JPH09208268A - Bundling agent for glass fiber and fabric of glass fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fabric almost free from fluffing in a working process and having satisfactory suitability to impregnation with a resin by blending a bundling agent for glass fibers with specified inorg. solid particles and sticking a specified amt. of the solid particles to glass fibers. SOLUTION: A bundling agent for glass fibers deoiled by heating is blended with inorg. solid particles of at least one selected from among colloidal silica, light calcium carbonate, kaolin and fine particle-shaped talc having 5-2,000nm average particle diameter and the solid particles are stuck to glass fibers by 0.001-2.0wt.% (expressed in terms of solid).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a glass fiber sizing agent and a glass fiber having the sizing agent attached thereto.

[0002]

2. Description of the Related Art A sizing agent for glass fibers is a roller applicator for a large number of glass filaments immediately after spinning in order to protect the glass fibers when the molten glass is spun at high speed into glass fibers. And a belt applicator. The sizing agents for glass fibers are roughly classified into those for yarn and those for roving. The yarn sizing agent will be described below. The glass fiber bundle coated with the sizing agent is wound into a cylinder as a cake. The cake is appropriately dried, twisted by a twisting machine and wound on a bobbin to obtain a glass fiber yarn. The yarn is mainly woven into a woven fabric, and is subjected to deoiling treatment such as thermal deoiling by heating the sizing agent at a high temperature to remove it by oxidation or washing with water, and deoiling by washing with a vibro washer, and then adhesiveness with resin and heat resistance. It is common to apply a surface treatment agent such as a silane coupling agent to improve the glass fiber surface to the glass fiber surface.

This cloth is impregnated with an uncured resin or is impregnated with a resin containing a solvent and having a reduced viscosity to remove the solvent, and then stacked and pressed to form a laminated plate. Conventionally, the sizing agent used for this purpose has been mainly composed of starch which prevents fiber fluffing and is easy to deoil.

Recently, however, PVA has been used as a sizing agent for yarns.
In some cases, synthetic resin materials such as (polyvinyl alcohol), urethane resin, and epoxy resin are used. There are various processed starches used for starch paste, including the following ones. Natural raw starch, such as corn and potato (potato) starch, and their chemically modified products, such as etherification products such as hydroxyalkylation, esterification products such as acetylation, and cross-linking agents such as epichlorohydrin. Cross-linked product reacted by
There are known low-viscosity products in which the molecular weight of starch is reduced and the viscosity is lowered, such as acid treatment. A concrete example of the compounding of the conventional sizing agent using these starches is as follows: starch-based material, 2 wt% -10 wt%, lubricant, 0.2 wt% -5
% By weight, surfactant 0.05% by weight-1.0% by weight,
Preservative 0.01% to 0.5% by weight with the balance being water.

Starch is used for film forming purposes to bond hundreds of glass filaments together into a single strand to protect the yarn from any mechanical bending and rubbing. As a raw material of starch, corn, potato and the like are often used, and their chemically modified products, for example, etherified products such as hydroxyalkylated products are often used. Lubricants are used to lubricate the strands, reduce friction on the machine and protect the yarn. As the type of lubricant, hydrogenated hardened oil of animal or vegetable oil, paraffin wax, ester of higher saturated fatty acid and higher saturated alcohol and the like are often used. Cationic lubricants are used for the purpose of softening the glass yarn and reducing the friction between filaments in the strand, for example,
Alkyl quaternary ammonium salts and amides or imidazolines obtained by condensation reaction of polyethylene polyamine and higher fatty acids are often used. Surfactants are mainly used as emulsifiers for lubricants.
Polyoxyethylene alkyl ether and the like are often used. Formalin is mainly used as a preservative.

As a glass fiber treating agent containing colloidal silica as solid particles, Japanese Patent Publication No. 1-203247 discloses a glass fiber roving binder for spray-up of FRP in which polyvinyl acetate is mixed with colloidal silica. It is disclosed. In addition, JP-A-6-248572
The publication discloses a technique in which glass fiber woven fabric is impregnated with colloidal silica and dried, the glass fiber woven fabric is opened with a vibro-washer, and the woven fabric is impregnated with resin, laminated, heated and pressed. The former is one in which a sizing agent containing colloidal silica is attached to the glass fiber roving so that the glass fiber lobing is less likely to slip and the cuttability is improved. The latter is one in which colloidal silica is added to the glass fabric and then the fibers are opened by a means such as a vibro washer to insert colloidal silica between the glass fibers to form a gap between the fibers to improve resin impregnation. is there. However, since the woven fabric has the warps and the wefts crossing each other, it is difficult to make the colloidal silica evenly infiltrate when seen in detail.

[0007]

The sizing agent composed of such a combination of compounds has quite excellent properties and has been used up to now. However, as the production of glass fiber becomes faster and more efficient, the amount of glass fiber to be wound up is gradually increased to make the rolled up cake larger. A part of the inside of the cake is accompanied by the large packaging of the cake. Fiber breakage occurs and the fluffing of the glass fiber yarn increases.This phenomenon occurs when the glass fiber wound on the cylinder increases, the diameter increases, and the tension applied to the glass fiber gradually increases when it is wound up. It is thought that some glass fibers are cut due to the force that crushes the glass. Alternatively, there is a demand for a solution to the problem of shortening the time for impregnating a glass fiber woven fabric obtained by weaving glass fibers with a resin to increase the production efficiency of the laminate and reduce the production cost of the laminate.

The present invention relates to a sizing agent for glass fibers, which has been newly developed to solve the above-mentioned problems, and has an excellent cake shape stability during the spinning of glass fibers and a processing step. Even in the case of fluff generation, even if the winding amount is increased, it is extremely small as in the case of the conventional winding amount, and it is possible to obtain a glass fiber yarn having good resin impregnation property of the woven glass fiber woven fabric. The purpose of the present invention is to provide an agent and a glass fiber to which the sizing agent is attached.

[0009]

According to the present invention, at least one inorganic solid particle such as colloidal silica, kaolin, and light calcium carbonate is mixed in a sizing agent for glass fiber, and the solid particle is added to glass fiber. 0.0 in solid content
The above-mentioned problem was solved by adhering 01-2.0% by weight.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION It is an attempt to solve the above problems by adding inorganic solid particles such as colloidal silica to such a sizing agent. However, some surfactants and the like are not compatible with colloidal silica. There are cases where gelation, separation, etc. may occur when these are blended, and the ingredients of the sizing agent to be blended are determined in consideration thereof. Although the sizing agent component is effective for the conventional type mainly composed of starch, PVA (polyvinyl alcohol), urethane resin,
It is also effective when synthetic resin materials such as epoxy resin are used. The inorganic solid particles used in the present invention include kaolin, light calcium carbonate, fine talc, powdered fumed silica (manufactured by Nippon Aerosil Co., Ltd.) and colloidal silica. These particles do not decompose at the temperature of deoiling by heating, and the particles having a size of 5-2, 000 nm can be used.

Colloidal silica has a particle size of 5-1.
Amorphous silica having a size of about 00 nm is stably dispersed in water or an organic solvent without settling, and is also known as silica sol. This colloidal silica is obtained by highly polymerizing silicic acid obtained by hydrolysis of sodium silicate aqueous solution (water glass), silicic acid ester, silicon halide, or the like to grow into a colloidal size. The particles of colloidal silica thus obtained are generally spherical, and most of the inside is a siloxane bond (-Si-O-Si-), but the particle surface layer is covered with silanol groups (-SiOH). ing.

In the present invention, one kind of inorganic solid particles such as colloidal silica may be mixed and used with a sizing agent, or two or more kinds of inorganic solid particles may be mixed and used with a sizing agent. As the sizing agent compound to be used by mixing with the inorganic solid particles of the present invention, any compound having no compatibility problem can be used.

The solid content of the inorganic solid particles such as colloidal silica in the sizing agent is 0.001-20.0% by weight.
, Preferably 0.01-5.0% by weight, and more preferably 0.1-2.0% by weight. If it is less than 0.001% by weight, the amount of inorganic solid particles such as colloidal silica that can accelerate the resin impregnation cannot be attached to the glass fiber, and if it is more than 20.0% by weight, it can be applied to the glass fiber. Absent.

Yarns are produced from glass fiber strands to which a sizing agent containing the inorganic solid particles of the present invention is attached, but are limited by the glass composition, the diameter of the filaments, the cross-sectional shape of the filaments and the number of filaments constituting the fiber bundle. Instead, it can be applied to any fiber bundle. The solid content of the sizing agent containing the inorganic solid particles of the present invention attached to the yarn is 0.001-10.00% by weight, preferably 0.
1-4.00% by weight, more preferably 0.3-1.
50% by weight. If it is 0.001% by weight, the effect as a sizing agent is not obtained, and if it is 10.0% by weight or more, the fiber bundle becomes too hard and becomes a problem in weaving the glass cloth.

The inorganic solid particles adhering to the glass fiber are 0.001-2.0% by weight in solid content, preferably 0.1.
01-0.98% by weight, more preferably 0.1-0.6
% By weight.

[0016]

【Example】

 <Example 1> High amylose type corn etherified starch 4.0% by weight Hydrogenated cottonseed oil 0.5% by weight Paraffin wax 1.0% by weight Polyoxyethylene polyoxypropylene ether 0.2% by weight Tetraethylene pentamine and stearin Acid reaction product 0.3% by weight Formalin (40% by weight aqueous solution) 0.1% by weight Colloidal silica (20% by weight aqueous solution) 0.5% by weight

The method for preparing 100 kg of the sizing agent of Example 1 is as follows. 4 kg of high amylose-type corn etherified starch is dispersed in 80 kg of water, heated to 95 ° C, kept stirred for 30 minutes, and then cooled to 65 ° C (Liquid A). In a separate container, heated and melted hydrogenated cottonseed oil 5
00 g, paraffin wax 1000 g, and polyoxyethylene polyoxypropylene ether 200 g are weighed, hot water is added while stirring with a homomixer, after inversion emulsification, diluted with hot water to 5 kg (liquid B). In a separate container, weigh 300 g of the acetic acid activated product of the condensate of tetraethylenepentamine and stearic acid and dilute with hot water.
Set to kg (C liquid). In addition, 100 g of formalin is weighed and diluted with water to make 1 kg (solution D). Further, colloidal silica "SNO-TEX: ST-20" (manufactured by Nissan Chemical Industries, Ltd., particle size 10-20 nm, SiO2 20)
(Weight%) 500 g is weighed and diluted with water to make 5 kg (liquid E). Solution B, Solution C, Solution D, and Solution E are sequentially added to Solution A, and then water is added to adjust the total weight to 100 kg.
Keep at ℃.

The sizing agent is adhered to glass fibers by a roller applicator in a solid content of 0.90% by weight, bundled, made into glass fiber strands, and wound as a cake. Furthermore, this strand is twisted and G75 1/0
The yarn is 0.7Z. Next, this yarn is warped with a high-speed warper (manufactured by SUCker) and glued (SUC).
KER) and woven with a high-speed air jet loom (Tsukoma Kogyo KK), weaving density, 44 warps / 2
A glass cloth having 5 mm and 32 wefts / 25 mm is prepared. Further, the glass cloth was thermally deoiled to remove the sizing agent, and then the silane coupling agent SZ6032 (manufactured by Toray Dow Corning Silicone Co., Ltd.) was surface-treated at a concentration of 0.3% by weight. The FR-4 resin was impregnated. Table 1 shows the stability of the cake shape and the quality of the glass cloth, but the cake shape was extremely stable and the resin impregnation property was excellent.

Example 2 High amylose type corn etherified starch 3.5% by weight Normal type corn crosslinked starch 1.5% by weight Hydrogenated cottonseed oil 1.0% by weight Paraffin wax 1.0% by weight Polyoxyethylene poly Oxypropylene ether 0.2% by weight Reaction product of tetraethylenepentamine and stearic acid 0.4% by weight Formalin 0.1% by weight Colloidal silica (trade name: Catalog S-30H, manufactured by Catalysts & Chemicals Industries Co., Ltd., particles Diameter 10-20 nm, SiO2 content 30% by weight) Solid content conversion 0.5% by weight Same as Example 1 except that 0.97% by weight in solid content of the sizing agent was adhered to the glass fiber of G75. . In Table 1,
The cake shape stability and the quality of the glass fiber woven fabric were shown, but the cake shape was extremely stable and the resin impregnation property was excellent.

<Example 3> The same procedure as in Example 1 was carried out except that 0.4% by weight of light calcium carbonate having an average particle diameter of 40 nm was used in place of colloidal silica. The test results are shown in Table 1.

Comparative Example 1 The same procedure as in Example 1 was carried out except that water was added instead of 0.5% by weight of colloidal silica, and the results obtained are shown in Table 1.

[0023]

【Evaluation method】

1. Shape stability of cake The appearance of the cake was observed with the naked eye to distinguish it from those that were clearly deformed and those that were not. 2. Evaluation of fluff The number of fluffs on the product surface after twisting and the number of fluffs on the surface of the glass fiber woven fabric after weaving by a loom were counted and comprehensively judged, and 1 rank was the lowest and 7 was the lowest. The highest number is shown, and if it is 2-3 or less, it can sufficiently withstand normal use.

3. Evaluation of resin impregnation property Glass fiber woven fabric (10 × 10c) which has been surface-treated after thermal deoiling
A certain amount (10 ml) of resin was dripped on m), and the time until the bubbles in the glass fiber escaped was measured and divided into 7 ranks. The smaller the value, the better the result obtained. Indicates. Resin composition used: Epicote 1001 (Epoxy resin manufactured by Shell Chemical Co., Ltd.) 100 parts by weight Dicyandiamide 2 〃 Benzyldimethylamine 0.2 〃 Methyloxytol 100 〃

[0025]

[Effect] According to the present invention, since the deformation of the outer shape of the rolled cake can be reduced, the obtained glass fibers are less cut, and the yarn and the fluff of the glass fiber woven fabric are reduced. . In addition, since the solid particles are uniformly attached to the entire bundle of glass fibers constituting the glass fiber yarn, when a woven fabric is used, the warp yarn and the weft yarn also have the highest density in the portion where the crossing occurs between the fibers due to the solid particles. A gap was secured, and it became possible to uniformly impregnate the resin and shorten the impregnation time.

[0026]

Claims (3)

[Claims] 1. A sizing agent for glass fibers, wherein the sizing agent for glass fibers to be deoiled by heating contains inorganic solid particles. 2. The average particle diameter of the glass fiber sizing agent is 5 to 5.
The glass fiber sizing agent according to claim 1, comprising at least one kind of inorganic solid particles selected from 2000 nm colloidal silica, light calcium carbonate, kaolin, and fine talc. 3. A glass fiber yarn in which the inorganic solid particles according to claim 2 are adhered in an amount of 0.001 to 2.0% by weight in terms of solid content.
Fiberglass woven fabric.