JPH10226941A - Glass fiber fabric and fiber-reinforced resin molded product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject woven fabric excellent in water resistance, thermal expansion coefficient, permittivity and strength by combining a high- strength glass fiber with a glass fiber, having a low permittivity and good in water resistance. SOLUTION: This glass fiber woven fabric is composed of (A) a high-strength glass fiber yarn such as T glass, S glass or R glass and (B) a glass fiber yarn having a glass composition of 45-60wt.% SiO2 , 8-20wt.% Al2 O3 , 15-30wt.% B2 O3 , 0-5wt.% MgO, 5-12wt.% CaO, 0-1.0wt.% total amount of Li2 O, Na2 O and K2 O, 0.5-5wt.% TiO2 and 0-2wt.% F2 and regulating the weight ratio (A/B) of the yarns A to B used to 0.4-1.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass fiber woven fabric for fiber reinforced plastic and a fiber reinforced plastic product using the same, and more particularly to a fiber reinforced plastic woven fabric which requires a low dielectric constant, a low coefficient of thermal expansion and a high strength. The present invention relates to a fiber-reinforced plastic product using the same.

[0002]

2. Description of the Related Art Fiber-reinforced plastic products in which glass fibers are impregnated in a resin have been used in various fields. As one of the uses, it has been used as a material of a radar dome (radome) for protecting an antenna such as a radar mounted on an aircraft or the like. When used for this purpose, the radome material must have a low dielectric constant that allows radio waves to pass easily. However, conventional fiber-reinforced plastics made of E glass fiber have a large loss due to an excessively high dielectric constant. was there. on the other hand,
In general, a glass fabric made of E glass is used as an insulating base material of a printed wiring board, and a laminate obtained by impregnating the glass fabric with a thermosetting resin and molding under heat and pressure has been produced. However, in recent years, there has been an increasing demand for miniaturization, high-speed processing of signals, and high strength of ultra-thin substrates in the electric and electronic fields, and low thermal expansion, low dielectric constant, and high strength have been required for glass substrates. It is becoming necessary. High-strength glass fibers such as T-glass, S-glass and R-glass are used for applications requiring high strength, which cannot be satisfied with E-glass, and D-glass fibers for low-dielectric constant applications. Is used.

[0003]

However, glass fibers having a high tensile strength such as T glass (manufactured by Nitto Boseki Co., Ltd.), S glass and R glass have a low coefficient of thermal expansion and a high strength.
Although the dielectric constant is as high as 5.3 at 1 MHz, the dielectric constant of D glass is as low as 4.1, but the tensile strength of glass fiber is as low as 245 kg / mm ² and the water resistance is poor. However, there is a problem that it is not suitable for applications used outdoors. An object of the present invention is to provide a glass fabric for a fiber-reinforced plastic and a printed wiring board excellent in water resistance, thermal expansion coefficient, dielectric constant, and strength, and a fiber-reinforced plastic product and a printed wiring board using the same. is there.

[0004]

SUMMARY OF THE INVENTION The object is to provide a T glass,
S-glass, high-strength glass fiber yarn, such as R-glass - and down (hereinafter referred to as A), in weight%, SiO ₂ 45-60%,
_{Al 2 O 3 8-20%, B} 2 O 3 15-30%, Mg
O 0-5%, CaO over 5%, up to 12%, Li
₂ O + Na ₂ O + K ₂ O 0-1.0%, TiO ₂
A glass fiber yarn (hereinafter referred to as B) having a glass composition of 0.5-5% and F ₂ O-2%;
It can be achieved by setting the use weight ratio (A / B) of B and B to 0.4-1.5.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The composition of the T glass fiber yarn used in the present invention is 55-80% by weight of SiO ₂ ,
_{l 2 O 3 12-32%, RO} (CaO and / or M
gO) 4-20%, ZnO ₂ 0-1%, the typical composition of which is wt%, SiO ₂ 66.5%, Al ₂
O ₂ 22.3%, MgO 10.4%, ZrO ₂
The physical properties are a specific gravity of 2.49, a tensile strength of 450 kg / mm ² , and a dielectric constant of 5.3 at 1 MHz, t
an δ is 0.0026 at 1 MHz. The composition of the S glass-fiber yarn is SiO ₂ 55-80 by weight.
_{%, Al 2 O 3 13-32%} , RO (CaO and / or MgO) is 4-20%. A typical composition of the yarn B is, for example, 51.5% by weight of SiO _{2 in} terms of% by weight.
%, A1 ₂ O ₃ 12.0%, B203 25.0%,
CaO 7.4%, MgO 0%, Li ₂ O 0.2%,
Na ₂ O 0.2%, K ₂₀ 0.5%, TiO ₂
The physical properties were specific gravity 2.30, tensile strength 290 kg / mm ^2, dielectric constant 4.4 at 1 MHz, t
an δ is 0.0006 at 1 MHz.

[0006] These glass fibers are produced by a process of drawing a known molten glass from a platinum alloy nozzle at a high speed and applying a sizing agent to form a strand, and then rewinding and twisting or not forming a yarn. . The yarns A and B used for the warp yarns are designed to have a predetermined weight ratio when wound on a warping beam, and that the arrangement of A and B is repeated in as small a unit as possible. It is desirable.
The same applies to the order of A and B to be driven as weft yarns. It is preferable in terms of production efficiency to use either one of the above A or B for the warp and the other strand as the weft. It is desirable to use the same filament diameter, number of bundles, and number of twists of these yarns A and B as much as possible. The fiber diameter is 3-23 μm, and the number of bundles of single yarn is 50-1200.
This yarn has a single yarn of 0-10 turns / 1 inch.
Alternatively, it is usually used in the form of a plied yarn.

[0007] The usage ratio of the yarns A and B is 0.4-1.5.
, Preferably in the range of 0.8 to 1.3.
If the use weight ratio of the yarns A and B is out of the range of 0.4-1.5, if the warp is woven as A and the weft is woven as B, the weaving density becomes too coarse or too dense, so that it is difficult to make a woven fabric. ,Also,
If it is less than 0.4, it cannot be said that it is advantageous in strength, and if it is more than 1.5, it cannot be said that it is advantageous in terms of dielectric constant.

In the glass cloth thus produced, organic substances such as a sizing agent are removed from the surface of the glass fiber in a deoiling step, and a surface treatment agent is applied according to the type of matrix resin of the composite material and the purpose of use. The surface treatment agent is selected from known silane coupling agents such as vinyl silane, acrylic silane, epoxy silane, amino silane and the like used for surface treatment of glass fibers, and those which are more suitable for the corresponding resin. Resin that can be used as a matrix resin is a thermosetting resin represented by a polyimide resin, a phenol resin, an unsaturated polyester resin, an epoxy resin, and the like; a thermoplastic resin represented by a polyamide resin, a PBT resin, polypropylene, and a fluorine resin. Are selected according to the purpose, and are not particularly limited. There is no problem in using a matrix resin that can be used together with ordinary E glass cloth. In addition, a known material such as a filler having a low dielectric constant, a flame retardant such as a halogen-containing organic compound or antimony oxide, or a coloring agent may be added to the resin or may be appropriately selected according to the purpose of use.

Glass fiber yarn B has a lower strength than E glass, but has a coefficient of thermal expansion close to that of T glass and a lower dielectric constant than T glass, and therefore should be mixed with high strength T glass. Therefore, it has a lower coefficient of thermal expansion, a lower dielectric constant, and a higher strength than the conventional glass cloth of only E glass,
A laminate manufactured by impregnating with an epoxy resin or the like also has a lower coefficient of thermal expansion, a lower dielectric constant, and a higher strength than a laminate using an E glass glass cloth.

[0010]

【Example】

Example 1 _{wt%, Si0 2 66.5%, Al} 2 O 3 22.
T of 3%, MgO 10.4%, ZrO ₂ 0.8%
A starch-based sizing agent was applied to a glass fiber of E225 (fiber diameter 7 μm, number of bundles: 200) having a glass composition applied during spinning and wound up. Rewind this, twist and JIS
ECE 225-1 / 0 specified in R 3413
Yarn A of 1.0Z was obtained. The yarn coated with a polyvinyl alcohol-based secondary sizing agent was used as a warp. On the other hand, in terms of% by weight, 51.5% of SiO ₂ and Al ₂ O ₃ 1
_{2.0%, B 2 O 3 25.0} %, CaO 7.4%, M
gO 2.0%, Li ₂ O 0.2%, Na ₂ O 0.1%
A starch-based sizing agent is applied to a glass fiber of E225 (fiber diameter 7 μm, bundle number: 200) having a composition of 2%, K ₂ O 0.5%, and TiO ₂ 1.2% during spinning and wound.
This was rewound to obtain a yarn B of ECE 225 1/0 1.0Z.

Comparing the water resistance of the yarn with the weight loss of 13 μm glass fiber treated with distilled water at 99 ° C. for 60 minutes, 0.1% by weight for E and T glasses and 1.% for D glass. The content was 5% by weight and the content of yarn B was 0.2% by weight. Using this yarn as a weft, the weaving density is 60 yarns / 25 mm and the weft 58 yarns / 25 on an air jet loom.
mm plain woven glass fabric (weight ratio A / B of A and B = 1.1)
2) was created. This glass fabric is subjected to surface treatment after heat cleaning, and impregnated and dried with an epoxy resin to obtain a prepreg. Eight such prepregs were laminated for each layer so that the warp direction and the weft direction of the glass fabric were alternately obtained to obtain a laminated plate having a thickness of 0.8 mm. Dimensional change rate of this laminate,
Table 1 shows the dielectric constant and the bending strength, and Table 2 shows the water absorption and the insulation resistance.

Test method 1. Dimensional change rate: 300 mm x 300 mm, thickness 0.8
Using a laminate having a size of 2 mm, two holes were made in the vertical and horizontal directions, and the dimension a between the holes was measured. The mixture was treated in a heating furnace at 180 ° C. for 45 minutes. b is measured and calculated by the following equation. Dimensional change rate (%) = (ba) / a × 100 2, dielectric constant: based on JIS K 6911. 3. Bending strength: based on JIS R3420. 4. Water absorption: pressure-cooker-150 at 121 ° C
Measured after min processing. The weight increase due to water absorption is shown in% by weight. 5. Insulation resistance: insulation resistance after boiling for 2 hours and 4 hours.

Example 2 The weaving density was 60 warps / 25 mm and 70 wefts / 25 mm.
Table 1 shows the dimensional change, the dielectric constant, and the bending strength of the obtained laminated plate in the same manner as in Example 1 except that the above conditions were satisfied. Comparative Example 1 Weaving density: 60 warp / 25 mm, weft 38/25 mm
Table 1 shows the dimensional change, the dielectric constant, and the bending strength of the obtained laminated plate in the same manner as in Example 1 except that the above conditions were satisfied.

Comparative Example 2 The dimensional change, the dielectric constant and the bending strength of the obtained laminated board are shown in Table 1 in the same manner as in Example 1 except that both the warp and the weft are made of T glass. Table 2 shows the resistance. Comparative Example 3 Table 1 shows the dimensional change, dielectric constant, and flexural strength of the obtained laminated board in the same manner as in Example 1, except that the warp and the weft were the most popular E glass yarns on the market. Water absorption,
Table 2 shows the insulation resistance.

Comparative Example 4 The same procedure as in Example 1 was repeated except that both the warp and the weft yarns had a D glass composition.
The insulation resistance was measured. Table 2 shows the results.

[0016]

The glass fiber woven fabric of the present invention has water resistance, a low coefficient of thermal expansion, a low dielectric constant, and a high strength.
A fiber-reinforced plastic product using this glass fiber fabric has better water resistance, dimensional stability, dielectric constant, and strength than conventional products. Particularly, it is useful as an ultra-thin base material such as a radome material which requires water resistance, low dielectric constant and high strength and a card which requires low thermal expansion coefficient, low dielectric constant and high strength.

[0017]

[Table 1]

[0018]

[Table 2]

Claims (3)

[Claims] Claims: 1. A high-strength glass fiber yarn (A), comprising:
_{In, SiO 2 45-60%, A1 2} O 3 8-20%, B
₂ O ₃ 15-30%, MgO 0-5%, CaO 5%
Over 12%, Li ₂ O + Na ₂ O + K ₂ O 0
_{-1.0%, TiO 2 0.5-5%,} F 2 0-2
% Of the glass fiber yarn (B) having a glass composition of 0.4% and the used weight ratio (A / B) of A and B is 0.4%.
A glass fiber woven fabric for fiber-reinforced plastics, which is -1.5. 2. A fiber reinforced plastic product using the glass fiber woven fabric according to claim 1. 3. A printed wiring board using the glass fiber fabric according to claim 1.