JPH046665B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to glass fibers for reinforcing plastics. Thermosetting resins such as epoxy resins and phenolic resins, polyolefins such as polyethylene and polypropylene, nylon 6, nylon 6,6
It is well known that glass fibers are mixed into thermoplastic resins such as polyamide resins and acetal resins to significantly improve the strength, dimensional stability, etc. of molded articles made of the resins. The present inventors have conducted extensive research with the aim of further improving the mechanical strength of molded products, and have completed the present invention that achieves this aim. That is, the present invention provides a glass fiber for plastic reinforcement surface-treated with a copolymer of maleic anhydride and an ethylene hydrocarbon or vinyl acetate represented by CnH ₂ n (where n = 2 to 5) and a silane coupling agent. It exists. The present invention will be explained in detail below. In the present invention, the comonomer that forms a copolymer with maleic anhydride is CnH ₂ n (however, n = 2 to
5) is selected from the group consisting of ethylene hydrocarbons (eg, ethylene, propylene, isobutylene, etc.) and vinyl acetate, and two or more of these may be used in combination. Moreover, other unsaturated monomers may be used in combination with the main amount of the above-mentioned comonomers. The ratio of maleic anhydride and the above-mentioned ethylene hydrocarbon or vinyl acetate in the copolymer of the present invention is not particularly limited, but in order to make the resulting copolymer soluble in an alkaline aqueous medium, It is preferable to contain a large proportion of the maleic anhydride component, for example, 30 to 75 mol%.
A copolymer having a proportion within this range is soluble in an alkaline aqueous medium. The alkali components (alkali metal compounds, ammonia, amines) in the aqueous solution transform it into a salt form. When the ratio of maleic anhydride used to the ethylene hydrocarbon or vinyl acetate becomes smaller, the degree of hydrophilicity of the resulting copolymer decreases. For such materials, an emulsifier can be added and the glass fibers can be surface-treated in the form of an emulsion. As the silane coupling agent used in the present invention, any silane coupling agent conventionally used for surface treatment of glass fibers can be used. For example, it may have at least one organic group directly bonded to a silicon atom, and may further bond a halogen atom such as chlorine. The organic groups mentioned above include alkyl groups such as methyl, ethyl, propyl, and hexyl, alkenyl groups such as vinyl, cycloalkyl groups such as cyclohexyl, alkoxy groups such as ethoxy, or these organic groups have amino substituents. Examples include those that have. Specific examples include vinyltrichlorosilane, vinyl-tris-β-methoxyethoxysilane, vinyltriethoxysilane, and γ-aminopropyltriethoxysilane. One or more types of these coupling agents may be used. The proportions of the maleic anhydride copolymer and the coupling agent to be used can vary over a wide range, but it is usually preferable to use, for example, 100 parts by weight of the former to 0.01 to 10 parts by weight of the latter. The maleic anhydride copolymer and the silane coupling agent are mixed in an aqueous medium, and if necessary, an emulsifier or other auxiliary agent such as a thickener is added, and with this, glass fibers are spun and manufactured. When applied during the process of manufacturing or after being manufactured and dried, a coating consisting of the above-mentioned copolymer and coupling agent is formed on the surface of the glass fiber. The glass fibers of the present invention obtained as described above include polyolefins such as polyethylene and polypropylene, polyamides such as nylon 6,6 and nylon 6, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, acetal resin,
It is used to strengthen thermoplastic resins such as polyphenylene oxide and acrylonitrile-styrene copolymers, and can produce molded products with excellent physical properties in terms of tensile strength, bending strength, and impact strength. The glass fiber reinforced nylon of the present invention also has excellent water resistance. Furthermore, the glass fibers of the present invention can also be used to strengthen thermosetting resins. Next, examples of the present invention will be described, but these are representative examples for helping understanding of the present invention, and the present invention is not limited by these examples. Example 1 A copolymer consisting of maleic anhydride and a comonomer shown in Table 1 below in an approximately 1:1 molar ratio was added to an ammoniacal aqueous solution (concentration 0.5%) and stirred well.
γ-Aminopropyltriethoxysilane is added to the obtained liquid and mixed to prepare a glass fiber surface treatment liquid. In this case, the silane compound was used at a ratio of 0.6 parts by weight to 2.0 parts by weight of the above copolymer (as solid content). The above surface treatment solution was applied to glass fibers with a diameter of 13 μm that were melt-spun into filaments.
This was applied and bundled using an applicator provided during winding on a rotating drum, and then dried to obtain a fiber bundle covered with a coating composed of the above-mentioned copolymer and a silane coupling agent. Next, the above glass fiber bundle was cut into a length of 3 mm, added to nylon 6,6, and formed into pellets according to a conventional method, and the pellets were made into a molded product by injection molding. The tensile strength, flexural strength, flexural modulus, and Izod impact strength of this product are shown in Table 1 below. In Table 1, SS is strand solid,
In other words, it shows the weight percent of the coated solid content (total amount of maleic anhydride copolymer and silane coupling agent) with respect to the glass fiber (in Example 2 and below, SS
). Further, GC indicates the glass content, that is, the amount of glass fibers in the reinforced resin in weight% (this is also abbreviated as GC in Example 2 and below).

[Table] Example 2 This example shows that when nylon 6,6 is used as the reinforcing resin, the resulting resin molded product has a high water resistance value. Comonomer copolymerized with maleic anhydride, SS
and GC as shown in Table 2 below, and surface-treated glass fibers were prepared in the same manner as in Example 1, and a reinforced resin was produced using the glass fibers, and the tensile strength of the fibers was measured. The results are shown in Table 2.

[Table] In terms of tensile strength, DRY is the value measured by directly measuring the molded product made of glass fiber reinforced resin, WET is the value measured after the molded product is immersed in hot water at 142℃ for 20 hours, and the retention rate is the value measured after immersing the molded product in hot water at 142℃ Measured value/DRY measured value, which indicates the degree of water resistance. In addition, an example of the tensile strength of conventional glass fiber-reinforced nylon 6,6 is
DRY 14.4, WET 7.1, retention rate 49, and the water resistance improved by the present invention is remarkable. Example 3 This example shows the case where polybutylene terephthalate is used as the resin to be reinforced. Comonomer copolymerized with maleic anhydride, SS
and GC as shown in Table 3 below, and surface-treated glass fibers were prepared in the same manner as in Example 1, and a reinforced resin was manufactured using the glass fibers. The physical properties of the obtained product are shown in Table 3.

[Table] Example 4 In this example, polyethylene terephthalate (abbreviated as PET in the table below) was used as the resin to be reinforced.
Modified polyphenylene oxide (PPO in the table below)
(abbreviated as AS) and acrylonitrile-styrene copolymer (abbreviated as AS in the table below). Comonomer copolymerized with maleic anhydride, SS
and GC as shown in Table 4 below, and otherwise surface-treated glass fibers were prepared in the same manner as in Example 1, and a reinforced resin was manufactured using the glass fibers. The physical properties of the obtained product are shown in Table 4.

[Table] Example 5 In this example, polypropylene was reinforced. Comonomers copolymerized with maleic anhydride and GC were shown in Table 5 below, and surface-treated glass fibers were prepared in the same manner as in Example 1, and a reinforced resin was manufactured using the same. Table 5 shows the physical properties of the obtained product.

【table】

Claims (1)

[Claims] 1 Maleic anhydride and CnH ₂ n (however, n = 2 ~
5) A glass fiber for reinforcing plastics surface-treated with a copolymer with ethylene hydrocarbon or vinyl acetate and a silane coupling agent.