JPH01135868A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having excellent electrical properties, mechanical properties, heat-resistance, moisture resistance, etc., and suitable for the sealing material for electric parts, etc., by compounding an inorganic filler coated with a polyphenylene ether resin. CONSTITUTION:The objective resin composition is produced by coating 100pts.wt. of an inorganic filler (e.g., silica or glass fiber) with 1-50pts.wt., preferably 1-20pts.wt. of a polyphenylene ether (co)polymer having a structural unit of formula (R<1> is 1-3C lower alkyl; R<2> and R<3> are H or 1-3C lower alkyl) [e.g., poly(2,6-dimethyl-1,4-phenylene) ether] and compounding the coated filler to a thermosetting resin or a thermoplastic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a resin composition containing an improved inorganic filler. More specifically, electrical properties, mechanical properties,
We provide compositions with excellent heat resistance, moisture resistance, and crack resistance, and are used as sealing materials for electronic and electrical components, automobiles,
It provides materials suitable for aircraft, boats, building materials, daily necessities, etc.

(Prior Art) For the purpose of improving resin compositions, methods such as modifying resins by blending various resins and strengthening them by adding fillers have been studied and put into practical use. However, in order to obtain greater durability and reliability, the interface between the resin and the filler becomes an important issue.

Insufficient interfacial adhesion between the resin and the filler results in problems such as a decrease in the strength of the composition, propagation of cracks caused by external and internal stresses across the interface, and loss of moisture resistance.

For example, a method of coating the silica surface with polybutane rubber, silicone rubber, etc. for the purpose of improving crank resistance, etc.
160) has been proposed, but although crack resistance can be obtained, the moisture resistance and heat resistance are not necessarily satisfactory. In addition, for the purpose of improving thermal conductivity and mold wear, a method of coating the filler with resin used in advance (
JP-A No. 61-203121) has been proposed, but the electrical properties, mechanical properties, crank resistance, etc. are not particularly improved.

(Problems to be Solved by the Invention) The present invention solves the above conventional problems by using a filler coated with a polyphenylene ether commercial resin in advance to reinforce the interface between the bulk resin and the filler. At the same time,
This provides a resin composition that is electrically and mechanically superior.

(Means for Solving the Problems) The composition provided by the present invention is composed of an inorganic filler coated with a polyphenylene ether resin, and a thermosetting resin and/or a thermoplastic resin.

The polyphenylene ether resin mentioned here refers to the general formula [I] Z (R1 is a lower alkyl group having 1 to 5 carbon atoms, fi, 2- and R3 are hydrogen atoms or lower alkyl groups having 1 to 3 carbon atoms) ) is a polyphenylene ether homopolymer and/or copolymer having a structural unit represented by the general formula [■] (几1 is a lower alkyl group having 1 to 3 carbon atoms, 几2 and 几3 are hydrogen atoms or It is a lower alkyl group having 1 to 3 carbon atoms. This manufacturing method is already known, for example, US Pat.
No. 5, No. 5257557, No. 3257358, No. 3
No. 455880, Special Publication No. 46-27539, Special Publication No. 4
It is disclosed in Japanese Patent Publication No. 9-16120, Japanese Patent Publication No. 52-17880, etc.

Specific examples of polyphenylene ether resins include poly(2,6-dimethyl-1,4-phenylene) ether,
Poly(2,6-ethyl-1,4-phenylene) ether, poly(2,6-diprobyl-1,4-phenylene)
Ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-broby-1,4-phenylene) ether, poly(2-ethyl-
6-broby-1,4-phenylene)ether, 2,6
-nomethylphenol/2,5.6-)limethylphenol copolymer, 2,6-trimethylphenol/2,3
．． 6-triethylphenol copolymer, 2.6-diethylphenol/2,3.6-dolinotylphenol copolymer, 2.6-dipylphenol/2,3.6-)
Examples include trimethylphenol copolymer.

Further, the polyphenylene ether resin may be modified at the side chain or at the end, as long as the main chain structure is within the range described above. Examples include polyphenylene ether resins modified with maleic anhydride, chlorosilane or hydroxyethyl acrylate, and polyphenylene ether resins whose molecular chain ends are blocked by acetylation.

The advantages of polyphenylene ether resin include extremely good electrical properties, excellent mechanical strength, flame retardancy and self-extinguishing properties, and excellent water resistance and hot steam resistance. It is compounded into many resins for the purpose of electrical modification and strength improvement.

The filler used in the present invention is not particularly limited as long as it is a commonly known inorganic filler and can be selected depending on the use and purpose. For example, silica, glass fiber, talc, mica, alumina, calcium carbonate, clay, magnesium carbonate, calcium oxalate, glass balloon,
Kaolin, asbestos, titanium oxide, potassium titanate, barium titanate, silicon nitride, silicon carbide, zirconium silicate, lead silicate, calcium silicate, aluminum hydroxide, calcium sulfate, barium sulfate, magnesium phosphate, boron nitride, Inorganic fillers such as zinc oxide, iron oxide, and lead oxide can be mentioned.

Furthermore, the surface of the inorganic filler may be modified for the purpose of reacting with the terminal reactive group of the polyphenylene ether resin. Examples include various silane coupling agents, titanate coupling agents, aluminum coupling agents, and the like.

In the composition of the present invention, the polyphenylene ether resin is preferably used in a coating range of 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight per 100 parts by weight of the total weight of the inorganic filler. The range of parts is good. If the blending amount is less than 0°1, the target resin
The effect of modification by compositing the polyphenylene ether resin is small, and if the amount exceeds 50 parts by weight, the reinforcing effect by the inorganic filler becomes small and moldability is significantly reduced, which is not preferable.

Examples of the method for coating the inorganic filler with the polyphenylene ether resin include solution blending and melt blending, which can be selected as required. The polyphenylene ether resin and the inorganic filler are physically in contact with each other due to van der Waals forces, or their reactive groups are chemically bonded to each other. In addition, the coated polyphenylene ether resin and the surrounding bulk resin are similarly physically and chemically bonded to each other, and a continuous buffer layer of polyphenylene ether resin is formed between the inorganic filler and the bulk resin. This means that it has been formed.

The resin component used in the present invention is not particularly limited as long as it is a commonly known thermosetting resin or thermoplastic resin, and can be selected depending on the use and purpose. There is no problem in using it.

Examples of thermosetting resins include epoxy resins, polyimide resins, phenol resins, bismaleimide triazine resins, silicone resins, unsaturated polyester resins, and melamine resins.

In addition, thermoplastic resins include polypropylene, polystyrene, polystyrene, polyphenylene ether, polyphenylene sulfide, polycarbonate, polyacetal, polyamide, polyethylene terephthalate, polybutylene terephthalate, AB8 resin, nylon, vinyl chloride, polyarylate resin, polysulfone resin, polyether sulfone. /, polymethylpentene, aromatic polyester, etc.

The composition of the present invention can be mixed by a commonly known method, in which the inorganic filler coated with polyphenylene ether resin and all resin components are mixed in a Nauta mixer, ribbon mixer, Henschel mixer, etc., and then kneaded. , a method of melt-mixing using an extruder or roll, or a method of melt-mixing only the resin components in advance and then adding an inorganic filler coated with polyphenylene ether resin to make the mixture uniform. .

The composition according to the present invention may contain various additives depending on the purpose and use as long as it does not impede the purpose of the present invention, such as color rejuvenating agents such as carbon black, various pigments, and dyes. , fatty acid esters, mold release agents such as carnauba wax, surface treatment agents such as antimony compounds, antimony compounds, flame retardants such as phosphorus compounds, and flexibilizing agents such as reactive silicone, reactive liquid polybutadiene, and silicone resin powder. I can do things.

(Effect of the invention) By intensively and unevenly distributing the polyphenylene ether resin at the interface between the inorganic filler and the bulk resin, it is possible to suppress the occurrence of peeling and cracks that occur at the interface between the filler and the resin, and to prevent them from propagating across the interface. It has a great effect on inhibiting the progression of cracks and furthermore preventing a decrease in strength caused by the cracks.

Furthermore, by combining polyphenylene ether resins, a resin composition with excellent electrical properties, high temperature properties, and moisture resistance can be obtained.

(Example) Next, the present invention will be explained in detail with reference to Examples and Comparative Examples, in which all amounts (parts) shown are parts by weight.

Example 1.2 Poly(2,6-cymethyl-1.
10 parts of 4-phenylene) ether (intrinsic viscosity measured in chloroform at 50°C: 0.3 al/El), 10 parts of maleic anhydride, dicumyl peroxide
1 part, 5.6 parts of maleic acid-modified poly(2,6-dimethyl-1,4-phenylene) ether obtained by extrusion molding at a resin temperature of 320°C, and 3-(2-aminoethylaminoprobyl)tri Methoxysilane (Shin-Etsu Chemical Exhibition LS
-2480) surface-treated amorphous silica powder (
After heating and stirring 100 parts of Tatsumori Co., Ltd.'s Koriichi 8) in toluene, the mixture was heated and stirred, and the toluene was distilled off and dried to obtain a polyphenylene ether resin-coated silica powder (Example 1).

Similarly, 9.3 parts of maleic acid-modified polyC2,6-dimethyl-1,4-phenylene) ether and 100 parts of surface-treated silica powder (Fa Mori RD-8) were added to polyphenylene ether resin-coated silica powder B. was obtained (Example 2).

Polyphenylene ether resin coated silica powder and polyphenylene ether resin nuclide silica powder B1 Cresol novolac epoxy (Sumitomo Chemical B5CN 19
5-XL), phenol novolac (Gun-ei Chemical PS
F4261), brominated bisphenol A epoxy (ESB-400 manufactured by Sumitomo Chemical), diantimony trioxide (Kokoku Seiryu Co., Ltd.), triphenylphosphine (KAI Chemical Co., Ltd.)
PP-360), carnauba wax, and carbon black were mixed in a Henschel mixer with the composition shown in Table 1, and kneaded in a kneader at 90 to 100"C. Furthermore, the kneaded product was cooled and pulverized to obtain Example 1. and 20 compositions were obtained.

The above composition was heated at a mold temperature of 175°C and a pressure cuff of 0 K9/r.
Various test pieces were prepared by transfer molding using Fl, and after kneading these test pieces in a constant temperature bath at 180'C for 5 hours, they were subjected to physical property measurements and crack resistance tests. The obtained physical property values and crack resistance test results are shown in Table 1. The physical property measurement conditions and crack resistance test conditions are explained below.

<Measurement of glass transition temperature> A prismatic column of 3 squares and 15 mm in length was cut out from a disk test piece with a thickness of 5 mm and a diameter of 100 mm, and heated using a dictometer manufactured by Shinku Riko (heating rate of 5℃/min). The temperature at which the linear expansion curve bends at is defined as the glass transition temperature.

<Measurement of bending strength> According to JIS K 6911, thickness 4 plates, width 10
Me, the bending strength was measured using a test piece with a length of 100 mm.

<Measurement of volume resistivity> Using a disk test piece with a thickness of 2 tnm and a diameter of 100 mm, JIS
Measured according to K 6911. Measured values were expressed in logarithms.

Measurement of dielectric constant〉 Using the above test piece for measuring volume resistivity, JIS K
Measured in accordance with 6911.

<Crack resistance test A> Silicone chips (5,
OX5. A test frame on which (1++++) was mounted was molded and after-cured in the same manner as the other test pieces, and then subjected to testing.

The sealed molded product was taken out every 200 cycles, each cycle consisting of 150°C (silicone oil) for 60 seconds, room temperature for 5 seconds, and -196°C (liquid nitrogen) for 60 seconds, and the presence or absence of cracks was checked. The number of tests was 10 per type of composition.

Crack Resistance Test B〉 The above sealed molded product was left in a pressure cooker at 121°C and 2 atm for 18 hours to absorb moisture, and then immediately subjected to
It was immersed in a 60°C solder bath for 30 seconds. After taking it out, the presence or absence of cracks was observed.

The number of tests was 10 per type of composition.

Comparative Example 1.2 As an example showing the effect of the present invention, in place of the polyphenylene ether-coated silica A and B of Examples 1 and 2, silica powder (RD-8 manufactured by Tatsumori) and the polyphenylene ether used in Example 1 were used. The compositions of Comparative Examples 1 and 2 were produced in the same manner as in Example 1 using powder and having the compositions shown in Table 1. The physical property measurement results and crack resistance test results are shown in Table 1.

Example 3 Polyphenylene ether resin-coated silica powder used in Example 1, bismaleimide triazine resin (Mitsubishi Gas Chemical BT2170), cresol novolak epoxy (ECN-1275 manufactured by Ciba Geigy), zinc octylate, dicumyl peroxide, Hoechst Wax OP was mixed with the composition shown in Table 2 in a Henschel mixer, and
The mixture was kneaded in a kneader at 0 to 100°C.

Further, the mixed material was cooled and pulverized to obtain the composition of Example 3.

The above composition was heated to a mold temperature of 175°C and a pressure cuff of 0 to 9/ad.
Various test pieces were prepared by transfer molding, and these test pieces were after-cured for 4 hours in a constant temperature bath at 200°C, and then subjected to physical property measurements and crack resistance tests. The obtained physical property values and crack resistance test results are shown in Table 2.

Comparative Example 3.4 In place of the polyphenylene ether resin-coated silica powder of Example 3, silica powder (ft [Morikorin D-8) and the maleated modified polyphenylene ether powder used in Example 1 were used, and the second It was manufactured in the same manner as in Example 3 with the composition shown in the table, and the physical properties were measured and the crack resistance test was conducted. The results obtained are shown in Table 2.

Example 4.5 100 parts of glass fiber (Glasron 03-MA-497, manufactured by Asahi Fiberglass Co., Ltd.) and the maleic acid-modified POIJ used in Example 1 (2,6-cymethyl-1.4
-phenylene ether (5.6 parts) was heated and stirred in toluene, mixed and reacted, and the toluene was distilled off and dried to obtain a glass fiber coated with polyphenylene ether.

Polyphenylene ether resin coated class fiber people,
Polyphenylene sulfide resin (Toprene T-4 manufactured by Toprene) and polycarbonate (Niepilon S-2000 manufactured by Mitsubishi Gas Chemical) were mixed with the composition shown in Table 3, and extrusion molding was performed at a resin temperature of 290°C.
After producing pellets, injection molding was performed at a resin temperature of 320 to 340°C, a mold temperature of 120°C, and an injection pressure of 100 oK4r/- to produce various test pieces, which were used for physical property measurements.

The obtained physical property values are shown in Table 3. The physical property measurement conditions are explained below.

<Measurement of heat deformation temperature> According to JI8 K 7207, thickness 6.4 tofu straw,
Bending stress 1 using a test piece with a width of 12.7 mm and a length of 127 mm
The heat distortion temperature was measured at 8.5 Kg/ca.

<Izotsu impact test> According to JIS K 7110, thickness 12° 71m
The Izot impact strength was measured using a test piece with a width of 3.3 mm and a length of 63 mm with V/yy-.

<Method for measuring tensile strength> Tensile strength was measured using a No. 1 test piece according to JIS K 7113.

Measurement of bending strength> According to JIS K 7203, thickness 4 mm.

The bending strength was measured using a test piece with a width of IQiml and a length of 10,100l.

Measurement of volume resistivity〉 J
Measured according to IS K 6911. Measured values were expressed in logarithms.

Crack Resistance Test C〉 A silicone chip (5, OX
A test frame mounted with 5.0η1) was molded and after-cured in the same manner as the other test pieces, and then subjected to the test.

The sealed molded product was subjected to 200 cycles of 200°C (gas phase) for 10 minutes, room temperature for 5 minutes, and -50°C (gas phase) for 10 minutes, and then taken out and checked for cracks. Note that the number of tests was 10 for each class 18 composition.

Crack Resistance Test D〉 The sealed molded product obtained in the same manner as Crank Resistance Test C was
C. (gas phase) for 10 minutes, room temperature for 1 minute, and -40.degree. C. (gas phase) for 10 minutes as one cycle for 200 cycles, and then taken out and checked for cracks. In addition, the number of tests is composition 1
There are 10 pieces per type.

Comparative Example 5.6.7.8 Instead of the polyphenylene ether resin-coated glass fiber A used in Example 4, glass fiber (Glaslon 05-MA-497 manufactured by Asahi Fiberglass Co., Ltd.) and the polyphenylene used in Example 1 were used. The third method using ether resin powder was carried out in the same manner as in Example 4.5.
Compositions of Comparative Example 5.6.7.8 were obtained with the compositions shown in the table.

The results of physical property measurements are shown in Table 3.

Example 6.7 The polyphenylene ether resin-coated glass fiber A1 used in Example 4.5 polybutylene terephthalate resin (PBT1401-XO6 manufactured by Toshi) and polypropylene (Highball J'800 manufactured by Mitsui Petrochemicals) are shown in Table 4. Perform extrusion molding with the composition and conditions shown in
After producing pellets, injection molding was performed under the conditions shown in Table 4, and various test pieces were produced and used for physical property measurements.

The obtained physical property values are shown in Table 4.

Comparative Example 9.10.11.12 Polyphenylene ether untreated glass fiber B used in Comparative Example 5 and polyphenylene ether used in Example 1 instead of polyphenylene ether resin coated glass fiber of Example 6.7 Comparative Example 9.10.11.12 compositions having the compositions shown in Table 4 were obtained in the same manner as in Example 6.7 except that resin powder was used.

The results of physical property measurements are shown in Table 4.

1 in Table 1: Silica powder umbrella coated with polyphenylene ether at a weight ratio of 15:270 2: Polyphenylene ether coated at a weight ratio of 25:270
Silica powder coated with -3; Polyphenylene ether untreated silica powder -4
;Display the number of cracks that occur in Ikuru Atsushi (number of tests: 10)
) Umbrella 5; Number of cracks after solder immersion (number of tests: 10)
) Table 2 Umbrella 1; Silica powder coated with polyphenylene ether at a weight ratio of 15:270 2; Silica powder untreated with polyphenylene ether 11
3; Number of cracks generated at the number of cycles displayed (number of tests: 1
0) $4; Number of cracks after solder immersion (number of tests: 1)
0) Procedural amendment (voluntary) January 1, 1988

Claims (1)

[Scope of Claims] 1. A resin composition characterized by containing an inorganic filler coated with a polyphenylene ether resin. 2. A polyphenylene ether resin having the following general formula [I
] The composition according to claim 1, which is a polyphenylene ether homopolymer and/or copolymer having a structural unit represented by the following. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (R_1 is a lower alkyl group with 1 to 3 carbon atoms, R_2 and R_3 are hydrogen atoms or lower alkyl groups with 1 to 3 carbon atoms.)