JP3033907B2 - Thermoplastic resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a thermoplastic resin composition, and more particularly, to a resin composition comprising a polycarbonate resin, a polyamide resin, and a copolymer having a reactive group.

[Conventional technology]

Polycarbonate resin, a type of thermoplastic resin, known as engineering plastic, has excellent properties such as weather resistance, creep resistance, and electrical properties, and has a wide range of uses. In terms of sex, etc.
Further improvements are desired. In addition, polyamide resin, also known as engineering plastic, has excellent properties such as moldability, thermal stability, abrasion resistance and solvent resistance, and is widely used for various molded products. Is high, there is a problem in dimensional stability and the like, and the use may be restricted.

From such a viewpoint, if a polycarbonate resin and a polyamide resin are blended to obtain a resin composition having characteristics of both, a possibility of a new use can be expected, and various studies have been made. For example, Japanese Patent Application Laid-Open No. 50-116541 discloses that 5 to 20% by weight of nylon 12 used for an electrical insulator is used.
Blends with 80-95% by weight polycarbonate are disclosed. Japanese Patent Publication No. 52-26936 discloses an adhesive composition containing 5 to 40% by weight of a polycarbonate resin and 60 to 95% by weight of a polyamide resin.

[Problems to be solved by the invention]

The blends disclosed above are useful for their intended purpose. However, in the case of a simple blend by melting, a blend of a polycarbonate resin and an polyamide resin has a low molecular weight due to an exchange reaction between a carbonate bond of the polycarbonate resin and an amide bond of the polyamide resin, and molding is difficult. At present, various physical properties such as strength do not reach the expected levels.

[Means for solving the problem]

As a means for preventing such a situation, use of a compatibilizing agent can be considered.

According to the study of the present inventors, a copolymer obtained by copolymerizing a monomer mixture comprising a monomer having a cyclic imino ether group as a reactive group and a monomer copolymerizable therewith is used. It has been found that the problem can be solved by using a polymer as a compatibilizer as one component in a thermoplastic resin composition.

That is, the thermoplastic resin composition according to the present invention comprises the following copolymer (C) based on 10 to 90 parts by weight of the polycarbonate resin (A) and 90 to 10 parts by weight of the polyamide resin (B).
It is a composition comprising 0.1 to 50 parts by weight.

Copolymer (C): 1 to 60% by weight of a monomer containing a cyclic imino ether group as a reactive group Other monomers copolymerizable therewith (excluding vinyl cyanide compounds) 99 to
A copolymer having a weight average molecular weight of 3,000 to 300,000, obtained by copolymerizing a monomer mixture containing 40% by weight.

The polycarbonate resin (A) used in the present invention includes, for example, aromatic, aliphatic, and combined aromatic-aliphatic polycarbonate resins obtained by a phosgene method or a transesterification method. Alternatively, a modified polycarbonate resin such as a hetero bond copolymer having a carbonate bond and another bond such as an ester bond, a urethane bond or a siloxane bond in the main chain is also included.

The polyamide resin (B) used in the present invention is nylon 6,
Aliphatic polyamide resins such as nylon 6.6, nylon 6.6, nylon 6.6, nylon 11, nylon 12, nylon 4.6, etc .; polyhexamethylene diamine terephthalamide, polyhexamethylene diamine isophthalamide, xylene Aromatic polyamide resins such as group-containing polyamides, modified products thereof, and mixtures thereof are exemplified. Particularly preferred polyamide resins are nylon 6, nylon 6.6 and the like.

As the copolymer (C) used in the present invention, 1 to 60% by weight of a monomer having a cyclic imino ether group as a reactive group, and 99 to 40% by weight of another monomer copolymerizable therewith %
What was obtained by copolymerizing is used.

The cyclic imino ether group preferably has the following general formula (1)
In general formula (1) (Here, each R is independently hydrogen or an inert substituted hydrocarbon having 18 or less carbon atoms, and n is a number of 1 to 5.) As the monomer having a cyclic imino ether group, preferred is Is 2-alkenyl-2-oxazoline wherein the alkenyl group has 2 to 8, preferably 2 to 4 carbon atoms. Most preferably, the monomer is 2-
Isopropenyl-2-oxazoline.

In the copolymer (C), 1 to 60% by weight of a monomer having a cyclic imino ether group is used. If the amount is less than 1% by weight, the compatibility and dispersibility of the polycarbonate resin (A) and the polyamide resin (B) is poor. If the amount exceeds 60% by weight, the melt viscosity increases, and workability and various physical properties are deteriorated.

Other monomers copolymerizable therewith include styrene,
Non-cyanic vinyl aromatic compounds such as o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene; acrylic acid, methacrylic acid, etc. Unsaturated carboxylic acids; or esters thereof. The other copolymerizable monomer is preferably a non-cyanic vinyl aromatic compound.
These copolymerizable other monomers are not limited to one kind,
More than one species may be used in combination.

The molecular weight of the copolymer (C) was 3,000 in weight average molecular weight.
0 to 300,000 is preferable, and if it is less than 3,000, a resin having the expected physical properties cannot be obtained. If it exceeds 300,000, the melt viscosity increases, and workability and various physical properties are deteriorated.

The copolymer (C) can be prepared 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. In addition, it can be produced by a generally known suspension polymerization method or emulsion polymerization method.

The amount of the copolymer (C) used in the present invention is 100% of the mixture of the polycarbonate resin (A) and the polyamide resin (B).
The amount is 0.1 to 50 parts by weight with respect to the parts by weight. If the amount is less than 0.1 parts by weight, there is a problem in compatibility dispersibility and molding processability is deteriorated. The ratio of the polycarbonate resin (A) to the polyamide resin (B) can be used in the range of 9/1 to 1/9, preferably 8/2 to 2/8. When the ratio is 9/1 or more, the abrasion resistance is not sufficient, and when it is 1/9 or less, a resin having sufficiently satisfactory dimensional stability cannot be obtained.

The thermoplastic resin composition comprising the polycarbonate resin (A), the polyamide resin (B) and the copolymer (C) of the present invention is a fiber-reinforced composite material such as glass fiber, carbon fiber, polyamide fiber, silica, alumina, and carbonic acid. It can also be used as a composite material to which an inorganic filler such as calcium, talc, mica, titanium oxide or the like, a lubricant, a nucleating agent, a pigment, an antistatic agent, an antioxidant, an ultraviolet absorber and the like are added.

As a method for using the copolymer (C) of the present invention, a commonly known method can be used. A method in which the copolymer (C) is mixed with the polycarbonate resin (A) and the polyamide (B) in a solution state, and the solvent is evaporated and then melt-kneaded, or together with the polycarbonate resin (A) and the polyamide resin in a powder state. A method of uniformly mixing and melt-kneading with a tumbler, a Henschel mixer or the like, a method of separately supplying the mixture to a melt-kneader, and a method of melt-kneading are used.

〔Example〕

Hereinafter, the present invention will be described with reference to examples. However, these are merely examples, and the present invention is not limited thereto. The taper abrasion test in the examples is based on ASTM D1044, and the molding shrinkage test is based on ASTM D955.

As the polycarbonate resin (A) and the polyamide resin (B) used in Examples and Comparative Examples, commercially available ones were used as described below.

(A) Polycarbonate resin Iupilon S-2000 manufactured by Mitsubishi Gas Chemical Co., Ltd. (B) Polyamide resin Alamine CM1007, CM1017, CM1021, CM104 manufactured by Toray Industries, Inc.
1 (and above nylon 6) The copolymer (C) and the comparative (co) polymer were obtained by the following formulation.

Production Example (C-1) Oxazoline group (5%)-containing polystyrene: A reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas blowing tube were attached to a glass four-necked flask equipped with a stirrer of 2,
1260 parts of deionized water and polyvinyl alcohol (PVA-220
E, Kuraray Co., Ltd.) (0.54 parts) was charged, heated to 80 ° C. in a nitrogen gas atmosphere to dissolve the polyvinyl alcohol, and then cooled to 50 ° C.

Separately, 513 parts of styrene and 2-isopropenyl-2
-27 parts of oxazoline were mixed in a separate container, and 2.7 parts of benzoyl peroxide were added to obtain a uniform monomer solution. The monomer solution thus obtained was added to the flask, and the mixture was kept under a nitrogen gas atmosphere with stirring at 300 rpm for 10 minutes to bring the monomer solution into a suspended state. Then, the temperature was raised to start the polymerization. Thereafter, the temperature was maintained at this temperature for 7 hours to complete the polymerization. The resulting reaction solution was filtered through a 200-mesh wire gauze, washed thoroughly with deionized water, and dried in a hot air circulating drier at 80 ° C. for one day and night. About 500 parts of the combined (C-1) were obtained.

Production Example 2 (C-2) Polystyrene containing oxazoline group (1%): In (C-1), the monomer composition in the monomer solution was 534.6 parts of styrene and 5.4 parts of 2-isopropenyl-2-oxazoline. The same operation as in (C-1) was repeated except that the amount of benzoyl oxide was changed to 27 parts to obtain about 500 parts of a granular copolymer (C-2) having a diameter of about 0.2 mm and a weight average molecular weight of 14,000.

Comparative Production Example 1 (C'-1) Epoxy Group-Containing Polystyrene: Same as (C-1) except that 27 parts of glycidyl methacrylate was used in place of 2-isopropenyl-2-oxazoline in (C-1). Repeat the operation to obtain a diameter of about
0.2 mm, granular copolymer having a weight average molecular weight of 125,000 (C'-
1) About 500 parts were obtained.

Comparative Production Example 2 (C′-2) Polystyrene: The same operation as (C-1) was repeated except that the monomer composition in the monomer solution was changed to 540 parts in (C-1). Thus, about 500 parts of a granular copolymer (C'-2) having a weight average molecular weight of 138,000 and a weight average molecular weight of 138,000 were obtained.

Examples 1 to 8 and Comparative Examples 1 to 10 A polycarbonate resin, a polyamide resin and a (co) polymer were blended in the proportions shown in Table 1 and premixed in a dry system. Was melt-kneaded and extruded under the conditions described above, and pellets were obtained by strand cutting. Test pieces were prepared from the obtained pellet samples by injection molding under the conditions of a molding temperature of 250 ° C. and a mold temperature of 60 ° C., and the physical properties of the test pieces were evaluated. The results are shown in Table 1.

[Effect of the Invention] By using the copolymer (C) according to the present invention, blending of the polycarbonate resin (A) and the polyamide resin (B) becomes easy, and the balance of physical properties and molding processability and appearance of the molded product are improved. A novel thermoplastic resin composition which is good and has particularly excellent wear resistance and dimensional stability can be obtained, and its application can be expanded to various industrial fields.

Continued on the front page (56) References Patent 2852098 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 69/00 C08L 77/00-77/12

Claims (4)

(57) [Claims] 1. A thermoplastic resin obtained by blending 0.1 to 50 parts by weight of the following copolymer (C) with 10 to 90 parts by weight of a polycarbonate resin (A) and 90 to 10 parts by weight of a polyamide resin (B). Composition. Copolymer (C): 1 to 60% by weight of a monomer containing a cyclic imino ether group as a reactive group Other monomers copolymerizable therewith (excluding vinyl cyanide compounds) 99 to 40
A copolymer having a weight-average molecular weight of 3,000 to 300,000, obtained by copolymerizing a monomer mixture containing% by weight. 2. The thermoplastic resin composition according to claim 1, wherein the other monomer contains a non-cyanic vinyl aromatic compound. 3. The thermoplastic resin composition according to claim 1, wherein the monomer mixture comprises only a monomer containing a cyclic imino ether group and a non-cyanic vinyl aromatic compound. 4. The thermoplastic resin composition according to claim 1, wherein the cyclic iminoether group of the copolymer (C) is a 2-oxazoline group.