JP2002105333A - Thermoplastic resin composition, method for producing the same, and package for receiving semiconductor element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which has low water permeability and high adhesivity to metals. SOLUTION: This thermoplastic resin composition characterized by comprising (A) at least one thermoplastic resin having a melting point of >=250 deg.C and selected from aromatic polyamide resins, liquid crystal polymer resins and styrenic polymers mainly having syndiotactic configuration (B) at least one of polyamide 46 resin and an ethylenic copolymer comprising ethylene, an alkyl α,β-unsaturated carboxylate, and maleic anhydride, and (C) an inorganic filler. The thermoplastic resin composition having the composition can be molded into molded articles having good moisture resistance and adhesivity to metals in good moldability.

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 higher, which is made of at least one selected from styrene polymers having a syndiotactic structure, (B) ethylene, α, β-unsaturated carboxylic acid alkyl ester, anhydrous It is characterized by comprising at least one of an ethylene-based copolymer composed of maleic acid, a polyamide 46 resin, 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 the ethylene copolymer (B) is 50 to 90% by mass of ethylene, α, β-
It is characterized by comprising 5 to 49% by mass of an unsaturated carboxylic acid alkyl ester and 0.5 to 10% by mass of maleic anhydride.

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

According to a fifth aspect of the present invention, the polyamide 46 resin (B) has a temperature rise of 10 ° C. /
The mass loss at a temperature of 330 ° C. per minute is not more than 5% by mass.

The invention according to claim 6 is characterized in that the amount of the polyamide 46 resin (B) is 0.5 to 20% by mass of the total of the components (A) to (C). Is what you do.

The invention of claim 7 is characterized in that (A) the melting point
Thermoplastic resin having a temperature of 50 ° C. or higher shows that the mass loss at a temperature rise of 10 ° C./minute and a temperature of 330 ° C. is 5% by mass in thermo mass analysis
It is characterized by the following.

The invention of claim 8 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 according to claim 9 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 10 is characterized in that the linear polyarylene sulfide resin is a polyparaphenylene sulfide having a paraphenylene sulfide unit of 70% by mass or more.

The invention of claim 11 is characterized in that 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.

Further, the invention of claim 12 provides the thermoplastic resin having a melting point of at least 250 ° C., wherein 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.

The invention of claim 13 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.

The invention of claim 14 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.

According to a fifteenth aspect of the present invention, the inorganic filler (C) is a glass fiber having a fiber diameter of 5 to 15 μm, an average fiber length of 30 to 100 μm, and an aspect ratio of 20 or less. It is.

The invention of claim 16 is that the inorganic filler (C) is spherical silica and has an average particle size of 0.5 to 40 μm.
m.

Further, in the invention according to claim 17, in the inorganic filler (C), the mass ratio of glass fiber to spherical silica is 1%.
00/0 to 30/70.

The invention according to claim 18 is characterized in that the inorganic filler (C) is a whisker.

The invention of claim 19 is characterized in that the whisker of the inorganic filler (C) has an average fiber length of 1 to 50 μm and an average fiber diameter of 0.1 to 5 μm. .

According to a twentieth aspect of the present invention, the whisker of the inorganic filler (C) is an aluminum borate whisker.

The invention of claim 21 is characterized in that the inorganic filler (C) is a scaly inorganic filler.

The invention according to claim 22 is characterized in that the scaly inorganic filler (C) has an average thickness of 0.3 to 10 μm.
m, and an average particle diameter of 10 to 4000 μm.

The invention of claim 23 is characterized in that the scale-like inorganic filler of the inorganic filler (C) is glass flake or granular glass flake.

The invention according to claim 24 is characterized in that in the inorganic filler (C), the mass ratio of the whisker to the scale-like inorganic filler is 100/0 to 50/50.

Further, the invention of claim 25 is characterized in that the inorganic filler (C) is contained in an amount of 30 to 8 in the total of the components (A) to (C).
0 mass%.

[0032] The method for producing a thermoplastic resin composition according to claim 26 of the present invention provides the method for producing a thermoplastic resin composition according to any one of claims 1 to 25, wherein
It is characterized by kneading the component (C).

According to a twenty-seventh aspect of the present invention, a package for housing a semiconductor element has a concave portion formed of the thermoplastic resin composition according to any one of the first to twenty-fifth aspects and for housing 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.

[0034]

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 higher, and (B) an ethylene-based copolymer comprising ethylene, an α, β-unsaturated carboxylic acid alkyl ester, and maleic anhydride. And a thermoplastic resin composition comprising at least one of polyamide 46 resin and (C) an inorganic filler.

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

FIG. 1 shows an example of a package for accommodating a semiconductor device according to the present invention, and an insulating substrate 3 provided with a concave portion 2 for accommodating a semiconductor device 1 having an upper surface opened.
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 melted 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 higher was subjected to thermogravimetric analysis to raise the temperature to 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) Among the thermoplastic resins 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 has been 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).

In the case of (A) a thermoplastic resin having a melting point of 250 ° C. or higher, a styrene polymer having a syndiotactic structure (hereinafter sometimes referred to as an SPS resin) mainly comprises 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 in the case of two, a triad in the case of three, and a pentad in the case of 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 from 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 SPS resin as described above 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 sometimes 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.

The linear PAS resin has a melting point of 260 ° C. or more, 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 Formula 1”, “Chemical Formula 2”, and “Chemical Formula 2”. 3 "," 4 "," 5 "," 6 "and the like.

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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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 linear polyarylene sulfide resin as described above 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, in the present invention, as the component (B), either one of an ethylene copolymer and a polyamide 46 resin,
Alternatively, both are used.

The ethylene copolymer used as the component (B) in the present invention has a monomer component of ethylene, α, β-
An unsaturated carboxylic acid alkyl ester and maleic anhydride, wherein ethylene is 50 to 90% by mass,
More preferably, 60 to 85% by mass, the α, β-unsaturated carboxylic acid alkyl ester is 5 to 49% by mass, more preferably 7 to 45% by mass, and the maleic anhydride is 0.5 to 1% by mass.
0 mass%, more preferably 1 to 8 mass%. In the ethylene copolymer of the component (B),
α, β-unsaturated carboxylic acid alkyl ester having a ratio of 4
If it exceeds 9% by mass, the thermal stability of the ethylene copolymer of the component (B) may be insufficient, and conversely, 5% by mass.
If it is less than 3, the mechanical strength of the obtained molded article may be insufficient. When the proportion of maleic anhydride exceeds 10% by mass, the thermal stability of the ethylene copolymer as the component (B) may be insufficient, and conversely, 0.5% by mass.
If it is less than 3, the mechanical strength of the obtained molded article may be insufficient.

Here, as the α, β-unsaturated carboxylic acid alkyl ester, an unsaturated carboxylic acid having 3 to 8 carbon atoms, for example, an alkyl ester such as acrylic acid and methacrylic acid can be used. . Specific examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-acrylate.
-Butyl, t-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, and the like. Of these, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are particularly preferable.

Examples of the ethylene copolymer (B) comprising ethylene, an α, β-unsaturated carboxylic acid alkyl ester, and maleic anhydride include “Bondane” manufactured by Sumitomo Chemical Co., Ltd. and Nippon Petrochemical Co., Ltd. "Rescu Pearl E
A commercially available product as “T” can be appropriately selected and used.

The amount of the ethylene copolymer used as the component (B) is preferably in the range of 0.5 to 20% by mass, more preferably the total of the components (A) to (C). 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 composition are impaired. And the moldability may be impaired.

The polyamide 46 resin used as the component (B) in the present invention is a resin obtained from tetramethylene diamine and adipic acid, and is also called polytetramethylene adipamide or nylon 46. In the present invention, the polyamide 46 resin contains, in addition to polytetramethylene adipamide, a copolymerized polyamide having a polytetramethylene adipamide unit as a main component. The monomer used as the copolymer component is not particularly limited,
Any amide-forming component can be used. Representative examples of the copolymerization component include 6-aminocaproic acid, 11
Amino acids such as -aminoundecanoic acid, 12-aminoundecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-lauryl lactam, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane,
1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4- (Aminocyclohexyl) propane, 2,2-bis (aminoprosyl) piperazine, diamine such as aminoethylpiperazine and adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane diacid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, Examples thereof include dicarboxylic acids such as 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and diglycolic acid. As a commercially available product, for example, “Stanyl” (trade name) manufactured by DSMJSR Engineering Plastics can be used.

The method for producing polyamide 46 resin is described, for example, in JP-A-56-149430 and JP-A-56-1.
Methods described in JP-A-49431, JP-A-58-83029, JP-A-61-43631 and the like can be used. That is, first, a prepolymer having a small number of cyclic end groups is produced under specific conditions, and then subjected to solid-phase polymerization under a steam atmosphere, or
The high viscosity polyamide 46 can be prepared by heating in a polar organic solvent such as pyrrolidone or N-methylpyrrolidone. The degree of polymerization of the polyamide 46 is not particularly limited, but a polyamide 46 resin having a relative viscosity in a range of 2.0 to 6.0 at 1 g / dl in 25% sulfuric acid and 96% sulfuric acid is preferably used.

Here, in the thermal mass spectrometry, the polyamide 46 resin (B) was heated at a rate of 10 ° C./min and a temperature of 330 ° C.
It is preferable that the mass decrease at 5 ° C. is 5% by mass or less. When the polyamide 46 resin whose mass decrease exceeds 5% by mass is used, voids may be generated in a molded article molded using the polyamide 46 resin. The mass loss is preferably as small as possible, ideally 0% by mass,
The practical lower limit is 0.1% by mass.

The amount of the polyamide 46 resin used as the component (B) is preferably in the range of 0.5 to 20% by mass, more preferably 0.1 to 20% by mass of the total of the components (A) to (C). It is in the range of 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 composition are impaired. And the moldability may be impaired.

Next, as the inorganic filler (C) used in the present invention, 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 100 μm, and aspect ratio of 20 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 100 μm, the moldability may be deteriorated. The silica is preferably spherical and has an average particle size of 0.5 to 40 μm. If it is less than 0.5 μm, the melt viscosity increases and moldability deteriorates. If it exceeds 40 μm, the mechanical strength decreases. If it exceeds 100 μm, 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, the mass ratio is preferably 100/0 to 30/70. If the ratio of the spherical silica exceeds 70% by mass, the mechanical strength may be reduced.

Whiskers can also be used as the inorganic filler (C). As this whisker, an aluminum borate whisker can be preferably used. In addition to aluminum borate whiskers, even if silicon carbide whiskers and silicon nitride whiskers are blended in large amounts, the smoothness of the surface of the molded product is not impaired, but silicon carbide whiskers and silicon nitride whiskers are very expensive. In addition, because of its high hardness, it has disadvantages such as severely abrasion of a kneader, a molding machine, a mold, and the like during molding. For this reason, it is preferable to use aluminum borate whiskers. In order to improve the strength of the molded article by mixing whiskers, it is necessary to improve the adhesion and wettability between the resin and the surface of the whisker, so the surface of the whisker is surface-treated with the above various silane coupling agents. Is preferred.

The whiskers preferably have an average fiber length of 1 to 50 μm and an average fiber diameter of 0.1 to 5 μm. If the average fiber length and the average fiber system are out of this range, the melt viscosity of the resin composition may increase and the moldability may deteriorate, or the mechanical strength of the molded product may decrease.

As the whisker, a commercially available product can be used. Examples of the commercially available product include "Albolex; product number YS3A" manufactured by Shikoku Chemicals Corporation. (C) By adding whiskers as an inorganic filler, it is possible to obtain a high effect of improving mechanical properties such as warpage and dimensional stability of a molded article.

Further, a scaly inorganic filler can be used as the inorganic filler (C). As the scaly inorganic filler, any inorganic scaly filler can be used as long as it is a scaly inorganic filler, and is not particularly limited, but preferred examples are industrial availability, price, From the viewpoint of easy handling, glass flake, talc, mica and the like can be mentioned. These flaky inorganic fillers can be used alone or in combination of two or more. Since glass flakes are thin, light and scaly, they are easily scattered and are not preferable in terms of workability, so that granular glass flakes can also be used. Granular glass flakes are obtained by binding individual flakes to each other with a binder and superimposing them in layers to improve handling and feedability. These can be used as commercial products. Examples of glass flakes include "Micro Glass; Part No. REF140A" manufactured by Nippon Sheet Glass Co., Ltd., and granular glass flakes manufactured by Nippon Sheet Glass Co., Ltd. "Micro glass flexure; Part number RE
FG301 "and the like.

As the scaly inorganic filler, an average thickness of 0.1 is preferable.
Those having a thickness of 3 to 10 μm and an average particle diameter of 10 to 4000 μm are preferred, and those having an average thickness of 1 to 9 μm and an average particle diameter of 50 to 1000 μm are more preferred. When the average particle size of the flaky inorganic filler exceeds 1000 μm, particularly 4000 μm, or when the average thickness exceeds 9 μm, especially 10 μm, the surface beauty of the obtained molded article may be impaired. When the average thickness of the flaky inorganic filler is 1 μm, particularly less than 0.3 μm, or when the average particle size is less than 50 μm, particularly less than 10 μm, the melt viscosity of the obtained thermoplastic resin composition increases. , Moldability may be deteriorated. In the present invention, the “average particle size of the flaky inorganic filler” is a value measured according to JIS Z-8820.

(C) By using a flaky inorganic filler as the inorganic filler, it is possible to improve the mechanical properties such as warpage and dimensional stability of the obtained molded article, and to obtain the moisture during absorption of moisture of the molded article. The effect of greatly suppressing the transmittance can be obtained at a high level.

In the inorganic filler (C), a whisker and a flaky inorganic filler can be used in combination.
When the whisker and the flaky inorganic filler are used in combination, the mass ratio of the whisker to the flaky inorganic filler is 10%.
It is preferably 0/0 to 50/50, and particularly preferably 100/0 to 70/30. When the compounding ratio of the whisker and the flaky inorganic filler is in the range of 100/0 to 50/50, a molded article excellent in warpage and dimensional stability and excellent in moisture resistance can be obtained and molded. The package for accommodating a semiconductor element has excellent moisture resistance reliability.
If the ratio is out of this range, the fluidity during molding may be poor, and the warpage of the molded article may increase, resulting in a decrease in dimensional stability.

In the present invention, the amount of the inorganic filler (C) added to the thermoplastic resin composition is preferably 30 to 80% by mass in the total of the components (A) to (C). 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 according to 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, copolymer nylon resin), polycarbonate Resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyetheretherketone resin, polyacetal resin, polyetherimide resin, polyamideimide resin, polyimide resin, polystyrene resin, AS resin, A
Synthetic resins such as BS resin, phenoxy resin, polyether nitrile resin, polytetrafluoroethylene resin, petroleum resin, coal resin, epoxy resin, phenol resin, silicone resin, urethane resin and polyolefin rubber,
Elastomers such as olefin copolymers and hydrogenated rubbers can be mentioned. These may be used in combination of two or more.

Examples of the antioxidant include phosphorus 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, aluminum compounds and the like, 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.

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

Next, in the package for accommodating the semiconductor element 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, or resin.

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
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 achieved by adding an ethylene-based copolymer consisting of ethylene, an α, β-unsaturated carboxylic acid alkyl ester and maleic anhydride as the component (B) used in the present invention. It is considered that the addition of the polyamide 46 resin enhances the adhesion between the metal terminal 11 and the resin and suppresses the invasion of moisture from the interface. The effect of improving the adhesion between the metal terminal 11 and the resin by adding the polyamide 46 resin is as follows.
This is particularly high when the metal terminal 11 is plated with gold.

The present invention is not limited to the above embodiment, and various modifications 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 for closing the opening of the recess 2 is provided.
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.

[0095]

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

Example 1 An aromatic polyamide resin (Kuraray “Genestar”) was used as a thermoplastic resin.
Ethylene 68% by mass, ethyl acrylate 30 as an ethylene copolymer in 50 parts by mass of an aromatic polyamide resin
% By mass and 2% by mass of maleic anhydride (“Bondane” manufactured by Sumitomo Chemical Co., Ltd., product number “A”).
X8390 ”) 10 parts by mass, and 40 parts by mass of milled fiber (“ REV8 ”manufactured by Nippon Sheet Glass Co., Ltd .: aminosilane treatment, fiber diameter 13 μm, average fiber length 70 μm, aspect ratio 5.6) as an inorganic filler are mixed and melted. The mixture was kneaded 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 later 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 19, Comparative Examples 1 to 3) The following were used as thermoplastic resins, ethylene-based copolymers, and inorganic fillers, and were blended in the amounts shown in Tables 1 to 3. And melt-kneaded to obtain a thermoplastic resin composition 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., 330 -Resin C: Styrene-based polymer having mainly 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
° C / min.-Mass loss at 330 ° C-4.5%)-Resin D: linear polyarylene sulfide resin ("LR01" manufactured by Topren Co., Ltd., melting point 280 ° C, melt viscosity 6 Pa · s (parallel plate method) , Temperature rise 10 ℃ /
(M / min, 300 ° C, 100 rad / s), mass decrease at 330 ° C-2.2%) (B) Ethylene copolymer ・ Copolymer: Ethylene 68% by mass, ethyl acrylate 3
A copolymer comprising 0% by mass and 2% by mass of maleic anhydride (“Bondane” manufactured by Sumitomo Chemical Co., Ltd., product number “AX839”
0)) (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 (“REV12” manufactured by Nippon Sheet Glass Co., Ltd .: aminosilane treatment, fiber diameter 6 μm, average fiber length 50 μm, aspect ratio 8.3) 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, part number "KBM403": γ-glycidoxypropyltrimethoxysilane) Coupling agent C: Mercaptosilane-based coupling agent (Toshiba Silicone, part number "TSL8380E":
3-mercaptopropyltrimethoxysilane) Coupling agent D: vinylsilane-based coupling agent (manufactured by Toray Silicone Co., Ltd., product number "SZ6300": vinyltrimethoxysilane) (Evaluation) (1) Adhesion Adhesion to metal is evaluated To do so, 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 properties 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 in a moist heat environment at 21 ° C. and 100% RH for 0.5 hour, 1 hour, and 2 hours. 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 the column of PCT in Tables 1 to 3, with the number of measurements being taken as the denominator and the one with cloudiness being taken as the numerator.

Examples 1 to 19 and Comparative Examples 1 to 3
Could form the insulating substrate 3 as a good molded product, and a molded product could be obtained without unfilling out of 10 pieces. The results are shown in the columns of moldability in Tables 1 to 3, with the denominator being the measured number and the unfilled one being the numerator for the ten samples.

[0101]

[Table 1]

[0102]

[Table 2]

[0103]

[Table 3]

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

(Example 20) An aromatic polyamide resin ("Genestar" manufactured by Kuraray Co., Ltd.) was used as the thermoplastic resin, and the polyamide 4 was added to 50 parts by mass of the aromatic polyamide resin.
6 resin (DSM JSR Engineering Plastics Co., Ltd. “Stanyl” product number “TS200”) 10 parts by mass, milled fiber as inorganic filler (“REV8” manufactured by Nippon Sheet Glass Co., Ltd .: aminosilane treatment, fiber diameter 13)
μm, average fiber length 70 μm, aspect ratio 5.6) 40
Parts by mass were blended and melt-kneaded to obtain 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.

(Examples 21 to 40, Comparative Example 4) The following were used as the thermoplastic resin, the polyamide 46 resin, the inorganic filler, and the coupling agent, and were blended in the blending amounts shown in Tables 4 to 6. And melt-kneaded to obtain a thermoplastic resin composition 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. (A) Thermoplastic resin Resin A, Resin B, Resin C, Resin D (B) Polyamide 46 resin ・ Polyamide 46 resin (DSM JSR Engineering Plastics' “Stanyl” part number “TS20”)
0 ", melting point 295 ° C, temperature decrease 10% / min, mass loss at 330 ° C, 1.2%) (C) Inorganic filler Filler A, Filler B, Filler C described above (D) Coupling Agent Coupling Agent A, Coupling Agent B, Coupling Agent C, Coupling Agent D (Evaluation) (Evaluation) (1) Adhesion To evaluate the adhesion to metal, a metal plate (insert portion: width 0) 0.6 mm x 0.25 mm thick, three types of material 42 alloy / no plating, 42 alloy / silver plating, 42 alloy / gold plating, in order to obtain adhesive A, B, C) to obtain a molded product. . 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 the columns of PCT in Tables 4 to 6, with the number of measurements taken as the denominator and the one with cloudiness as the numerator.

In Examples 21 to 40 and Comparative Example 4, the insulating substrate 3 can be molded as a good molded product.
Molded articles could be obtained without unfilling out of 10 pieces. Table 10 shows the results for the ten samples, with the measured number as the denominator and the unfilled one as the numerator.
-6 are shown in the column of moldability.

[0108]

[Table 4]

[0109]

[Table 5]

[0110]

[Table 6]

As can be seen from Tables 4 to 6, each of the examples showed good results in all of moldability, adhesiveness and moisture resistance.

Examples 41 to 48 The following were used as the thermoplastic resin, the ethylene copolymer, the polyamide 46 resin, the inorganic filler, and the coupling agent. And melt-kneaded to obtain a thermoplastic resin composition 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. (A) Thermoplastic resin Resin A, Resin B, Resin C, Resin D (B) Ethylene copolymer and polyamide 46 resin Copolymer and polyamide 46 resin (C) Inorganic filler already described Filler A, Filler B, Filler C Filler D: Whisker (manufactured by Shikoku Chemicals Co., Ltd., product name "Arbolex", product number "YS3A, average fiber length 10"
Filler E: glass flake (manufactured by Nippon Sheet Glass Co., Ltd., product name "Micro glass glass flake", product number "REF"
−140A ”, average thickness 3 μm, average particle diameter 140 μm) Filler F: glass flake (manufactured by Nippon Sheet Glass Co., Ltd., product name“ micro glass glass flake ”, product number“ REF ”
−015A ”, average thickness 3 μm, average particle size 15 μm) Filler G: glass flake (manufactured by Nippon Sheet Glass Co., Ltd., product name“ micro glass glass flake ”, product number“ REF ”
Filler H: Granular glass flake (Nippon Sheet Glass Co., Ltd., product name "Micro Glass Flaker", product number "REF"
G-301 ", average flake thickness 3 µm, average flake particle size 140 µm) Filler I: Granular glass flake (Nippon Sheet Glass Co., Ltd., product name" Micro Glass Flaker ", product number" REF "
G-101 ", average flake thickness 3 μm, average flake particle size 600 μm) (D) Coupling Agent Coupling Agent A, Coupling Agent B, Coupling Agent C, Coupling Agent D and Coating Agent D The adhesiveness, moisture resistance, and moldability were measured as described above, and the results are shown in Table 7. In addition, about moisture resistance, 0.1.
A pressure cooker test of 3 hours in addition to 5 hours, 1 hour and 2 hours was also performed.

[0113]

[Table 7]

As shown in Table 7, each of the examples showed good results in all of moldability, adhesiveness and moisture resistance.

[0115]

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) an ethylene copolymer comprising ethylene, an α, β-unsaturated carboxylic acid alkyl ester, and maleic anhydride, at least one of polyamide 46 resin, and (C) an inorganic filler. It is possible to mold a molded article having good adhesion to metal and moisture resistance with good moldability.

Further, 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. The thermoplastic resin composition for molding the insulating base contains at least one of the above-mentioned ethylene copolymer and polyamide 46 resin, and water is contained in the insulating base and the metal. The semiconductor element can be effectively prevented from entering the recess from the interface with the frame, and the semiconductor element housed in the recess can be normally and stably operated for a long period of time.

[Brief description of the drawings]

FIG. 1 is a sectional view showing 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

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08K 3/36 C08K 3/36 7/00 7/00 7/02 7/02 7/14 7/14 C08L 23/08 C08L 23/08 25/04 25/04 33/06 33/06 67/00 67/00 77/00 77/00 81/02 81/02 (72) Inventor Masaaki Otsu 1048 Okadoma, Oaza Kadoma, Osaka Prefecture Matsushita F-term in Denko Corporation (reference) 4F070 AA08 AA13 AA32 AA47 AA54 AC23 AC28 AC29 AD01 AD02 AE01 FA03 4F071 AA15X AA22 AA33X AA54 AA62 AA76 AB27 AB28 AB30 AF58 AH07 AH12 BA01 BB05 BC07 BC03BC08 BC07 BC03BC08 BC11X BG04Y CF04W CF04X CF06W CF06X CL00W CL03W CN01X DE136 DE146 DE236 DF016 DJ006 DJ016 DJ036 DJ046 DJ056 DK006 DL006 FA016 FA046 FA066 FB096 FB136 FB146 FD016 FD070 FD090 FD130 FD170 FD200 GN00 GQ00 GT00

Claims (27)

[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) at least one of an ethylene copolymer composed of ethylene, an α, β-unsaturated carboxylic acid alkyl ester and maleic anhydride, and a polyamide 46 resin, and (C) an inorganic filler A thermoplastic resin composition comprising: (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. An ethylene copolymer (B) comprising 50 to 90% by mass of ethylene, 5 to 49% by mass of an α, β-unsaturated carboxylic acid alkyl ester, and 0.5 to 10% of maleic anhydride.
3. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is constituted by mass%. 4. 4. The amount of (B) the ethylene copolymer to be added is:
0.5 to 20% by mass in the total of each component of (A) to (C)
The thermoplastic resin composition according to any one of claims 1 to 3, wherein 5. The method according to claim 1, wherein (B) the polyamide 46 resin has a mass decrease at a temperature rise of 10 ° C./min and a temperature of 330 ° C. of 5% by mass or less in a thermogravimetric analysis. Item 3. The thermoplastic resin composition according to Item 2. 6. The amount of the (B) polyamide 46 resin added is:
0.5 to 20% by mass in the total of each component of (A) to (C)
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is: 7. 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 6, wherein a mass loss at 5 ° C is 5% by mass or less. 8. The thermoplastic resin having a melting point of 250 ° C. or higher (A), wherein the aromatic polyamide resin has an intrinsic viscosity of from 0.5 to 0.5.
The thermoplastic resin composition according to any one of claims 1 to 7, wherein the composition is 1.4 dl / g. 9. 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.
9. The thermoplastic resin composition according to claim 1, wherein the nonanediamine or dicarboxylic acid component is terephthalic acid and the diamine component is 1,6-hexanediamine. 10. The thermoplastic resin according to claim 1, wherein the linear polyarylene sulfide resin is a polyparaphenylene sulfide having at least 70% by mass of a paraphenylene sulfide unit. Resin composition. 11. The linear polyarylene sulfide resin has a melt viscosity of 300 at a parallel plate method.
° C, angular velocity 100 rad / s, 1-30Pa ·
The thermoplastic resin composition according to any one of claims 1 to 10, wherein s is s. 12. (A) In a thermoplastic resin having a melting point of 250 ° C. or higher, a liquid crystal polymer resin is obtained by co-condensation of an acetylated product of p-hydroxybenzoic acid and polyethylene terephthalate. The thermoplastic resin composition according to any one of claims 1 to 11, wherein the thermoplastic resin composition is a liquid crystalline aromatic polyester. 13. (A) In a thermoplastic resin having a melting point of 250 ° C. or higher, the melt viscosity of a polystyrene polymer having a syndiotactic structure is mainly determined under the conditions of a parallel plate temperature of 300 ° C. and an angular velocity of 100 rad / s. The thermoplastic resin composition according to any one of claims 1 to 12, wherein the pressure is 1 to 250 Pa · s. 14. The method according to claim 1, wherein (C) the inorganic filler is treated with a coupling agent having an amino group, an epoxy group, or a mercapto group. Thermoplastic resin composition. 15. (C) The inorganic filler is glass fiber, a fiber diameter of 5 to 15 μm, and an average fiber length of 30 to 100 μm.
The thermoplastic resin composition according to any one of claims 1 to 14, wherein m and the aspect ratio are 20 or less. 16. The thermoplastic resin composition according to claim 1, wherein the inorganic filler (C) is spherical silica and has an average particle size of 0.5 to 40 μm. object. 17. The thermoplastic resin composition according to claim 15, wherein (C) the inorganic filler has a mass ratio of glass fiber to spherical silica of 100/0 to 30/70. object. 18. The thermoplastic resin composition according to claim 1, wherein the inorganic filler (C) is a whisker. 19. The whisker of the inorganic filler (C) has an average fiber length of 1 to 50 μm and an average fiber diameter of 0.1 to 5 μm.
The thermoplastic resin composition according to claim 18, wherein the thickness is μm. 20. The thermoplastic resin composition according to claim 18, wherein the whisker of the inorganic filler (C) is an aluminum borate whisker. 21. The thermoplastic resin composition according to claim 1, wherein the inorganic filler (C) is a scaly inorganic filler. 22. (C) The scaly inorganic filler of the inorganic filler has an average thickness of 0.3 to 10 μm and an average particle diameter of 10 to 400.
The thermoplastic resin composition according to claim 21, wherein the thickness is 0 µm. 23. The thermoplastic resin composition according to claim 21, wherein (C) the scaly inorganic filler of the inorganic filler is glass flake or granular glass flake. 24. In the inorganic filler (C), the mass ratio of whisker to scale-like inorganic filler is 100/0 to 50/50.
The thermoplastic resin composition according to any one of claims 18 to 23, wherein: 25. (C) The inorganic filler is one of (A) to (C)
The thermoplastic resin composition according to any one of claims 1 to 24, wherein the content of the thermoplastic resin is 30 to 80% by mass of the total of the components. 26. 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: 27. 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.