JP3375217B2 - Sealing material for electric and electronic parts - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin encapsulant for electric / electronic parts, which has good adhesion to the metal part of the electric / electronic part to be sealed and as a result has excellent sealing effect. .

[0002]

2. Description of the Related Art Electronic parts such as ICs, transistors, diodes, capacitors and resistors are widely sealed with resin for the purpose of maintaining electrical insulation, mechanical protection, and prevention of changes in physical properties due to the external atmosphere. Has been done. Conventional resin encapsulation is usually performed by transfer molding using a thermosetting resin such as an epoxy resin or a silicone resin. However, since the thermosetting resin is used, it takes a long time to form the resin composition. It has drawbacks such as poor storability and long post-cure. In order to solve the above-mentioned drawbacks, polyphenylene sulfide resin (PPS), which is one of engineering plastics, or thermotropic liquid crystal polymer (LCP) is injected and sealed as proposed in JP-A-60-40163. It is proposed to do. Usually, for electric and electronic parts, metals such as copper, silver and gold are used as conductive materials.
In order to seal the electric / electronic component, high adhesion between the sealing material and these metal materials is required. However, the thermotropic liquid crystal polymer (LCP) is
As such, the adhesiveness to metal is not always good, and therefore the sealing effect is insufficient.

[0003]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present invention has an object to provide an encapsulating material which is excellent in adhesiveness to a metal which is a conductive material and has a high encapsulating effect as a result. And

[0004]

The first aspect of the present invention is (a)
70 to 99 parts by weight of thermotropic liquid crystal polymer,
(B) 30 to 1 part by weight of a phenoxy resin, and (c) an inorganic filler in an amount of 20 to 8 relative to the whole composition (a + b + c).
The present invention relates to a sealing material for electric / electronic parts, which is characterized by comprising 0% by weight. A second aspect of the present invention is that the inorganic filler according to the first aspect of the present invention is 10 W /
The present invention relates to a non-conductive encapsulating material for electric and electronic parts having a thermal conductivity of (m ° K) or more. Third of the present invention
Relates to a sealing material for electric and electronic parts, wherein the inorganic filler in the first invention is at least one kind selected from silica, alumina, talc, glass beads and glass fibers.

The present invention will be described in more detail below. The thermotropic liquid crystal polyester referred to in the present invention is a polymer which exhibits optical anisotropy when melted and has thermoplasticity. As described above, the polymer exhibiting optical anisotropy when melted has a property that the polymer molecular chains have a regular parallel arrangement in the melted state. The properties of the optically anisotropic molten phase can be confirmed by a usual polarization inspection method using a crossed polarizer. As the liquid crystal polymer, for example, liquid crystalline polyester, liquid crystalline polycarbonate, liquid crystalline polyester imide, etc. are used, and specifically, (all) aromatic polyester, polyester amide, polyamide imide, polyester carbonate, polyazomethine, etc. Can be mentioned. Thermotropic liquid crystal polymers are generally elongated and have a flat molecular structure, and have high rigidity along the long chain of the molecule. In the thermotropic liquid crystal polymer used in the present invention, a part of one polymer chain is composed of a polymer segment forming an anisotropic melt phase, and the remaining part is a polymer segment not forming an anisotropic melt phase. Polymers composed of are also included. Further, it also includes a composite of a plurality of thermotropic liquid crystal polymers.

Typical examples of the monomer constituting the thermotropic liquid crystal polyester include (A) at least one aromatic dicarboxylic acid, (B) at least one aromatic hydroxycarboxylic acid compound, and (C) aromatic diol. At least one compound, (D) (D ₁ ) aromatic dithiol, (D ₂ ) aromatic thiophenol, (D ₃ ) at least one aromatic thiolcarboxylic acid compound, (E) aromatic hydroxylamine, aromatic An aromatic compound such as at least one kind of group diamine-based compound can be used. In some cases, these are composed independently, but in many cases (A) and (C);
(A) and (D); (A), (B) and (C); (A),
(B) and (E); or combinations such as (A), (B), (C) and (E).

The above-mentioned (A) aromatic dicarboxylic acid type compounds include terephthalic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-terphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4- Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenoxyethane-
4,4'-dicarboxylic acid, diphenoxybutane-4,4'-
Dicarboxylic acid, diphenylethane-4,4'-dicarboxylic acid, isophthalic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenoxyethane-3,3'-dicarboxylic acid, diphenylethane-3,3'-dicarboxylic acid, 1,6
-Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, or chloroterephthalic acid, dichloroterephthalic acid, bromoterephthalic acid, methylterephthalic acid, dimethylterephthalic acid, ethylterephthalic acid, methoxyterephthalic acid,
Examples thereof include alkyl, alkoxy or halogen substitution products of the above aromatic dicarboxylic acids represented by ethoxyterephthalic acid and the like.

Examples of the aromatic hydroxycarboxylic acid compound (B) include aromatic hydroxy such as 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and 6-hydroxy-1-naphthoic acid. Carboxylic acid, or 3-methyl-4-hydroxybenzoic acid, 3,
5-Dimethyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3,5-dimethoxy-4-hydroxybenzoic acid, 6-hydroxy-5- Methyl-2-naphthoic acid, 6-hydroxy-5-methoxy-2-naphthoic acid, 2-chloro-4-hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 2,3-dichloro-4-hydroxybenzoic acid Acid, 3,5-dichloro-4-hydroxybenzoic acid, 2,5-dichloro-4-hydroxybenzoic acid, 3-bromo-4-hydroxybenzoic acid, 6-hydroxy-5-chloro-2-naphthoic acid, 6 -Hydroxy-
7-chloro-2-naphthoic acid, 6-hydroxy-5,7
-Alkyl, alkoxy or halogen substitution products of aromatic hydroxycarboxylic acid such as dichloro-2-naphthoic acid.

As the aromatic diol (C), 4,4'-
Dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 4,4'-dihydroxyterphenyl, hydroquinone, resorcin, 2,6-naphthalenediol, 4,
4'-dihydroxydiphenyl ether, bis (4-hydroxyphenoxy) ethane, 3,3'-dihydroxydiphenyl ether, 1,6-naphthalenediol, 2,2-
Aromatic diols such as bis (4-hydroxyphenyl) propane and bis (4-hydroxyphenyl) methane, or chlorohydroquinone, methylhydroquinone, tert-
Butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4-
Examples thereof include alkyl, alkoxy or halogen-substituted aromatic diols such as chlororesorcin and 4-methylresorcin.

Examples of (D ₁ ) aromatic dithiol include benzene-1,4-dithiol, benzene-1,3-dithiol, 2,6-naphthalene-dithiol, and 2,7-naphthalene-dithiol. Examples of (D ₂ ) aromatic thiophenol include 4-mercaptophenol, 3-mercaptophenol, and 6-mercaptophenol. Examples of (D ₃ ) aromatic thiol carboxylic acid include 4-mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercapto-2-naphthoic acid and 7-mercapto-2-naphthoic acid.

(E) Aromatic hydroxylamine and aromatic diamine compounds include 4-aminophenol and N
-Methyl-4-aminophenol, 1,4-phenylenediamine, N-methyl-1,4-phenylenediamine,
N, N'-dimethyl-1,4-phenylenediamine, 3-
Aminophenol, 3-methyl-4-aminophen-
2-chloro-4-aminophenol, 4-amino-
1-naphthol, 4-amino-4'-hydroxydiphenyl, 4-amino-4'-hydroxydiphenyl ether, 4-amino-4'-hydroxydiphenylmethane,
4-amino-4′-hydroxydiphenyl sulfide,
4,4'-diaminophenyl sulfide (thiodianiline), 4,4'-diaminodiphenyl sulfone, 2,5-
Diaminotoluene, 4,4'-ethylenedianiline, 4,
4'-diaminodiphenoxyethane, 4,4'-diaminodiphenylmethane (methylenedianiline), 4,4'-diaminodiphenylether (oxydianiline) and the like can be mentioned.

The thermotropic liquid crystal polyester used in the present invention can be produced from the above-mentioned monomers by various ester forming methods such as a melt acidolysis method and a slurry polymerization method.

The thermotropic liquid crystalline polyesters suitable for use in the present invention have a molecular weight of about 2,000 to 200,000.
0, preferably about 4,000-100,000. The molecular weight can be measured, for example, by measuring the end groups of a compressed film by infrared spectroscopy. GPC can also be used as a general measuring method performed in the form of a solution.

Among thermotropic liquid crystal polyesters obtained from these monomers, aromatic polyesters which are (co) polymers containing the monomer unit represented by the general formula 1 as an essential component are preferable. Particularly preferred is an aromatic polyester containing 5 mol% or more of the above monomer units.

[0015]

[Chemical 1]

One of the particularly preferred aromatic polyesters of the present invention is the polyester represented by Chemical Formula 2 having repeating units derived from three compounds, p-hydroxybenzoic acid, phthalic acid and dihydroxybiphenyl, respectively. The repeating units derived from dihydroxybiphenyl of this polyester can be partially or entirely substituted with repeating units derived from dihydroxybenzene. Further, the polyester represented by Chemical formula 3 having repeating units derived from two compounds of p-hydroxybenzoic acid and hydroxynaphthoic acid is also preferable.

[0017]

[Chemical 2]

[Chemical 3]

The thermotropic liquid crystal polyester of the present invention can be used alone or as a mixture of two or more kinds.

The wholly aromatic liquid crystal polyester is specifically composed of repeating constitutional units derived from terephthalic acid, isophthalic acid, p-hydroxybenzoic acid and dihydroxybiphenyl, and has a weight average molecular weight of 20,0.
The wholly aromatic liquid crystal polyester in the range of 100 to 100,000 is exemplified. The composition ratio of terephthalic acid (p), isophthalic acid (q), p-hydroxybenzoic acid (r) and dihydroxybiphenyl (s) as repeating structural units is not particularly limited, but usually (p + q): s is 10:15 to 15:10, and r: s is 1: 100 to
It is 100: 1. Here, p, q, r and s represent molar ratios.

When the weight average molecular weight of the wholly aromatic liquid crystal polyester is less than 20,000, the heat resistance and the thermal shock resistance are insufficient, and the leak current, crack generation rate and wire breakage rate of the sealing element become high. Not preferable.
When the weight average molecular weight exceeds 100,000, the fluidity becomes insufficient, which is also not preferable. The weight average molecular weight can be measured by gel permeation chromatography. For example, about 0.4 ml of a solution prepared by dissolving 0.03% by weight of a polymer in a solvent composed of a mixture of pentafluorophenol and chloroform in a weight ratio of 35:65.
, Shodex KF-80M (manufactured by Showa Denko KK) as a column, and 0.45 μ-Shode as a packing material.
x DT ED-13CR (manufactured by Showa Denko KK) and a concentration detector R-401 type differential refractive index detector (Wate)
It is introduced into a gel permeation chromatograph using an rs company) at room temperature (about 23 ° C.) for measurement.

In the present invention, 30 to 1 part by weight of the phenoxy resin (b) is blended with 70 to 99 parts by weight of the thermotropic liquid crystal polymer (a). Here, the total amount of the thermotropic liquid crystal polymer and the phenoxy resin is 100 parts by weight. Phenoxy resin is a condensation resin of an aromatic diol such as bisphenol A and epichlorohydrin. As one of them, a resin having a structural formula represented by the following formula 4 is exemplified.

[0022]

[Chemical 4]

Such a resin can be obtained, for example, from Union Carbide Co., USA under the trade name of "Bakelite PKHH". The weight average molecular weight of the phenoxy resin of the present invention is 20,000 or more, preferably 25.0.
The range is from 00 to 500,000. Molecular weight is 20,000
If it is less than 0, the effect of improving the sealing material is low, which is not preferable. Further, if the compounding ratio of the phenoxy resin is less than 1 part by weight, the effect of improving the adhesiveness to the metal is small, and if it exceeds 30 parts by weight, the mechanical properties of the encapsulant are seriously deteriorated, which is not preferable. As the phenoxy resin, a polymerized product can be blended as it is, but it is preferable to use one obtained by previously heating at a temperature of 200 ° C. or higher for 1 hour or more to remove light components.

In the present invention, the above-mentioned resin composition is further blended with the inorganic filler (c). The inorganic filler is not particularly limited as long as it has a small coefficient of thermal expansion, a large coefficient of thermal conductivity, and contains as little as possible a harmful substance that may interfere with the electrical operation of the electronic component. Preferably, the thermal conductivity at 300 ° K is 10 W /
(m ° K) or more, and a non-conductive inorganic filler. For example, silica, alumina, titania, zirconia, titanium silicate, aluminum silicate, lithium aluminum silicate, magnesium aluminum silicate,
Aluminum titanate, aluminum nitride, silicon nitride,
Examples thereof include inorganic powder such as spherical particles such as talc and mica and crushed particles, glass beads, and glass fiber. Two or more of these may be mixed and used.
Of these, it is preferable to use one or a mixture of two or more of silica, alumina, talc, glass beads and glass fibers as the inorganic filler.

The inorganic filler (c) is the whole composition (a +
20 to 80% by weight based on b + c). It is preferably 30 to 65% by weight. If it is less than 20% by weight, the heat resistance is insufficient, while if it exceeds 80% by weight, the fluidity is insufficient.

In producing the composition of the present invention,
The wholly aromatic liquid crystal polyester of (a), the phenoxy resin of (b) and the inorganic filler of (c) can be appropriately melt-mixed by a known method to give a composition. It is also possible to previously mix the wholly aromatic liquid crystal polyester (a) and the phenoxy resin (b) and then mix the inorganic filler (c) therein.

Any known method can be used to seal an electronic component with the composition of the present invention.
For example, when the composition of the present invention is used at a resin temperature of 290 ° C to 370 ° C.
Injection molding can be performed by insert molding or the like under conditions of a temperature of 20 ° C. and a mold temperature of 20 ° C. to 170 ° C.

[0028]

EXAMPLES The present invention will be specifically described below with reference to examples. First, the test method used in the examples will be described. All measurements are performed at 20 ± 3 ° C. and humidity of 50 ± 5%. (1) Tensile strength, tensile modulus, and elongation at break test pieces are performed in accordance with ASTM D638.
In addition, after the pressure cooker test, which will be described later, the measurement was carried out to obtain a tensile strength of 2, a tensile elastic modulus of 2 and a breaking elongation of 2, respectively, and these were compared with the values before the test to evaluate the hydrolysis resistance. (2) Peel strength (adhesion with metal) A metal and a test piece are adhered to each other by a melt press, a cut having a width of 10 mm is made in the obtained press sample, and one end of the cut is directed at 90 degrees with respect to the adhesion surface. And peel strength to metal is measured. (3) Leak current value For 100 sealing elements, the average leak current value after the pressure cooker test described below is obtained. (4) Breakage occurrence rate, crack occurrence rate With respect to 1,000 sealing elements, a test of leaving them in a temperature environment of −50 ° C. and 155 ° C. for 30 minutes each was performed for 500 cycles, and the rate of occurrence of breakage and cracks (%) Ask for.
Note that, regarding the wire breakage occurrence rate, 100 pieces of sealing elements were used and the measurement was performed after the pressure cooker test described later, and the wire breakage occurrence rate was set to 2. (5) The bar flow length test piece was injection molded under the conditions of a resin temperature of 340 ° C. and an injection pressure of 950 kg / cm ² using a mold having a depth of 80 mm, a width of 8 mm and a thickness of 0.3 mm, and the flow length was measured. It is shown as a relative value to a certain reference value. (6) The pressure cooker test sample is left for 100 hours in an oven at 121 ° C., 2 atmospheric pressure and 100% relative humidity.

<Reference Production Example 1> (Production of LCP) In a polymerization tank having an anchor type stirring blade and having a small clearance between the wall of the polymerization tank and the stirring blade, 625 g of p-hydroxybenzoic acid, 200 g of terephthalic acid, Isophthalic acid 66.5g, 4,4 '
-301 g of dihydroxybiphenyl and 96 of acetic anhydride
3 g was added, nitrogen was introduced and mixed, and the mixture was refluxed at 150 ° C. for 3 hours, then, while removing acetic acid, the temperature was raised to 280 ° C. and kept for 45 minutes. Then raise the temperature to 300 ° C and hold for 45 minutes.
After holding for 0 minutes, the fluid substance in a molten state in the tank was extracted from the tank and cooled to room temperature. The cooled material is ground with a grinder and transferred into a rotary oven for 3
The temperature is raised to 20 ° C at a rate of 0.5 ° C / minute, and then at 320 ° C for 4
A thermotropic liquid crystal polymer was obtained by holding for a period of time. This polymer exhibited optical anisotropy when melted.

<Examples 1 to 5, Comparative Examples 1 and 2> Reference Thermotropic liquid crystal polymer obtained in Production Example 1, phenoxy resin (condensation resin of bisphenol A and epichlorohydrin, glass transition temperature 120 ° C, weight) Average molecular weight 4
5,000) and fused silica in the proportions shown in Table 1 and melt-kneaded with a twin-screw extruder (manufactured by Toshiba Corp.) having a diameter of 30 mm to obtain pellets. 2 using the above pellets
A test piece was injection-molded by a 5-ton injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.), and an IC semiconductor element was resin-sealed by insert molding. Table 1 shows the results of the tests performed on the obtained test piece and the sealing element. In addition, Example 1
5 and the relationship between the tensile elastic modulus and the phenoxy resin content of the test pieces of Comparative Example 1 are shown in FIG. Further, regarding the tensile elastic modulus in FIG. 1, the relationship between the retention rate after the test and the phenoxy resin content rate with respect to the value before the pressure cooker test is shown in FIG.

[0031]

[Table 1]

[0032]

Since the encapsulant of the present invention has good adhesion to a metal, a resin-encapsulated electric / electronic component using the encapsulant has low leakage current, wire breakage rate, crack rate, etc. Can be obtained.

[Brief description of drawings]

FIG. 1 is a graph showing a relationship between a tensile elastic modulus of a test piece and a phenoxy resin content rate.

FIG. 2 is a graph showing the relationship between the retention rate of tensile modulus and the phenoxy resin content rate in a pressure cooker test.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI H01L 23/31 H01L 23/30 R // (C08L 101/12 71:12) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 H01L 23/29-23/31

Claims (3)

(57) [Claims] 1. (a) Thermotropic liquid crystal polymer 7
0 to 99 parts by weight, (b) 30 to 1 parts by weight of the phenoxy resin, and (c) the inorganic filler are the entire composition (a + b +).
20-80 weight% with respect to c), The sealing material for electric / electronic parts characterized by the above-mentioned. 2. The electric / electronic device according to claim 1, wherein the inorganic filler has a thermal conductivity of 10 W / (m ° K) or more at 300 ° K and is non-conductive. Sealant for parts. 3. The inorganic filler is silica, alumina,
2. At least one selected from talc, glass beads, and glass fiber.
The encapsulant for electric and electronic parts according to.