JPH05179140A - Polymer composition and its preparation - Google Patents

Abstract

PURPOSE:To prepare a polymer compsn. which has a good compatibility and is excellent not only in heat resistance, mechanical properties, etc., but also in electrical insulating properties, dielectric characteristics, etc., by thermally melt mixing a polyetherimide resin, a polyphenylene ether resin, and a styrene copolymer. CONSTITUTION:A polyetherimide resin of formula I (wherein n is 1-1,000; R1 is a group of, e.g. formula II, III, or IV; and R2 is a group of, e.g. formula III or V), a polyphenylene ether resin of formula VI (wherein n is 1-1,000; Y1 to Y4 are each H or CH3), and a styrene copolymer (e.g. a copolymer of styrene with an epoxy-modified styrene) are thermally melt mixed to give a polymer compsn., which has an excellent compatibility without detriment to the excellent heat resistance, mechanical properties, electrical insulating properties, dielectric characteristics, moldability, etc., inherent in polyetherimide and polyphenylene ether resins.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polymer composition having excellent heat resistance, electrical insulation, dielectric properties and the like, which can be suitably used as an electrical insulation material for IC substrates, printed wiring boards and the like, and its production. Regarding the method.

[0002]

BACKGROUND OF THE INVENTION Polyetherimide is used in many applications as an engineering plastic because it has excellent properties such as heat resistance, electrical insulation, and mechanical properties. Further, due to its excellent heat resistance and electric insulation, it is often used as an electric insulating material for IC substrates, printed wiring boards and the like.

However, a condensed aromatic heat-resistant polymer such as polyetherimide generally has a relatively high dielectric constant, so that it is an insulating material for high-density / multilayer integration or high-speed / high-frequency circuits. As a result, its performance is limited.

On the other hand, polyphenylene ether, aromatic polyvinyl compounds and the like are inferior in mechanical strength, moldability and heat resistance, but have a low dielectric constant and relatively excellent electric characteristics.

By blending two or more polymers having different properties, a polymer blend having the characteristics of each polymer has been actively designed, but many polymers are incompatible systems. However, in the case of an incompatible polymer blend, there was a problem in properties, particularly mechanical properties.

Conventionally, there has been known a polymer blend in which a polyether imide having the above-mentioned characteristics and a polyphenylene ether having the above-mentioned characteristics are heated and melt-mixed. However, this polymer blend
There was a problem in compatibility and the mechanical properties were not satisfactory.

[0007]

It is an object of the present invention to solve the compatibility problem in the above polymer blend of polyetherimide and polyphenylene ether, and to have excellent heat resistance and mechanical properties, as well as electrical insulation and dielectric properties. An object is to provide an excellent polymer blend (composition) and a method for producing the same.

[0008]

Means for Achieving the Object The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, have a polyetherimide having excellent heat resistance and mechanical properties, and a relatively low dielectric constant. Polyphenylene ether, which has excellent electrical properties, was blended with a styrene-based copolymer, which can be said to be the third component, and as a result, the excellent heat resistance, mechanical properties, and electrical insulation inherent in polyetherimide and polyphenylene ether were obtained. It has been found that a polymer composition which retains properties, dielectric properties, moldability, etc., and is excellent in compatibility is obtained, and has proposed the polymer composition of the present invention and a method for producing the same.

That is, the polymer composition of the present invention is obtained by intimately mixing the polyetherimide represented by the general formula A, the polyphenylene ether represented by the general formula B, and the styrene copolymer. It is characterized by

[0010]

[Chemical 3]

[0011]

[Chemical 4]

Further, the method for producing the polymer composition of the present invention comprises heating and melting the polyetherimide represented by the general formula A, the polyphenylene ether represented by the general formula B, and the styrene copolymer. It is characterized by mixing.

Preferred examples of the performance of the polyetherimide of the general formula A used in the polymer composition of the present invention, the production of the polyetherimide, the cost and the like are represented by the following structural formulas. Is mentioned.

[0014]

[Chemical 5]

Further, specific examples preferable in terms of the performance of the polyphenylene ether of the general formula B, the production of the polyphenylene ether, the cost and the like include those represented by the following structural formula.

[0016]

[Chemical 6]

Further, preferred specific examples in terms of performance, production, cost, etc. of the styrene-based copolymer used in the present invention are epoxy-modified styrene-styrene copolymer and epoxy-modified styrene-methylmethacrylate copolymer. ,
Styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, styrene-phenylmaleimide copolymer, styrene-polycarbonate copolymer, styrene-methylmethacrylate copolymer, styrene-butylmethacrylate copolymer and the like. More preferably, it is an epoxy-modified styrene-styrene copolymer, an epoxy-modified styrene-methyl methacrylate copolymer, or a styrene-maleic anhydride copolymer.

The present invention will be described in more detail. About 1 to 98.9 parts by weight, preferably about 5 to 95 parts by weight of the polyetherimide represented by the general formula A including the above structural formula,
The polyphenylene ether represented by the general formula B including the above structural formula is about 1 to 98.9 parts by weight, preferably about 5 to 95.
Parts by weight, and at least one styrene-based copolymer selected from the above-mentioned styrene-based copolymers from about 0.1 to about 50.
It is a polymer composition obtained by blending parts by weight, preferably about 1 to 20 parts by weight.

In this composition, when the amount of polyetherimide is small, the mechanical strength, molding processability, heat resistance and the like are lowered, but the dielectric constant is lowered and the electrical characteristics are improved. On the other hand, when the amount of polyetherimide is large, mechanical strength, molding processability, heat resistance, etc. are improved, but the dielectric constant is increased and the electrical characteristics are deteriorated. On the other hand, when the amount of polyphenylene ether is small, the mechanical strength, moldability and heat resistance are improved, but the dielectric constant is increased and the electrical characteristics are deteriorated. On the other hand, when the amount of polyphenylene ether is large, mechanical strength, moldability, heat resistance, etc. are lowered, but the dielectric constant is lowered and the electrical characteristics are improved.

As described above, since polyetherimide and polyphenylene ether have contradictory properties, the dielectric constant, mechanical strength, etc. can be adjusted by appropriately adjusting the mixing ratio of the two within the above range. It is possible to obtain a polymer composition of the present invention having

If the amount of the styrenic copolymer to be referred to as the third component is too small, the compatibility will decrease,
The mechanical strength is lowered, and conversely, if it is too large, the compatibility may be lowered. Therefore, the polymer composition of the present invention has the above range.

The polymer composition of the present invention may be added with any component other than the above three components, for example, a filler, a heat stabilizer, a flame retardant, a colorant, a reinforcing agent and the like.

As the method for producing the polymer composition of the present invention, a melt blending method, a solution blending method or the like can be adopted. The solution blending method can be blended at a low temperature and does not require complicated equipment, but has a problem that a large amount of solvent is required, the process is complicated, and the yield is low. On the other hand, the melt blending method requires high temperatures and requires equipment such as an extruder, but the process is simple and yields almost 100%. The method for producing the polymer composition of the invention is preferably a melt blending method.

The above-mentioned three components of polyether imide, polyphenylene ether and styrene copolymer may be kneaded at once, but may be kneaded in any order. Specifically, kneading the polyether imide and the styrene copolymer, then kneading the polyphenylene ether, or kneading the polyphenylene ether and the styrene copolymer, and then kneading the polyetherimide, or It is to knead the ether imide and the polyphenylene ether and then knead the styrene copolymer. At this time,
The above-mentioned fillers, heat stabilizers, flame retardants, colorants, reinforcing agents, and other optional components may be kneaded simultaneously with polyetherimide, polyphenylene ether, and styrene-based copolymers, but the above-mentioned order combinations It is also possible to knead at any time.

Examples of the mixer used for blending the above components include a conventional kneading mixer having a heating function and a mixing function, a single-screw or twin-screw extruder, and the like.

Preferred blending conditions are, for example, in the case of using a kneading mixer, the rotor speed is about 1
0-200 rpm, preferably about 30-100 rpm,
Blend temperature about 200-400 ° C, preferably about 250
˜350 ° C., blending time about 1-60 minutes, preferably about 2-10 minutes. Rotor speed is about 10 rp
If it is less than m or more than about 200 rpm, a good blend cannot be obtained. When the blending temperature is lower than about 200 ° C, the polyetherimide does not melt, and when it exceeds about 400 ° C, the components are decomposed, which is not preferable. When the blending time is less than about 1 minute, sufficient mixing is not performed, and about 6
Even if blending is continued for more than 0 minutes, no further effect can be obtained.

Further, in order to prevent deterioration of each of the above components due to oxidation, blending is preferably performed in an inert gas atmosphere. Specific preferred examples of the inert gas include:
Nitrogen gas, argon gas, helium gas, etc. may be mentioned.

The polymer composition kneaded as described above can be molded into a pellet, a film, or another suitable shape by a molding machine depending on the purpose.

[0029]

In the present invention, the polyether imide and the polyphenylene ether, which are originally poor in compatibility, exhibit good compatibility and close contact with each other due to the presence of the styrene-based copolymer which is a polymer which should be called the third component. The polymer blend is in a mixed state and therefore has excellent mechanical properties. In addition, this styrene-based copolymer does not impair the heat resistance, moldability, electrical properties, mechanical properties, etc. inherently possessed by polyetherimide and polyphenylene ether. As described above, according to the present invention, the various excellent properties originally possessed by both of these polymers are retained as they are,
Moreover, since it is a tight polymer blend, a polymer composition having various properties required for recent engineering plastics is provided.

[0030]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. First, for comparison, physical properties of polyetherimide and polyphenylene ether are shown in Table 1.

[0031]

[Table 1]

Examples 1 to 6 and Comparative Example 1 (Example 1) Polyetherimide [trade name "Ultem 1000" manufactured by General Electric Company, USA] 10
g, polyphenylene ether [poly (2,6-dimethyl-p-phenylene oxide)] 10 g, and an epoxy-modified styrene-styrene copolymer [trade name “RESEDA GP-500”] manufactured by Toagosei Kagaku Kogyo Co., Ltd.
Using a Labo Plastomill mixer (trade name "Labo Plastomil 30C150 type" manufactured by Toyo Seiki Co., Ltd.), the mixture was heated and melt-blended at 300 ° C. and 50 rpm for 3 minutes in a nitrogen atmosphere.

(Example 2) Heat melting blending was carried out in the same manner as in Example 1 except that 10 g of polyetherimide was changed to 16 g and 10 g of polyphenylene ether was changed to 4 g.

(Example 3) Heat melting blending was carried out in the same manner as in Example 1 except that 10 g of polyetherimide was changed to 4 g and 10 g of polyphenylene ether was changed to 16 g.

(Example 4) Heat melting blending was carried out in the same manner as in Example 1 except that 1 g of the epoxy-modified styrene-styrene copolymer was changed to 2 g.

(Example 5) Heat melting blending was carried out in the same manner as in Example 1 except that 1 g of the epoxy-modified styrene-styrene copolymer was changed to 4 g.

(Example 6) Heat melting blending was carried out in the same manner as in Example 1 except that the epoxy modified styrene-styrene copolymer was changed to the epoxy modified styrene-methyl methacrylate copolymer.

Comparative Example 1 Polyetherimide [Ult
em 1000] 10 g, polyphenylene ether [poly (2,6-dimethyl-p-phenylene oxide)]
Using a Labo Plastomill mixer [“Labo Plastomill 30C150 type”]
Heat melt blending was performed at 0 ° C. and 50 rpm for 3 minutes.

For the polymer blend compositions obtained in Examples 1 to 6 and Comparative Example 1, a differential scanning calorimeter [trade name "DSC-100" manufactured by Seiko Denshi Kogyo KK] and a thermogravimetric measuring apparatus [Seiko Denshi Kogyo KK] were used. Product name "T
G / DTA-200 ″], the glass transition temperature (T
g), and the 10% weight loss temperature were measured. Further, the obtained polymer blend composition was subjected to a vacuum press [Shibayama Scientific Instruments Co., Ltd., trade name “Vacuum Press VP-50”] at 250 to 300 ° C., a diameter of about 40 mm and a thickness of about 1 m.
1MHz for the obtained molded product
The dielectric constant and the dielectric loss tangent were measured at the frequency of.
Furthermore, using a small injection molding machine, the obtained polymer blend composition was heated at 250 to 350 ° C. and had a length of 20 mm,
Formed into a dumbbell shape with a large diameter of 4 mmφ and a small diameter of 1 mmφ, and made by US Custom Scientific Instrument
product name "MINI MAX TENSI"
The tensile modulus, tensile strength, and elongation were measured using LE TESTER CS-183 ". The above results are shown in Tables 2 and 3. Also, the compatibility of the obtained polymer blend composition was determined by scanning type. When evaluated by an electron microscope [trade name "JSM-840" manufactured by JEOL Ltd.], the domains were uniformly dispersed with a diameter of 1 to 3 [mu] m in each case, and the compatibility was extremely good.

[0040]

[Table 2]

[0041]

[Table 3]

[0042]

The polymer blend composition obtained by the present invention is a blend having excellent compatibility of various polymer components, retains the excellent heat resistance of polyetherimide, and is superior to polyetherimide. It can have dielectric properties. That is, the polymer composition obtained by the present invention has remarkably better compatibility than the two-component polymer composition of polyetherimide and polyphenyl ether, and mechanical properties are improved accordingly.
In addition, the polymer composition obtained by the present invention is about 2.5 to
It shows a dielectric constant in the range of 3.0, which is a very good value as compared with the dielectric constant of 3.68 of polyetherimide alone. Further, regarding the heat resistance, the glass transition temperature of the polymer blend composition obtained in the present invention is in the range of about 210 to 220 ° C., and the excellent heat resistance of the polyetherimide alone can be maintained as it is.

In addition, according to the present invention, the polyetherimide, polyphenylene ether and styrene copolymer can be blended in any ratio, and the heat resistance and phase having predetermined dielectric properties and the like can be obtained according to the purpose. A polymer blend composition having excellent solubility can be obtained.

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Claims (2)

[Claims] 1. A polymer composition comprising a polyetherimide represented by the general formula A, a polyphenylene ether represented by the general formula B, and a styrene copolymer. [Chemical 1] [Chemical 2] 2. The method for producing a polymer composition according to claim 1, wherein the polyetherimide, the polyphenylene ether, and the styrene copolymer are heated and melt mixed.