JPS624344B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an alkali-resistant glass fiber that can be used as a reinforcing material for inorganic hydraulic cement matrices such as cement, cement mortar, and cement concrete with a high alkali content. Conventionally, it has been considered undesirable to use glass fibers such as E-glass fibers and C-glass fibers as reinforcing materials for inorganic hydraulic cement matrices having a high alkali content. This is because the glass fibers are severely eroded by the alkaline components of the cement matrix, and are no longer able to function as a reinforcing material. Therefore, in order to use the above glass fiber as a reinforcing material for an inorganic hydraulic cement matrix with a high alkali content, it is necessary to further improve the alkali resistance. In order to improve the alkali resistance of the above-mentioned glass fibers, the present inventors have conducted intensive studies on various surface treatment agents, and as a result, the present inventors have found that they contain various types of rubber as a main component,
In addition, the surface is treated with a surface treatment agent containing a small amount of an aminosilane coupling agent, and the treatment composition is applied to the surface.
It has been found that the alkali resistance of glass fibers to which 0.5% by weight or more is attached is significantly improved. The alkali-resistant glass fiber of the present invention combines various rubbers with relatively high alkali resistance and an aminosilane coupling agent that has a large effect of imparting water resistance and alkali resistance among various coupling agents that have been conventionally used as a surface treatment agent for glass fibers. and are simultaneously attached to the surface of the glass fiber, and due to the synergistic effect of the above components, very high alkali resistance, which cannot be obtained with conventional treated glass fibers, can be obtained. Rubbers contained as main components of the surface treatment agent used in the production of the alkali-resistant treated glass fibers of the present invention include styrene and butadiene rubber (hereinafter referred to as
(abbreviated as SBR), nitrile-butadiene rubber (hereinafter referred to as
NBR), natural rubber (NR), chloroprene rubber (CR), polyisoprene rubber, butyl rubber, acrylic ester rubber, silicone rubber, ethylene propylene rubber (hereinafter referred to as CR),
(abbreviated as EPR) etc. Among these rubbers,
SBR, NBR, CR, NR, acrylic rubber, silicone rubber, and EPR are particularly preferred because they have excellent alkali resistance and provide treated glass fibers with high tensile strength. The aminosilane coupling agents contained in small amounts in the surface treatment agent used for the alkali-resistant glass fibers of the present invention include γ-aminopropyltriethoxysilane, N-(β-aminoethyl )―
γ-Aminopropyltrimethoxysilane, N-
Examples include (β-aminoethyl)-γ-aminopropylmethyldimethoxysilane. The above surface treatment agents include various rubber latexes, small amounts of aminosilane coupling agents, and various modifiers (softeners, lubricants, antistatic agents, vulcanizing agents, rubber anti-aging agents, vulcanization accelerators) as necessary. etc.) are preferably dispersed in water, but benzene,
The above components may be dissolved in an organic solvent such as toluene or xylene. If the amount of the treatment agent composition attached to the alkali-resistant glass fiber of the present invention is less than 0.5% by dry weight, it cannot be expected to obtain excellent alkali resistance; However, since the contribution rate to alkali resistance becomes small and the cost becomes high, the amount of the treatment agent component attached to the alkali-resistant glass fibers is preferably in the range of 0.5 to 30% by dry weight. The present invention will be explained below with reference to Examples. The alkali resistance evaluation method of this example involves immersing alkali-resistant glass fibers in a calcium hydroxide solution at 60°C adjusted to pH 12 for a predetermined time, washing with 0.1% diluted hydrochloric acid, thoroughly washing with water, and drying the fibers. This was used as a sample for a tensile test. The tensile test was carried out using a Tensilon tensile tester (manufactured by Baldwin Corporation) in a room at a temperature of 20° C. and a humidity of 60%, with a span of 150 mm and a heel speed of 200 mm/min. Note that the glass fibers were immersed in the calcium hydroxide solution with the solution closed tightly to prevent carbonation. Example 1 A heat-cleaned glass cloth was immersed in a treatment agent with the following composition A, and after removing the excess treatment agent with a nip roller, it was heated at 110°C.
Dry for 120 minutes to create a treated glass cloth with a coating amount of 0.51% by weight of the treatment agent. Similarly, B and C
Using the treatment agents of blends D to D, treated glass cloths with adhesion amounts of treatment agents of 5.2% by weight and 10.2% by weight to 19.8% by weight, respectively, are prepared.

[Table] The above-treated glass cloth was cut into samples with a width of 25 mm and a length of 300 mm, and an alkali resistance test was conducted.
The results are shown in Table 1.

[Table] Samples with sample numbers 1 to 4 of Examples have very high initial values of tensile strength and excellent alkali resistance compared to untreated samples and vinyl acetate treated samples of Comparative Examples. Recognize. Example 2 A heat-cleaned glass cloth was immersed in a treatment agent with the following composition, and then, after removing the excess treatment agent with a nip roller, it was heated at 150°C for 15 minutes.
After drying for a minute, a treated glass cloth with a coating amount of 10.3% by weight of the treatment agent was prepared. Ingredient parts by weight NBR latex (Nipol 1571, product of Zeon Corporation) 50 N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane 0.5 Silicone antifoaming agent 0.1 Deionized water 49.4 Width of the above-treated glass cloth Samples of 25 mm and 300 mm in length were cut and tested for alkali resistance. The results are shown in Table 2.

[Table] It can be seen that the sample No. 5 of the example has a very high initial value of tensile strength and is also very excellent in alkali resistance, compared to the untreated sample or the epoxy-treated sample of the comparative example. Example 3 A heat-cleaned glass cloth was immersed in a treatment agent with the following composition, and then, after removing the excess treatment agent with a nip roller, it was heated at 150°C for 15 minutes.
After drying for a minute, a treated glass cloth with a coating amount of 9.2% by weight of the treatment agent was prepared. Ingredient parts by weight Acrylic ester rubber emulsion (Nipol
L×811 Nippon Zeon Co., Ltd. product) 4.0 N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane 0.5 Diethanolamine 2.0 Nonionic surfactant (Solgen TW-60, Dai-ichi Kogyo Seiyaku Co., Ltd. product) 2.0 6N Acetic acid 1.5 parts by weight Deionized water 54.0 The above-treated glass cloth was cut into samples with a width of 25 mm and a length of 300 mm, and an alkali resistance test was conducted. The results are shown in Table 3.

[Table] Sample number 6 of the example has a much higher initial value of tensile strength than the untreated sample of the comparative example.
It can be seen that the alkali resistance is also very good. Example 4 During glass fiber spinning, filaments (thickness 10 μ) were sized with a treatment agent (= sizing agent) of the following composition immediately below the bushing and bundled into one filament with a thickness of 125 g/1000 m (125 tex). The glass strand was dried at 125°C for 6 hours, and the alkali resistance test of the glass strand was conducted. The results are shown in Table 4. Ingredient parts by weight SBR latex (Nipol 2507, Nippon Zeon Co., Ltd. product) 16.0 Nonionic surfactant (Sorgen TW-60 Dai-ichi Kogyo Seiyaku Co., Ltd. product) 2.0 Triethalamine 0.5 6N acetic acid 0.6 γ-Aminopropyltriethoxysilane 0.4 Deionized water 80.5

[Table] It can be seen that the glass strand sample of sample number 7 of the example has extremely superior alkali resistance compared to the vinyl acetate-based sizing treated glass strand of the comparative example. Example 5 A heat-cleaned glass cloth was immersed in a treatment agent with the following composition, and after removing the excess treatment agent with a nip roller, it was heated at 150°C for 15 minutes.
Dry for a minute to create a treated glass cloth with a coating amount of 5.5% by weight. Ingredient parts by weight Silicone emulsion (Toray Silicone)
SH8200, Toray Silicone Co., Ltd. product) 6.0 Catalyst (Toray Silicone SH22T, Toray Silicone Co., Ltd. product) 0.6 γ-Aminopropyltriethoxysilane 0.1 Deionized water 93.3 Use the above-treated glass cloth as a sample with a width of 25 mm and a length of 300 mm. It was cut and tested for alkali resistance. The results are shown in Table 5.

[Table] Example 6 A heat-cleaned glass cloth was immersed in a treatment agent with the following composition, and then the excess treatment agent was removed using a doctor roller, and then dried at 150°C for 30 minutes to determine the amount of treatment agent attached. 12.2% by weight to create a treated glass cloth. Ingredient parts by weight Ethylene propylene rubber (Ep43, manufactured by Nippon Gosei Rubber Co., Ltd.) 10 Ions 0.15 Mercaptobenzothiazole 0.1 Tetramethylthiuramine 0.2 Ingredient parts by weight γ-Aminopropyltriethoxysilane 0.1 Toluene 100 Width 25 mm of the above treated glass cloth The samples were cut into 300mm long samples and tested for alkali resistance. The results are shown in Table 6.

[Table] For further comparison, a heat cleaning cloth was immersed in the processing agent shown below, and then the excess processing agent was removed using a nip roller.
Dry at 150°C for 15 minutes to create a treated glass cloth with a coating amount of 10% by weight. Ingredient weight part E SBR latex (Onoda CXB, Onoda Kenzai Co., Ltd. product) 69.0 Deionized water 31.0 Ingredient weight part F SBR latex (Onoda CXB, Onoda Kenzai Co., Ltd. product) 69.0 γ-glycidoxypropyltrimethoxy Silane 0.6 Deionized water 30.4 Parts by weight of components G SBR latex (Onoda CXB, Onoda Kenzai Co., Ltd. product) 69.0 γ-methacryloxypropyltrimethoxysilane 0.6 Deionized water 30.4 The above treated glass cloth is 25mm wide and 300mm long The samples were cut into samples and tested for alkali resistance. The results are shown in Table 7.

【table】

Claims (1)

[Claims] 1. A rubber emulsion containing the necessary rubber auxiliaries;
1. An alkali-resistant glass fiber, characterized in that a composition comprising a small amount of an aminosilane coupling agent is adhered to the surface of the glass fiber in an amount of 0.5 to 30% by dry weight based on the glass fiber.