JPS63179929A - Packaging material for electronic part without contacting element - Google Patents

Abstract

PURPOSE:To obtain the titled package material, consisting of a polyphenylene sulfide resin prepared by polymerizing specific two kinds of repeating units in a specific proportion, having excellent adhesive property, toughness as well a moldability and suitable as electronic parts in integrated circuits. CONSTITUTION:For example, a dihalogenated substance mixture consisting of 85-99.5mol% p-dichlorobenzene and 15-0.5mol% m-dichlorobenzene and sodium (hydro)sulfide and sodium hydroxide are heated in an aprotic polar solvent, e.g. N-methylpyrrolidone, etc., to afford a polyphenylene sulfide resin consisting of 85-99.5mol% repeating units expressed by formula I and 15-0.5mol% repeating units expressed by formula II. A filler, preferably glass fiber, etc., is added to the above-mentioned resin to provide the aimed package material.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to electronic components using polyphenylene sulfide resin as a packaging material. This invention relates to electronic components that are non-contact packaging materials.

<Prior Art> Ceramic materials have conventionally been used as sealing package materials for electronic components. However, in recent years, epoxy resin (
For example, JP-A-58-176958, JP-A-57-
180626, JP 11557-8821, etc.), thermosetting resins such as silicone resins, and polyphenylene sulfide resins which are thermoplastic resins (e.g. JP 52-149348, JP 57-17)
153, JP-A-59-167040, etc.)
have been proposed and are actually being used industrially.

Furthermore, m-dichlorobenzene block copolymer PP S has also been proposed as a sealing material that comes into direct contact with the device (Japanese Patent Application Laid-Open No. 61-55148).

<Problems to be Solved by the Invention> However, all of the package materials described in the above-mentioned publications propose a type of sealant that comes into contact with the element as shown in FIG. Each has a certain effect. On the other hand, in the case of packages that do not come into direct contact with the elements, such as the hollow cavity package shown in Figure 1 or the bin grid array shown in Figure 2, the elements may not be tightly sealed, so more toughness is required. However, all of the package materials described in the above-mentioned publications have poor toughness and are unsatisfactory as package materials that do not come into direct contact with elements. In the case of conventional polyphenylene sulfide resin, it is possible to improve the toughness to some extent by increasing the degree of polymerization of the resin.
The melt fluidity during molding is significantly reduced, making it impossible to satisfy the balance between toughness and fluidity. Furthermore, conventional polyphenylene sulfide resins also had the problem of poor adhesion to various reinforcing agents used in packages that do not come into direct contact with elements, or lead frames.

As mentioned in the previous section, there is a proposal to use polyphenylene sulfide, which is block copolymerized with m-dichlorobenzene, as a sealing material that comes into direct contact with the device. It has not been previously known to be used as a packaging material.

On the other hand, conventionally used ceramic packages that do not come into direct contact with elements have fewer problems in terms of performance, but have problems in terms of cost, productivity, etc.

Therefore, the present invention aims to improve the balance between toughness and fluidity, adhesion to various reinforcing agents and lead frames, as well as cost and
The objective is to obtain a packaging material for electronic components that has excellent productivity and does not allow direct contact between the element and the package.

Means for Solving the Problems〉 As a result of intensive studies to solve the above problems, the present inventors have found that by using sita polyphenylene sulfide partially copolymerized with m-dichlorobenzene as a packaging material. The inventors have discovered that the problem can be solved, and have arrived at the present invention. That is,
The present invention provides a resin package material for electronic components that does not come into contact with an element, characterized in that polyphenylene sulfide resin, which is a repeating unit, is used as a packaging material for an electronic component where the package and the element do not come into direct contact.

If the amount of polyphenylene used in the package material of the present invention is increased, the thermal deformation temperature of the material will decrease, and the heat resistance will decrease, which is not preferable. On the other hand, if the amount is too low, the effect of improving the balance of toughness/melt fluidity during molding and adhesive strength will hardly be achieved, which is undesirable.

The packaging material of the present invention consists of polyphenylene units, but in addition to these units, a small amount of other (Ar-8
) one unit, and/or where Ar represents a divalent aromatic group and Ar' represents a trivalent aromatic group). Like this -(A
Examples include r-8)-1 units.

These units can be contained in one type or in a mixed unit of two or more types.

The polyphenylene sulfide of the packaging material of the present invention as described above can be produced by several methods, and among them, the following method is a preferred method. That is, p-dichlorobenzene 85
~99.5 mol% and m-dichlorobenzene 15-0
A dihalide mixture consisting of 5 mol % and sodium sulfide or sodium bisulfide/sodium hydroxide is combined with N
- React in an aprotic polar solvent such as methylpyrrolidone at a temperature of 200°C or higher. It is also possible to carry out the reaction in the presence of a catalyst such as a carboxylic acid metal salt for the purpose of obtaining a highly polymerized product. It is also possible to use the polyphenylene sulfide produced by the reaction as it is as a packaging material, or by heating the polyphenylene sulfide produced by the reaction in an oxygen atmosphere,
Alternatively, it is also possible to increase the degree of polymerization by adding a crosslinking agent such as a peroxide and heating.

When using the polyphenylene sulfide obtained in this way as a packaging material of the present invention, it is not impossible to use it without a filler depending on the application;
It is usually used with the addition of fillers. The amount of the filler added varies depending on the type of filler used and the type of package, but it is usually preferably 10 to 400 parts by weight per 100 parts by weight of polyphenylene sulfide. The filler used in the present invention can be a fibrous filler, a non-fibrous filler, or both. Examples of such fillers include glass fines, glass peas, glass powder, fused silica, crystalline silica, calcium silicate, calcium sulfate, calcium carbonate, talc, calcium titanate, potassium titanate, alumina powder, titanium oxide. Examples include powder, iron oxide powder, clay, mica, wollastenite, and ceramic fiber. These fillers can be used alone or in a mixture of two or more. When blending these fillers, use the polyphenylene sulfide 1li1o of the present invention.

It is preferably 10 to 400 parts by weight.

Polyphenylene Jl/Fi F [fat xo] of the present invention.

If the amount exceeds 4 ooN parts by weight, the melt viscosity will be high, impairing fluidity and inhibiting moldability, which is not preferable. On the other hand, if it is less than 10 parts by weight, it is not preferable because the effects of filler compounding, such as improving strength and reducing the coefficient of thermal expansion, cannot be obtained.

When a filler is added to the polyphenylene sulfide resin of the packaging material of the present invention, in order to improve the adhesion between the filler and the resin or to improve the hygroscopicity, the filler may be mixed with a run-coupling agent or a titanium coupling agent. It is also possible to use those treated with a coupling agent or the like, or it is also possible to directly blend these coupling agents into the polyphenylene sulfide resin.

When a filler or the like is blended into the polyphenylene sulfide resin of the packaging material of the present invention, there is no particular limitation on the blending method, but a melt mixing method is usually used. For example, after tri-blending each component such as a polyphenylene sulfide resin and a filler, a method of melt-kneading and pelletizing in an extruder, a method of supplying each component from separate supply ports of an extruder and melt-kneading and pelletizing, or a method of melt-kneading and pelletizing each component, or It can be blended by a combination of methods.

Electronic components (devices) using packaging materials that do not come into direct contact with the device of the present invention are not particularly limited as long as they can be considered under the concept of ordinary electronic components;
10), l-run sisters, capacitors, resistors, diodes, triodes, thyristors, coils, varistors, connectors, converters, microswitches, etc., and composite parts thereof. Among these,
It is particularly suitably applied to integrated circuits (ICj).

There are no particular restrictions on the method for molding the package material of the present invention into a package, and injection molding or transfer molding is usually used, but injection molding is particularly preferred.

<Example> The present invention will be further described in detail with reference to Examples below. Note that the values of % and parts used in the examples indicate weight % and parts by weight, respectively, unless otherwise specified. In addition, the bending strength, bending modulus, tensile strength, tensile elongation, Izod impact strength, and heat distortion temperature in the examples were each measured by the methods described below.

Bending strength A8TM D790 Flexural modulus A8TM n7j.

Tensile strength A8TM D638 Tensile elongation A8TM D638 Izot impact strength A8TM D256 Production Example I Cm -/p- = 3/97 Polymerization of polyphenylene sulfide copolymer] 30% sodium hydrogen sulfide aqueous solution 4.67 in an autoclave with an internal volume of 201 kq (25 moles of sodium hydrosulfide), 2.00 kg of 50% aqueous sodium hydroxide solution
(25 mol of sodium hydroxide) and N-methyl-2-
Prepare 8 kg of pyrrolidone (hereinafter abbreviated as NMP),
While stirring, the temperature was raised to approximately 200°C, and 4.1 kg, including 3.8 kg of water, was distilled out. , 1. . After distillation, p
-dichlorobenzene 3,566 ky (24,25 moJl/), lll-dichlorobenzene 0.110
kq (0.75 mol) and NMp2 kl were added and polymerized for 3 hours at 250°C.

After the polymerization was completed, the reaction mixture was poured into 501 stirring water, filtered, and then poured into the same amount of water at 70 to 80° C. and washed and filtered, which was repeated five times. The product was then heated to 120°C
When vacuum drying was carried out for 24 hours, about 2.4 kl of polyphenylene sulfide powder was obtained. When the IR of this polymer was measured, it was found to be a copolymer with m-/p-=3/97.

Production Example 2 (Polymerization of m-/p-=10/90 polyphenylene sulfide block copolymer) In an autoclave similar to Production Example 1, 3.737 kg of a 30% sodium bisulfide aqueous solution (sodium bisulfide 2
0 mol), 50% aqueous sodium hydroxide solution 1. a O
kq (20 moles of sodium hydroxide) and N M P
7 kQ was added, the temperature was raised to about 200°C under stirring, and 3.0 kQ of water was added. 3.3 kg containing Oksu was distilled out. After completion of distillation, p-dichlorobenzene 2.941 people 9 (20
mol) and NMP 2k at 250°C.
．． A reaction mixture A was obtained by polymerizing for 5 hours.

Next, in the same autoclave, add 0.374 kq of 30% sodium bisulfide aqueous solution (2 moles of sodium bisulfide).
, 0.1 bky of a 50% aqueous sodium hydroxide solution (2 moles of sodium hydroxide) and 2 kg of NMP were added, the temperature was raised to about 200°C under stirring, and 0.3 kg of water was added.
A total of 0.4 kg was distilled out.

After the distillation, 0.294 kg of m-dichlorobenzene (
2 mol) and 90% of the reaction mixture A obtained above were added and mixed, and polymerized at 250°C for 2 hours.

After the polymerization was completed, the reaction mixture was subjected to the same post-treatment operation as in Production Example 1, and about 1.9 kQ of polyphenylene sulfide block copolymer powder was obtained.

Also, when we measured the IR of this polymer, “-/p-=
It was a 10/90 copolymer.

Production Example 3 [Polymerization of m~/p-=5/95 polyphenylene sulfide copolymer] p-dichlorobenzene 3.566 kg (2425 mol) and m-dichlorobenzene 0.110 kg (0
, 75 mol), p-dichlorobenzene 3.49
3kQ (23,75 mol), m-dichlorobenzene 0184 (1,2-5 mol) and l.

2.4-) Polyphenylene sulfide copolymer powder of 2.5 to Obtained. Also, the I of this polymer
When R was measured, it was found that it was the same as the preparation ratio "-/p-=5/
It was a copolymer of 95.

Example 1 60 parts of the m-/p-=3/97 polyphenylene sulfide copolymer obtained in Production Example 1 and 40 parts of glass fiber treated with a silane coupling agent were sufficiently triblended, and then 30 parts Temperature 2 in MJ12-screw extruder
It was extruded into pellets at 80 to 31oC.

Using the obtained pellets, a test piece was molded by injection molding. Molding temperature: 28 o ~ 310 ° C, mold temperature = 130 ° C.
), the physical properties were measured, and as shown in Table 1, it showed excellent physical properties as a package material. Also, using this pellet, two 4210 plates were bonded together using a hot press, and the adhesive strength was measured using a tensile shear method.
It showed an excellent adhesive strength of Q/d.

In addition, when the obtained pellets were actually used to manufacture the bin grid array package shown in Fig. 2 by injection molding, it showed good adhesion to the reinforcing material and the bins, was strong, and was excellent as a package. there were.

Comparative Example 1 "-/p-=3/97 Extrusion pelletization/
Test pieces were obtained by injection molding, and the physical properties were measured as shown in Table 2.
The results were obtained. In addition, the adhesive strength with the 4270 plate was measured in the same manner as in Example 1 and was found to be 12 ky/d.

In this way, compared to the first embodiment of the present invention, the conventional point IJ (p
-phenylene sulfide) has poor elongation, -15 = toughness, and is a typical material for lead frames.
The adhesive force with 210i is also significantly low, and it is clear that it is inferior to the material of the present invention as a packaging material.

Example 2 65 parts of the m-/p-=l O/90 polyethylene sulfide block copolymer obtained in Production Example 2, 20 parts of silane coupling agent-treated glass fiber, and silane coupling agent-treated fiber After sufficiently triblending with 15 parts of fused silica, extrusion pelletization/injection molding was performed in the same manner as in Example 1 to obtain a test piece, and the physical properties were measured. Table 3
results, and the adhesion strength with 4270i was 45 kg.
/d and showed excellent properties as a packaging material.

Example 3 Completely the same as Example 1 except that m-/p-=5/95 polyphenylene sulfide obtained in Production Example 3 was used instead of "-/p-=3/97 polyphenylene sulfide." The operation was carried out to obtain a test piece.The physical properties of this test piece were measured and the results shown in Table 4 were obtained, and the adhesive strength with 42 alloy was 44 kq/d, indicating excellent properties as a package material.

Furthermore, using the obtained pellets, the IC shown in FIG.
When a cavity package was manufactured by injection molding, it was found to have good adhesion to the lead frame, high toughness, and excellent thermal shock resistance.

<Effects of the Invention> The packaging material of the present invention has excellent properties such as adhesiveness and toughness. It is then molded using a highly productive molding method such as injection molding, and can be used for various electronic components as packages that do not come into direct contact with elements, such as bin grid arrays and cavity packages.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of an IO hollow cavity package according to the present invention, which is an example of a package that does not come into direct contact with an element, FIG. 2 is a perspective view showing a bin grid array package according to the present invention, and FIG. 3 is a conventional , is a cross-sectional view showing an IC package (sealing material) in contact with an element. l... Cavity package, 2.e.81 chip (element), 3... Bonding wire, 4... Lead frame, 5... Bin grid array package, 6... Sealing material, 7... Bin Patent Applicant Toshi Co., Ltd. Figure 1 Figure 2 Figure JlB

Claims (1)

[Claims] As packaging materials for electronic components where the package and the element do not come into direct contact, there are repeating units ▲ mathematical formulas, chemical formulas, tables, etc. ▼ 85 to 99.5 mol% and ▲ mathematical formulas, chemical formulas, tables, etc. ▼15-0.5 mol%
An electronic component resin packaging material that does not come into contact with an element, characterized in that it uses a polyphenylene sulfide resin consisting essentially of: