JPH0930840A - Glass fiber and manufacturing method thereof - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To obtain a glass fiber having excellent strength, water resistance, and durability by improving the adhesion between the glass fiber and the resin, and between the glass fibers. SOLUTION: A compound obtained by mixing an alkoxysilane and / or a hydrolyzate thereof with an organic compound having two or more functional groups capable of reacting with a hydroxyl group obtained by hydrolyzing the alkoxysilane and water. Coated glass fiber formed by coating glass fiber.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a glass fiber and a method for producing the same.

Glass fiber is a method of drawing molten glass into thin pieces.
It is a fibrous material made by stretching and rapid solidification. This
Silane couplers (typically RS
iX _Three : X is a hydrolyzable group and R is a functional group)
Glass-treated, mixed with resin, glass fiber reinforced resin, glass
Used as a heat insulating and heat retaining material by mixing fibers
You. However, the binding and affinity between glass fiber and resin,
Insufficient bonding strength between lath fibers, strength, water resistance, durability
Insufficiency may cause problems.

[0003]

Therefore, the present inventor has earnestly studied in order to improve the adhesion between the glass fiber, the resin, and the glass fibers, and arrived at the present invention.

[0004]

That is, the present invention relates to an organic compound having at least two functional groups capable of reacting with a hydroxyl group produced by hydrolyzing an alkoxysilane in an alkoxysilane and / or its hydrolyzate, and water. 5 to 300 parts by weight of water is added in advance to 100 parts by weight of the coated glass fiber obtained by coating the glass fiber with the compound obtained by mixing
After adjusting the pH to 3 or less with an inorganic acid and / or an organic acid and stirring for 1 to 180 minutes, water is further added to adjust the pH to more than 3 and 5 or less,
Further, an organic compound having two or more functional groups capable of reacting with a hydroxyl group generated by hydrolyzing an alkoxysilane is blended, and the resulting blend is coated on glass fiber to produce a coated glass fiber. Method.

Hereinafter, the present invention will be described in detail. First, as the alkoxysilane in the present invention, tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, or tetrapropoxysilane is usually used. As the hydrolyzate of these alkoxysilanes, for example, a partially hydrolyzed condensate (oligomer) obtained by partially hydrolyzing and condensing these can be used.

The hydrolysis reaction itself for obtaining the oligomer can be carried out by a known method. For example, a predetermined amount of water is added to the above tetraalkoxysilane to distill off by-produced alcohol in the presence of an acid catalyst. However, the reaction is usually performed at about room temperature to 100 ° C. The alkoxysilane is hydrolyzed by this reaction, and a liquid silicate oligomer is obtained by the condensation reaction.

In order to further improve the adhesion to glass fiber, tetraalkoxysilane among alkoxysilanes,
Of these, tetramethoxysilane is particularly preferable.

The tetramethoxysilane oligomer (hereinafter referred to as "tetramethoxysilane oligomer") obtained by the above hydrolysis reaction usually has an average degree of polymerization of 2 to 2.
About 8 and most of them are 3 to 7 transparent liquid substances. The degree of hydrolysis can be appropriately adjusted depending on the amount of water used, and the theoretical amount of water necessary for hydrolytically condensing all the hydrolytically condensable groups of the alkoxysilane, that is, the mole of the hydrolytically condensable group. It is expressed as a percentage of the actual amount of added water with respect to 1/2 mole of water. In the present invention,
Usually, an oligomer having a hydrolysis rate of about 20 to 80%, preferably about 30 to 60% is preferable because it is easy to handle without problems such as gelation.

Tetramethoxysilane thus obtained
The oligomer usually contains about 2 to 10% of the monomer. Since the monomer of tetramethoxysilane is highly toxic and is associated with the risk of eye damage, poisoning, etc., the monomer removal is carried out by flash distillation so that the content of the monomer is 1% by weight or less, preferably 0.3% by weight or less. It is desirable to carry out by vacuum distillation or the like.

The water used in the present invention may be tap water, but dechlorinated water is preferably used. By using dechlorinated water, the corrosion resistance of the coating film formed on the glass fiber becomes more excellent. The amount of water to be added to the alkoxysilane and / or its hydrolyzate is usually 200 to 100,000 parts by weight, preferably 3 parts by weight, per 100 parts by weight.
50 to 35,000 parts by weight.

If the amount is less than 200 parts by weight, the storage stability of the coating solution tends to be poor, and if it exceeds 100,000 parts by weight, the thickness of the film coated on the glass fiber is too thin, which is not preferable. In the method of mixing the above components, for example, 5 to 300 parts by weight of water is first added to 100 parts by weight of alkoxysilane and / or its hydrolyzate, and the pH is adjusted to 3 or less with an inorganic acid or an organic acid. At a pH of 3 or higher, it is difficult to dissolve the alkoxysilane and / or its hydrolyzate in water, and it is easy to separate it from water. It is preferable to stir upon blending. A stirring time of about 1 to 180 minutes is sufficient. Once a clear concentrate is obtained, dilute with any amount of water. Considering the storage stability of the resulting liquid composition,
The pH is preferably 5 or less. By mixing the alkoxysilane and / or its hydrolyzate with water by such a method, a large amount of hydroxyl groups can be formed in the alkoxysilane and / or its hydrolyzate, and the organic compound described below It is possible to obtain a coating liquid having particularly excellent reactivity, excellent adhesion to glass fiber, and excellent storage stability in the liquid.

In the present invention, the alkoxysilane and / or its hydrolyzate is provided with a functional group capable of reacting with a hydroxyl group produced by hydrolyzing the alkoxysilane.
The organic compound having the above (hereinafter, referred to as “reactive organic compound”) is mixed to obtain a liquid composition. Examples of such a reactive organic compound include compounds having two or more functional groups capable of undergoing a condensation reaction with a hydroxyl group such as a carboxyl group, a hydroxyl group, an amino group and an alkoxy group (provided that the above alkoxysilane is (Excluding hydrolysates), specifically, for example

(I) Silane coupling agent (generally R
SiX ₃ : X is a hydrolyzable group, R is a functional group) (ii) Alkylalkoxy silicones (iii) Acrylic resins, epoxy resins, polyester resins, urethane resins, etc., having the above-mentioned groups and epoxy structures Polymers, resin emulsions or water-soluble polymers thereof, etc. (iv) 1,4-butanediol, glycerin, catechol, polyhydric alcohols such as resorcin, and the like, but (i), (iii) and (iv ) Group.

More specifically, for example, as the silane coupling agent (i),

[0015]

Embedded image Such as methyl acrylate,

[0016]

Embedded image Epoxy type,

[0017]

Embedded image Amino system, such as

[0018]

Embedded image Such as vinyl,

[0019]

Embedded image HS—C ₃ H ₆ Si (OCH ₃ ) ₃ , HS-C
_{3 H 6 Si (OC 2 H} 5) 3, HS-C 3 H 6 Si (OC
₂ H ₄ OCH ₃ ) ₃ and the like, and the like. Further, as the alkyl alkoxy silicones of (ii),

[0020]

[Chemical 6] And the like.

Further, examples of the polymers (iii) include the followings. Acrylic resin (a)

[0022]

[Chemical 7] etc

(B) Acrylic resin containing a silyl group, such as one obtained by adding γ-methacryloxypropyltrimethoxysilane to the above structure (a).

[0024]

Embedded image Epoxy resin

Polyester resin

Embedded image

Polyurethane resin

[0027]

Embedded image

The above reactive organic compounds may be used in combination of two or more depending on the purpose. The reactive organic compound is 1 to 900 parts by weight, preferably 30 to 100 parts by weight based on 100 parts by weight of the alkoxysilane and / or its hydrolyzate.
Parts by weight. If it is less than 1 part by weight, the coated glass fiber may lose compatibility with the resin which is the matrix when the glass fiber is mixed with the resin. 900
If it is more than 1 part by weight, the hardness of the coating film will be low and the adhesion to the matrix may be reduced.

When the reactive organic compound is incompatible with water and the alkoxysilane and / or its hydrolyzate, a silane coupling agent may be added. The addition method is a conventional method, and preferably stirring is performed. Glass fibers are coated using the above liquid composition as a coating liquid. The coating treatment is not particularly limited, but the following method is usually adopted. The glass fiber is impregnated with the coating liquid. Then dry at room temperature to 100 ° C,
Obtain coated glass fibers. Although the drying time depends on the amount of water, 1 minute to 60 minutes is usually sufficient. The above-mentioned liquid composition obtained by the present invention can also be substantially free of an organic solvent, so for environmental hygiene,
It is also preferable in terms of safety.

[0030]

The present invention will be described in more detail with reference to the following examples. The parts and% are parts by weight and% by weight, unless otherwise specified.

Example 1 500 equipped with a stirrer, a condenser for reflux and a thermometer
In a ml four-neck round bottom flask, add tetramethoxysilane 2
After adding 34 g and 74 g of methanol and mixing, 0.0
22.2 g of 5% hydrochloric acid was added, and a partial hydrolysis-condensation reaction was performed at an internal temperature of 65 ° C. for 2 hours.

Then, the condenser is replaced with a distilling pipe,
The temperature was raised until the internal temperature reached 130 ° C., and methanol was distilled off. Thus, a tetramethoxysilane oligomer which is a partially hydrolyzed condensate was obtained. The degree of polymerization is 2
8, the weight average molecular weight was 550. The amount of monomer in the tetramethoxysilane oligomer was 5%. Then, the above tetramethoxysilane oligomer was put into a flask heated to 100 to 130 ° C, and the vaporized monomer was discharged to the outside of the system together with an inert gas at 150 ° C.
The temperature was raised to and held for 3 hours. The amount of the monomer in the tetramethoxysilane oligomer after removing the monomer was 0.2%.

To 100 parts by weight of the tetramethoxysilane oligomer after removal of the monomer, 66 parts of dechlorinated water was added.
Parts by weight was added. Next, maleic acid was added to adjust the pH to 1.5. After stirring at room temperature for 5 minutes, a transparent concentrate was obtained. Then, 20,000 parts by weight of dechlorinated water was added. Subsequently, 30 parts by weight of an epoxy silane coupler (manufactured by Nippon Unicar Co., Ltd., product number A-187) was added, and the mixture was stirred at room temperature for 1 hour. The obtained liquid material had a pH of 3.7. The liquid material was impregnated with glass fiber (diameter 5 μm) for 1 minute. Then, the glass fiber was pulled up and dried in an electric furnace at 100 ° C. for 10 minutes to obtain coated glass fiber.

Example 2 To 100 parts by weight of the tetramethoxysilane oligomer obtained in Example 1, dechlorinated water and maleic acid were added and p
It was adjusted to H2.0. Stir for 2 minutes at room temperature to obtain a clear concentrate. Subsequently, 1100 parts by weight of dechlorinated water was added. Methyl acrylate-based silane coupler (manufactured by Nippon Unicar, product number A-174) was used as an organic compound.
0 part by weight was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid substance.
This liquid had a pH of 3.5. The liquid material was impregnated with glass fiber (diameter 5 μm) for 1 minute. Then, the glass fiber was pulled up and dried in an electric furnace at 100 ° C. for 10 minutes to obtain coated glass fiber.

[0035]

Industrial Applicability According to the present invention, glass fibers having excellent adhesion to the resin which is the matrix can be suitably obtained from the viewpoint of environmental hygiene and safety.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hozumi Endo Hozumi Endo 1-1, Kurosaki Shiroishi, Hachimansai-ku, Kitakyushu City Mitsubishi Chemical Corporation Kurosaki Development Laboratory (72) Inventor Nobuyuki Matsuzoe 2-5-2 Marunouchi, Chiyoda-ku, Tokyo Sanryo Chemical Co., Ltd. New Business Development Room

Claims (6)

[Claims] 1. A compound obtained by mixing an alkoxysilane and / or a hydrolyzate thereof with an organic compound having two or more functional groups capable of reacting with a hydroxyl group obtained by hydrolyzing an alkoxysilane and water. , Coated glass fiber made by coating glass fiber. 2. The coated glass fiber according to claim 1, wherein the organic compound is a silane coupling agent. 3. The coated glass fiber according to claim 1, wherein the alkoxysilane is tetramethoxysilane. 4. The alkoxysilane is tetramethoxysilane, and the amount of monomer in the hydrolyzate is 1% by weight.
The coated glass fiber according to any one of claims 1 to 3, wherein: 5. Coated glass fiber according to claim 1, characterized in that the formulation is substantially free of organic solvents. 6. To 100 parts by weight of alkoxysilane, 5 to 300 parts by weight of water is added in advance, the pH is adjusted to 3 or less with an inorganic acid and / or an organic acid, and the mixture is stirred for 1 to 180 minutes. It is more than 5 and is further mixed with an organic compound having 2 or more functional groups capable of reacting with a hydroxyl group produced by hydrolysis of an alkoxysilane, and the obtained composition is coated on glass fiber. Method for producing glass fiber.