JPS5824386B2 - Alkali-resistant treated glass fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to alkali-resistant treated glass fibers that can be used as reinforcing materials for inorganic hydraulic cement matrices such as cements with high alkali content, cement mortars, and cement concretes.

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 were significantly eroded by the alkaline components of the cement matrix, making them impractical as reinforcing materials.

Therefore, in order to use the glass fiber as a reinforcing material for inorganic hydraulic cement IJTx 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 conducted extensive studies on various surface treatment agents, and as a result, the present inventors discovered a method that contains various rubbers as a main component, and a small amount of an aminosilane-based or mercaptosilane-based coupling agent. It has been discovered that the alkali resistance of glass fibers treated with a surface treatment agent containing 0.5% by weight or more of the treatment agent composition on the surface is extremely excellent.

The alkali-resistant treated glass fiber of the present invention is based on various rubbers with relatively high alkali resistance and aminosilane-based which has a large effect of imparting water resistance and alkali resistance among various coupling agents conventionally used as surface treatment agents for glass fibers. Alternatively, a mercaptosilane coupling agent is attached to the surface of the glass fiber at the same time, and due to the synergistic effect of the above components on alkali resistance, it has extremely high resistance that cannot be obtained with conventionally treated glass fibers. It is characterized by being alkaline.

Rubbers contained as main components of the surface treatment agent used in the production of the alkali-resistant treated glass fiber of the present invention include styrene, butadiene rubber (hereinafter abbreviated as SBR), nitrile-butadiene rubber (hereinafter abbreviated as NBR), natural rubber (
(hereinafter abbreviated as NR), chloroprene rubber (hereinafter abbreviated as CR), polyisoprene rubber, butyl rubber, acrylic ester rubber, silicone rubber, ethylene propylene rubber (
(hereinafter abbreviated as EPR), etc.

Among these rubbers, SBR, NBR, CR, NR, acrylic acid rubber, silicone rubber, and EPR are particularly desirable because they have excellent alkali resistance and provide treated glass fibers with high tensile strength.

The aminosilane or mercaptosilane coupling agent contained in a small amount in the surface treatment agent used in the production of the alkali-resistant treated glass fiber of the present invention is γ-aminopropyltriethoxy, which has been conventionally used as a coupling agent for glass fiber. Silane, N-(β-aminoethyl)-
Examples include γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, and γ-mercaptopropyltrimethoxysilane.

The above surface treatment agents include various rubber latexes, a small amount of aminosilane-based or mercaptosilane-based coupling agents, and various modifiers (softeners, lubricants, antistatic agents, vulcanizing agents, rubber anti-aging agents) as needed. vulcanization accelerator, vulcanization accelerator, etc.) dispersed in water.

Although preferred, the above components may be dissolved in an organic solvent such as benzene, toluene, or xylene.

If the amount of the treatment agent component attached to the alkali-resistant treated glass fiber of the present invention is less than 0.5% by weight, it cannot be expected to obtain excellent alkali resistance.

In addition, even if the amount is more than 30% by weight, the contribution to alkali resistance will be small and the cost will be high.
The amount of the treatment agent component deposited on the alkali-resistant treated glass fiber is preferably in the range of 0.5 to 30% by weight.

The present invention will be explained below with reference to Examples.

The alkali resistance evaluation method of this example was to immerse the alkali resistance treated glass fiber in a 60°C calcium hydroxide solution adjusted to pH=12 for a predetermined time, wash it with 0.1% dilute hydrochloric acid, and then rinse thoroughly with water. .

The post-dried sample was used as a tensile test sample.

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 1501 m and a head speed of 200 II.
/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 of the following composition A, then sandwiched between nip rollers to remove excess treatment agent, and dried at 110°C for 120 minutes.
A treated glass cloth with a coating amount of treatment agent of 0.51% by weight is prepared.

Similarly, B. Treated glass cloth with a coating amount of treatment agent of 5.2% by weight and 10.2% by weight to 19.8% by weight, respectively, is prepared using treatment agents of C to 10% by weight.

The above-mentioned 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 the table below. It can be seen that the samples of sample numbers 1 to 4 of the examples have very high initial values of tensile strength and are also very excellent in alkali resistance, compared to the untreated samples to the vinyl acetate treated samples of the comparative examples.

Example 2 A common glass cloth was dipped in a treatment agent with the following composition,
Next, after removing the excess treatment agent with a nip roller, it was dried at 110°C for 120 minutes until the amount of treatment agent attached was 1.
0.2% by weight treated glass cloth The treated glass cloth described above was cut into samples with a width of 25 mm and a length of 300 mrrt, and an alkali resistance test was conducted.

The results are shown in the table below. create a

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 polyester-treated sample of the comparative example.

Example 3 A heat-cleaned glass cloth was immersed in a treatment agent of the following composition, then placed between nip rollers to remove excess treatment agent, and dried at 150° C. for 15 minutes until the amount of treatment agent attached was 10. A 3% by weight treated glass cloth is prepared.

The above-mentioned 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 the table below.

It can be seen that the sample No. 6 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 4 A heat-cleaned glass cloth was immersed in a treatment agent of the following composition, then placed between nip rollers to remove excess treatment agent, and dried at 150° C. for 15 minutes until the amount of treatment agent attached was 9. A 2% by weight treated glass cloth is prepared.

The 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 the table below. Sample number 7 in the example is:
It can be seen that the initial value of the tensile strength is very high and the alkali resistance is also very excellent compared to the untreated sample of the comparative example.

. Example 5 During glass fiber spinning, a filament (thickness 10μ
) is sized and bundled into a single piece with a thickness of 125 grams/
A glass strand of 1000 ml (1000 ml) was dried at 125° C. for 6 hours, and an alkali resistance test of the glass strand was conducted.

The results are shown in the table below. It can be seen that the glass strand sample of Sample No. 8 of the Example has much better alkali resistance than the vinyl acetate-based sizing-treated glass strand of the Comparative Example.

Example 6 A heat-cleaned glass cloth was immersed in a treatment agent of the following composition, then placed between nip rollers to remove excess treatment agent, and dried at 150° C. for 15 minutes until the amount of treatment agent attached was 10. A 0% by weight treated glass cloth is prepared.

The above-mentioned 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 the table below. Example 7 A heat-cleaned glass cloth was immersed in a treatment agent of the following composition, then placed between nip rollers to remove excess treatment agent, and dried at 150° C. for 15 minutes until the amount of treatment agent adhered was 9. An 8% by weight treated glass cloth is made.

The 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 the table below. Example 8 A heat-cleaned glass cloth was immersed in a treatment agent with the following composition, and then the excess treatment agent was removed by nip rollers, and the cloth was dried at 150°C for 15 minutes until the amount of treatment agent attached was 5. .5% by weight treated glass cloth is prepared.

The above-mentioned 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 the table below. Example 9 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, resulting in an adhesion amount of treatment agent of 12.2 % by weight to create a treated glass cloth.

*Width 25mm of the above treated glass cloth
Samples were cut into 300 mm long samples and tested for alkali resistance.

The results are shown in the table below. For further comparison, a heat cleaning cloth was immersed in the processing agent described below, and then the excess processing agent was removed using a nip roller.
It is dried at 150° C. for 15 minutes to produce a treated glass cloth with a coating amount of 10% by weight of the treatment agent.

E SBR latex (Onoda CXB, Onoda Kenzai product) 69.0 deionized 31.0F SB
R latex (Onoda CXB, Onoda Kenzai product) 69.0γ
, glycidoxypropyltrimethoxysilane 0.
6 Deionized water 30.4G S
BR latex (Onoda CXB, Onoda Kenzai product) 69.0γ
, methacryloxypropyltrimethoxysilane 0.6 deionized water
30.4 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.

Claims (1)

[Claims] 1. An alkali-resistant treated glass fiber characterized by having a composition containing rubber as a main component and a small amount of an aminosilane-based or mercaptosilane-based coupling agent adhered to the surface of the glass fiber in an amount of 05 to 30% by weight. .