JPH047355A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition improved in compatibility between the resins, molding appearance, etc., by mixing a polycarbonate resin with a functional thermoplastic resin other than that and a specified copolymer. CONSTITUTION:1-60wt.% monomer having a cyclic iminoether group, desirably a 2-oxazoline group (e.g. 2-isopropenyl-2-oxazoline) is copolymerized with 0.01-98.99wt.% vinylaromatic compound (e.g. styrene) and 0.01-98.99wt.% vinyl cyanide compound (e.g. acrylonitrile) to obtain a copolymer (A) of a weightaverage mol.wt. of 3000-300000. 100 pts.wt. mixture of 10-90 pts.wt. polycarbonate resin (B) with 10-90 pts.wt. thermoplastic resin (C) having a functional group selected from among COOH, CN, amino, amide, OH and mercapto and being other than component B is mixed with 0.1-50 pts.wt. component A.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a new thermoplastic resin composition, and more specifically, a resin composition comprising polycarbonate, a thermoplastic resin having a functional group, and a copolymer having a reactive group. relating to things.

[Conventional technology]

Polycarbonate resin, which is a type of thermoplastic resin and is known as engineering plastic, has excellent properties such as weather resistance, creep resistance, and electrical properties, and has a wide range of uses. Improvements in the -layer are desired in terms of paintability, moldability, etc.

On the other hand, carboxyl group, amino group, amide group.

Thermoplastic resins having functional groups such as hydroxyl groups and mercapto groups include polyamide resins, polyester resins, which are also known as engineering plastics,
Examples include polyphenylene sulfide resin. These have features such as heat resistance, impact resistance, and chemical resistance, but improvements in creep resistance, electrical properties, water resistance, etc. are desired.

From this perspective, if polycarbonate resin and thermoplastic resin with other functional groups can be blended to obtain a resin composition that has the features of both polycarbonate resin and other thermoplastic resins, there is a possibility of new applications. can be expected. For example, in Special Publication No. 36-14035,
Attempts have been made to uniformly mix the two in a molten state to complement each other's moldability and physical properties.

[Problems to be Solved by the Invention] However, polycarbonate resins and thermoplastic resins having other functional groups have poor compatibility, and simply melt-mixing them causes phase separation, resulting in poor molding workability.

Moreover, injection molded products exhibit non-uniformity, have a poor appearance, and have the problem of being unsuitable for practical use. In addition, when polyester resins and polyamide resins are simply blended by melting, an exchange reaction occurs between the carbonate bonds in the polycarbonate resin and the ester bonds and amide bonds in the thermoplastic resin, resulting in a decrease in molecular weight, making it difficult to mold. It also causes the problem.

[Means for solving problems]

As a means to prevent this, the use of a compatibilizer may be considered.

According to studies by the present inventors, a monomer mixture comprising a monomer containing a cyclic iminoether group as a reactive group and a specific monomer copolymerizable with the monomer is copolymerized. It has been found that the problems can be solved by using the obtained copolymer as a compatibilizer and as one component in a thermoplastic resin composition.

That is, the present invention includes 10 to 90 parts by weight of a polycarbonate resin (A), a thermoplastic resin other than a polycarbonate resin having a functional group (B
) 10-90 parts by weight, 1-60% by weight of a monomer containing a cyclic iminoether group as a reactive group, 001-98.9% of a vinyl aromatic compound
9% by weight and vinyl cyanide compound 0.01-98.
A copolymer (C) obtained by copolymerizing a monomer mixture containing 99% by weight and having a weight average molecular weight of 3,000 to 300,000 is added to the polycarbonate resin (A) and the thermoplastic resin ( 0.1 to 50 parts by weight per 100 parts by weight of the mixture B).

The polycarbonate resin (A) used in the present invention includes aromatic, aliphatic, and aromatic-aliphatic combination polycarbonate resins obtained, for example, by the phosgene method or the transesterification method. Alternatively, modified polycarbonate resins such as Peter bond copolymers having carbonate bonds and other bonds such as ester bonds, urethane bonds, or siloxane bonds in the main chain are also included.

Carboxyl group, amino group, amide group used in the present invention,
Thermoplastic resins (B) having functional groups such as hydroxyl groups and mercapto groups include polyamide resins, polyester resins, polyphenylene sulfide resins, etc. Examples of polyamide resins include nylon 6, nylon 6.6, and nylon 6.10°. Aliphatic polyamide resins such as nylon 6/12, nylon 11, nylon 12, nylon 4/6, etc.; polyhexamethylene diamine terephthalamide, polyhexamethylene diamine isophthalamide, xylene group-containing polyamide Aromatic polyamide resins, modified products thereof, mixtures thereof, etc. can be used. As the polyester resin, saturated polyesters such as polyethylene terephthalate and polybutylene terephthalate can be used, and random polycondensates of polyester and polyamide can also be used. The polyphenylene sulfide resin contains 70% by weight or more of the following repeating units,
More preferably, a polymer containing 90% by weight or more can be used, and if the content of the repeating unit is less than 70% by weight, heat resistance will be impaired, which is not preferable. Polyphenylene sulfide resin is generally a polymer with a relatively small molecular weight obtained by a manufacturing method typified by Japanese Patent Publication No. 45-3368, and
There are essentially linear and relatively high molecular weight polymers obtained by the production method typified by Japanese Patent Publication No. 52-12240, and polymers obtained by the method described in Japanese Patent Publication No. 45-3368. After polymerization, it is possible to increase the degree of polymerization and use it by heating in an oxygen atmosphere or by adding a crosslinking agent such as peroxide and heating. It is also possible to use the obtained polyphenylene sulfide resin, but because of its excellent toughness,
More preferred are essentially linear and relatively high molecular weight polymers obtained by the production method typified by Japanese Patent No. 2-12240.

The copolymer (C) used in the present invention includes 1 to 60% by weight of a monomer containing a cyclic iminoether group as a reactive group, 0.01 to 98.99% by weight of a vinyl aromatic compound,
0.01 to 98.99% by weight of a vinyl cyanide compound and, if necessary, 0 to 98.9% of a monomer copolymerizable therewith.
A product obtained by copolymerizing 8% by weight is used.

The cyclic iminoether group preferably has the following general formula (1) (where each R is independently hydrogen or an inert substituted hydrocarbon having 18 or less carbon atoms, and n is 1 to 5 ) The monomer containing a cyclic iminoether group is preferably 2-alkenyl-2-oxazoline (where the alkenyl group has 2 to 8, preferably 2 to 4 carbon atoms). It is. Most preferably the monomer is 2-impropenyl-2-oxacillin.

In the copolymer (C), the monomer containing a cyclic iminoether group is used in an amount of 1 to 60% by weight. If it is less than 1% by weight, the compatibility and dispersibility of the polycarbonate resin (A) and thermoplastic resin (B) will be poor (and if it exceeds 60% by weight, it will increase the melt viscosity and cause a decrease in workability and various physical properties, so it is not preferable. .

Examples of vinyl aromatic compounds include styrene, 0-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, and vinylanthracene, preferably styrene, α-methylstyrene is mentioned. These may be used not only as a single type but also as a mixture of two or more types.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.

In the present invention, a vinyl aromatic compound and a vinyl cyanide compound are essential components, and each
It is necessary that the copolymer (C) has a skeleton that can be compatible with the polycarbonate resin (A) by using 1 to 98.99% by weight, preferably 5 to 94% by weight.

Other copolymerizable monomers used as necessary include unsaturated carboxylic acids such as acrylic acid and methacrylic acid;
Alternatively, these esters can be mentioned.

The molecular weight of the copolymer (C) is 300 in terms of weight average molecular weight.
It is preferably from 0 to 300,000; if it is less than 3,000, a resin with the expected physical properties cannot be obtained, and if it exceeds 300,000, the melt viscosity increases, causing a decrease in workability and various physical properties, which is not preferable.

The copolymer (C) can be produced by various methods.

For example, in the solution polymerization method, it can be obtained by copolymerizing a mixture of monomers in a solvent at 40 to 150° C. in the presence of an appropriate radical generator or chain transfer agent. It can also be produced by other generally known suspension polymerization methods and emulsion polymerization methods.

The amount of the copolymer (C) used in the present invention is the amount of the polycarbonate resin (A) and the thermoplastic resin (B) having other functional groups.
) is 0.1 to 50 parts by weight per 100 parts by weight of the mixture; if it is less than 0.1 part by weight, there will be problems with compatibility and dispersion, and moldability will deteriorate; if it exceeds 50 parts by weight, the expected physical properties will be reduced. resin cannot be obtained. In addition, polycarbonate resin (A
) and other functional groups, the efficiency of the thermoplastic resin (B) is 9
It can be used at a ratio of /1 to 1/9, preferably 8/2 to 2/8. If the specific gravity is 9/1 or more or 1/9 or less, a resin that is fully satisfactory in terms of moldability and physical properties cannot be obtained.

Polycarbonate resin (A) of the present invention, thermoplastic resin (
The thermoplastic resin composition consisting of B) and copolymer (C) is a composite material reinforced with fibers such as glass fiber, carbon fiber, and polyamide fiber, and inorganic filler such as silica, alumina, calcium carbonate, talc, mica, and titanium oxide. agents and lubricants,
It can also be used as a composite material with added nucleating agents, pigments, antistatic agents, antioxidants, ultraviolet absorbers, etc.

The copolymer (C) of the present invention can be used by any commonly known method. A method of mixing the copolymer (C) in a solution state with a polycarbonate resin (A) and a thermoplastic resin having a functional group (B), evaporating the solvent, and then melt-kneading the mixture, or a method of mixing the copolymer (C) in a solution state with a polycarbonate resin (A) and a thermoplastic resin having a functional group (B), and then melting and kneading the copolymer (C) in a powder state. ) and ; = Functional group - A method of uniformly mixing and melt-kneading with a thermoplastic resin (B) in a tumbler, Henschel mixer, etc., or a method of melt-kneading by feeding them separately to a melt mixer, etc. is used. .

[Examples] The present invention will be explained below with reference to Examples, but these are merely illustrative and the present invention is not limited thereto. The Izod impact strength in the examples is JIS K7.
The results are for a test piece with a notch according to No. 110 and a thickness of 3.2 mm.

Polycarbonate resin (A
) and other functional group-containing thermoplastic resins (B) were commercially available as shown below.

(A) Polycarbonate resin manufactured by Mitsubishi Gas Chemical ■ Kneepilon S-2000 (B) Thermoplastic resin (B-1) Polyamide resin manufactured by Toshi ■ Amiran CM1007. CMI017, CM
1021. CM1041 (more than nylon 6), CM
3006. CM3007 (Nylon 6/6) (B-2) Polyester resin Polyethylene terephthalate resin Velvet manufactured by Kanebo EFG-6, EFG-7, DFG
-1 Polybutylene terephthalate resin; Toshi ■ 1401-XO6,1101-0G (B-3) Polyphenylene sulfide resin ■ Toblen T-4 (C) Copolymer and comparative copolymer were obtained by the following formulation .

Production Example 1 (C-1) Oxazoline group (5%)-containing styrene-acrylonitrile copolymer: 21! A four-hole glass flask with a stirrer was equipped with a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas blowing tube, and 1260 parts of deionized water and polyvinyl alcohol (P
VA-220E, Kuraray @l! 81) 0.54 part was charged, heated to 80°C under a nitrogen gas atmosphere to dissolve polyvinyl alcohol, and then cooled to 50°C.

Separately, 378 parts of styrene, 135 parts of acrylonitrile, and 27 parts of 2-impropenyl-2-oxazoline were mixed in a separate container, and 2.7 parts of benzoyl peroxide was added to form a uniform monomer solution. The monomer solution obtained in this manner was added to the flask, and the mixture was heated for 300 minutes under a nitrogen gas atmosphere.
After keeping the monomer solution in a suspended state under stirring at rpm for 10 minutes, the internal temperature was raised to 80°C to start polymerization, and then kept at the same temperature for 7 hours to complete polymerization. Ta. The resulting reaction solution was filtered through a 200-mesh wire mesh, thoroughly washed with deionized water, and then dried in a hot air circulation dryer at 80°C for 1 day to obtain a product with a diameter of about 0.21 and a weight average molecular weight of 130.00.
About 500 parts of a granular copolymer (C-1) of No. 0 was obtained.

Production Example 2 (C-2) Styrene-acrylonitrile copolymer containing oxazoline group (1%): In (C-1), the monomer composition in the monomer solution was 399.6 parts of styrene, 135 parts of acrylonitrile, and The same operation as (C-1) was repeated except that 2-impropenyl-2-year-old xacillin was used as 5.4 parts and benzoyl peroxide was used as 27 parts. About 500 parts of copolymer (C-2) was obtained.

Comparative Production Example 1 (C'-1) Epoxy group-containing styrene-acrylonitrile copolymer; (C-1) except that 27 parts of glycidyl methacrylate was used instead of 2-impropenyl-2-oxacillin. The same operation as in 1) was repeated to obtain about 500 parts of a granular copolymer (C'-1) having a diameter of about 0.2 mm and a weight average molecular weight of 125,000.

Comparative Production Example 2 (C'-2) Styrene-acrylonitrile copolymer: Same as (C-1) except that the monomer composition in the monomer solution was 405 parts of styrene and 135 parts of acrylonitrile. Repeat the same operation to obtain a diameter of approximately 0.2m.
m, granular copolymer (C
'-2) Approximately 500 copies were obtained.

Examples 1 to 11 and Comparative Examples 1 to 9 Polycarbonate resin, polyamide resin, and copolymer were blended in the proportions shown in Table 1, premixed in a dry process, and then heated at a cylinder temperature of 250°C using a 40 parts mm extruder. Melt-kneading extrusion was performed under the following conditions, and pellets were obtained by strand cutting. Test pieces were prepared from the obtained pellet sample by injection molding at a molding temperature of 250°C and a mold temperature of 60°C, and the physical properties of the test pieces were evaluated. These results are also shown in Table-1.

Examples 12 to 8 and Comparative Examples 1O to 17 Polycarbonate resin and polyethylene terephthalate resin (PET)
and the copolymer in the proportions shown in Table 2, and after dry premixing, 270 mm
Melt cross-extrusion was performed at a cylinder temperature of °C, and pellets were obtained by strand cutting. For the obtained pellet sample, the molding temperature was 270°C and the mold temperature was 60°C.
Test pieces were prepared by injection molding under the following conditions, and their physical properties were evaluated. These results are also shown in Table-2.

Examples 19-24 and Comparative Examples 18-25 Polycarbonate resin and polybutylene terephthalate resin (PBT)
and copolymer were blended in the proportions shown in Table 3, pre-mixed in a dry process, melt cross-extrusion was performed using a 40φl1lffi extruder at a cylinder temperature of 250°C, and pellets were obtained by strand cutting. Test pieces were prepared from the obtained pellet sample by injection molding at a molding temperature of 250°C and a mold temperature of 60°C, and the physical properties of the test pieces were evaluated. Table these results.
It is also shown in 3.

Examples 25-29Σ and hb-Comparative Examples 26-33 Polycarbonate resin and polyphenylene sulfide resin (PPS
) and copolymer in the proportions shown in Table 4, and after dry premixing, 2
Melt cross-extrusion was performed at a cylinder temperature of 80° C., and a pellet was obtained by strand cutting. For the obtained pellet sample, the molding temperature was 280°C and the mold temperature was 6.
Test pieces were prepared by injection molding at 0°C, and their physical properties were evaluated. These results are also shown in Table 4.

〔Effect of the invention〕

If the copolymer (C) according to the present invention is used, the polycarbonate resin (A) and a thermoplastic resin having other functional groups (
B) can be easily blended, and a new thermoplastic resin composition with a good balance of physical properties, moldability, and appearance of molded products can be obtained, and its applications can be expanded to various industrial fields.

Claims (1)

[Scope of Claims] 1. 10 to 90 parts by weight of polycarbonate resin (A), 10 to 90 parts by weight of thermoplastic resin (B) other than polycarbonate resin having a functional group, containing a cyclic iminoether group as a reactive group 1 to 60% by weight of monomers, 0 vinyl aromatic compounds
．． obtained by copolymerizing a monomer mixture comprising 0.01 to 98.99% by weight and a vinyl cyanide compound of 0.01 to 98.99% by weight, and has a weight average molecular weight of 3,000 to 300,000. Mixture 1 of the copolymer (C) with the above polycarbonate resin (A) and thermoplastic resin (B)
A thermoplastic resin composition comprising 0.1 to 50 parts by weight per 00 parts by weight. 2. The functional group of the thermoplastic resin (B) is a carboxyl group,
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is one or more selected from amino groups, amide groups, hydroxyl groups, and mercapto groups. 3. The thermoplastic resin composition according to claim 1 or 2, wherein the cyclic iminoether group of the copolymer (C) is a 2-oxazoline group. 4. The thermoplastic resin composition according to claims 1 to 3, wherein the vinyl aromatic compound of the copolymer (C) is styrene. 5. The thermoplastic resin composition according to claims 1 to 4, wherein the vinyl cyanide compound of the copolymer (C) is acrylonitrile.