JP2001172055A - Glass fiber and glass fiber-reinforced thermoplastic resin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide glass fibers which can improve the tracking resistance and hydrolysis resistance of FRTP molded products, and to provide a glass fiber-reinforced thermoplastic resin using the glass fibers as a reinforcing material. SOLUTION: The glass chopped strand is obtained by producing a bundling agent comprising 3 wt.% of a polytetrafluoroethylene dispersion, 4 wt.% of a phenol novolak type epoxy emulsion, 2 wt.% of a non-yellowing type urethane emulsion, 1 wt.% of γ-aminopropyltriethoxysilane and 90 wt.% of deionized water, coating the bundling agent on the surfaces of glass fibers in a spinning process for bundling 2,000 glass fibers (filaments) (the diameter of the single filament is 13 μm) to form a strand, chopping the formed strand in a length of 3 mm and then drying the chopped glass strand.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a glass fiber and a glass fiber reinforced thermoplastic resin (FR) using the same as a reinforcing material.
TP).

[0002]

2. Description of the Related Art Generally, glass fibers are formed by drawing molten glass from a number of nozzles provided at the bottom of a platinum bushing, and a sizing agent is applied to the surface of each glass fiber (glass filament). After that, several hundred to several thousand pieces are bundled into one strand and then wound.

[0003] In addition, FRTP is obtained by cutting a strand obtained as described above into a predetermined length to form a chopped strand, kneading the resulting strand with a thermoplastic resin (matrix resin) while heating, and then using various molding methods. It is manufactured by molding into a predetermined shape.

[0004] The above-mentioned sizing agent is selected from urethane resins, acrylic resins, epoxy resins, coupling agents, lubricants, antistatic agents in consideration of the adhesiveness to various thermoplastic resins as matrix resins and the fluidity during the kneading process. Contains agents and the like.

[0005]

However, FRTP is
Used in various applications, such as distributor caps, connectors and relay housings as automotive electrical components, connectors and coil bobbins as electrical and electronic components,
It is also used for applications such as sockets. This type of FRTP is required to improve the reliability and durability, that is, the so-called tracking resistance and hydrolysis resistance of an FRTP molded product. Incidentally, the tracking resistance is a characteristic indicating the reliability indicating the difficulty of current flow when a voltage is applied to the FRTP molded article, and the hydrolysis resistance is the exposure of the FRTP molded article to wet heat. This is a characteristic expressing durability showing the strength deterioration at the time.

An object of the present invention is to provide a glass fiber capable of improving the tracking resistance and the hydrolysis resistance of an FRTP molded product, and a glass fiber reinforced thermoplastic resin using the glass fiber as a reinforcing material. It is in.

[0007]

The glass fibers of the present invention are:
It is characterized in that a sizing agent containing a fluorine compound having a fluorine-containing aliphatic chain, an epoxy resin and an aminosilane is applied.

The glass fiber reinforced thermoplastic resin of the present invention is characterized by using glass fibers coated with a sizing agent containing a fluorine compound having a fluorine-containing aliphatic chain, an epoxy resin and aminosilane.

[0009]

The glass fiber of the present invention is coated with a sizing agent containing a fluorine compound having a fluorine-containing aliphatic chain.
Has improved tracking resistance.

The inventor of the present invention has found that the tracking resistance is higher than that of the FRT.
It is a property that is greatly affected by the surface condition of the P molded product.
If there is a contaminant such as electrolyte on the surface of the P molded product,
It is presumed that the tracking resistance is deteriorated because the contaminant forms a conductive path, and the action of the fluorine compound having a fluorine-containing aliphatic chain makes it difficult for the contaminant to adhere to the surface of the FRTP molded article, thereby reducing the resistance. It has been found that tracking performance can be improved. That is, a fluorine compound having a fluorine-containing aliphatic chain is a substance having a property of improving stain resistance, and a glass fiber coated with a sizing agent containing a fluorine compound having a fluorine-containing aliphatic chain on the surface of an FRTP molded product. Is exposed, and furthermore, a fluorine compound having a fluorine-containing aliphatic chain having a low surface energy causes some of its molecules to separate from the glass fiber surface when kneading or molding the glass chopped strand with a thermoplastic resin, and the FRTP molding Transfer to the surface of the product makes it difficult for contaminants to adhere.

Examples of the fluorine compound having a fluorine-containing aliphatic chain include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and perfluoropolymer. A copolymer containing alkylethyl acrylate as one component is suitable.

Further, since the glass fiber of the present invention is coated with a sizing agent containing an epoxy resin and aminosilane, if this is used as a reinforcing material for FRTP,
Has improved hydrolysis resistance. In other words, the inorganic functional group of aminosilane is on the surface of the glass fiber, the organic functional group of aminosilane is the glycidyl group of the epoxy resin, and the glycidyl group of the epoxy resin is highly reactive with the thermoplastic resin. This is because the interfacial adhesive strength is improved.

As the epoxy resin, polyfunctional epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin are preferable.

As the aminosilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane and the like are preferable.

The sizing agent in the present invention may be, if necessary,
Each component such as a urethane resin, an acrylic resin, a lubricant, and an antistatic agent can be included. The amount of the sizing agent attached to the glass fibers is preferably 0.05 to 2% by mass. That is, the adhesion amount of the sizing agent to the glass fiber is 0.05% by mass.
When the amount is less, the effect on tracking resistance improvement and hydrolysis resistance is small, and even if it is more than 2% by mass,
This is because the effect does not increase and it is not economical.

The matrix resin of FRTP of the present invention is not particularly limited, but among them, a thermoplastic polyester resin is preferred. The ratio of the glass fiber to the matrix resin is preferably 5 to 70% by mass, and the glass fiber is desirably used in a dry state.

[0017]

The glass fiber and the glass fiber reinforced thermoplastic resin of the present invention will be described below in detail based on examples and comparative examples. The sizing agent is used in terms of solid content.

Example 1 First, 3% by weight of polytetrafluoroethylene dispersion, 4% by weight of phenol novolak type epoxy emulsion, 2% by weight of non-yellowing type urethane emulsion, 1% by weight of γ-aminopropyltriethoxysilane, A sizing agent consisting of 90% by mass of ionized water was prepared, and then the sizing agent was applied to the surface of the glass fiber in a spinning step of bundling 2,000 glass fibers (filaments) having a diameter of 13 μm into strands. Next, this strand was cut into a length of 3 mm and dried to obtain a glass chopped strand. The amount of the sizing agent adhered to the obtained glass chopped strand was 0.1%.
It was 8% by mass.

30% by mass of this glass chopped strand and 70% by mass of polybutylene terephthalate
After kneading while heating at ℃, and pelletizing according to a conventional method, FRTP is obtained by injection molding the pellets.
A molded article was produced.

Example 2 An FRTP molded article was produced in the same manner as in Example 1 except that a polyvinylidene fluoride emulsion was used instead of the polytetrafluoroethylene dispersion of Example 1.

Comparative Example 1 An FRTP molded article was produced in the same manner as in Example 1 except that the polytetrafluoroethylene dispersion of Example 1 was omitted and the deionized water was changed to 93% by mass. .

Comparative Example 2 An FRTP molded product was produced in the same manner as in Example 1 except that the phenol novolak type epoxy emulsion of Example 1 was omitted and deionized water was 94% by mass.

The comparative tracking index (CTI) and the tensile strength of the thus obtained FRTP molded article under normal conditions and after immersion in hot water were measured. The results are shown in Table 1.

[0024]

[Table 1]

CTI in the table is measured based on the International Electrotechnical Commission (IEC) 112, and the larger the value, the better the tracking resistance. Further, the tensile strength was measured based on ASTM D-638, and indicates that the higher the tensile strength after immersion in hot water, the better the hydrolysis resistance.

As is clear from Table 1, Comparative Example 1 has poor tracking resistance because the sizing agent does not contain a fluorine compound having a fluorine-containing aliphatic chain.
Has poor hydrolysis resistance because the sizing agent does not contain an epoxy resin. In contrast, each of the FRTPs of Examples 1 and 2
The molded article has excellent tracking resistance and hydrolysis resistance.

[0027]

As described above, when the glass fiber of the present invention is used, the tracking resistance and the hydrolysis resistance of the FRTP molded article can be improved.

Further, the glass fiber reinforced thermoplastic resin of the present invention is excellent in tracking resistance and hydrolysis resistance, and thus is particularly suitable for automotive electronic components such as distributor caps, connectors, relay housings, and electric and electronic parts. It is suitable for applications such as connectors, coil bobbins, and sockets.

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Claims (2)

[Claims] 1. A glass fiber which is coated with a sizing agent containing a fluorine compound having a fluorine-containing aliphatic chain, an epoxy resin and an aminosilane. 2. A glass fiber reinforced thermoplastic resin comprising a glass fiber coated with a sizing agent containing a fluorine compound having a fluorine-containing aliphatic chain, an epoxy resin and an aminosilane.