JPS6056753B2 - thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin composition.
The present invention relates to thermoplastic resin compositions with significantly improved chemical and mechanical properties.

2. Description of the Related Art Conventionally, thermoplastic resins such as polycarbonate resins and polystyrene resins have been widely used in mechanical parts, electrical parts, and the like due to their excellent moldability.

However, this thermoplastic resin cannot be said to have sufficient mechanical properties or thermal properties, and improvement thereof is desired.

On the other hand, although polyphenylene oxide has extremely good mechanical properties, it generally has poor moldability and somewhat poor impact resistance.

Therefore, by mixing thermoplastic resins such as polycarbonate resins and polystyrene resins with polyphenylene oxide, it is possible to improve the shortcomings of both and improve the mechanical and chemical properties and processability of the polymer. It is being done.

However, in these mixtures, the fluidity of polyphenylene oxide and the compatibility with thermoplastic resins are insufficient, making it difficult to knead, making it difficult to obtain a uniform kneaded product, and the physical properties are also poor. It was not something to be satisfied with. Furthermore, in recent years, special methods such as solution blending using a common solvent, synthesis of polyphenylene oxide in the presence of a styrene polymer, or blend polymerization in which a styrene polymer is synthesized in the presence of polyphenylene oxide have been developed. Alternatively, methods using low molecular weight oligophenylene oxide have been proposed.

However, these methods have drawbacks such as poor compatibility, resulting in loss of transparency of the resulting mixture, and insufficient improvement in physical properties. The present inventors have conducted extensive research in order to overcome the drawbacks of the above-mentioned conventional techniques and develop a thermoplastic resin composition with excellent physical properties.

As a result, a specific block copolymer already developed by the present inventors (Japanese Unexamined Patent Publication No. 182318/1983) or a block copolymer of the same type with a higher or lower degree of polymerization than this polymer was blended into a thermoplastic resin. They discovered that the object could be achieved by doing the following, and completed the present invention. That is, the present invention comprises polycarbonate resin and/or polystyrene resin in an amount of 20 to 20 parts by weight and (B) the general formula (
In the formula, R is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, -0-, -S-, -SO2-, or -CO-, Y1 and Y2 are hydrogen or halogen, and a and b are 1 An integer of ~4, Ql, Q2, Q3, Q4 are hydrogen, halogen, or an alkyl group, M, nl and N2 are integers of 2 or more.

) A thermoplastic resin composition comprising 80 to 2% by weight of a block copolymer represented by the following formula is provided.

As mentioned above, component (4) constituting the composition of the present invention is polycarbonate resin (PC), polystyrene resin, or a mixture thereof. Here, examples of the polystyrene resin include styrene polymers such as general purpose polystyrene (GPPS), high impact polystyrene (HIPS), styrene-acrylonitrile copolymer, and acrylonitrile-butadiene-styrene copolymer. Next, component (B) of the composition of the present invention is the general formula (
The block copolymer represented by 1) has repeating units m≧
2 polycarbonate blocks x and repeating units Nl,n
Y consisting of 2≧2 polyphenylene oxide blocks Y
-XY type block copolymer, which is a novel block copolymer that essentially has various properties as polycarbonate.

In particular, repeating unit m = n ~ 40 to Nl, n2 = 2 ~ 200
Preferably. The production of the block copolymer represented by the general formula (1) is described in JP-A-57-18231.
This can be carried out by the method disclosed in Japanese Patent No. 8. Further, during this production, the degree of polymerization M and nl of each repeating unit of the block copolymer can be adjusted by appropriately selecting conditions. The composition of the present invention contains 20 to 20 parts by weight of a polycarbonate resin and/or a polystyrene resin as the above-mentioned component (4) and (
It is obtained by blending 80 to 2% by weight of a block copolymer represented by general formula (1) as component B.
In addition to component (4) and component (B), the composition of the present invention may optionally contain stabilizers, colorants, flame retardants, or reinforcing agents such as glass fiber or carbon fiber, as well as talc, calcium carbonate, wood, etc. Fillers such as powders can be added.

The composition of the present invention can be obtained by sufficiently mixing component (4) and component (B) as well as other desired components. , a melt-kneading method using an extruder, solution mixing, etc. may be used.

The composition of the present invention thus obtained has significantly improved mechanical properties, thermal properties, and chemical resistance while retaining the excellent properties of a thermoplastic resin, and has extremely good transparency. be.

In addition, the composition of the present invention allows easy mixing of each component, and
A product with high uniformity can be obtained, and therefore there are no problems such as surface layer peeling. Therefore, the composition of the present invention can be widely and effectively used in the fields of mechanical parts, electrical parts, daily necessities, etc.

Next, the present invention will be explained in more detail with reference to Examples.

Reference Example 1 [Manufacture of bisphenol A oligomer] In a jacketed stirring tank equipped with 3 swept blades, 1.6N strength soda aqueous solution 15e and bisphenol A 263Oy
was added, mixed and dissolved, and methylene chloride 7e was further added thereto.

Then, phosgene was bubbled into it at a rate of 1.1 k9/hour while stirring. The reaction temperature was kept below 30°C by passing cooling water through the jacket, and the pH reached 11.5 after 90 minutes.
The phosgene injection was discontinued at the point when After the stirring was stopped and the mixture was left standing to separate the reaction solution into two layers, the water in the upper layer was separated and removed to obtain a bisphenol A polycarbonate oligomer. The number average molecular weight of this oligomer was 750. Reference example 2 [Manufacture of polyphenylene oxide] 2,6-dimethylphenol 1000V1 toluene 92
0m11 methanol 3700m11 Cuprous chloride 20' and pyridine 200ml were charged into a 10e reactor, and oxygen gas was blown in at a rate of 1.5e1 min for 3 hours at room temperature.
A time reaction was performed.

After the reaction, the resulting precipitate was filtered, washed with methanol containing a small amount of hydrochloric acid, and dried to obtain polyphenylene oxide.
The yield of the polymer was 82%, the number average molecular weight was 2650 (two molecules), and ηInh=0.10. Reference Example 3 Production of polyphenylene oxide] 2,6-dimethylphenol 1000fI1 toluene 1
The procedure was carried out according to Reference Example 2 using 700 ml of methanol, 250,077!11 methanol, 20 f of cuprous chloride, and 200 mt of pyridine to obtain polyphenylene oxide.

The yield of the polymer was 87%, the number average molecular weight was 4800 (40-mer), and ηIrtl=0.17. Reference Example 4 [Production of block copolymer] Polyphenylene oxide (PP) obtained in Reference Examples 2 and 3
O) in chloroform (ethanol removed by washing with water) 80
It was dissolved in mt.

To this, 10 mt of the methylene chloride solution of the bisphenol A oligomer (bischloroformate) obtained in Reference Example 1 was added.
and bisphenol A 2N strength soda aqueous solution 30
Add m1 to make an emulsion, then 10 more! A polycondensation reaction was carried out by adding triethylamine (No. 9) and stirring for three times. After the reaction is complete, dilute with 200 ml of chloroform, wash with 500 ml of water, 300 ml of 0.01 N aqueous sodium chloride solution, 300 ml of water, 300 ml of 0.01 N aqueous hydrochloric acid solution, and 300 ml of water, then separate the organic layer and remove calcium chloride. The moisture was removed. Then 3-8
After standing for a period of time, it was filtered and the solvent was distilled off to obtain a transparent polymer.
The results are shown in Table 1. The obtained transparent polymer 2y was dissolved in 30 ml of methylene chloride and allowed to stand for 6 hours, but there was no precipitate, confirming that there was no polyphenylene oxide homopolymer in the produced polymer.

Examples 1 and 2 and Comparative Example 1 According to the formulations shown in Table 2, a thermoplastic resin and a block copolymer or polyphenylene oxide were dissolved in chloroform to make a solution of about 7% by weight, and a 200 μm solution was prepared on a glass plate.
A casting film was obtained.

The physical properties of this product are shown in Table 2. Examples 3 and 4 After dissolving and mixing a thermoplastic resin and a block copolymer in chloroform according to the formulations shown in Table 2, the chloroform was removed and dried, and the mixture was further heated at a temperature of 25 (range) and a pressure of 100 k9 using a press. A film of 300μ was obtained under the condition of 1 coat per hour.

The physical properties of this product are shown in Table *'''2. Comparative Examples 2 to 6 Table 2 shows various physical properties of injection molded products as samples.

Examples 5 to 10 and Comparative Examples 7 to 9 After producing pellets according to the formulations shown in Table 3, test pieces were produced by injection molding.

Claims (1)

[Claims] ▲ Numerical formulas, chemical formulas, tables, etc.
, Y_1 and Y_2 are hydrogen or halogen, a
and b is an integer from 1 to 4, Q_1, Q_2, Q_3, Q
_4 is hydrogen, halogen or alkylene group, m, n_1
and n_2 is an integer of 2 or more. ) A thermoplastic resin composition comprising 80 to 2% by weight of a block copolymer represented by: