JP3339027B2 - Polyarylene sulfide resin composition, protection / supporting member for integrated module of electric / electronic component, and protection / supporting member for electric / electronic component corresponding to SMT - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide resin composition and a protective / supporting member for an integrated module of electric / electronic parts, and a protective / supporting member for electric / electronic parts compatible with SMT.
Regarding the support member, more specifically, a polyarylene sulfide resin composition particularly suitable for the production of a molded member for electronic and electrical equipment, and a molded article made of the polyarylene sulfide resin composition, particularly, a power module and the like Modules with encapsulation, relays such as SMT-compatible relays and solid-state relays, switches such as SMT-compatible switches, and base materials such as modules, cases, bases, cards, and connectors that contain electrical circuits. And a protection and support member for an SMT-compatible electrical and electronic component.

[0002]

2. Description of the Related Art The demand for a power control circuit, particularly a power module used as a power conversion unit, has been rapidly expanding in the last decade or so, especially with the spread of inverter air conditioners. A power module is a kind of power device, but is a kind of hybrid IC because it combines individual semiconductor chips and devices to provide one or more functions.
In general, a plurality of power devices (individual semiconductor chips and devices such as diodes, thyristors, transistors, etc.) are combined or connected in a predetermined configuration into a single package to form a unit. Things.

[0003] In forming a package of devices such as a power module, resin molding by transfer molding of a thermosetting resin such as an epoxy resin or a silicone resin has been widely adopted.

[0004] However, the package size may be considerably large depending on the application, such as the case of a power module, and various problems arise when such a large module is sealed with a resin. come.
In fact, when the package size of these modules becomes a certain size, especially about 4 cm or more,
Resin sealing with epoxy resin or the like has problems such as occurrence of cracks due to internal stress or increase in production cost.

In such a case, a method is adopted in which a case and a substrate are separately prepared and integrated with the case and the substrate by a casting resin sealing method or the like to form a stronger package.

[0006] In addition to power modules, similar treatments using cases and substrates have been taken for general modules with sealing and modules containing electric circuits, such as sensors.

By the way, recently, a metal terminal for connecting to an external circuit has been provided on such a case or substrate by integral molding, and the metal terminal and the circuit terminal of the module itself have been provided. The connection with the like is usually made by soldering.

[0008] Accordingly, as a material of such a case or a substrate, a resin is basically preferred in terms of lightness, insulation, moldability, and the like. However, these resin materials are required to have high solder heat resistance. In particular, when a large current flows as in a power module to generate a large amount of heat, it is necessary to have high-temperature durability (lifetime).

Further, in addition to high-temperature heat resistance, strict conditions such as mechanical strength, high shape accuracy, especially dimensional stability at high temperatures, moisture resistance, and flame retardancy are required for resins used for such cases and substrates. I have. Therefore, conventionally, as these resins, engineering resins, particularly polyethylene terephthalate (sometimes abbreviated as PET), polybutylene terephthalate (sometimes abbreviated as PBT), especially engineering resins reinforced with glass fibers and inorganic fillers. Nylon 66 (sometimes abbreviated as PA-66) and the like have been widely used.

On the other hand, in recent years, SMT (however, this is a surface-mount-technolo
gy is an abbreviation for gy. ) Is expanding. Applying this SMT, it has become increasingly common to simultaneously incorporate mechanical components such as connectors, switches, and relays into one package. In this case as well, the individual components are directly exposed to the molten solder or the melting temperature of the solder, as described above. So these connectors, switches,
For relays and the like, it has become necessary to use a resin that satisfies the above strict requirements such as satisfying high solder heat resistance.

Thus, a molded member for electric / electronic equipment,
In particular, as a resin used for a base or a member such as a case, a base, a card, a board, a sheet, a film, or a switch in the above-described module or SMT product, generally, at least mechanical strength, high-temperature heat resistance, and shape accuracy are used. For example, those that satisfy high-temperature dimensional stability, insulation properties, moisture resistance, flame retardancy, moldability and the like as much as possible are preferred.
With higher performance of various modules or the spread of SMT products, the requirements of the above properties for these resins are becoming increasingly severe.

Therefore, recently, in order to cope with such severe requirements, conventional PET, PBT, PA-66
Attempts have been made to use a polyphenylene sulfide resin (which may be abbreviated as PPS) having excellent properties at high temperatures, such as heat resistance, in place of the above.

However, PPS resins have excellent properties such as dimensional stability at high temperatures, heat resistance, flame retardancy, and moisture resistance, but generally have low toughness at least as far as the prior art is concerned. In particular, it has been evaluated to have a serious disadvantage that adhesion to a sealing material is poor. That is, the PPS resin is converted to the electric and
When applied to electronic device parts, in the conventional case, it peels off from the encapsulant, causing corrosion and poor contact on the enclosed metal parts and circuits, and press-fitting metal parts during post-processing. Due to the serious problem of cracking and cracking when screwing or screwing,
Even if this is applied, the field of use is limited to a very narrow range.

The present invention has been made based on the above circumstances.

An object of the present invention is to solve the above problems,
Various electric and electronic equipment members, especially base materials for cases and bases of modules with sealing such as power modules,
Mechanical strength and high temperature heat resistance when molded into SMT compatible relays and solid state relay cases, bases or base materials for cards, SMT compatible switch members, module cases including electric circuits, base materials, etc. For example, it fully satisfies basic characteristics such as high solder heat resistance and high temperature durability, high shape accuracy, especially high dimensional stability at high temperature, insulation properties, high moisture resistance, flame retardancy, etc., and has sufficient toughness , Another object of the present invention is to develop and provide a novel resin composition exhibiting excellent practical performance such as good adhesion to a sealing material and good metal corrosion resistance .

Another object of the present invention is to provide an electric / electronic component integrated module formed by using the resin composition of the present invention having the above-mentioned excellent characteristics into the above-mentioned members for electric / electronic devices. It is an object of the present invention to provide a protection / supporting member for electric and electronic parts and a protection / supporting member for SMT-compliant electric / electronic parts.

[0017]

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that polyarylene sulfides such as PPS (sometimes abbreviated as PAS).
At least a specific ethylene-based copolymer , a specific oxide solid solution, and di (cyclohexyl) ammonium nitride
A specific PAS-based resin composition containing light and a reinforcing filler in a specific ratio has excellent properties satisfying the above-mentioned object, and the resin composition is used for the above-mentioned various electric / electronic device members. When these materials were evaluated and applied, these materials suffered from problems such as low toughness and poor adhesion to sealing materials and poor metal corrosion resistance, which were disadvantages of conventional PPS resin materials. And the above-mentioned basic properties as a predetermined member such as mechanical strength, high-temperature heat resistance, shape accuracy, especially high-temperature dimensional stability, insulation, moisture resistance, flame retardancy, moldability and the like are sufficiently satisfied. I found that the above purpose was fully achieved.

When a specific polyarylene sulfide having a branched chain by having an amino group and / or an amide group in the molecule is used as the above PAS, the adhesion to the sealing material is further improved. It has also been found that a better molded member for electric and electronic equipment can be obtained.

The present inventors have completed the present invention based mainly on the above findings.

That is, the first aspect of the present invention relates to 100 parts by weight of a polyarylene sulfide which is not substantially thermally oxidized and crosslinked, and 50 to 9 as a monomer unit.
0% by weight of ethylene, 5-49% by weight of an α, β-unsaturated carboxylic acid alkyl ester and 0.5 to 10% by weight
1 to 25 parts by weight of an ethylene copolymer containing maleic anhydride, 0.5 to 10 parts by weight of a solid solution of Mg / Al oxide, 0.5 to 3 parts by weight of di (cyclohexyl) ammonium nitrite And a polyarylene sulfide resin composition containing a reinforcing filler of 150 parts by weight or less, and the invention according to claim 2,
The polyarylene sulfide resin composition according to claim 1, wherein the polyarylene sulfide has an amino group and / or an amide group in a molecule. The invention according to claim 3, wherein the polyarylene sulfide resin has an amino group and / or an amide group. A protection and support member for an electric / electronic component integrated module, which is obtained by molding the polyarylene sulfide resin composition according to claim 1 or 2. The invention according to claim 4 is the invention according to claim 1 or 2. A protection and support member for an SMT-compatible electric / electronic component, which is obtained by molding the polyarylene sulfide resin composition according to item 2.

Among the protection and support members for the electric / electronic component integrated module, a case and a base of a module including an electric circuit, such as a case and a base of a module with sealing, are representative.
Among the electronic component protection and support members, cases such as SMT compatible relays, SMT compatible solid state relays, etc.
Representative examples include a base and a card, and various molded bodies in an SMT-compatible switch.

In particular, when a more specific polyarylene sulfide having an amino group and / or an amide group in a molecular chain is used as the polyarylene sulfide, the electric / electronic component integrated module of the present invention is used. The characteristics and performance of the protection / supporting member for SMT and the protection / supporting member for SMT compatible electric / electronic parts can be further improved.

Hereinafter, the present invention will be described in detail.

-Polyarylene sulfides- The polyarylene sulfides of the present invention are not substantially thermally oxidized and crosslinked.

On the other hand, thermal oxidative crosslinking type polyarylene sulfides are obtained by obtaining a polyarylene sulfide having a relatively low molecular weight, for example, polyphenylene sulfide by polymerization, and then converting the polyarylene sulfide to a melting point below the melting point in the presence of oxygen. Baking is performed at a high temperature to promote oxidative crosslinking to improve the viscosity. Generally, the poly (arylene sulfide) of the thermal oxidation cross-linking type is colored brown, has a high oxygen concentration in the resin, and is thermally unstable. The thermal oxidation cross-linked polyarylene sulfides generally have high mechanical strength, but have a drawback of low toughness, that is, brittle. However, since it has excellent fluidity during molding, it is still widely used in the field of thin-wall molding, and is widely used as a general engineering resin. A specific example of the thermal oxidation cross-linkable polyarylene sulfide is PPS-M1900 manufactured by Toray Industries, Inc.
And the like.

On the other hand, the polyarylene sulfides which are not substantially thermally oxidized and crosslinked according to the present invention are prepared by allowing a polymerization auxiliary and / or a branching agent such as trichlorobenzene and dichloronitrobenzene to coexist at the time of polymerization. It has been adjusted to the target viscosity in the polymerization stage and is therefore substantially not thermally oxidatively crosslinked. In addition, the polyarylene sulfides that are not substantially thermally oxidized and crosslinked are one of the reasons that the oxygen concentration in the resin is extremely low as compared with the thermally oxidatively crosslinked polyphenylene sulfides. It is extremely stable, and has the advantage that the generation of corrosive gas such as SO ₂ is significantly reduced as will be described later, and there is no practical problem. The polyarylene sulfides which are not substantially thermally oxidized and crosslinked are electric / electronic parts which are superior in toughness, especially impact resistance or elongation during post-processing, as compared with the above-mentioned thermally oxidized and crosslinked polyarylene sulfides. It can be formed into a protection / support member for an integrated module and a protection / support member for an SMT-compatible electric / electronic component.

As one type of the polyarylene sulfides which are not substantially thermally oxidized and crosslinked, there are polyarylene sulfides having an amino group and / or an amide group in a molecular chain. Polyarylene sulfides having an amino group and / or an amide group in the molecular chain include:
By copolymerization (it may be mentioned, for example -NH ₂ and the like.) Amino group in the molecular chain and / or can be exemplified an amide group (e.g. -NHCOR like. However,
R is usually H or a hydrocarbon group such as an alkyl group. ) And can be obtained without performing thermal oxidative crosslinking after polymerization.

In the above description, "substantially no thermal oxidative crosslinking is performed" means that at least 150% in the presence of oxygen.
It means that heat treatment for improving the viscosity is not performed at a temperature of not less than ° C.

The determination of whether or not the polyarylene sulfide is substantially thermally oxidatively cross-linked or not is made depending on whether or not the above-mentioned heat treatment is performed. It can also be determined from an analysis as shown.

(A) Method for Judging from the Amount of SO ₂ Generated from Polyarylene Sulfides 0.2 g of a polyarylene sulfide as a sample was
00 ml / min. Is heated at 300 ° C. for 1 hour in an N ₂ gas stream, and the obtained outgas is introduced into a 1% aqueous H ₂ O ₂ solution to be collected to obtain a collected liquid. After obtaining the collected liquid,
The outgas passage is washed with a certain amount of a 1% aqueous solution of H ₂ O ₂ , and the obtained washing liquid is added to the collected liquid to obtain a final collected liquid. The final concentration of SO ₄ ²⁻ in the collected liquid was determined by ion chromatography, and S
It is converted to the amount of O ₂ and quantified. The order of quantification is ppm
(Μg / g). According to this determination method, the amount of SO ₂ generated from polyarylene sulfides that have not been substantially thermally oxidatively crosslinked is usually 50 ppm or less, and more strictly, the amount of SO ₂ generated is 10 ppm or less. SO ₂ emissions of oxidized cross-linked polyarylene sulfides exceeds the 50 ppm.

(B) Method of Judging from Oxygen Concentration in Polyarylene Sulfides The amount of oxygen in the polyarylene sulfide as a sample is determined by elemental analysis and quantified by the amount of oxygen per resin. According to this quantitative evaluation method, the oxygen content of the polyarylene sulfides that are not substantially thermally oxidized and cross-linked is usually
Strictly speaking, the oxygen content of the polyarylene sulfide is not more than 0.1% by weight, and the oxygen content of the thermally oxidatively crosslinked polyarylene sulfide is not more than 0.5% by weight. % By weight or more.

The polyarylene sulfides in the present invention are defined as substantially not thermally oxidized and crosslinked, but the polyarylene sulfides in the present invention have some crosslinkability even when heated under oxygen-free condition. And the viscosity is substantially improved. However, in such a case, it can be easily determined by the above-mentioned quantitative evaluation method, in particular, the above-mentioned method (a) that it does not correspond to the thermal oxidative crosslinking type polyarylene sulfide.

In the present invention, it is important to use polyarylene sulfides which are not substantially thermally oxidized and crosslinked. Here, if the polyarylene sulfides which have not been substantially thermally oxidized and crosslinked are used instead of the polyarylene sulfides which have been subjected to the thermal oxidative crosslinking, the object of the present invention can be achieved. Can not do it.

Hereinafter, unless otherwise specified, the term “polyarylene sulfide” simply refers to the polyarylene sulfide that is not substantially thermally oxidized and crosslinked.

In the present invention, the polyarylene sulfides can be produced by various methods. Specifically, it can be produced, for example, by the method described in JP-A-53-25588.

The outline of specific examples of this preferred production method and examples of the types of polyarylene sulfides preferably used are shown below.

The polyarylene sulfide used in the present invention is a complex represented by the general formula-(Ar- S- ) _n- . Here, -Ar- is, for example, a divalent aromatic residue containing at least one carbon 6-membered ring as shown in the following (Chemical Formula 1).
There l, and a halogen atom such as Br, also various atoms or substituents including the like alkyl groups such as -CH ₃ are introduced.

[0038]

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A particularly typical polyarylene sulfide is a polyphenylene sulfide represented by the following chemical formula (2), which is generally marketed under the trademark "Ryton" by Phillip Spetrolium of the United States. The production method thereof is disclosed in U.S. Pat. No. 3,354,129 and the corresponding Japanese Patent Publication No. 45-3368, in a N-methylpyrrolidone solvent at 160 to 250 ° C.
It can be produced by reacting paradichlorobenzene with sodium sulfide (Na ₂ S.H ₂ O) under pressurized conditions. Also, Japanese Patent Publication No. 52-12240, Japanese Patent Publication No. 53-25588 and Japanese Patent Publication No.
When a catalyst such as lithium acetate or lithium chloride is used in combination as disclosed in Japanese Patent No. 255889, polyphenylene sulfide having a higher degree of polymerization can be produced.

[0040]

Embedded image

As described above, the viscosity may be adjusted by, for example, imparting a chemically crosslinked structure by appropriately coexisting or adding a branching agent during the polymerization. In addition, in the above-mentioned polymerization method, as described above, if copolymerization is performed using a monomer having an amino group and / or an amide group, similarly, a polymer having an amino group and / or an amide group in a predetermined molecular chain can be obtained. Arylene sulfides can be obtained.

Among these various polyarylene sulfides, polyarylene sulfides having an amino group and / or an amide group in the molecular chain are preferable.

Among these various polyarylene sulfides, some specific examples of particularly preferred ones are as follows: PPS, amino group-containing PPS, amide group-containing PPS, PPS containing both amino and amide groups simultaneously.
And the like. -Ethylene-based copolymer- The ethylene-based copolymer used in the present invention has 50 to 90% by weight, preferably 60 to 85% by weight of ethylene when the copolymer composition is represented by a monomer component. An ethylene copolymer comprising 5-49% by weight, preferably 7-45% by weight of an α, β-unsaturated carboxylic acid alkyl ester and 0.5-10% by weight, preferably 1-8% by weight of maleic anhydride. It is a polymer.

Here, α, in the ethylene copolymer is used.
If the proportion of the β-unsaturated carboxylic acid alkyl ester exceeds 49% by weight, the thermal stability of the ethylene copolymer itself becomes insufficient, while if it is less than 5% by weight, the effect of improving the toughness becomes insufficient. In any case, the object of the present invention cannot be sufficiently achieved.

When the proportion of the maleic anhydride component in the ethylene-based copolymer exceeds 10% by weight, the thermal stability of the ethylene-based copolymer itself decreases, and foaming due to decomposition cannot be ignored. , Less than 0.5% by weight,
The effect of improving the toughness is insufficient, and the adhesion to the sealant is reduced. In any case, the object of the present invention cannot be sufficiently achieved.

The α, β-unsaturated carboxylic acid alkyl ester is an unsaturated carboxylic acid having 3 to 8 carbon atoms, for example, an alkyl ester of acrylic acid, methacrylic acid and the like. , Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate And t-butyl methacrylate, among which ethyl acrylate, n-butyl acrylate, methyl methacrylate and the like are particularly preferable.

[0047] -Mg / Al oxide solid solution - the Mg / Al oxide solid solution used in this invention, a composite oxide der consisting oxidation magnesium and aluminum oxide
You .

Among them, usually, the composition is formally represented by the general formula Mg _{1 -X} Al _X O _{1 + X / 2} (where X is usually 0.5 or less, preferably 0.1 (Representing a real number in the range of 0.35 to 0.35).

The shape of these Mg / Al oxide solid solutions is not particularly limited, and may be various shapes such as spherical, substantially spherical or irregular particles, leaves, plates, needles, and the like. There may be. However, usually, a Mg / Al oxide solid solution having a large BET specific surface area, specifically, an Mg / Al oxide solid solution of 50 m ² / g or more is preferable. Mg as small as possible like solid solution
/ Al oxide solid solution is preferred.

These Mg / Al oxide solid solutions usually have an allowable water content of crystal water, adsorbed water, etc. of 0.1.
3% by weight.

Further, these Mg / Al oxide solid solutions may contain impurities such as other metal components.
Normally, it is preferable that other metal components other than Mg and Al be as small as possible. Therefore, this Mg / Al oxide solid solution can be used as long as it is a natural product as long as it has high purity, but an artificially synthesized Mg / Al oxide solid solution is usually preferable.

Particularly preferred examples of the Mg / Al oxide solid solution include, for example, KW2200 (composition formula: Mg _0.7 Al _0.3 O _1.15 ; B) manufactured by Kyowa Chemical Industry Co., Ltd.
(ET specific surface area: about 150 m ² / g).

These Mg / Al oxide solid solutions may be of two or more different compositions, if necessary.

[0054] - di (cyclohexyl) nitrite - di (cyclohexyl) ammonium na used in the present invention
Itoraito the formula (C ₆ H ₁₁₎ represented by ₂ NH · HNO ₂
Compound .

This di (cyclohexyl) ammonium salt
Itolite has a melting point of about 176 ° C and a molecular weight of 22.
8 The di (cyclohexyl) ammonium
High purity munlite is white crystalline.
You .

The di (cyclohexyl) ammonium
Nitronite is commercially available, for example,
There is a brand name "DICHAN" manufactured by Gaku Kogyo .

When the di (cyclohexyl) ammonium nitrite is added to the polyarylene sulfide resin composition of the present invention, it is usually preferable to add it in the form of fine particles. However, after the addition of di (cyclohexyl) ammonium nitrite, especially in the melt-kneaded polyarylene sulfide resin composition, its chemical structure does not always remain as the above formula (C ₆ H ₁₁ ) ₂ NH.HNO ₂ . It does not need to be held.

By adding an appropriate amount of the di (cyclohexyl) ammonium nitrite to the polyarylene sulfide resin composition of the present invention, its characteristics, for example, the characteristics described below can often be further improved.

-Reinforcing filler-In the present invention, various fillers can be used as the reinforcing filler, for example, glass fibers such as chopped glass fiber and milled glass fiber, chopped carbon fiber, Examples include carbon fibers such as milled carbon fibers, whiskers such as potassium titanate whiskers, zinc oxide whiskers, and vapor grown carbon fiber whiskers, and plate-like inorganic fillers such as mica, talc, and glass flakes. These may be one or more types depending on the characteristics and shape, size, dimensional accuracy, etc. required for the protection and support members for integrated modules for electric and electronic components and the protection and support members for SMT compatible electric and electronic components. However, glass fibers, whiskers, mica, glass flakes and the like are usually preferably used because they are generally required to be non-conductive.

[0060] - other components as optional components - The polyarylene sulfide resin composition in this invention, the polyarylene sulfides, wherein the ethylene copolymer, Mg / Al oxide solid solution, di (cyclohexyl) In addition to the ammonium nitrite and the reinforcing filler, various components may be added and blended as needed, as long as the object of the present invention is not impaired. For example,
General fillers, other thermoplastic resins and / or thermosetting resins, rubbers, pigments, and the like can be appropriately added.

-Mixing ratio of each component in polyarylene sulfide resin composition-The above-mentioned polyarylene sulfide, ethylene copolymer and Mg / A for preparing the resin composition of the present invention.
The mixing ratio of the oxide solid solution is such that the ethylene copolymer is 1 to 25 parts by weight, preferably 3 to 15 parts by weight, per 100 parts by weight of the polyarylene sulfide.
The Mg / Al oxide solid solution is 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight.

If the proportion of the ethylene copolymer is less than 1 part by weight based on the above criteria, the effect of improving the toughness cannot be sufficiently obtained, and the effect of improving the adhesion to the sealing material. On the other hand, if it exceeds 25 parts by weight, the mechanical strength, the heat resistance and the flame retardancy are extremely reduced, and the excellent properties of polyarylene sulfide are significantly impaired.

When the ratio of the Mg / Al oxide solid solution is less than 0.5 part by weight based on the above criteria, the effect of reducing burrs and gas is reduced, and the corrosion of metals and the epoxy sealing material are reduced. On the other hand, if it exceeds 10 parts by weight, the mechanical strength, particularly the impact strength, will be extremely reduced, and in any case, the object of the present invention cannot be achieved.

The mixing ratio of the di (cyclohexyl) ammonium nitrite is usually preferably not more than 3 parts by weight, more preferably not more than 1 part by weight, per 100 parts by weight of the polyarylene sulfide. Is preferred. It is to be noted that whether or not it is preferable to add di (cyclohexyl) ammonium nitrite or a preferable addition amount varies depending on the use.

For example, when the power module is used in a case of a power module and is sealed with a sealing material, the di (cyclohexyl) ammonium nitrite is generally added without addition or in a very small amount. preferable. On the other hand, when the application is the above-mentioned relays, it is preferable to add this di (cyclohexyl) ammonium nitrite in a very small amount. Thus, the amount of di (cyclohexyl) ammonium nitrite to be added is appropriately selected depending on the application.

By adding an appropriate amount of the di (cyclohexyl) ammonium nitrite, the polyarylene sulfide resin composition according to the present invention may be used for a long time at a relatively low temperature to obtain a metal which is close to the metal. Characteristics such that the resulting metal corrosion can be significantly reduced are improved, and the molded product obtained by molding with the polyarylene sulfide resin composition by such improved characteristics is used for an electric / electronic component integrated module, and It is suitable for SMT compatible electric / electronic parts.

The amount of the reinforcing filler to be added varies depending on the application, the ratio of other components, and the like. Most usually, the reinforcing filler is used in an amount of usually not more than 150 parts by weight per 100 parts by weight of the polyarylene sulfide.
Preferably, the heat resistance of the polyarylene sulfide resin composition, in particular, the high-temperature properties is more effectively exhibited, or the molded article of the polyarylene sulfide resin composition is added by selecting and adding it in a ratio of 25 to 100 parts by weight. Can be expected to further improve the heat resistance dimensional stability, mechanical strength, and the like.

If the reinforcing filler is added in excess of 150 parts by weight on the basis of the above, the fluidity and
In some cases, the workability is extremely reduced and the material cannot be used substantially.

—Preparation of Polyarylene Sulfide Resin Composition— The polyarylene sulfide resin composition according to the present invention comprises at least the polyarylene sulfide, the ethylene-based copolymer, and the Mg / Al oxide solid solution as defined above. It can be prepared by blending in proportions and, if necessary, further blending other components, for example, by melt-kneading. This melt-kneading can be carried out by a commonly known method. In any case, the respective components are uniformly mixed and dispersed in a resin to obtain a predetermined resin composition. In particular, it is preferable that the ethylene copolymer is uniformly dispersed as much as possible.

For the melt-kneading, an ordinary twin-screw kneader, single-screw extruder or the like can be suitably used.

The conditions for the melt-kneading are not particularly different from those of ordinary polyphenylene sulfide.
Usually, the same conditions as in that case can be suitably adopted,
In particular, to limit the decomposition or foaming of the ethylene copolymer and di (cyclohexyl) ammonium nitrite added as necessary, use extremely high temperatures, extremely long residence times, or extreme suction from vents. It is preferable to avoid.

The polyarylene sulfide resin composition thus prepared by melt-kneading is usually granulated or cut into a shape and size suitable for a material for secondary processing such as pellets, particularly a material for injection molding. Is obtained. At this time, it is preferable to appropriately dry the granules such as pellets. In this case, it is preferable to avoid drying at an excessively high temperature, particularly in consideration of the possibility of decomposition or foaming of the ethylene copolymer. Is desirable. The drying temperature is usually 10
A temperature of 0 to 120 ° C is sufficient, and the drying time may be about 3 to 6 hours.

Protection for integrated modules of electric and electronic parts
Supporting member and protection / supporting member for SMT-compatible electric / electronic parts-An electric / electronic part integrated module is a package in which a plurality of individual semiconductors or modules are enclosed in a small resin package. It may be molded with a curable resin. Among electric / electronic component integrated modules, there is a power module in which power devices are integrated to form a unit for power conversion. The large power module adopts a casting resin method in which the outer case is manufactured by injection molding, individual elements and modules are inserted into the obtained outer case, and sealed with the thermosetting resin. Often done. Also, in some cases,
In many cases, the external metal terminal and the outer case are integrally formed and soldered to the terminal.

As the protection / support member for an electric / electronic component integrated module of the present invention, mounting such as housing or mounting the electric / electronic component integrated module, or mounting of a module including an electric circuit is performed. For molding. Examples of the molded body include a case, a base, a frame, a board, a sheet, and a film for mounting a module sealed with a thermosetting resin or for mounting a module including an electric circuit. Can be. The shape and size of these compacts are appropriately determined according to the scale and shape of the module and the like.

SMT is called a surface mount technology. SMT
Is a technology aiming at higher density and simplification of integration. An SMT-compatible protection / supporting member for an electric / electronic component is a molded body used to realize high-density surface mounting, such as a high-density surface-mounting relay, a high-density surface-mounting solid-state relay, and a high-density surface-mounting member. Examples include a mounting switch, a micro cellular phone, a camera-integrated VTR, a case for surface mounting in a liquid crystal display, a base, a board, a sheet, a film, a card, and the like.

The protection / supporting member for an electric / electronic component integrated module and the protection / supporting member for an SMT-compatible electric / electronic component according to the present invention have mechanical strength, high heat resistance, particularly high solder heat resistance, high temperature durability, and high shape. Accuracy Satisfies basic characteristics such as high dimensional stability at high temperatures, insulation properties, high humidity resistance, flame retardancy, etc., and has sufficient toughness and good adhesion to sealing materials. Demonstrate excellent practical performance.

[0077]

EXAMPLES The present invention will be described more specifically with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples.

(Examples 1 to 8 and Comparative Examples 1 to 6) Using poly-p-phenylene sulfide, an ethylene copolymer and a reinforcing filler shown in the following <1>,
Was melt-kneaded according to the method described in <2> below to prepare a polyphenylene resin composition.

Next, the moldability of each of the obtained polyphenylene sulfide resin compositions and the evaluation of the molded articles were evaluated by the method described in the following <3>. Table 2 shows the results.
Shown in

<1> Raw Materials, Sub-Materials, and Method for Producing the Same (1) Thermally Oxidized Crosslinkable Polyarylene Sulfide; Polyphenylene Sulfide (manufactured by Toray Industries, Inc.) as a thermally oxidatively crosslinked polyarylene sulfide used in Comparative Examples No .: M1900, color of polymer; brown, η _{app of} polymer; 3,300 poise @ 300 ° C., shear rate =
200 sec ^-1 }) was used. Was measured according to the above-mentioned "(a) a method for determining the SO ₂ emission from in polyarylene sulfides", SO ₂ emissions from the polyphenylene sulfide is 120 ppm,
The content of oxygen in the polyphenylene sulfide was 1.2% by weight as measured according to the above-mentioned "(b) Method for determining from oxygen concentration in polyarylene sulfides". In Table 1, this polyphenylene sulfide is represented by C
-Indicated as PPS.

(2) Polyarylene sulfide substantially not thermally oxidized and crosslinked Using 120 kg of Na ₂ S.5H ₂ O, 110 kg of p-dichlorobenzene and 30 kg of LiCl, 34
In 0 liter of N-methylpyrrolidone, dehydration was performed by heating to 145 ° C for 1 hour, and then polycondensation reaction was performed for 3 hours while heating to 260 ° C. The product obtained by separating after the reaction was washed with acetone, and the polymer after washing was heated to 120 ° C. to be dried for 24 hours. The obtained granular polymer is homopoly p
-Phenylene sulfide, the granule yield of which is 68 k
g, the yield was 87%, and it was white, and its η _app was 540 poise. When measured in accordance with the above-mentioned “(a) Method for determining from the amount of SO ₂ generated from polyarylene sulfides”, the amount of SO ₂ generated from this homopoly p-phenylene sulfide was 5 ppm, and the amount of SO ₂ generated from homopoly p-phenylene sulfide was 5 ppm. Determination by Oxygen Concentration in Polyarylene Sulfides ", the amount of oxygen in this homo p-polyphenylene sulfide was 0.2% by weight. In Table 1, this homopoly p-phenylene sulfide was designated as L-PPS.

(3) Amino group-containing polyarylene sulfide: 510 liters using 140 kg of Na ₂ S.5H ₂ O, 130 kg of p-dichlorobenzene, 6.8 kg of p-dichloroaniline and 35 kg of LiCl In N-methylpyrrolidone at 145 ° C. for 1 hour for dehydration, and then while heating at 260 ° C. for 3 hours.
The polycondensation reaction was performed over time. The product obtained by separation after the reaction is washed with acetone, and the polymer after washing is washed with 1
Drying was performed by heating to 20 ° C. for 24 hours. The obtained granular polymer is a homopoly p-phenylene sulfide having an amino group in the molecular chain and a side chain formed by the amino group, and the granular yield is 73%.
kg, the yield is 78%, it is white,
Its η _app was 650 poise. Aforementioned was measured in accordance with "(a) determining how the SO ₂ emission from in polyarylene sulfides", SO ₂ emissions from the homo p- phenylene sulfide is 1 ppm, the aforementioned "(b) Determination by Oxygen Concentration in Polyarylene Sulfides ", the amount of oxygen in this homo p-polyphenylene sulfide was 0.2% by weight. In Table 1, this homopoly p-phenylene sulfide was designated as DCA-PAS.

(4) Ethylene-based copolymer The ethylene-based copolymer used was Bondyne-AX8390 manufactured by Sumitomo Chemical Co., Ltd., and its MI was 7 g /
10 minutes (however, this is a value measured according to JIS-K6730). The copolymer composition of the ethylene copolymer is such that ethylene as a monomer unit is 68% by weight, ethyl acrylate is 30% by weight, and maleic anhydride is 2% by weight.

(5) Mg / Al Oxide Solid Solution Magnesia aluminum represented by the formula Mg _0.7 Al _0.3 O _1.15 was used. This is a product sold under the trade name KW2200 manufactured by Kyowa Chemical Industry Co., Ltd., and has a BET specific surface area of 150 m ² / g.

(6) Di (cyclohexyl) ammonium nitrite A commercially available product (trade name: DICHAN) of the formula (H ₁₁ C ₆ ) ₂ NH.HNO ₂ manufactured by Johoku Chemical Co., Ltd. was used.

(7) Reinforcing Filler The reinforcing filler used was chopped glass fiber (manufactured by Asahi Fiberglass Co., Ltd., 03JAFT59).
1｝, Szolite Mica ｛Kuraray Co., Ltd., 32
5Kl｝.

<2> Production of Polyarylene Sulfide Resin Composition The components shown in Table 1 were dry-blended with the indicated compositions and per 100 parts by weight of polyarylene sulfide.
However, only chopped glass fiber was side-fed to the kneader. Two of these dry blended products
Using a shaft kneading extruder (manufactured by Toshiba Machine Co., Ltd., TEM35B), the mixture was melt-kneaded at a resin temperature of 320 ° C., and then granulated to finally obtain a composition shown in Table 1. Table 1
In the figure, the mark ▲ indicates an item outside the claims.

[0088]

[Table 1]

<3> Evaluation (1) Evaluation of mechanical strength, especially toughness An injection molding machine (J50EP, manufactured by Nippon Steel Works, Ltd.)
The resin temperature is set to 320 ° C, the mold temperature is set to 135 ° C,
A family test specimen was molded. Using this molded product, the breaking strength and breaking elongation were measured according to ASTM D6.
A tensile test was conducted in accordance with No. 38, and the impact strength was rated as A
An Izod impact test (no notch) was performed according to STM D256. In addition, the number of samples was set to 5, and the average value of the test results for five samples is shown in Table 2.

(2) Evaluation of Metal Corrosion Degree at Practical Use Temperature After polishing the surface of this mold material using # 800 sandpaper and a mold polishing compound using a general mold material equivalent to JIS-S55C. The oil on the surface was removed by washing with acetone to prepare a test piece for evaluation.

5 g of pellets of the polyarylene sulfide resin composition as a sample are placed in a glass petri dish, and the opening of the glass petri dish is covered with the polished surface of the above-mentioned mold material facing down. The glass petri dish is placed in a thermostat kept at 150 ° C. and heated for 500 hours. During this time, the metal surface is exposed to the gas generated from the polyarylene sulfide resin composition.

The exposed metal test piece is placed on the upper stage of a desiccator containing ion-exchanged water in the lower stage with the exposed surface facing upward, and the desiccator is kept in a constant temperature bath at 40 ° C. for 100 hours. The test piece was taken out, and the corrosion degree of the metal surface after air drying was determined according to the following criteria.

<< Judgment of Corrosion Degree >> Judgment State of Corrosion on Exposed Surface ◎ No rust to very small corrosion ○ Very small corrosion △ Corrosion of less than half of the whole area × More than half of the whole area Corrosion of area XX Notable corrosion on the entire surface (3) Evaluation of initial adhesion / adhesion holding power to sealing material A polyarylene sulfide resin composition was injection-formed by the above-mentioned injection molding machine, and 90 × 75. A box having a size of 40 mm (thickness: 3 mm) is formed, and a stock solution obtained by kneading a bisphenol A type epoxy sealant and a curing agent is poured into the box. 130
After heating to 2 ° C. and curing for 2 hours, the mixture is allowed to cool to room temperature (first stage). After cooling, the presence or absence of separation between the epoxy resin and the outer frame was evaluated by observing with a stereoscopic microscope. After the evaluation, the molded article was further placed in an oven heated to 120 ° C., heated for 10 hours, then allowed to cool (second stage), and observed for peeling after cooling, and evaluated. .

<4> Results and Discussion The evaluation results are shown in Table 2. The mark * in Table 2 indicates an item that is particularly problematic.

[0095]

[Table 2]

-Consideration- From the results of the examples and comparative examples shown in Table 2, the solid solution of the ethylene copolymer and the Mg / Al oxide, and the DICH
When AN and AN are used together in an amount added within the range specified in the present invention, no extreme decrease in mechanical strength is observed, elongation, high toughness such as impact strength, and long-term operation at low temperature. It can be seen that typical metal corrosion is suppressed to a low level.

On the other hand, when the amount of the Mg / Al oxide solid solution falls below the range specified in the present invention, the adhesion to the epoxy resin is reduced and initial peeling occurs, and the ethylene-based copolymer is used in the present invention. If the amount falls below the range specified in the above, the effect of improving toughness, which only compensates for the decrease in toughness due to the addition of various fillers and additives, becomes small.

When the amount of DICHAN exceeds the range specified in the present invention, the mechanical strength and toughness, and the adhesiveness to the epoxy resin of polyphenylene sulfide of thermal cross-linking type or its combination with Mg / Al oxide solid solution are exceeded. Causes a drop.

From the results shown in Table 2, it is also understood that when DICHAN is added, the ratio is preferably set to 3 parts by weight or less.

When the Mg / Al oxide solid solution and the ethylene-based copolymer are added in excess of the amounts specified in the present invention, the mechanical strength is extremely reduced.

When a heat-crosslinkable polyphenylene sulfide is used as a base, the adhesion to an epoxy resin is reduced and the degree of corrosion is increased. In general, even when an ethylene-based copolymer is blended, The effect of improving toughness is reduced.

[0102]

According to the present invention, various electric and electronic equipment members, in particular, cases and bases of modules and bases for sealing of power modules and the like, cases and bases of SMT compatible relays and solid state relays, and the like. When used as a card base material, SMT compatible switch member, case base for modules or modules containing electric circuits, base strength, etc., mechanical strength, high temperature heat resistance, especially high solder heat resistance and high temperature durability, high shape Accuracy Satisfies basic characteristics such as high dimensional stability at high temperatures, insulation properties, high humidity resistance, flame retardancy, etc., and has sufficient toughness and good adhesion to sealing materials. By using the polyarylene sulfide resin composition exhibiting excellent practical performance, and the use of this polyarylene sulfide resin composition, there is no rust, Peeling no, it is possible to provide an electric and electronic equipment integrated module compacts and SMT corresponding moldings for electric and electronic equipment capable of prolonged high-density mounting electrical and electronic component life.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI // (C08L 81/02 23:08) (56) References JP-A-4-304264 (JP, A) JP-A-4- 123461 (JP, A) JP-A-62-167355 (JP, A) JP-A-61-207462 (JP, A) JP-A-2-218754 (JP, A) (58) Fields investigated (Int. ⁷ , DB name) C08L 81/00-81/02 C08K 3/18-3/22 C08K 5/16-5/17 C08L 23/08

Claims (4)

(57) [Claims] 1. 100 substantially non-thermo-oxidatively crosslinked
Parts by weight of polyarylene sulfides, containing as monomer units 50 to 90% by weight of ethylene, 5 to 49% by weight of an α, β-unsaturated carboxylic acid alkyl ester and 0.5 to 10% by weight of maleic anhydride Do 1-2
5 parts by weight of ethylene copolymer, 0.5 to 10 parts by weight of Mg / Al oxide solid solution, 0.5 to 3 parts by weight of di (cyclohexyl) ammonium nitrite, and 15 parts by weight
A polyarylene sulfide resin composition comprising 0 part by weight or less of a reinforcing filler. Wherein said polyarylene sulfides are, der which have a amino group and / or amide groups in the molecule
The polyarylene sulfide resin composition according to claim 1 . 3. A protection and support member for an electric / electronic component integrated module obtained by molding the polyarylene sulfide resin composition according to claim 1 or 2 . 4. A protection and support member for an SMT-compatible electric / electronic component, which is obtained by molding the polyarylene sulfide resin composition according to claim 1 or 2 .