JPS6044535A - Reinforced thermoplastic resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin having excellent mechanical strength, and improved water resistance when the base resin is nylon resin, by reinforcing a thermoplastic resin with glass fibers surface-treated with a mixture of a silane coupling agent and a copolymer of maleic anhydride and an unsaturated monomer. CONSTITUTION:A copolymer of maleic anhydride and an unsaturated monomer (preferably butadiene or styrene) (having an average molecular weight of preferably >=2,000) is added to an alkaline aqueous solution, and mixed with a silane coupling agent (e.g. gamma-amino-propyltriethoxysilane). Glass fibers are treated with the resultant liquid mixture, added to a thermoplastic resin (e.g. nylon, PE, PP, etc.) and formed to obtain the objective reinforced resin.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a glass fiber reinforced thermoplastic resin composition.

Glass fiber reinforced thermoplastic resin (hereinafter referred to as FRTP)
Generally, it has excellent performance in terms of strength, heat resistance, and dimensional stability, and is widely used in various molded products. The present invention has been completed to achieve the object. That is, the present invention resides in a glass fiber-reinforced thermoplastic resin obtained by reinforcing a thermoplastic resin with glass fibers surface-treated with a copolymer of maleic anhydride and an unsaturated monomer and a silane-based coupling agent. I'll go.

In the present invention, unsaturated monomers that form a copolymer with maleic anhydride include styrene, α-methylstyrene,
Examples include butadiene, isoprene, chlorobrene, 2,3-dichlorobutadiene, 1,3-u-ntadiene, cyclooctadiene, methyl acrylate, ethyl thicrylate, methyl methacrylate, ethyl thicrylate, among others, butadiene and styrene. htL. And these precious Iit bodies are 2&! The above may be used in combination.

The maleic anhydride copolymer in the present invention has an average molecular weight of 2
The ratio of maleic anhydride to the unsaturated monomer is preferably 000 or more, and the ratio of maleic anhydride to the unsaturated monomer is not particularly limited. For example, 60 to 75 molar maleic anhydride is preferably used. A copolymer having such a proportion is soluble in an alkaline aqueous solution, and the alkaline substance (alkali metal) used in the aqueous solution.

compounds, ammonia, amines) in the form of salts.

When the ratio of maleic anhydride to the unsaturated monomer is small, the hydrophilicity of the resulting copolymer decreases. 8. The silane coupling agent used in the present invention is as follows:
Any silane coupling agent conventionally used for surface treatment of glass fibers can be used. Specific examples include vinyltrichlorosilane, vinyl-tris-β-methoxyethoxysilane, vinyltriethoxysilane, and γ-aminopropyltriethoxysilanka. One or more types of these coupling agents can be used.

Although the proportions of the maleic anhydride copolymer and the silane coupling agent used can vary over a wide range, it is usually preferable to use, for example, 100 parts by weight of the former and 0.01 to 10 parts by weight of the latter.

The maleic anhydride copolymer and the silane coupling agent are usually mixed in an aqueous medium, and if necessary, an emulsifier or other auxiliary agent, such as a thickener, is added, and a glass fiber is produced using this process. When the glass fiber is surface-treated or dried, a coating consisting of the copolymer and the coupling agent is formed on the surface of the glass fiber.

As the thermoplastic resin reinforced by the above-mentioned surface-treated glass fibers, any thermoplastic resin conventionally used in FRTP can be applied, and specifically, polyolefins such as polyethylene and polypropylene, nylon, polyethylene terephthalate, Examples include polybutylene terephthalate, polycarbonate, acetal resin, polyphenylene oxide, acrylonitrile-styrene copolymer, and the like.

These resins exhibit excellent physical properties such as mechanical strength, such as transverse tensile strength, bending strength, and impact strength, as shown in the following examples, and nylon resins exhibit improved water resistance.

Next, the present invention will be described in detail, but these are representative examples to aid understanding of the present invention, and the present invention is not limited to these examples.

Example 1 A copolymer consisting of maleic anhydride and a comonomer shown in Table 1 below in a molar ratio of approximately 1:1 was added to an ammoniacal aqueous solution (concentrated & 0.5%) and stirred well to obtain a copolymer. γ-aminopropyltriethoxysilane was added to the solution and mixed,
Prepare the processing solution. In this case, the above copolymer (tNjl
The silane compound is used at a ratio of 0.6 parts by weight to 2.8 parts by weight (form).

The above-mentioned surface treatment liquid is applied to glass fibers having a diameter of 13 μm that have been melt-spun into filaments using an applicator installed in the middle of winding them around a rotating drum, and then dried. A glass fiber bundle covered with a coating having a composition consisting of the above copolymer and a coupling agent was obtained.The above glass fiber bundle was cut into a length of 3 cm.
In addition to nylon 6 and Otsu, it was made into a glet according to a conventional method, and this glet was made into a molded product by injection molding. The tensile strength, bending strength, bending modulus and Izot impact strength of this product are shown in Table 1 below. In Table 1, SS indicates the weight difference of the coated solid content (i.e., maleic anhydride copolymer and silane compound) (also abbreviated as SS in Example 2 and below) with respect to the strand solid, i.e., glass fiber. , and GC indicates the glass content, that is, the amount of glass fibers in the reinforced resin in weight percent. This is also abbreviated as GC in Example 2 and below.

Example 2 This example shows that when nylon is used as the reinforcing resin, the water resistance of the resulting resin molded product is significantly improved.

Comonomers copolymerized with maleic anhydride, SS and G
C was shown in Table 2 below, and glass fibers were surface-treated in the same manner as in Example 1, and a reinforced thermoplastic resin was manufactured using this, and its tensile strength was measured. did. The results are shown in Table 2 below.

DRY in Table 2 tensile strength is measured as is for molded products made of glass fiber reinforced resin, while WJliT is measured after immersing the molded products in hot water at -142°C for 20 hours. The retention rate is the value of W, ]l!!T measured value/measured value side constant value.In addition, an example of the tensile strength of a conventional glass fiber-reinforced nylon 6.6 is DRY14.4. , wgT7.1, retention rate 49,
The water resistance of the product according to the present invention is significantly improved. .

Example 3 In this example, holybutylene terephthalate was reinforced.

Comonomers copolymerized with maleic anhydride, SS and G
C was shown in Table 3 below, and red-treated glass fibers were produced in the same manner as in Example 1, and a reinforced resin was produced using the glass fibers. The physical properties of this product are shown in Item 3 below.

In addition, the copolymer used in Experiment No. 1 in Table 3 is maleated polybutadiene.

Example 4 In this example, d-seriethylene terephthalate was strengthened. Comonomer copolymerized with maleic anhydride 1.
SS and GC were as shown in Table 4 below, and glass fibers treated in Table m1 were prepared in the same manner as in Example 1, and a reinforced resin was manufactured using this. Its physical properties are shown in Table 4.

Example 5 This example uses polycarbonate (abbreviated as PC in the table below), polyoxymethylene (abbreviated as POM in the table below), and modified polyphenylene oxide (abbreviated as P in the table below).
(abbreviated as PO), O, and acrylonitrile-styrene copolymer (abbreviated as AS in the table below).

The resin to be reinforced, the comonomer to be copolymerized with maleic anhydride, SS and GS are as shown in Table 5 below, and a surface-treated glass fiber was prepared in the same manner as in Example 1, and using this. Made of reinforced resin 1c'M. Its physical properties are shown in Table 5.

In the examples shown in Examples, polypropylene was reinforced. Comonomer and GC″f copolymerized with anhydrous maleic acid:
Glass fibers as shown in Table 6 below were surface-treated in the same manner as in Example 1, and a reinforced resin was produced using the glass fibers. The physical properties of the product are shown in Table 6 below.

Table 6

Claims (1)

[Claims] A glass fiber-reinforced thermoplastic resin made by reinforcing a thermoplastic resin with glass fibers surface-treated with a copolymer of maleic anhydride and an unsaturated monomer and a silane thread coupling agent.