JPH0395258A - Aromatic polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain an aromatic polyester resin composition improved in the adhesion to a metal, moisture resistance, dimensional stability, etc., without detriment to other properties by blending a liquid crystal polymer with a bismaleimidotriazine resin. CONSTITUTION:100 pts.wt. melt-processable aromatic polyester resin which can form an anisotropic molten phase [a liquid crystal polymer with a melt viscosity (flow beginning temperature of + 20 to 400 deg.C and a shear rate of 10<3>sec<-1>) of 1000P or below is preferred] is blended with 5-90 pts. bismaleimidotriazine resin (preferably having a Tg>100 deg.C after being cured) and 5-120 pts. inorganic filler (if it is in the form of fiber or whisker, one having an aspect rate of 5-700, a diameter of 0.1-100mum, and a length of 5-700 is preferred), thereby obtaining an aromatic polyester resin composition useful for electric and electronic parts.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an aromatic polyester resin composition that has excellent heat resistance, toughness and dimensional stability, and has improved adhesion and adhesion to metals. be.

[Prior art and problems to be solved by the invention] Melt-processable aromatic polyester resins that can form an anisotropic melt phase are also called liquid crystal polymers, and have high heat resistance, high strength, high toughness, and low mold shrinkage. In recent years, its use has been expanding as a material with excellent dimensional stability and chemical resistance, but even more stringent requirements have been placed on it.

For example, in the electrical and electronic fields, thermosetting resins have traditionally been used for many sealing materials, printed circuit boards, etc., but with the shift to surface mounting of parts, various issues surrounding thermosetting resins have been introduced in recent years. Due to this problem, liquid crystal polymers are being considered as a useful material.

However, because liquid crystal polymers have poor adhesion to metals, there are concerns about moisture resistance and airtightness, especially in sealants, etc., and this has caused problems such as deteriorating the performance and reliability of electronic components. There is.

Conventionally, attempts have been made to incorporate silane coupling agents and thermosetting resins such as Evokin Jugetsuji, but none have been able to achieve the desired effect.

[Means for Solving the Problems] The inventors of the present invention have made extensive studies in view of the above circumstances, and have found that:
We have discovered that by blending bismaleimide triazine resin into liquid crystal polymer, performance such as adhesion to metals, moisture resistance, strength, and dimensional stability can be improved, while other physical properties are not impaired. It's arrived.

That is, the present invention comprises 100 parts by weight of a melt-processable aromatic polyester resin capable of forming an anisotropic melt phase, 5 to 90 parts by weight of a bismaleimide triazine resin, and 5 to 12 parts by weight of an inorganic filler.
The present invention relates to a resin composition characterized by containing 0 parts by weight ε, and to electrical and electronic components made of the resin composition.

The present invention will be explained in detail below.

The aromatic polyester used in the present invention is a melt-processable polymer exhibiting an anisotropic melt phase, and has the property that molecular chains are oriented in the flow direction and arranged regularly.

As a result, it is a thermoplastic resin that exhibits high rigidity specifically in the orientation direction, and is generally classified as a thermoplastic liquid crystal polymer. The constituent components of the above polymer include an aromatic polyester obtained by copolymerizing one or more compounds selected from aromatic hydroxycarboxylic acids, or an aromatic dicarboxylic acid containing mainly aromatic hydroxycarboxylic acids. Aromatic polyester copolymerized with a compound of at least IFJ or higher that forms an ester bond stoichiometrically from among acids, aliphatic dicarboxylic acids, aromatic diols, and aliphatic diols, and aromatic dicarboxylic acids. ,
It is an aromatic polyester obtained by copolymerizing an aliphatic dicarboxylic acid and one or more compounds selected from aromatic diols and aliphatic diols.

Examples of aromatic hydroxycarboxylic acids include 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and 5-hydroxybenzoic acid.
- Aromatic hydroxycarboxylic acids such as hydroxy-2-naphthoic acid or 4-hydroxy-2-methylbenzoic acid,
4-Hydroxy-3-methylbenzoic acid, 4-hydroxy-2-phenylbenzoic acid, 2-chloro-4-hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 6-hydroxy-5-chloro-2-naf1 - Examples include alkyl, allyl, and halogen substituted aromatic hydroxycarboxylic acids such as engineering acid, 6-hydroxy-7-chloro-2-naphthoic acid, and 6-hydroxy-5.7-dichloro-2-naphthoic acid.

Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 4.4''-diphenyldicarboxylic acid, 2.6-naphthalene dicarboxylic acid, diphenyl ether-4.4''-dicarboxylic acid, diphenoxyethane-4. 4'-dicarboxylic acid, diphenoxybutane-4,4'-dicarboxylic acid, diphenylmethane-3,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenoxyethane-3,3' - Alkyl or halogen substitution of aromatic dicarboxylic acids such as dicarboxylic acid, diphenylethane-3,3''-dicarboxylic acid, or aromatic dicarboxylic acids such as chloroterephthalic acid, promoterephthalic acid, methylterephthalic acid, t-butylterephthalic acid, etc. One example is the body.

Examples of aliphatic dicarboxylic acids include cycloaliphatic dicarboxylic acids such as trans-1,4-cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and derivatives thereof. It will be done.

Aromatic diols include hydroquinone, 1/zorcin, 4,4-dihydroxydiphenyl, 3,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 3,3- -dihydroxybenzophenone, 4.4=
-dihydroxydiphenylsulfone, 4.4"-dihydroxydiphenylsulfide, 4.4-dihydroxydiphenylmethane, 3.4-dihydroxydiphenylsulfone, 3.4"-dihydroxydiphenylsulfide, 3.4"-dihydroxydiphenylmethane , 3.3
”-dihydroxydiphenyl sulfone, 3,3゜-dihydroxydiphenyl sulfide, 3,3-dihydroxydiphenylmethane, 2,6゛-naphthalenediol,
Aromatic diols such as 16゛naphthalene diol, 2,2-bis(4-hydroxyphenyl)broban, bis(4-hydroxyphenoxy)ethane, or chlorohydroquinone, promohydroquinone, methylhydroquinone, t-butyl Examples include alkyl- and halogen-substituted aromatic diols such as hydroquinone, 4-chlorresorcinol, and 4-methylresorcinol.

Examples of aliphatic diols include trans-1,4-cyclohexanediol, cis-1,4-cyclohexanediol, trans-1,4-cyclohexanedimethanol,
Cis-1,4-cyclohexanedimethanol, trans-1,3-cyclohexanediol, cis-1,2-cyclohexanediol, trans-1,3-cyclohexanedimethanol, ethylene glycol, 1,4-butanediol, 1,6- Examples include cyclic, linear, or branched aliphatic diols such as hexanediol and 1,8-octanediol, and derivatives thereof.

Depending on the composition, composition ratio, and sequence distribution of the above-mentioned aromatic polyesters, there are those that exhibit an anisotropic melt phase and those that do not. The polymers that can be used are limited to those that form an anisotropic melt phase.

There are no particular limitations on the method for producing an aromatic polyester that can form an anisotropic melt phase using the above monomers.

A typical manufacturing method includes, for example, a method in which 4-acetoxybenzoic acid is reacted with 4.4"-diacetoxydiphenyl, terephthalic acid, or isophthalic acid. The reaction is generally started at a low temperature, and the reaction progresses. At the same time, the temperature is continuously increased.

The obtained raw material is further heated for 20 minutes under reduced pressure or at normal pressure.
The secondary solid phase polycondensation reaction can be carried out at a temperature of 0 to 350°C. This operation increases the molecular weight and significantly improves the properties of the resulting polyester. Further, in order to promote the above reaction, catalysts such as Lewis acids, hydrogen halides, organic acids, or inorganic acid salts, and antimony or germanium compounds can be used in an amount of 0.01 to 1.0% by weight.

The aromatic polyester (ie, melt anisotropic polymer) used in the present invention can be fairly easily molded in a molten state.

This melt anisotropic polymer has a self-reinforcing effect, has high strength and toughness, and is also an excellent material in terms of dimensional stability (linear expansion coefficient).

Particularly for the applications described in the present invention, aromatic polyester resins capable of forming an anisotropic melt phase at temperatures below 400° C. are preferred, and those resins preferably exhibit high fluidity, ie, low melt viscosity.

The melt viscosity of aromatic polyester resin is the flow start temperature + 2
10 to 10000 Poise, especially 1000 Poise when measured at a shear rate of 103 seconds at a temperature of 0°C to 400°C
Poise or less is preferable in terms of molding process. (This melt viscosity can be measured using an ordinary cavillary rheometer equipped with a capillary having a length of 2 mm and an inner diameter of 0.5 mm.) The bismaleimide triazine resin used in the present invention is a thermosetting resin. It has high heat resistance and dimensional stability, and is often used in electrical and electronic parts.

Bismaleimide triazine resins generally consist of a polyfunctional maleimide compound and a triazine resin.

These are thermosetting resins that form triazine rings, triazine-imidazole rings, oxazole rings, etc. by heating them. In particular, N,N" (methylene p-
A compound consisting of (phenylene) bismaleimide and 2,2-bis(p-cyanatophenyl)propane can be used for the purpose of this purpose because desired properties can be obtained depending on the fractionation ratio and molecular weight of each. It is effective against

Such bismaleimide triazine resin is commercially available from Mitsubishi Gas Chemical Co., Ltd. under the trade name "rBT Resin".

In addition, from the viewpoint of heat resistance, the Tg after curing is preferably 100° C. or higher.

Next, an example of a method for preparing the bismaleimide triazine resin will be shown.

For example, uncured bismaleimide triazine resin and a small amount of a known polymerization curing catalyst are mixed in dimethylformamide solvent (
Hereinafter, it will be abbreviated as DMF. ) and remove the solvent while stirring at approximately 120°C using a commonly used mixer such as a planetary mixer, then heat cure in an oven at 170°C for 1 to 4 hours. This is then further heated and cured at about 230° C. for 1 to 4 hours.

The adjustment method is not limited to this, and various known methods can be used. As the polymerization curing catalyst, commonly used peroxide type catalysts, organic gold salts, metal powder catalysts, etc. are used.

For example, examples of peroxides include tertiary butyl barpenzoate, dicumyl peroxide, benzoyl peroxide, and tertiary butyl peroctoate.

Examples of organic metal salts include zinc octylate, tin octylate,
Other examples include organic tin oxides such as dioctyltin oxide.

As the metal powder, iron, zinc, copper, etc. can be used.

Generally, the amount of catalyst to be blended is 0.01 to 0.50 parts by weight per 100 parts by weight of resin.

In addition to the above-mentioned additives, antioxidants, heat stabilizers, etc. may be added.

Furthermore, an epoxy resin or the like may be added for the purpose of accelerating curing of the bismaleimide triazine resin.

The effective blending amount is 100fffffi of liquid crystal polymer.
5 to 9 of bismaleimide triazine resin per part
part is preferred. Even if it is blended in an amount exceeding 90 parts by weight, it will only significantly increase the melt viscosity of the resin composition.
There is no effect when the amount exceeds parts by weight, and there is almost no effect when the amount is less than parts by weight.

Various inorganic fillers are added to the resin composition of the present invention for the purpose of improving mechanical properties, thermal properties, dimensional stability, etc.

Examples of inorganic fillers that can be used in the present invention include glass fibers, carbon fibers, asbestos fibers, boron fibers, boron nitride fibers, calcium silicate fibers, wollastenite, silicon carbide whiskers, and potassium titanate whiskers. Examples include carbon whiskers. As for the size of the fibers or whiskers, the length/diameter ratio, that is, the aspect ratio, is preferably 5 to 700, preferably 0.1 to 100 μm in diameter and 5 to 700 μm in length.

Especially for electrical and electronic component applications, diameters of 0.1 to 10
μm, length 5-70 μm, more preferably length 5-50 μm
A μm one is preferable.

The plate-like and granular materials are compounds selected from metal oxides, metal nitrides, and metal carbides. For example, silicon oxide, beryllium oxide, magnesium oxide, aluminum oxide, thorium oxide, zinc oxide,
Zirconium oxide, titanium oxide, silicon nitride, boron nitride,
Examples include compounds such as aluminum nitride and silicon carbide.

In plate-like materials, the ratio of the average major axis to the average thickness, that is, the aspect ratio, is 5 to 200, and the average major axis is generally 0.1 μm.
~5 mm, preferably 1 μm ~ 1 mm. However, for electrical and electronic component sealing applications, those with a diameter of 0.1 to 50 μm are preferable.

For particulate materials, those having an aspect ratio of 5 or less, preferably 2 or less are used. The particle size is preferably 200 μm or less, particularly 70 μm or less for electrical and electronic component sealing applications. However, granular materials do not necessarily refer to completely spherical or elliptical materials, but also include finely pulverized materials.

Such an inorganic filler can be blended in an amount of 5 to 120 parts by weight. If the amount is less than 5 parts by weight, there is no effect, and if it exceeds 120 parts by weight, problems such as an increase in melt viscosity may occur in terms of processability during processing into a certain shape, which is not preferable.

The filler shape for electrical and electronic component encapsulation is not particularly limited, but in order not to impede fluidity and reduce damage to elements, etc., powder fillers are mainly blended, and fibrous or One or more types of plate-like fillers may be blended.

In particular, the melt viscosity of the resin composition for electrical and electronic component applications is 1000 poise or less, and further 100 poise or less when measured under the same conditions as aromatic polyester resins.
se or less is more preferable.

These fillers may be treated with a coupling agent, a convergence agent, or the like.

Examples of electrical and electronic parts made of the resin composition of the present invention include semiconductors, sealing parts including transistors, printed circuit boards, connectors, FDD carriages, compact discs, and optical pickup lens holders for laser discs.

Electrical and electronic parts made of the resin composition of the present invention include parts that require heat resistance, high dimensional stability, strength, etc., and parts that require adhesion in parts where resin and metal are in contact.

(Example) The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

The following items were tested for the molded product.

O Adhesion rate (%) due to red ink content Evaluate the degree of ink penetration in the longest lead part 0 Lead wire bending test Evaluate the presence or absence of resin cracks and cracks by bending the lead wire (If there is no problem, 01 Resin cracks, cracks, etc.) 0 solder heat-resistant molded parts are immersed in a 300°C solder bath for 10 seconds to evaluate the surface condition (for those with no problems, 0 indicates roughness on the surface, Δ indicates the beginning of surface roughness, etc.); Items are Example 1 Aromatic polyester forming an anisotropic melt phase (100 parts by weight of 4-hydroxybenzoic acid, 10.4 parts by weight of terephthalic acid, 24.2 parts by weight of isophthalic acid, 43.8 parts by weight of 4,4-dihydroxydiphenyl) 100 parts by weight of a copolymer consisting of a bismaleimide triazine tree Ifi
(Mitsubishi Gas Chemical Co., Ltd., BT resin, BT-2480
, Tg after curing 280 to 290°C) and 25 parts by weight of fused silica (manufactured by Micron Co., Ltd., S-CO grade, average particle size 24 μm), and heated at 280°C with a commonly used extrusion molding machine. After granulation by a known method, DIP type 16-pin semiconductor encapsulation was performed using an insert injection molding machine. The temperature of the injection molding machine is 360°C.

The melt viscosity behavior during molding of this resin composition was measured using a cavilograph manufactured by Toyo Seiki at a temperature of 0.5 mmφ at a temperature of 360°C.
Table 1 shows the test results of the 〇-shaped product, which was measured using a die of 5mm x 50mm and had a shear rate of 50poise when the shear rate was 103sec-'.

Example 2 Aromatic polyester forming an anisotropic melt phase (100 parts by weight of 4-hydroxybenzoic acid, 10.4 parts by weight of terephthalic acid!
I! bismaleimide triazine resin (Mitsubishi Gas Chemical Co., Ltd., BT Resin, BT-26
80, Tg after curing 280-290°C) 10 parts by weight and glass fiber (Asahi Fiberglass, 03MAPI-11)
, average size 13μmφ
A P-type 16-pin semiconductor was sealed. The temperature of the injection molding machine is 360°C. The melt viscosity behavior of this resin composition during molding was measured using a Capillograph manufactured by Toyo Seiki at a temperature of 360°C using a die of 0.5 mmφ x 5 mm.
It was ise. Table 1 shows the test results for the round products.

Example 3 Aromatic polyester forming an anisotropic melt phase (100 parts by weight of 4-hydroxybenzoic acid, 10.4 parts by weight of terephthalic acid)
fi, 24.2 parts by weight of isobutaric acid, and 43.8 parts by weight of 4,4-dihydroxydiphenyl), and 100 parts by weight of a copolymer consisting of bismaleimide triazine resin (manufactured by Mitsubishi Gas Chemical Co., Ltd.). , BT resin, BT-26
80, Tg after curing 280-290°C) 10 parts by weight and carbon fiber #@ (manufactured by Toho Rayon, HTA-CMFO1
60N/S, average size 6μmφ×160μm) and 25 parts by weight, and molded at 280°C using a commonly used extrusion molding machine.
After granulation using a known method, DIP type 16-pin semiconductor encapsulation was performed using an insert injection molding machine. The temperature of the injection molding machine is 360°C. The melt viscosity behavior of this resin composition during molding was measured using a cavilograph manufactured by Toyo Seiki.
When measured at a temperature of 0° C. using a die of Q, 5 mmφ x 5 mm, it was 30 po i s 6 when the shear rate was 10'sec'''1.The test results for the large-sized product are shown in Table 1.

Example 4 Aromatic polyester forming an anisotropic melt phase (100 parts by weight of 4-hydroxybenzoic acid, 10.1 parts by weight of terephthalic acid, 23.6 parts by weight of isophthalic acid, 43.8 parts by weight of 4.4-dihydroxydiphenyl) 1 part by weight)
00 parts by weight, bismaleimide triazine resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., BT resin, BT-2680)
, Tg after curing: 280 to 290°C) and 30 parts by weight of talc (A-5000 manufactured by Hayashi Kasei, average diameter 5.5 μm, thickness 0.5 μm) were mixed at 300°C using a commonly used extrusion molding machine. , after granulation by a known method,
DIF type 16ptn semiconductor encapsulation was performed using an insert injection molding machine. The temperature of the injection molding machine is 360°C. The melt viscosity behavior during molding of this resin composition was measured using a cavilograph manufactured by Toyo Seiki at a temperature of 360°C.
When measured using a 5 mm die, the shear rate was 1
At 03sec-', it was 300potse.

Table 1 shows the test results for the rounded products.

Comparative Example 1 Aromatic polyester forming an anisotropic melt phase (100 parts by weight of 4-hydroxybenzoic acid, 10.4 parts by weight of terephthalic acid, 24,2 parts by weight of isophthalic acid, 43 parts by weight of 4,4-dihydroxydiphenyl) .8 parts by weight),
After granulation by a known method at 280° C. using a commonly used extrusion molding machine, DIP type 16-pin semiconductor encapsulation was performed using an insert injection molding machine. The temperature of the injection molding machine is 3
The temperature is 60°C. The melt viscosity behavior during molding of this resin composite bottom was measured using a Toyo Seiki cavilograph at a temperature of 360°C using Q, 5 mm φ x 5 mm dies, and found that it was 35 poise when the shear rate was 10'sec-1.
Met. Table 1 shows the test results for the molded products.

Comparative Example 2 Aromatic polyester forming an anisotropic melt phase (100 parts by weight of 4-hydroxybenzoic acid, 10.4 parts by weight of terephthalic acid, 24.2 parts by weight of isophthalic acid, 43 parts by weight of 4,4-dihydroxydiphenyl) 8 parts by weight)
00 parts by weight, bismaleimide triazine tree W
1 (manufactured by Mitsubishi Gas Chemical Co., Ltd., BT resin, BT-268
0, Tg after curing 280 to 290°C) and 25 parts by weight of fused silica (manufactured by Micron Co., Ltd., S-CO grade, average particle size 24 μm) were mixed and heated at 280°C using a commonly used extruder or molding machine. After granulation using a known method, it was granulated using an insert injection molding machine.
Semiconductor encapsulation was performed. The temperature of the injection molding machine is 360°C. The melt viscosity behavior during molding of this resin composite was measured using a Toyo Seiki cavilograph at a temperature of 360°C, O, 5 m
When measured using a die of mφ x 5 mm, it was found to be 50 potse when the shear rate was 10'sec-'.

Table 1 shows the test results for the precept articles.

Comparative Example 3 Aromatic polyester forming an anisotropic melt phase (100 parts by weight of 4-hydroxybenzoic acid, 10.4 parts by weight of terephthalic acid, 24.2 parts by weight of isophthalic acid, 4.4 parts by weight of isophthalic acid)
100 ffi parts of a copolymer consisting of dihydroxydiphenyl (43.8 parts by weight), bismaleimide triazine resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., BT resin, B
T-2680, Tg after curing 280-290℃〉100
Parts by weight and fused silica (manufactured by Micron Co., Ltd., S=CO
grade, average particle size 24 μm) and 55 parts by weight,
After granulation by a known method at 280° C. using a commonly used extrusion molding machine, DIP type 16 pin semiconductor encapsulation was performed using an insert injection molding machine. The temperature of the injection molding machine is 360°C. The melt viscosity behavior of this resin composite during molding was measured using a Toyo Seiki cavilograph at a temperature of 360°C using a die of 0.5 mmφ x 5 mm.
It was ise. Table 1 shows the test results for the molded products.

(100 parts by weight of 4-hydroxybenzoic acid, 10.1 parts by weight of terephthalic acid, 23.6 parts by weight of isophthalic acid, 43.8 parts by weight of 4,4-dihydroxydiphenyl). , and talc (A-50001 made by Hayashi Kasei, average diameter 5.5 μm, thickness 0.
5 μm) was blended and granulated by a known method at 300° C. using a commonly used extruder or molding machine, and then DIF' type 16-pin semiconductor encapsulation was performed using an insert injection molding machine. The temperature of the injection molding machine is 360°C. The melt viscosity behavior during molding of this resin composition was measured using a cavilograph manufactured by Toyo Joki Co., Ltd. at a temperature of 360°C.
When the shear rate was 520 poise when the shear rate was 103 sec-', it was determined using a mm die. Table 1 shows the test results for the molded products.

Comparative Example 4 Aromatic polyester forming an anisotropic melt phase [Effects of the invention] According to the present invention, the adhesion and adhesive strength of aromatic polyester resins to metals, which had been problems in the past, were improved, and the mechanical It has excellent physical strength and heat resistance, and also has good fluidity and electrical properties. According to the present invention, the sealing of electrical and electronic components such as ICs and h-transistors, printed wiring boards, each tli. ? It can be suitably used as a child part or a shaped material.

[Brief explanation of drawings]

FIG. 1 is a plan view showing the state of an IC dummy frame sealed using the composition of the present invention and a comparative product used in a molded product test as a sealing material. In the figure, ■ indicates a lead, ■ indicates the longest lead, and ■ indicates a sealing material.

Claims (2)

[Claims] (1) A resin composition comprising 100 parts by weight of a melt-processable aromatic polyester resin capable of forming an anisotropic melt phase, 5 to 90 parts by weight of a bismaleimide triazine resin, and 5 to 120 parts by weight of an inorganic filler. (2) An electrical and electronic component comprising the resin composition according to claim 1.