosslinked.

In addition, the polyarylene sulfide of the present invention has a methyl group, a nitro group, a phenyl group, a carboxylic acid group, a metal base of carboxylic acid, an alkoxy group, and a nylon 11 and nylon 12 used in the basic invention have the general formula +HN ( C1 is a polyamide corresponding to n=11 and I and 12 in C+.The nylon is
Other nylon (6
, 66, 69, 610, 9, 13) and N-alkoxymethyl modified products. The nylon contains 0.1 parts by weight per 100 parts by weight of polyarylene sulfide.
The amount is in the range of 30 parts by weight, and more preferably 0.2 to 20 parts by weight.

If the amount added is too large, the original properties of polyarylene sulfide will be lost, which is not preferable.

In the present invention, it is necessary that the nylon is dispersed in polyarylene sulfide with an average particle size of 1.0μ or less, and by setting the particle size to this particle size, the adhesion to metals and elements of electronic parts and solder adhesion are improved. The characteristics are improved. A particularly preferable average particle diameter is 0.9 μm or less. In order to keep the particle size of the nylon within a predetermined range, it is preferable to knead the nylon used in the form of fine powder rather than pellets with polyarylene sulfide. The melt viscosity of polyarylene sulfide and nylon may be appropriately combined, and if the melt viscosity of the polyarylene sulfide is low, it is preferable to lower the melt viscosity of the nylon.Nylon with a high melt viscosity has a high dispersibility in polyarylene sulfide. This often results in restrictions on the kneading equipment and cross-wire conditions.

As the mixing device, various known devices such as a single-screw or multi-screw extruder or a roll can be used, but in order to keep the average particle size of nylon within a predetermined range, it is preferable to increase the degree of kneading. The cross-crossing conditions can be carried out in the range of 260 to 400°C, and are appropriately determined depending on the melt viscosity, properties, physical shape of polyarylene sulfide and nylon, or the type of cross-wire device.

Furthermore, in order to further improve the dispersion of the nylon into the polyarylene sulfide, it is possible to add a compatibilizing agent such as a compound or polymer having an epoxy group.

It is preferable that the polyarylene sulfide composition of the present invention contains an inorganic or organic filler in order to reduce stress on electronic components and improve reliability. Specific examples of the filler include glass fiber, potassium titanate, etc. Fibers, asbestos, silicon carbide, silicon nitride, ceramic fibers,
Known fibrous fillers such as Zr01 fiber, silica fiber, aluminum fiber, gypsum fiber, organic fiber (e.g. aramid fiber), silicon carbide, potassium titanate, whiskers,
Tetrapod zinc oxide whiskers, barium sulfate, calcium sulfate, calcium sulfite, kaolin, clay, pyrophyllite, bentonite, sericite,
Zeolite, mica, mica, nephelinsinite, talc, atalpulgite, wollastonite, PMF,
Calcium silicate, calcium carbonate, magnesium carbonate,
Dolomite, antimony oxide, zinc oxide, lead oxide, titanium oxide, magnesium oxide, zirconium oxide, alumina, iron oxide, molybdenum disulfide, gypsum, glass peas, glass balloon, glass powder, glass flakes,
Known inorganic fillers such as silica powder and silica beads can be used.

These fillers may be used alone or in combination of two or more in an amount of 10 to 80% by weight based on the polyarylene sulfide composition.
It is blended within the range of.

In the present invention, in order to improve the moisture resistance of the composition and the reliability of electronic parts, it is preferable to add 0.01 to 20% by weight of organic silane to the filler. A method such as a combination of both is used.

The organic silane is generally called a silane coupling agent, and is a - compound or a polycondensate thereof. Here, Q is a carbon group with or without a functional group such as a vinyl group, acrylate group, amino group, halogen group, epoxy group, or mercapto group, R is a lower alkyl group, and X is a chloro group or alkoxy group. Indicates the group. Specifically, vinyltrichlorosilane, vinyltris (β-methoxyethoxy)
Silane, vinyltriethoxysilane, vinyltrimethoxysilane, T-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, T-glycidoxypropyltrimethoxysilane, T-glycidoxypropyltrimethoxysilane, Sidoxypropylmethyljethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)
-T-aminopropylmethyldimethoxysilane, γ-anopropyltriethoxysilane, N-phenyl-T-
Acanopropyltrimethoxysilane, T-mercaptopropyltrimethoxysilane, T-chloropropyltrimethoxysilane 1-C1@H! l (OCH3) s, C
Fs(CFz) tcHzcHts j! (OCRs
)! N-cyclohexyl-γ-antanoprobyltrimethoxysilane, N-β-(N-vinylbenzylamino)
Ethyl-T-aξnopropyltrimethoxysilane, T-
Examples include, but are not limited to, ureidopropyltriethoxysilane, T-glycidoxypropylmethyldiisopropenoxysilane, and the like.

Antioxidants, heat stabilizers, corrosion inhibitors, lubricants, and colorants may be added to the polyarylene sulfide composition of the present invention, and other thermoplastic or thermal A curable resin can be added. Particularly useful resins depending on the application include epoxy resins, phenoxy resins, silicone polymers (e.g. silicone oil) modified with epoxy, carboxyl groups, amino groups, etc.
Olefin and/or vinyl aromatic compound polymers modified with epoxy or acid groups or derivatives thereof, and copolymers thereof (e.g., acid- or epoxy-modified polypropylene, acid- or epoxy-modified polyethylene, acid- or epoxy-modified polyethylene/propylene) , acid- or epoxy-modified polymethylpentene, styrene-maleic acid copolymer, acid- or epoxy-modified hydrogenated styrene-butadiene rubber, acid- or epoxy-modified polyisoprene rubber, acid- or epoxy-modified polyisobutylene rubber, etc.). However, it is not necessarily limited to these.

It is useful to add polyarylene sulfide to improve the heat resistance of the electronic component obtained in the present invention. For example, it can be added in an amount of 0.1 to 2001 parts by weight per 100 parts by weight of polyarylene 741.

A specific example of an electronic component that can be sealed or covered in the present invention is an IC.
, Hybrid IC2 transistor diode, triode, capacitor, resistor, resistor network, thyristor, chip inductor, coil, transformer, motor, varistor Transducer-1 crystal oscillator, haze, rectifier, LC filter, connector power supply, switch, Relays, sensors, Hall elements, surge absorbers, arresters, pin grid arrays,
Examples include photocouplers and composite parts thereof.

The composition of the present invention has a shear rate of 320°c1 of 10-'5ec-
Under the condition ', the melt viscosity is 5,000 voids or less, preferably 3,000 voids or less, and the above-mentioned electronic components can be sealed or coated without stress.

The sealing or covering can be carried out at 260 to 400°C using an injection molding machine or a transfer molding machine.

(Effects of the Invention) Electronic components sealed or coated with the composition of the present invention have improved reliability and can therefore be used in place of conventionally used epoxy resins. Since the present invention is a thermoplastic resin composition, disadvantages such as a long molding cycle, occurrence of flaking, and necessity of post-curing due to the epoxy resin being a thermosetting resin are eliminated.

(Example) The invention will be further explained by way of example.

Examples 1-2, Comparative Example 1 ASTM method D-1238-74 (315,5°C, 5k
The melt flow rate measured at g load) is 25,000
g / 10 minutes of powdered polyphenylene sulfide 100 parts by weight, various types of nylon 11 or 1 shown in Table 1
After uniformly mixing 210 parts by weight of fused silica and 180 parts by weight of fused silica, the mixture was melt-kneaded at a resin temperature of 320°C in a 6511+111-shaft full-flight single-screw extruder (L/D=30, CR-4). The obtained pellets were molded using a 1 oz injection molding machine at a molding temperature of 300'C and a holding pressure of 60 kg/cd.
An IC lead frame (manufactured by 11metsuki 42 A11oy) was injection molded, and an adhesion test with metal was conducted using the red ink test method (Note 1).

(Note 1) Red ink test method A molded molded 16 pin lC lead frame with leads is boiled in red ink at 100°C for 24 hours, and evaluated by the percentage (%) of red ink penetration into the resin sealed part of the lead. .

ioo%: Intrusion at all costs? ? 0%: No intrusion at all Meanwhile, a test piece with a size of 12.7 x 50 x 3 mm was made under the same molding conditions, and one side of the piece was left in a 240°C solder bath for 10 seconds, then taken up and the amount of solder adhesion was measured. (Note 2) was measured.

Example 4 Meltflow - 12000g/10min powdered polyphenylene sulfide 62 parts by weight, nylon 12 pellets (molecular weight 24000, Ube Industries Co., Ltd. 302)
4tl) 8 parts by weight, 20 parts by weight of glass fiber (diameter 6μ, average length 150μ), glass flakes (average diameter 1
5μ, aspect ratio of about 5), and 2 parts by weight of T-anotrimethoxysilane were uniformly mixed, and a 65Wl-shaft Dalme screw extruder (L/D-45, CR=
After melt-kneading and pelletizing at 320''C in 4.5), the pellets were encapsulated into an 8-pin resistance network using a 1-ounce injection molding machine at a molding temperature of 300°C and a holding pressure of 70 kg/cd. The average particle diameter of nylon 12 in the sealant was 0.7μ.
When placed in pressurized steam under C12 atmosphere, the defective rate is 1.
After 00° hours, the temperature was 0150°.

Comparative Example 2 An experiment similar to Comparative Example 2 was conducted except that the melt cross-wire conditions in Example 4 were changed to 290°C using a four-kiln extruder Dalmage type (L/D=25, cR=3). Nylon 1 in the encapsulation molding
The average particle diameter of No. 2 was 1.5 μm, and the defect rate of electronic components was 21,150.

Comparative Example 3 In Comparative Example 2, an experiment similar to Comparative Example 2 was conducted except that the polyarylene sulfide used was melt float -450 g/10 min (crosslinked type, Rydon PPS manufactured by Phillips, P-4 powder). However, in order to seal the resistor network, it was necessary to maintain a holding pressure of 500 kg/cii, which caused the element to move and could not be replaced to a normal state. Note that the particle size of nylon 12 in the molded article was 1.4μ.

Claims (4)

[Claims] 1. Nylon 11 and (
or) a polyarylene sulfide resin composition comprising nylon 12. 2. The polyarylene sulfide resin composition according to claim 1, wherein the polyarylene sulfide has a melt flow rate of 1000 g/10 minutes or more. 3. The polyarylene sulfide resin composition according to claims 1 and 2, which is used for sealing or coating electronic parts. 4. An electronic component sealed or coated with the resin composition according to claim 3.