JPH0688016A - Polymer composition and its production - Google Patents

Abstract

PURPOSE:To obtain a polymer composition excellent in electrical insulation properties, dielectric properties, heat resistance, chemical resistance, mechanical properties, etc., by melt-mixing a polycarbonate with a polyphenylene oxide and a styrene copolymer or a divinyl compound. CONSTITUTION:A polymer composition is produced by melt-mixing a polycarbonate of formula I (wherein R is a group of formula II, III or IV or the like; and n is a positive integer) with a polyphenylene oxide of formula V (wherein Y1, Y2, Y3 and Y4 are each H or CH3; and n is 1-1000) and a styrene copolymer or a divinyl compound. This composition has improved compatibility of a blend of the former two components, and therefore retains the excellent properties inherent in these components.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention has excellent electrical insulation, dielectric properties, heat resistance, chemical resistance, mechanical strength, etc., which can be suitably used as electric / electronic parts in the electric / electronic fields. And a polymer composition having excellent compatibility, and a method for producing the same.

[0002]

[Technical background] Polycarbonate has superior properties in impact resistance, dimensional stability, moldability, etc. compared to polyphenylene oxide, but in terms of electrical insulation, heat resistance, and chemical resistance. It is extremely inferior and has a considerably low elastic modulus. On the other hand, polyphenylene oxide is superior to polycarbonate in terms of electric insulation, heat resistance, and chemical resistance, and has a slightly high elastic modulus, but also in impact resistance, dimensional stability, molding processability, etc. Is inferior.

By blending two or more polymers having different properties as described above, a polymer blend having the characteristics of each polymer has been actively designed, but many polymers are incompatible systems. In the case of an incompatible polymer blend, there is a problem especially in mechanical properties.

Even in the above blend of polycarbonate and polyphenylene oxide, since it becomes an incompatible system, a practical blend of these has not been obtained so far, and the excellent characteristics of both of the above are utilized. The reality is that there is none.

[0005]

An object of the present invention is to solve the compatibility problem in the blend of the above-mentioned polycarbonate and polyphenylene oxide, and to retain the excellent properties originally possessed by polycarbonate and polyphenylene oxide as they are, And a manufacturing method thereof.

[0006]

[Means for Achieving the Object] The inventors of the present invention, in order to achieve the above-mentioned object, have been studying repeatedly, and a polycarbonate excellent in impact resistance, dimensional stability, etc. With excellent polyphenylene oxide,
When blended with a styrene-based copolymer or a divinyl-based compound that should be called a third component, the above-mentioned various properties originally possessed by polycarbonate and polyphenylene oxide are retained as they are, and the compatibility is not only excellent. The inventors have found that a polymer composition having excellent heat resistance can be obtained, and have proposed the present invention.

That is, the polymer composition of the present invention comprises a polycarbonate represented by the general formula (A) of Chemical formula 3,
1 of polyphenylene oxide represented by the general formula (B), a styrene-based copolymer, and a divinyl-based compound
It is characterized by consisting of more than one kind.

[0008]

[Chemical 3]

[0009]

[Chemical 4]

Further, the above-mentioned method for producing the polymer composition of the present invention comprises a polycarbonate represented by the general formula (A), a polyphenylene oxide represented by the general formula (B), and a styrene copolymer. Alternatively, it is characterized in that the divinyl compound is melted and mixed by heating.

The polycarbonate represented by the general formula (A) used in the present invention is preferably the one represented by the structural formula of Chemical formula 5 as a preferable specific example in terms of performance, production, cost and the like.

[0012]

[Chemical 5]

The polyphenylene oxide represented by the general formula (B) is preferably the one represented by the structural formula (6) as a preferable specific example in terms of performance, production, cost and the like.

[0014]

[Chemical 6]

The styrene-based copolymer blended with the above-mentioned polycarbonate and polyphenylene oxide is an epoxy-modified styrene-styrene copolymer as a preferred specific example in terms of its performance, production, cost and the like.
Epoxy-modified styrene-methylmethacrylate copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, styrene-phenylmaleimide copolymer, styrene-polycarbonate copolymer, styrene-methylmethacrylate copolymer, styrene -Butyl methacrylate copolymer and the like can be mentioned. Among them, an epoxy-modified styrene-styrene copolymer and an epoxy-modified styrene-methylmethacrylate copolymer are preferable.

The divinyl compound used in place of or together with the above styrene copolymer is preferably a compound represented by the general formula (C) of Chemical formula 7, particularly its performance. As a preferred specific example in terms of production, cost, etc., 2,6-
Examples include allyl naphthalene dicarboxylate and 2,6-naphthalene dimethacrylate.

[0017]

[Chemical 7]

[0018]

[Chemical 8]

The present invention will be described in more detail. About 1 to 98 parts by weight, preferably about 5 to 95 parts by weight of the polycarbonate represented by the general formula (A) including the structural formula of Chemical formula 5 and the structural formula of Chemical formula 6 Including about 2-98 parts by weight of polyphenylene oxide represented by the general formula (B), preferably about 5-90.
Parts by weight, more preferably about 10 to 80 parts by weight, and one or more of the above-mentioned styrene copolymer and divinyl compound, about 0.1 to 50 parts by weight, preferably about 0.5 to 20 parts by weight.
It is a polymer composition obtained by blending parts by weight, more preferably about 1 to 10 parts by weight.

In this polymer composition, when the amount of the polycarbonate is too large, impact resistance, dimensional stability, molding processability and the like are improved to the same level as or higher than those of the polycarbonate alone, but electrical insulation and heat resistance are improved. , Chemical resistance decreases. On the other hand, if the amount of polycarbonate is too small, electrical insulation, heat resistance, chemical resistance, etc. will be improved to the same level as or higher than those of polyphenylene oxide alone, but impact resistance, dimensional stability, molding processability, etc. descend.

On the other hand, when the amount of polyphenylene oxide is too large, the amount of polycarbonate is relatively decreased, so that the electrical insulating property, heat resistance and chemical resistance are improved, but impact resistance property, dimensional stability, Molding processability and the like decrease. On the other hand, if the amount of polyphenylene oxide is too small, the amount of polycarbonate increases relatively, so that impact resistance, dimensional stability, moldability, etc. are improved,
The electrical insulation, heat resistance and chemical resistance are reduced.

As described above, since polycarbonate and polyphenylene oxide have mutually contradictory properties, by appropriately adjusting the mixing ratio of the two within the above-mentioned range, it is possible to obtain arbitrary electric insulation, dielectric properties and heat resistance. It is possible to obtain the polymer composition of the present invention having properties, chemical resistance, impact resistance, dimensional stability, and moldability.

If the blending amount of the styrene-based copolymer or the divinyl-based compound, which should be called the third component, is too small, the compatibility of the polycarbonate and the polyphenylene oxide decreases, and the mechanical strength of the obtained blended product becomes low. If the amount is too large, the compatibility of the polycarbonate and the polyphenylene oxide may be lowered, and therefore the polymer composition of the present invention has the above range.

The polymer composition of the present invention may contain components other than the above components, for example, a filler, a heat stabilizer, a flame retardant, a coloring agent and a reinforcing agent.

The polymer composition of the present invention can be produced, for example, by a hot melt blending method or a solution blending method. Among them, the solution blending method can be blended at a low temperature and requires no equipment. There are problems that the process is complicated and the yield is low. On the other hand, the melt blending method requires high temperature and requires equipment such as an extruder,
The heat-melt blending method is adopted as the production method of the present invention because it is excellent in productivity and economic efficiency such that the process is simple and a yield of almost 100% can be obtained.

In the production method of the present invention, the above-mentioned polycarbonate, polyphenylene oxide, styrene-based copolymer and divinyl-based compound may be blended with these components at once, but may be blended in any order and combination. You can also To be specific, blend the polycarbonate and the styrene-based copolymer or the divinyl-based compound in advance, and then add the polyphenylene oxide and blend them, or blend the polyphenylene oxide and the styrene-based copolymer or the divinyl-based compound. Then, the polycarbonate may be added thereto and blended, or the polycarbonate and the polyphenylene oxide may be blended in advance, and then the styrene copolymer or the divinyl compound may be added thereto and blended.

At this time, optional components such as the above-mentioned filler, heat stabilizer, flame retardant, colorant, and reinforcing agent may be blended at the same time with polycarbonate, polyphenylene oxide, styrene copolymer or divinyl compound. Alternatively, the blending may be performed at any point in the above order and combination.

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

Preferred blending conditions are, for example, when a kneading mixer is used, the rotation speed of the rotor is about 5 to 150 rpm, preferably about 15 to 100 rpm,
More preferably about 25-60 rpm, the temperature is about 230
~ 380 ° C, preferably about 250-340 ° C, more preferably about 260-320 ° C, blending time about 1-50.
Minutes, preferably about 1.5 to 20 minutes, more preferably about 2 to 10 minutes.

A rotor composition of less than about 5 rpm or above about 150 rpm does not result in a good polymer composition. If the temperature is lower than about 230 ° C, the polycarbonate, polyphenylene oxide, styrene copolymer or divinyl compound will not melt, and if it exceeds about 380 ° C, the components will be decomposed, which is not preferable. When the blending time is less than about 1 minute, sufficient mixing is not performed, and about 50
Even if blending is continued for more than a minute, 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:
Examples thereof include nitrogen gas, argon gas, and helium gas.

The polymer composition blended as described above can be molded into pellets, films or other suitable shapes by a molding machine depending on the purpose.

[0033]

In the present invention, the originally poorly compatible polycarbonate and polyphenylene oxide exhibit good compatibility due to the presence of at least one of a styrene copolymer and a divinyl compound, and are intimately mixed. The polymer blend is in a state and therefore has excellent mechanical properties.

Moreover, the styrene-based copolymer and the divinyl-based compound have excellent electric insulating properties originally possessed by polycarbonate and polyphenylene oxide, respectively.
Does not impair dielectric properties, impact resistance, dimensional stability, molding processability, heat resistance, chemical resistance, etc.

From the above, the polymer composition of the present invention is
Polycarbonate, which retains the excellent properties inherent to polycarbonate, and is a tight polymer blend, and therefore has various excellent properties required for recent engineering plastics. .

[0036]

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, the physical properties of the polycarbonate and polyphenylene oxide used in the following examples are shown in Table 1.

[0037]

[Table 1]

Example 1 Polycarbonate represented by the structural formula of Chemical formula 5 [trade name "NOVAREX 7025A" manufactured by Mitsubishi Kasei Co., Ltd.] 10
g, 10 g of polyphenylene oxide [trade name "Noryl" manufactured by General Electric Company, USA] represented by the structural formula of Chemical formula 6, and an epoxy-modified styrene-methyl methacrylate copolymer [trade name "RASEDA manufactured by Toagosei Chemical Industry Co., Ltd.] 1g of GP-300 "] was heat-melt-blended with a Labo Plastomill mixer [trade name" Labo Plastomil 30C150 type "manufactured by Toyo Seiki Co., Ltd.] under a nitrogen atmosphere at 300 ° C and 50 rpm for 3 minutes. .

Example 2 Heat melting and blending was carried out in the same manner as in Example 1 except that the amount of polycarbonate was 16 g and the amount of polyphenylene oxide was 4 g.

Example 3 Heat melting and blending was carried out in the same manner as in Example 1 except that 4 g of polycarbonate and 16 g of polyphenylene oxide were used.

Example 4 Heat melting blending was performed in the same manner as in Example 1 except that the epoxy-modified styrene-methyl methacrylate copolymer was replaced with the epoxy-modified styrene-styrene copolymer.

Example 5 Heat melting blending was carried out in the same manner as in Example 1 except that the epoxy-modified styrene-methyl methacrylate copolymer was replaced with 2,6-naphthalene dimethacrylate represented by the structural formula (8).

Example 6 Heat melting and blending was carried out in the same manner as in Example 1 except that the epoxy-modified styrene-methyl methacrylate copolymer was replaced with diallyl 2,6-naphthalenedicarboxylate represented by the structural formula (8). .

Example 7 Same as Example 1 except that 1 g of epoxy modified styrene-methyl methacrylate copolymer was replaced with 0.5 g of epoxy modified styrene-methyl methacrylate copolymer and 0.5 g of 2,6-naphthalene dimethacrylate. Was melt-blended.

Comparative Example 1 Heat-melt blending was carried out in the same manner as in Example 1 except that the epoxy-modified styrene-methyl methacrylate copolymer was not used.

For the polymer compositions obtained in the above Examples 1 to 7 and Comparative Example 1, a differential scanning calorimeter [SEI
The glass transition temperature (Tg) was measured with a trade name "DSC-100" manufactured by KO Electronics Co., Ltd.].

Further, the obtained polymer composition was vacuum-pressed [Shibayama Scientific Instruments Co., Ltd. trade name "Vacuum press VP".
-50 "] at 250-300 ° C, diameter about 40m
It was molded into a disk having a thickness of m and a thickness of about 1 mm, and the obtained molded product was measured for dielectric constant and dielectric loss tangent at a frequency of 1 MHz.

Further, according to JIS K 6911, the obtained polymer composition was applied to a guard electrode (outer diameter 80
mm, inner diameter 70 mm) and a main electrode (diameter 50 mm), and the volume resistivity value was measured.

On the other hand, the obtained polymer composition was treated with a compact injection molding machine at 250 to 350 ° C. and a length of 20 m.
m, large diameter 4 mmφ, small diameter 1 mmφ, formed into a dumbbell shape and manufactured by US Custom Scientific Ins.
product name "MINI MAX TE"
With NSIL TESTER CS-183 ",
The tensile modulus, tensile strength and elongation were measured. The above results are shown in Tables 2 to 5.

The chemical resistances of the polymer compositions obtained in Examples 1 to 7 and the polycarbonates and polyphenylene oxides used in Examples 1 to 7 were
Conforms to STM-D543, diameter 50mm, thickness 3
For each sample molded into a disc shape of mm, a weak acid (10% C
H ₃ COOH solution), strong acid _(10% H 2 SO ₄ aqueous solution), a weak alkali (10% aqueous ammonia), strong alkali (10% NaOH aqueous solution), an oil (base oil for automobiles "hereinafter referred to as" hydraulic oil "" ， Grease）, Organic solvent (Ethyl alcohol << Hereinafter referred to as "alcohol"",
Benzene, chloroform, hexane) at 23 ° C,
After immersion for 7 days (immersing in 8 ± 2 ml of each chemical solution per 1 cm ^{2 of} test piece surface area and stirring each chemical solution every 24 hours), discoloration of the surface, corrosion, etc. were judged visually. The results are shown in Table 6.

The compatibility of the polymer components of the polymer compositions obtained in Examples 1 to 7 was evaluated by a scanning electron microscope. As a result, they were uniformly dispersed in the domain diameters shown in Tables 2 to 5. And the compatibility was extremely good.

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

[Table 6]

[0057]

INDUSTRIAL APPLICABILITY The polymer composition of the present invention has excellent compatibility between polycarbonate and polycarbonate, has excellent mechanical properties, and has the original properties of the polycarbonate and the polyphenylene oxide alone. It retains excellent properties as they are. Further, the polymer composition of the present invention has a volume specific resistance value of about 10 ¹⁷ , which is an improved value of about one digit as compared with the volume specific resistance value of 10 ¹⁶ of the polycarbonate alone. Furthermore, the polymer composition of the present invention can be blended with polycarbonate, polyphenylene oxide, a styrene-based copolymer or a divinyl-based compound in any ratio, and has electrical insulation properties and volume depending on the use and purpose as an engineering plastic. Specific resistance value, impact resistance,
It can be provided with chemical resistance, heat resistance, dimensional stability and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Mizoguchi 1134-2, Gongendo, Satte City, Saitama Prefecture Inside the Research and Development Center, Cosmo Research Institute Co., Ltd. (72) Takashi Yoshizawa, 1134-2, Gongendo, Satte City, Saitama Prefecture Cosmo Research Institute Co., Ltd.

Claims (2)

[Claims] 1. A polycarbonate represented by the general formula (A), a polyphenylene oxide represented by the general formula (B), and one or more of a styrene copolymer and a divinyl compound. And a polymer composition. [Chemical 1] [Chemical 2] 2. The method for producing a polymer composition according to claim 1, wherein the polycarbonate, the polyphenylene oxide, and the styrene copolymer or the divinyl compound are heated and melt mixed.