JP2002038005A - Thermoplastic resin composition, method for manufacturing the same, and semiconductor element housing package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition capable of producing resin moldings high in adhesion to a metal and low in water soaking. SOLUTION: The thermoplastic resin composition comprises (A) at least one thermoplastic resin having a melting point of 250 deg.C or higher selected from the group consisting of an aromatic polyamide resin, a liquid crystal polymer resin, and a styrene polymer having a structure which is mainly syndiotactic, (B) an olefin copolymer comprising an α-olefin and the glycidyl ester of an α,β-unsaturated acid, and (C) an inorganic filler. A thermoplastic resin composition having a structure like this produces nicely formed moldings excellent in adhesion to a metal and in moisture resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition, a method for producing the same, and a semiconductor element housing used for manufacturing a semiconductor device by housing the semiconductor element using the thermoplastic resin composition. It is related to a package for use.

[0002]

2. Description of the Related Art A semiconductor element housing package used for manufacturing and manufacturing a semiconductor device by housing and sealing a semiconductor element, particularly an inexpensive semiconductor element housing package, is formed by molding an insulating base with epoxy resin. ing. The insulating substrate is formed by providing a concave portion for accommodating a semiconductor element on the upper surface, and the semiconductor package includes the insulating substrate, a lid body attached to the upper surface of the insulating substrate with an adhesive and closing the concave portion, The insulating base includes a plurality of metal terminals provided so as to be led out from the inside to the outside of the concave portion. Then, the semiconductor element is bonded and accommodated on the bottom surface of the concave portion of the insulating base by die bonding paste, and each electrode of the semiconductor element is electrically connected to one end of the metal terminal by a bonding wire. The semiconductor device can be commercialized as a semiconductor device by bonding a lid to the substrate using an adhesive made of a resin such as an epoxy resin and hermetically sealing the semiconductor element with the insulating base and the lid.

The insulating base of such a package for housing a semiconductor element is formed of an epoxy resin as described above (see Japanese Patent Application Laid-Open No. Hei 6-232292), but is insulated by a thermosetting resin such as an epoxy resin. There are various problems in forming a substrate. For example, in order to be able to remove a molded product from the mold, the thermosetting resin in the mold cavity needs to be sufficiently cured,
It takes 1 to 2 minutes or more for molding, and the molding cycle is long and productivity is low. Also, when molding with a mold, the actual product portion is about several percent to several tens percent, and other waste materials such as sprue, runner, and cull cannot be reused with thermosetting resin. In addition, the burden on the global environment in terms of resource environment is large, and it is difficult to reduce costs.

On the other hand, in the case of a thermoplastic resin, there is no need to cause a curing reaction in a mold, so that the molding cycle can be shortened, and waste materials such as sprues and runners can be reused for molding. It is easy and does not have the above-mentioned problems unlike thermosetting resins.

[0005]

However, when an insulating substrate is produced using a thermoplastic resin, the thermoplastic resin generally has low moisture resistance and low adhesion to metal terminals, and moisture in the atmosphere is reduced by the insulating substrate and the insulating substrate. Easily penetrates from the interface between the metal terminal and the metal terminal. Therefore, there has been a problem that moisture acts on the semiconductor element in the recess sealed with the lid, and the semiconductor element may not operate stably.

The present invention has been made in view of the above points, and provides a thermoplastic resin composition capable of obtaining a resin molded product having high adhesion to metal and low permeation of moisture, and a method for producing the same. A semiconductor element housing package which prevents moisture from entering into a concave portion of an insulating base and allows a semiconductor element housed in the concave portion to operate normally and stably for a long period of time. It is intended to provide.

[0007]

The thermoplastic resin composition according to claim 1 of the present invention comprises (A) an aromatic polyamide resin,
A liquid crystal polymer resin, a thermoplastic resin having a melting point of 250 ° C. or more, which is mainly composed of at least one selected from styrene polymers having a syndiotactic structure;
An olefin copolymer comprising an olefin and a glycidyl ester of an α, β-unsaturated acid, and (C) an inorganic filler.

Further, the invention of claim 2 is characterized in that (A)
In the total amount of the thermoplastic resin at 50 ° C. or higher, the aromatic polyamide resin is 99 to 70% by mass, and at least one selected from a polyarylene sulfide resin, a liquid crystal polymer resin, and a styrene polymer mainly having a syndiotactic structure. One of which is 1 to 30% by mass.

The invention of claim 3 is characterized in that in the olefin copolymer (B), the α-olefin is ethylene.

The invention according to claim 4 is that the olefin copolymer (B) is added in an amount of 0.5 to 20% by mass based on the total amount of the components (A) to (C). It is a feature.

The invention of claim 5 is characterized in that (A) the melting point
Thermoplastic resin having a temperature of 50 ° C. or more shows that the mass loss at a temperature rise of 10 ° C./min and a temperature of 330 ° C. is 5% by mass in thermo mass analysis.
It is characterized by the following.

The invention of claim 6 is characterized in that (A) the melting point
In a thermoplastic resin having a temperature of 50 ° C. or higher, the intrinsic viscosity of the aromatic polyamide resin is 0.5 to 1.4 dl / g.

The invention of claim 7 is characterized in that (A) the melting point
In a thermoplastic resin at 50 ° C. or higher, the structural unit of the aromatic polyamide resin is such that the dicarboxylic acid component is terephthalic acid and the diamine component is 1,9-nonanediamine, or the dicarboxylic acid component is terephthalic acid and the diamine component is 1,
It is characterized by being 6-hexanediamine.

The invention of claim 8 is characterized in that the linear polyarylene sulfide resin is a polyparaphenylene sulfide having a paraphenylene sulfide unit of 70% by mass or more.

According to a ninth aspect of the present invention, the linear polyarylene sulfide resin has a melt viscosity of 1 to 30 Pa · s at a temperature of 300 ° C. and an angular velocity of 100 rad / s by a parallel plate method. It is assumed that.

According to a tenth aspect of the present invention, in the thermoplastic resin having a melting point of at least 250 ° C., the liquid crystal polymer resin is obtained by co-condensing an acetylated product of p-hydroxybenzoic acid and polyethylene terephthalate. , II
And III type liquid crystalline aromatic polyesters.

Further, the invention of claim 11 is characterized in that, in the thermoplastic resin (A) having a melting point of 250 ° C. or higher, the melt viscosity of a polystyrene-based polymer having a syndiotactic structure is mainly determined by a parallel plate method at a temperature of 300 ° C. and an angular velocity Under the condition of 100 rad / s, the pressure is 1 to 250 Pa · s.

A twelfth aspect of the present invention is characterized in that the inorganic filler (C) is treated with a coupling agent having an amino group, an epoxy group, or a mercapto group.

The invention of claim 13 is characterized in that the inorganic filler (C) is glass fiber, and has a fiber diameter of 5 to 15 μm, an average fiber length of 30 to 300 μm, and an aspect ratio of 30 or less. It is.

Further, the invention of claim 14 is characterized in that the inorganic filler (C) is spherical silica and has an average particle size of 0.5 to 40 μm.
m.

According to a fifteenth aspect of the present invention, the inorganic filler (C) is contained in an amount of 30 to 80% by mass in the total of (A) to (C).
It is characterized by being.

According to a sixteenth aspect of the present invention, in the inorganic filler (C), the mass ratio of glass fiber to spherical silica is 1%.
00/0 to 30/70.

[0023] The method for producing a thermoplastic resin composition according to claim 17 of the present invention is a method for producing a thermoplastic resin composition according to any one of claims 1 to 16, wherein
It is characterized by kneading the component (C).

According to a eighteenth aspect of the present invention, there is provided a package for accommodating a semiconductor element, the concave part being formed of the thermoplastic resin composition according to any one of the first to sixteenth aspects for accommodating a semiconductor element. It is characterized by comprising an insulating base, a metal terminal provided on the insulating base, and a lid closing a concave portion of the insulating base.

[0025]

Embodiments of the present invention will be described below.

According to the present invention, (A) a thermoplastic resin having a melting point of 250 ° C. or more; (B) an olefin copolymer comprising an α-olefin and a glycidyl ester of an α, β-unsaturated acid; A) A thermoplastic resin composition comprising an inorganic filler is provided.

Further, according to the present invention, there is provided a semiconductor housing package formed by using the thermoplastic resin composition.

FIG. 1 shows an example of a package for accommodating a semiconductor device according to the present invention. An insulating substrate 3 provided with a concave portion 2 for accommodating a semiconductor device 1 is provided on the upper surface.
And an adhesive 10 such as an epoxy resin on the upper surface of the insulating base 3.
A lid 4 that is adhered and fixed to close the opening of the recess 2, and an external lead terminal is attached to the insulating base 3 so that one end protrudes into the recess 2 and the other end protrudes outward from a side surface of the insulating base 3. Metal terminals 11 provided as inserts
Are provided.

In the present invention, the insulating substrate 3 is
It is produced by injection molding the thermoplastic resin composition according to the present invention using an injection molding machine. Hereinafter, the thermoplastic resin composition will be described.

The thermoplastic resin having a melting point of 250 ° C. or higher used as the component (A) in the thermoplastic resin composition of the present invention has a low viscosity when molten so that low-pressure molding is possible in terms of moldability. It is desirable to use a crystalline resin having high heat resistance that does not easily remelt by heating. If the melting point is 250 ° C. or higher, it can be used without any problem in actual use. Among them, preferred are aromatic polyamide resins,
A liquid crystal polymer resin is a styrene-based polymer having a syndiotactic structure, and one of these may be used, or two or more of them may be used in combination. They are,
In particular, they are excellent in heat resistance and moisture resistance, and are also excellent in mechanical properties, electrical properties, moldability, chemical resistance and the like. Although the upper limit of the melting point of the thermoplastic resin (A) is not particularly set, the melting point is 40 from the viewpoint of moldability during injection molding.
It is desirable that the temperature be about 0 ° C. or less.

Here, (A) the thermoplastic resin having a melting point of 250 ° C. or more is heated at a temperature of 10 ° C. /
It is preferable that the mass loss at a temperature of 330 ° C. per minute is 5% by mass or less. When a thermoplastic resin whose mass decrease exceeds 5% by mass is used, voids may be generated in a molded article molded using the thermoplastic resin composition.
The mass loss is preferably as small as possible, ideally 0% by mass, but the practical lower limit is 0.1% by mass.

When two or more (A) thermoplastic resins having a melting point of 250 ° C. or more are used in combination, it is preferable that the aromatic polyamide is 99 to 70% in the total amount of the thermoplastic resin (A) having a melting point of 250 ° C. or more. % By mass, and 1 to 30% by mass of at least one selected from a polyarylene sulfide resin, a liquid crystal polymer resin, and mainly a styrene-based polymer having a syndiotactic structure.
When the aromatic polyamide is 99 to 70% by mass, heat resistance and adhesion are excellent, and at least one selected from a polyarylene sulfide resin, a liquid crystal polymer resin, and a styrene polymer mainly having a syndiotactic structure is used. When one of them is contained in an amount of 1 to 30% by mass, excellent fluidity and water resistance are obtained.

(A) In the thermoplastic resin having a melting point of 250 ° C. or higher, the aromatic polyamide resin has an intrinsic viscosity of 0.5 to 1.4 dl / g in concentrated sulfuric acid at 30 ° C. Is preferred. 0.5d intrinsic viscosity
If it is less than 1 / g, the mechanical strength may be low and it may not be practically used, and if it exceeds 1.4 dl / g, the moldability may be deteriorated.

In the aromatic polyamide, the dicarboxylic acid component is terephthalic acid and the diamine component is 1,9-nonanediamine, or the dicarboxylic acid component is terephthalic acid and the diamine component is 1,6- Those which are hexadiamines are preferred. For example, nylon 9T (polynonane methylene terephthalamide), nylon 6T (polyhexamethylene terephthalamide), or (and) a polyamide mainly composed of this. Furthermore, this aromatic polyamide resin
Some other polyamides may be copolymerized as long as the properties of the aromatic polyamide are not impaired, and there is no particular limitation as long as they are conventionally used for molding materials. For example, "Genestar" (trade name) manufactured by Kuraray Co., Ltd., "Alen" (trade name) manufactured by Mitsui Chemicals, Inc., "Amodel" (trade name) manufactured by Teijin Amoco Engineering Plastics, "Zeitel" manufactured by DuPont HTN ”(product name) and the like can be appropriately selected and used.

In the thermoplastic resin (A) having a melting point of 250 ° C. or higher, the liquid crystal polymer resin is not particularly limited as long as it is conventionally used for molding materials, but acetyl of p-hydroxybenzoic acid is used. I, II obtained from the co-condensation of fluoride and polyethylene terephthalate
And III type liquid crystalline aromatic polyesters. Among them, preferred are I-type, II-type, and III-type liquid crystalline aromatic polyesters obtained from co-condensation of acetylated p-hydroxybenzoic acid and polyethylene terephthalate, which are preferable in terms of mechanical properties and moldability. It is preferable because it is excellent. For example, “Sumika Super” (trade name) manufactured by Sumitomo Chemical Co., Ltd., Nippon Petrochemical Co., Ltd.
"Xydar" (trade name) manufactured by Amoco, "Vectra" (trade name) manufactured by Polyplastics / Hoechst Celanese, "UENOCP" (trade name) manufactured by Ueno Pharmaceutical Co., Ltd., manufactured by Mitsubishi Engineering-Plastics Corporation "Novacurate" (trade name), "Rod Run" (trade name) manufactured by Unitika Ltd., "Tosoh LC" manufactured by Tosoh Corporation
It can be appropriately selected from commercially available liquid crystal polymer resins such as "P" (trade name).

(A) In a thermoplastic resin having a melting point of 250 ° C. or more, a styrene-based polymer having a syndiotactic structure (hereinafter sometimes referred to as an SPS resin) is mainly composed of a polystyrene resin having a syndiotactic structure. Wherein the three-dimensional structure is mainly a syndiotactic structure, that is, a three-dimensional structure in which phenyl groups and substituted phenyl groups which are side chains with respect to a main chain formed from carbon-carbon bonds are alternately located in opposite directions. And its tacticity is quantified by nuclear magnetic resonance ( ^13C -NMR) using isotope carbon.

The tacticity measured by the ¹³ C-NMR method is determined by the abundance ratio of a plurality of continuous structural units, for example, a dyad for two, a triad for three, and a pentad for five. Although it can be shown, the polystyrene resin mainly having a syndiotactic structure as referred to in the present invention usually means 7
5% or more, preferably 85% or more, or 30% or more in pentad (racemic pentad), preferably 50% or more.
% Of polystyrene, poly (alkylstyrene), poly (halogenated styrene), poly (alkoxystyrene), poly (vinylbenzoic acid ester) and a mixture thereof, or 1 shows a polymer. Here, poly (alkylstyrene) includes poly (methylstyrene),
There are poly (ethyl styrene), poly (isopropyl styrene), poly (t-butyl styrene) and the like, and poly (halogenated styrene) includes poly (chlorostyrene), poly (bromo styrene), poly (fluoro styrene) and the like. There is. Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene). Among them, particularly preferred polystyrene resins include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), and poly (p-methylstyrene).
t-butylstyrene), poly (p-chlorostyrene),
Examples thereof include poly (m-chlorostyrene), poly (p-fluorostyrene), and a copolymer of styrene and p-methylstyrene.

In the present invention, the melt viscosity of these SPS resins is 1 to 250 as measured by a parallel plate method at a temperature of 300 ° C. and an angular velocity of 100 rad / s.
Those having Pa · s are preferably used. The melt viscosity is
If it is less than this range, the mechanical strength is greatly reduced. If it exceeds this range, the molding fluidity is poor and unfilling tends to occur during molding. The parallel plate method is 1m thick
mx 25mm diameter pellets made by hand press,
The pellet is placed on the lower parallel plate having a diameter of 25 mm, and the upper parallel plate is lowered and sandwiched.
The measurement is carried out by holding the sample for 10 minutes, followed by measurement, for example, measurement by ARES (trade name) manufactured by Rheometric Scientific Inc. is appropriate.

Further, the molecular weight distribution is not particularly limited, and various molecular weight distributions can be applied.
In addition, it is preferable to reduce the amount of ionic impurities such as sodium and chlorine contained in the resin in advance. When the amount of ionic impurities increases, the moisture resistance reliability tends to deteriorate, which is not preferable.

The above-mentioned SPS resin has a high melting point,
The heat resistance is remarkably superior to that of the conventional atactic polystyrene resin. Such SPS resin is
For example, a styrene-based monomer (a monomer corresponding to an SPS resin) is polymerized in an inert hydrocarbon solvent or in the absence of a solvent, using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst. (See JP-A-62-187708).

Further, (A) a linear polyarylene sulfide resin (hereinafter may be referred to as a linear PAS resin) used as a thermoplastic resin having a melting point of 250 ° C. or higher includes:
Repeating unit -Ar- (where Ar is an aryl group)
And a typical substance thereof is a polyphenylene sulfide resin having a repeating unit represented by the structural formula -Ph-S- (where Ph is a phenyl group) in an amount of 70% by mass or more. PAS resins are generally classified into substantially cross-linked, semi-cross-linked, and linear types according to the production method.
It is preferable because of its excellent mechanical strength and ionic impurity content.

This linear PAS resin has a melting point of at least 260 ° C., and a melt viscosity of 1 to 30 Pa · s measured by a parallel plate method at a temperature of 300 ° C. and an angular velocity of 100 rad / s. What is s is used suitably. The molecular weight distribution is not particularly limited, and various molecular weight distributions can be applied. If the melting point is less than 260 ° C., the mechanical strength of the resin becomes weak, which is not preferable. There is no upper limit for melting point, but 2
About 90 ° C. is a practical limit. If the melt viscosity is less than this range, the mechanical strength of the molded article is greatly reduced, and if it exceeds this range, the molding fluidity is poor. The linear PAS resin preferred in the present invention is a copolymer copolymerized with other structural units as long as it contains 70% by mass or more, preferably 90% by mass or more of a repeating unit of P-phenylene sulfide. You may use together. This repeating unit is 7
If it is less than 0% by mass, the crystallinity, which is a characteristic of the crystalline polymer, tends to be low, and sufficient strength tends to be not obtained, and toughness tends to be poor.

The linear PAS resin used in the present invention may contain other copolymerized units. Examples of the constituent units of the copolymer include the following chemical formulas (1), (2) and (3). 3 "," 4 "," 5 "," 6 "and the like.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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Further, in the linear PAS resin used in the present invention, ionic impurities such as sodium and chlorine contained in the resin should be reduced in advance in order to prevent deterioration of the moisture resistance reliability. preferable.

Examples of the above-mentioned linear polyarylene sulfide resin include those commercially available from Topren Co., Ltd., Kureha Chemical Co., Ltd., Dainippon Ink Chemical Co., Ltd., Toray Co., Ltd., and the like. Can be used.

Next, the olefin copolymer used as the component (B) in the present invention is an olefin copolymer comprising an α-olefin and a glycidyl ester of an α, β-unsaturated acid.

Here, as the monomer derived from the α-olefin unit constituting the olefin copolymer, ethylene, propylene, butene-1 and the like can be mentioned, but ethylene is preferably used.

The glycidyl ester unit of the α, β-unsaturated acid constituting the olefin copolymer includes:
What is shown by the following general formula [Formula 7] is used.

[0055]

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(Where R ₁ represents a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms) Specific examples of monomers derived from the glycidyl ester unit of α, β-unsaturated acid include: , Glycidyl acrylate, glycidyl methacrylate,
Ethacrylic acid glycidyl ester and the like,
Glycidyl methacrylate is preferably used.

An olefin copolymer can be obtained by copolymerizing an α-olefin (for example, ethylene) and a glycidyl ester of an α, β-unsaturated acid by a well-known radical reaction.

When the glycidyl ester unit of the α, β-unsaturated acid is a glycidyl (meth) acrylate unit and the copolymerization ratio of the glycidyl (meth) acrylate unit is less than 40% by mass, (Meth) acrylate monomers such as methyl (meth) acrylate and ethyl (meth) acrylate; vinyl ester monomers such as vinyl acetate and vinyl propionate; vinyl ether monomers; (meth) acrylonitrile; It is also possible to copolymerize one or more group copolymers.
In addition, (meth) acrylic acid means acrylic acid or methacrylic acid.

In the construction of the olefin copolymer comprising an α-olefin and a glycidyl ester of an α, β-unsaturated acid, the α-olefin unit accounts for 60 to 98% by mass, preferably 70% by mass, of the olefin copolymer. It is preferably contained in an amount of from 90 to 90% by mass. Examples of the olefin copolymer include a copolymer of ethylene and glycidyl methacrylate, a copolymer of ethylene, vinyl acetate and glycidyl methacrylate, and a copolymer of ethylene, ethyl acrylate and glycidyl methacrylate. Copolymer, a copolymer of ethylene and glycidyl acrylate, a copolymer of ethylene and vinyl acetate and glycidyl acrylate, and the like, among which copolymers of ethylene and glycidyl methacrylate are preferred. .

The shape of these olefin copolymers is
It is desirable that the powder or the pellet has a particle size of about 0.1 to 5 mm.

The addition amount of the olefin copolymer used as the component (B) is preferably in the range of 0.5 to 20% by mass of the total of the components (A) to (C). Preferably it is in the range of 0.5 to 15% by mass. If the amount of the component (B) is too small, it is difficult to obtain the desired effect by adding the component (B). If the amount is too large, the rigidity and heat resistance of a molded article obtained from the thermoplastic resin composition are reduced. There is a fear that the moldability may be impaired, and further, the moldability may be impaired.

The inorganic filler (C) used in the present invention includes silica such as amorphous silica, crystalline silica and synthetic silica, alumina, glass, milled fiber glass, titanium oxide, calcium carbonate, clay, Fillers such as mica, talc, kaolin, silicon nitride, aluminum nitride and the like can be mentioned, and particularly preferred are milled fiber glass, silica such as amorphous silica, crystalline silica and synthetic silica, and spherical alumina. These may be used alone or in combination of two or more. Further, it is preferable that the surface of the inorganic filler is treated with a coupling agent. As the coupling agent, those having an amino group, an epoxy group, or a mercapto group described later can be used.These coupling agents may be used alone or in combination of two or more. May be processed.

Among the above, particularly preferred is a fiber having a diameter of 5 to 15 μm treated with a coupling agent having an amino group.
m, average fiber length of 30 to 300 μm, and aspect ratio of 30 or less. When the average fiber length is less than 30 μm,
The effect of improving the mechanical strength is reduced, and if it exceeds 300 μm, the moldability may be deteriorated. The lower limit of the aspect ratio is preferably set to 2, and if it is less than 2, the effect of improving the mechanical strength of the molded product becomes insufficient. These can use a commercial item.

The silica is spherical and has an average particle size of 0.1.
It is preferably from 5 to 40 μm. If it is less than 0.5 μm, the melt viscosity increases and moldability deteriorates.
If it exceeds 2,000, the mechanical strength decreases, and if it exceeds 100 μm, the moldability may deteriorate. Further, when the shape is a crushed shape, the moldability may be deteriorated and the mold wear may be increased.

When glass fiber and spherical silica are used in combination as the inorganic filler (C), the mass ratio is 100/0.
It is preferably about 30/70. If the ratio of the spherical silica exceeds 70% by mass, the mechanical strength may be reduced.

The amount of the inorganic filler (C) added to the thermoplastic resin composition is 30 to 30% of the total of the components (A) to (C).
80% by mass is preferred. If the addition amount is less than 30% by mass, low stress property due to a decrease in the linear expansion coefficient of the molded product cannot be expected. If it exceeds 80% by mass, the fluidity at the time of molding deteriorates, and the molded product is not practically used. There is a risk.

The thermoplastic resin composition of the present invention includes:
If necessary, an inorganic ion exchanger may be added. This inorganic ion exchanger can adsorb and capture ionic impurities and ions that are hydrolyzed when subjected to PCT treatment, and can prevent a decrease in the moisture resistance reliability of the resin.

Further, a flame retardant may be added to the thermoplastic resin composition of the present invention, if necessary. Commercially available flame retardants are used, such as tetrabromobutane, hexabromobenzene, pentabromoethylbenzene, hexabromobiphenyl, pentabromochlorocyclohexane, tetrabromobisphenolol S, tris (2,3-dibromo Propyl-1) isocyanurate, 2,2-bis [4 (2,3 dibromopropoxy) -3,5-dibromophenyl] propane, halogenated acetylene alcohol, brominated epoxy, decabromodiphenyl ether, tetrabromobisphenol A and the like Derivatives such as carbonate oligomers, octabromodiphenyl oxide, pentabromodiphenyl oxide, tetrabromophenol, dibromostyrene, pentabromobenzyl acrylate, tetrabromide Styrene, polydibromophenylene oxide, bistribromophenoxyethane, tetrabromophthalate diol, tetrabromophthalic anhydride, dibromocresyl glycidyl ether, epibromohydrin, dibromoneopentyl glycol, tribromoneopentyl alcohol, ethylene bis Bromides such as tetrabromophthalimide and brominated polystyrene;
Chlorinated paraffin, chlorinated polyolefin, dimethyl
Chlorinate, chlorendic anhydride, tetrachlorophthalic anhydride, phenylphosphonic dichloride, and other chlorine-based flame retardants, fluorine compounds such as polytetrafluoroethylene, red phosphorus, triphenyl phosphate, trimethyl phosphate, triethyl phosphate, triethyl Cresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl 2,
6 xylenyl phosphate, tris (chloroethyl)
Phosphate, tris (chloropropyl) phosphate, tris (dichloropropylphosphate, tris (tribromoneopentyl) phosphate, diethylphenylphosphate, dimethylphenylphosphate, bisphenol A-bis (dicresylphosphate), Phosphorus compounds such as condensed phosphate esters, melamine, melamine cyanurate, melamine phosphate, nitrogen compounds such as guanidine sulfamate, barium metaborate, zinc borate, boron-based compounds such as anhydrous zinc borate, silicone powder flame retardants, Silicon-containing compounds such as silicone resin, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium carbonate, kaolin clay, calcium aluminate, titanium hydroxide, zinc hydroxide, dosona And dihydrate gypsum, inorganic flame retardants such as antimony silico oxide, metal oxides such as antimony oxide, low melting point glass, etc. These may be used alone or in combination of two or more. Among these, a brominated product, particularly a brominated polystyrene, is desirable.In terms of form, powdery brominated polystyrene is preferable from the viewpoint of enhancing dispersibility. There is a possibility that dispersion of dispersion may occur in the resin.

The thermoplastic resin composition of the present invention may contain, if necessary, other synthetic resins, as long as the object of the present invention is not impaired.
Elastomers, antioxidants, nucleating agents, crystallization accelerators,
Coupling agents, release agents, lubricants, coloring agents, ultraviolet absorbers, antistatic agents and the like can be added.

As the above synthetic resins and elastomers,
For example, polyolefin resin, polyester resin, polyoxymethylene resin, polymethylpentene resin, polyvinylidene chloride resin, polyvinylidene fluoride resin, polyamide resin (nylon 6 resin, nylon 66 resin, nylon 610 resin, nylon 46 resin, copolymer nylon) Resin), polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyetheretherketone resin, polyacetal resin, polyetherimide resin,
Synthesis of polyamide imide resin, polyimide resin, polystyrene resin, AS resin, ABS resin, phenoxy resin, polyether nitrile resin, polytetrafluoroethylene resin, petroleum resin, coal resin, epoxy resin, phenol resin, silicone resin, urethane resin, etc. Examples include elastomers such as resins, polyolefin rubbers, olefin copolymers, and hydrogenated rubbers. These are 2
More than one kind can be mixed and used.

As the antioxidant, phosphorus-based antioxidants,
And phenolic antioxidants. These may be used alone or in combination of two or more. Examples of the crystal nucleating agent include a dibenzylidene sorbitol compound, an aluminum salt of t-butylbenzoic acid, and a sodium salt of a phosphate ester. These may be used alone or in combination of two or more.

Examples of the coupling agent include silane compounds, titanate compounds, and aluminum compounds, and silane compounds are particularly preferable. As the silane type, γ-aminopropyltriethoxysilane, N-β
Aminosilanes such as (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Epoxysilanes such as glycidoxypropyltriethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltrimethoxysilane, Vinyl silanes such as vinyl triethoxy silane and γ-methacryloxy propyl trimethoxy silane, mercapto silanes such as 3-mercapto propyl trimethoxy silane, and epoxy type, amino type and vinyl type polymer type silanes There are, in particular, aminosilanes, epoxysilanes, and mercaptosilane are suitable.
These may be used alone or in combination of two or more.

As the lubricant, both an internal lubricant and an external lubricant can be used, and examples thereof include hydrocarbons, fatty acids, fatty acid amides and fatty acid esters. These may be used alone or in combination of two or more.

As the coloring agent, various known pigments or dyes can be used. Examples of the coloring agent include black pigments such as carbon black, orange pigments such as red-mouthed graphite, red dyeing pigments such as red iron oxide, and cobalt violet. Purple dyes, blue dyes such as cobalt blue, and green dyes such as phthalocyanine green can be used. More specifically,
Latest Pigment Handbook (edited by Japan Pigment Technology Association, published in 1977)
With reference to the above, those described in this handbook can be used.

The method for producing the thermoplastic resin composition used in the present invention is generally carried out by mixing the above components with a mixer such as a Henschel mixer or, if necessary, preliminarily preparing a part of the necessary components in a master. After batch-mixing, a method of melting and kneading with a kneading machine such as an extruder and pelletizing is used. Of course, it is not limited to this.

A thermoplastic resin composition obtained by mixing and kneading the above components (A) to (C) at a specific mixing ratio can form an insulating substrate having excellent moisture resistance reliability with good moldability. Things.

Next, in the semiconductor device housing package of FIG. 1, the metal terminals 11 serving as external lead terminals are made of Kovar metal (iron-nickel-cobalt alloy), 42 alloy (iron-nickel alloy), copper (iron-nickel alloy). It is formed from a metal material such as copper alloy, and is formed into a predetermined plate shape by adopting a conventionally known metal working method such as a rolling method or a punching method from an ingot (lumps) such as Kovar metal. Can be used. At the time of injection molding using a thermoplastic resin in the form of a pellet, the metal terminal 11 is set in a cavity of a mold and molded, whereby the insulating substrate 3 is manufactured and at the same time, the metal terminal 11 is attached to the insulating substrate 3.
Can be integrally attached. Further, a metal having excellent corrosion resistance such as nickel and gold and having good wettability with the brazing material is applied to the exposed surface of the metal terminal 11 by 0.1 to 20.0.
When the metal terminal 11 is layered to a thickness of μm, oxidation corrosion of the metal terminal 11 can be effectively prevented, and the connection between the metal terminal 11 and a bonding wire 12 to be described later and the connection between the metal terminal 11 and an external electric circuit can be achieved. Can be strengthened.

The lid 4 may be made of a plate material such as glass, ceramic, metal, resin and the like.

In the semiconductor device housing package formed as described above, the semiconductor device 1 is bonded to the bottom surface of the concave portion 2 of the insulating base 3 with the die bond paste 13, and the semiconductor device 1 is stored in the concave portion 2. At the same time, each electrode of the semiconductor element 1 is electrically connected to one end of the metal terminal 11 in the recess 2 by a bonding wire 12, and then the lid 4 is attached to the upper surface of the insulating base 3 by a resin such as epoxy resin. A semiconductor device in which the opening on the upper surface of the concave portion 2 is sealed by bonding and bonding using an adhesive 10 and the semiconductor element 1 is hermetically sealed in a container including the insulating base 3 and the lid 4. It can be commercialized. In this semiconductor device, an end of the metal terminal 11 protruding from the insulating base 3 is connected to an external electric circuit and mounted on a circuit board or the like for use.

In the package for housing a semiconductor element formed as described above, moisture is removed from the recess 2 of the insulating base 3.
In the semiconductor element 1 accommodated in the recess 2 can be prevented from being oxidized and corroded, and the semiconductor element 1 can be normally and stably maintained for a long period of time. It can be operated by This is because the adhesiveness between the metal terminal 11 and the resin is improved by adding the olefin copolymer composed of the α-olefin of the component (B) and the glycidyl ester of the α, β-unsaturated acid used in the present invention. This is considered to be due to the fact that the penetration of moisture from the interface is suppressed.

The present invention is not limited to the above embodiment, and various changes can be made without departing from the spirit of the present invention. For example, a light receiving element, an optical pickup component mounted with a light emitting element, and a semiconductor element to be housed therein,
CCD (Charge Coupled Device), MOS (Metal Oxide
Semiconductor), solid-state imaging devices such as CPD (Charge Primming Device), and EPROM (Erasable and Pr
The present invention can also be applied to a semiconductor element housing package in which the lid 4 is made of a transparent material such as glass, such as a grammable / Read Only Memory). In this case, it is possible to prevent moisture from penetrating through the interface between the insulating base 3 and the metal terminal 11 and to enter the recess 2, so that the lid 4 closing the opening of the recess 2
It is possible to prevent clouding due to dew condensation on the solid-state image sensor, and to make it possible to cause the solid-state imaging device to perform accurate photoelectric conversion.

[0082]

Next, the present invention will be described by way of examples.

(Example 1) An aromatic polyamide resin (Kuraray Co., Ltd. "Genestar") was used as a thermoplastic resin.
An ethylene / glycidyl methacrylate copolymer (“Bond First” manufactured by Sumitomo Chemical Co., Ltd.) was used as an olefin copolymer in 50 parts by mass of an aromatic polyamide resin.
10 parts by mass of product number "2C") and 40 parts by mass of milled fiber ("REV8" manufactured by Nippon Sheet Glass Co., Ltd .: aminosilane treatment, fiber diameter 13 m, average fiber length 70 m, aspect ratio 5.6) as an inorganic filler. To obtain a molding material.

Then, this molding material was injection-molded to obtain a molded product obtained by insert-molding a metal plate described below for evaluation of adhesiveness. Also, by injecting this molding material, an insulating substrate 3 having a concave portion 2 as shown in FIG.
Then, a lid 4 formed of a transparent glass plate was adhered to the insulating base 3 with an epoxy resin adhesive 10 to produce a semiconductor element housing package in which the recess 2 was sealed.

(Examples 2 to 24, Comparative Example 1) The following were used as the thermoplastic resin, the olefin copolymer, and the inorganic filler, and were blended in the blending amounts shown in Tables 1 to 3 and melted. After kneading, a thermoplastic resin composition was obtained as a molding material.
Then, in the same manner as in Example 1 above, an insert molded product and a semiconductor element storage package were produced using this molding material.

In the examples using the coupling agent,
After the coupling agent was sprayed directly onto the filler, it was used for compounding. (A) thermoplastic resin ・ Resin A: aromatic polyamide resin (Kuraray Co., Ltd. “Genestar”, melting point 308 ° C .: intrinsic viscosity 0.72 dl / g)
(In concentrated sulfuric acid at 30 ° C.), temperature rise 10 ° C./min, mass loss at 330 ° C. 1.2%) resin B: liquid crystal polymer resin (“E6000” manufactured by Sumitomo Chemical Co., Ltd., melting point 320 ° C., temperature rise) Temperature 10 ℃ / min ・ 33
-Resin C: Styrene-based polymer mainly having a syndiotactic structure ("33EX00" manufactured by Idemitsu Petrochemical Co., Ltd.)
3 ", melting point 270 ° C, melt viscosity 54 Pa · s (parallel plate method, 300 ° C, 100 rad / s), temperature rise 10
Resin D: linear type polyarylene sulfide resin (“LR01” manufactured by Topren Co., Ltd., melting point 280 ° C., melt viscosity 6 Pa · s (parallel plate method, 300 ° C, 1
00 rad / s), temperature rise 10 ° C./min, mass loss at 330 ° C. 2.2%) (B) olefin-based copolymer • copolymer A: ethylene / glycidyl methacrylate copolymer (mass ratio 94) / 6) (Sumitomo Chemical Co., Ltd. “Bond First” part number “2C”, glycidyl methacrylate content 6% by mass, pellet form, temperature increase 10 ° C./min, mass decrease at temperature 330 ° C. 2.2% by mass) -Copolymer B: ethylene / glycidyl methacrylate ester copolymer (mass ratio 90/10) (manufactured by Nippon Petrochemical Co., Ltd., product number "RA4100", glycidyl methacrylate content: 10% by mass, pellet form 2.3 mass loss at a temperature rise of 10 ° C / minute and a temperature of 330 ° C
-Copolymer C: Ethylene / glycidyl methacrylate copolymer (weight ratio: 88/12) ("Bonfast" part number "E" manufactured by Sumitomo Chemical Co., Ltd., glycidyl methacrylate content: 12% by mass, pellets) Condition, temperature rise 10 ° C /
Copolymer D: ethylene / glycidyl methacrylate ester copolymer (weight ratio 85/15) (manufactured by Nippon Petrochemical Co., Ltd., product number "RA3150") "Glycidyl methacrylate content 15% by mass, pellet form, mass decrease at a temperature rise of 10 ° C / min. And a temperature of 330 ° C 2.2.
(C) Inorganic filler-Filler A: Milled fiber ("REV8" manufactured by Nippon Sheet Glass Co., Ltd .: aminosilane treatment, fiber diameter 13 m, average fiber length 70 m, aspect ratio 5.6)-Filler B:
Milled fiber ("REV1" manufactured by Nippon Sheet Glass Co., Ltd.)
2 ": aminosilane treatment, fiber diameter 6 µm, average fiber length 5
Filler C: spherical silica ("FB" manufactured by Denki Kagaku Kogyo KK)
60 ": average particle size 20 μm) (D) Coupling agent ・ Coupling agent A: aminosilane-based coupling agent (manufactured by Nippon Unicar, product number“ A1100 ”: γ-aminopropyltriethoxysilane) ・ Coupling agent B: Epoxysilane-based coupling agent (Shin-Etsu Silicone Co., Ltd., product number "KBM403": γ-glycidoxypropyltrimethoxysilane) Coupling agent C: Mercaptosilane-based coupling agent (Toshiba Silicone Co., product number "TSL8380E":
3-mercaptopropyltrimethoxysilane) Coupling agent D: vinylsilane-based coupling agent (manufactured by Toray Silicone Co., Ltd., product number "SZ6300": vinyltrimethoxysilane) (Evaluation) (1) Adhesiveness Adhesiveness to metal is evaluated In order to do this, a metal plate (insert part: width 0.6 mm x thickness 0.25 mm, material 42 alloy / no plating, 42 alloy / silver plating, 42 alloy / gold plating, adhesive A, B, C in order ) Was obtained by insert molding. Then, at a crosshead speed of 3 mm / min, the insert metal was pulled out and its strength was measured. The unit of the measured value is kgf (9.8N)
It is. (2) Moisture resistance and moldability The semiconductor element storage package manufactured as described above is
Put in a pressure cooker (PCT) tester, temperature 1
Exposure was performed for 0.5 hour, 1 hour, and 2 hours in a moist heat environment of 21 ° C. and 100% RH. Then, after cooling, it was measured whether or not clouding had occurred on the cover plate 4 of the transparent glass plate. Measurements were performed on 10 samples, and the results are shown in Table 1 to Table 3 in the column of PCT, with the number of measurements taken as the denominator and the one with cloudiness as the numerator.

In Examples 1 to 24 and Comparative Example 1, the insulating substrate 3 could be molded as a good molded product, and a molded product could be obtained without any unfilling out of ten pieces. For 10 samples, the results are shown in Tables 1 and 2, with the measured number as the denominator and the unfilled one as the numerator.
3 is shown in the column of moldability.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

[Table 3]

As shown in Tables 1 to 3, each of the examples showed good results in all of the moldability, adhesiveness and moisture resistance.

[0092]

As described above, the thermoplastic resin composition according to the present invention is selected from (A) at least one of an aromatic polyamide resin and a liquid crystal polymer resin, mainly a styrene-based polymer having a syndiotactic structure. 250 ° C
The above thermoplastic resin, (B) α-olefin and α, β-
An olefin copolymer comprising a glycidyl ester of an unsaturated acid and (C) an inorganic filler, capable of molding a molded article having good adhesion to metal and moisture resistance with good moldability. It is.

The semiconductor package according to the present invention comprises an insulating base formed of the thermoplastic resin composition and having a recess for accommodating a semiconductor element, a metal terminal provided on the insulating base, and a recess in the insulating base. And a lid that closes the olefin-based copolymer in the thermoplastic resin composition for molding the insulating substrate,
Moisture can be effectively prevented from entering into the recess from the interface between the insulating base and the metal frame, and the semiconductor element housed in the recess operates normally and stably for a long period of time. Is what you can do.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Semiconductor element 2 Depression 3 Insulating base 4 Lid 11 Metal terminal

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 7/14 C08K 7/14 7/18 7/18 9/08 9/08 C08L 23/26 C08L 23 / 26 25/04 25/04 81/02 81/02 H01L 23/08 H01L 23/08 A 23/14 23/14 RF term (reference) 4F071 AA22 AA42 AA45 AA55 AA56 AA63 AA84 AA88 AB18 AB21 AB22 AB26 AB28 AD01 AD02 AD06 AE17 AH05 AH12 BC02 BC04 4J002 BC022 BC031 BC081 BC111 BC121 CD192 CF061 CF062 CL031 CN011 CN012 DE136 DE146 DE236 DF016 DJ016 DJ036 DJ046 DJ056 DL006 FA046 FA086 FB086 FD016 GQ05

Claims (18)

[Claims] 1. A melting point of at least one selected from the group consisting of (A) an aromatic polyamide resin, a liquid crystal polymer resin and at least one styrene polymer having a syndiotactic structure.
0 ° C. or higher thermoplastic resin, (B) α-olefin and α,
A thermoplastic resin composition comprising: an olefin copolymer comprising a glycidyl ester of β-unsaturated acid; and (C) an inorganic filler. (A) In the total amount of the thermoplastic resin having a melting point of 250 ° C. or more, the aromatic polyamide resin is 99 to 70% by mass, and a polyarylene sulfide resin, a liquid crystal polymer resin, mainly styrene having a syndiotactic structure. At least one selected from the group consisting of
The thermoplastic resin composition according to claim 1, wherein the amount is 0% by mass. 3. The olefin copolymer (B),
The thermoplastic resin composition according to claim 1 or 2, wherein the α-olefin is ethylene. 4. The method according to claim 1, wherein the amount of the olefin-based copolymer (B) is 0.5 to 20% by mass based on the total amount of the components (A) to (C). The thermoplastic resin composition according to claim 3. 5. A method in which a thermoplastic resin having a melting point of 250 ° C. or higher is heated at a rate of 10 ° C./min and a temperature of 330 ° C.
The thermoplastic resin composition according to any one of claims 1 to 4, wherein the mass loss at 5 ° C is 5% by mass or less. 6. A thermoplastic resin having a melting point of 250 ° C. or higher, wherein the aromatic polyamide resin has an intrinsic viscosity of 0.5 to 0.5.
The thermoplastic resin composition according to any one of claims 1 to 5, wherein the composition is 1.4 dl / g. 7. A thermoplastic resin having a melting point of 250 ° C. or higher, wherein the structural unit of the aromatic polyamide resin is such that the dicarboxylic acid component is terephthalic acid and the diamine component is 1,9.
The thermoplastic resin composition according to any one of claims 1 to 6, wherein the nonanediamine or dicarboxylic acid component is terephthalic acid, and the diamine component is 1,6-hexanediamine. 8. The thermoplastic according to claim 2, wherein the linear polyarylene sulfide resin is a polyparaphenylene sulfide having 70% by mass or more of a paraphenylene sulfide unit. Resin composition. 9. The linear polyarylene sulfide resin has a melt viscosity of 300 ° C. by a parallel plate method,
The thermoplastic resin composition according to any one of claims 2 to 8, wherein the pressure is 1 to 30 Pa · s under the condition of an angular velocity of 100 rad / s. 10. A thermoplastic resin having a melting point of 250 ° C. or higher, wherein the liquid crystal polymer resin is obtained by co-condensing an acetylated product of p-hydroxybenzoic acid and polyethylene terephthalate. The thermoplastic resin composition according to any one of claims 1 to 9, wherein the thermoplastic resin composition is a liquid crystalline aromatic polyester. 11. (A) In a thermoplastic resin having a melting point of 250 ° C. or higher, the melt viscosity of a polystyrene-based polymer mainly having a syndiotactic structure is determined by a parallel plate method at a temperature of 300 ° C. and an angular velocity of 100 rad / s. The thermoplastic resin composition according to any one of claims 1 to 10, wherein the pressure is 1 to 250 Pa · s. 12. The method according to claim 1, wherein the inorganic filler (C) is treated with a coupling agent having an amino group, an epoxy group, or a mercapto group. Thermoplastic resin composition. 13. The inorganic filler (C) is a glass fiber having a fiber diameter of 5 to 15 μm and an average fiber length of 30 to 300 μm.
The thermoplastic resin composition according to any one of claims 1 to 12, wherein m and the aspect ratio are 30 or less. 14. The thermoplastic resin composition according to claim 1, wherein (C) the inorganic filler is spherical silica, and has an average particle size of 0.5 to 40 μm. object. 15. The inorganic filler (C) according to any one of the above (A) to (15).
The thermoplastic resin composition according to any one of claims 1 to 14, wherein the total amount of (C) is 30 to 80% by mass. 16. The heat according to claim 1, wherein in the inorganic filler (C), the mass ratio of glass fiber to spherical silica is from 100/0 to 30/70. Plastic resin composition. 17. The thermoplastic resin composition according to claim 1, wherein (A) to (C)
A method for producing a thermoplastic resin composition, comprising kneading the following components: 18. An insulating base formed of the thermoplastic resin composition according to claim 1 and having a recess for accommodating a semiconductor element; a metal terminal provided on the insulating base; A package for accommodating a semiconductor element, comprising a lid for closing a concave portion of a base.