JP2000247684A - Glass fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass fiber which is free from volatile components such as ZnO, B2O3 and F2, does not cause environmental pollution and which is excellent in chemical durability and high in productivity. SOLUTION: The glass fiber contains, by mole, 56 to 63% SiO2, 4 to 9% Al2O3, 0.1 to 3% ZrO2, however, the amount of SiO2+ZrO2-Al2O3 being not less than 52%, 1 to 7% MgO, 21 to 28% CaO, 0 to 1.5% Na2O, and 0 to 1.5% K2O, however, the amount of Na2O+K2O being not more than 1.5%, and is substantially free from ZnO, B2O3 and F2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing ZnO, B
_{The present invention} relates to a glass fiber which does not contain volatile components such as ₂ O ₃ and F ₂ and has excellent chemical durability, particularly a glass fiber suitable as a reinforcing material for a composite material such as FRP and resin for a printed wiring board.

[0002]

2. Description of the Related Art In order to produce glass fibers, a glass material prepared in a predetermined ratio is melted at a high temperature to obtain a homogeneous glass, and then the molten material is formed into a bushing having a number of nozzles at the bottom. Is supplied and glass is continuously drawn from the tip of the nozzle.

In the case of fiberization, if the devitrification temperature of the glass exceeds the spinning temperature, which is the temperature at which the glass is fiberized, a devitrified material is formed, and the yarn breaks easily near the bushing nozzle. Worsens sex. For this reason, the devitrification temperature of glass is lower than the spinning temperature, which is a condition for fiberization.

In order to improve the productivity, it is required to increase the difference (ΔT) between the spinning temperature and the devitrification temperature. However, increasing the spinning temperature of glass makes it difficult to control the temperature of the bushing. In addition, the life of the bushing is shortened, which is not preferable. In addition, the raw materials must be melted at high temperatures, which increases the energy consumption required. Therefore, it is desirable that the spinning temperature be as low as possible.

[0005] In the E glass fiber which is most used in industry, B ₂ O ₃ and F ₂ are used in the composition as components which lower the spinning temperature and the devitrification temperature. However, B ₂ O ₃ is that the raw material is expensive, since the B ₂ O _3, F ₂ is easy to volatilize melting process, now can cause the surrounding environment pollution are suggested as problems, B ₂ There is a need for new glass fibers that do not contain O ₃ and F ₂ .

US Pat. Nos. 3,847,627 and 3,847,627 disclose glass fibers containing neither B ₂ O ₃ nor F ₂ .
Nos. 876,481, 4,026,715 and 5,789,329.

The composition of glass fibers described in US Pat. Nos. 3,847,627 and 4,026,715 does not contain B ₂ O ₃ or F ₂ , but a flux instead of B ₂ O ₃ or F _2. Used are titanium dioxide (TiO ₂ ), and RO is strontium oxide (SrO), BaO, ZnO. The glass fiber described in U.S. Pat. No. 3,876,481 contains lithium monoxide (Li ₂ O) and TiO ₂ as fluxes instead of B ₂ O ₃ and F ₂ .

However, the raw materials of TiO ₂ , Li ₂ O, and ZnO are expensive to positively introduce them. In addition, ZnO volatilizes during melting and has a problem of shortening the life of the kiln. Further, TiO ₂ colors the glass, so that when used as a reinforcing material, the appearance may be impaired.

As described in US Pat. No. 5,789,329.
The glass composition listed is ZnO, B _TwoO_Three, F_TwoSuch as
No chemical components such as acid and water resistance
Excellent in durability, but equivalent to the spinning temperature described in the examples.
Temperature of 1,000 poise [P]
High temperature causes reduction of productivity and bushing life
Is concerned.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above background, and does not contain ZnO, B ₂ O ₃ , and F ₂ which are volatile components, thereby preventing environmental pollution and improving chemical durability. It is an object of the present invention to provide a glass fiber having excellent productivity and high productivity.

[0011]

Means for Solving the Problems To achieve the above object, the glass fiber according to the first aspect of the present invention has a molar percentage (hereinafter simply referred to as “%”) of SiO ₂ : 56 to 50%.
63%, Al ₂ O ₃ : 4 to 9%, ZrO ₂ : 0.1 to 3%, provided that SiO ₂ + ZrO ₂ -Al ₂ O ₃ ≧ 52%, MgO: 1 to 7%, CaO: 2
_{1~28%, Na 2 O: 0~1.5} %, K 2 O: 0~1.5
%, But containing Na ₂ O + K ₂ O ≦ 1.5%, ZnO, B ₂ O ₃ , F
₂ is not substantially contained.

The glass fiber according to the second aspect of the present invention has a spinning temperature of 1,245 ° C. in addition to the constitution of the first aspect of the present invention.
And the difference between the spinning temperature and the devitrification temperature is 40 ° C. or more.

The glass fiber according to the third aspect of the present invention has a molar percentage of SiO ₂ : 58-61% and Al ₂ O ₃ : 6-7.
%, ZrO ₂ : 0.1 to ₂ %, provided that SiO ₂ + ZrO ₂ -Al ₂ O ₃ ≧ 5
3%, MgO: 3~6%, CaO: 23~27%, Na 2 O: 0~
1%, K ₂ O: 0 to 1%, but containing Na ₂ O + K ₂ O ≦ 1%, containing substantially no ZnO, B ₂ O ₃ and F ₂ , and having a spinning temperature of 1,
235 ° C. or less, and the difference between the spinning temperature and the devitrification temperature is 50
It is at least ℃.

[0014]

Next, the reasons why the constituents of the glass fiber of the present invention are limited as described above will be described. SiO
₂ is a component that improves the acid resistance of glass, and is 56%
If it is less than 63%, the above effect cannot be obtained. On the other hand, if it is more than 63%, the viscosity of the glass at a high temperature increases, so that the spinning temperature increases and the meltability of the batch deteriorates. Therefore, the content is 56 to 63%, and preferably 58 to 61%.

Al ₂ O ₃ is a component that improves the water resistance of glass and improves the devitrification property when contained in an appropriate amount.
If it is less than 4%, sufficient action cannot be obtained, and if it is more than 9%, acid resistance and meltability deteriorate. Therefore, the content is 4 to 9%, preferably 6 to 7%.

ZrO ₂ is a component that improves the chemical durability of the glass, increases the refractive index of the glass, and has a particularly effective effect in lowering the spinning temperature and the devitrification temperature in a small amount.
If it is less than 0.1%, the above effect cannot be obtained, while if it is more than 3%, the glass tends to be devitrified or the meltability deteriorates. Therefore, the content is 0.1 to 3%, preferably 0.1 to 2%.

Here, SiO ₂ , ZrO ₂ , and Al ₂ O ₃ are components that affect the properties of the glass, particularly the durability against acids.
SiO ₂ and ZrO ₂ are components for improving acid resistance, and Al ₂ O ₃
Is a component that deteriorates the acid resistance, particularly SiO ₂ + ZrO ₂ -Al ₂ O
It was found that when the value of ₃ was 52% or more, the acid resistance was good. Therefore, SiO ₂ + ZrO ₂ —Al ₂ O ₃ ≧ 52%, preferably SiO ₂ + ZrO ₂ —Al ₂ O ₃ ≧ 53%.

MgO exhibits the effect of lowering the viscosity at high temperatures,
And a component that improves spinnability and batch meltability;
%, The above effect cannot be obtained. On the other hand, if it is more than 7%, the glass tends to be devitrified, and the productivity is reduced.
Therefore, the content is 1 to 7%, preferably 3 to 6%, and more preferably 5 to 6%.

CaO is a component that improves the water resistance and devitrification of the glass, reduces the viscosity of the glass, and improves the meltability and spinnability. If it is less than 21%, the above effect cannot be obtained. If the content is more than 28%, the glass tends to be devitrified. Therefore, the content is 21 to 28%, and preferably 23 to 27%.

Alkali metal oxides such as Na ₂ O and K ₂ O are fluxing agents for glass and improve the melting property.
Even a small amount exhibits the effect of lowering the devitrification temperature. However, when the total amount of these alkali metal oxides exceeds 1.5%, the chemical durability deteriorates, which is not preferable.
Therefore _{content, Na 2 O: 0~1.5%,} K 2 O: 0~
1.5%, and Na ₂ O + K ₂ O ≦ 1.5%, preferably
Na ₂ O: 0 to 1%, K ₂ O: 0 to 1%, and Na ₂ O + K ₂ O ≦ 1%
It is.

In the present invention, in addition to the above components, Sr
O, manganese oxide (MnO), iron oxide II (FeO), iron oxide III (Fe _{2
O 3), TiO 2, B} 2 O 3, F 2 , etc. as impurities in the raw material, may be mixed in a range of 0.5% or less in total.

As a glass fining agent, sulfur trioxide (S
O ₃ ) and a small amount of antimony oxide (Sb ₂ O ₃ ). However, other components except the fining agent color the glass, and since the raw material is expensive to introduce directly,
It is not preferable to propose an inexpensive glass fiber. Furthermore, ZnO, B ₂ O ₃ and F ₂ volatilize in the manufacturing process,
It is not preferable because it pollutes the environment. In the present invention, “substantially not containing ZnO, B ₂ O ₃ , and F _2” means that although it is contained as an impurity, it is not intentionally contained.

[0023]

The glass fiber of the present invention will be described below in detail with reference to examples.

[0024]

[Table 1]

[0025]

[Table 2]

Glasses having the compositions shown in Tables 1 and 2 were prepared, and the spinning temperature, devitrification temperature, water resistance and acid resistance were measured. First, clay, silica sand, limestone, dolomite, alumina and zirconium oxide are mixed so as to have the glass composition shown in Table 1 and Table 2, and the mixture is heated at 1,500 ° C. for 6 hours using a platinum crucible. Melted. After melting,
The melt was poured out onto a metal plate, formed into a plate having a thickness of about 5 mm, and gradually cooled to obtain a glass for property measurement. The spinning temperature, that is, the temperature corresponding to 1,000 P, was measured by a usual platinum ball pulling-up method.

The devitrification temperature was measured as follows.
That is, a part of the plate-like glass is pulverized to have a diameter of 1,190.
After being granulated to １，1,680 μm and washed with alcohol, it was placed in a platinum boat and kept in an electric furnace having a temperature gradient in the length direction for 2 hours. After the boat was taken out of the electric furnace and allowed to cool, the appearance position of the crystal was directly observed using a polarizing microscope of 50 times magnification, and the highest temperature was defined as the devitrification temperature.

The acid resistance is as follows.
After granulation of 20 to 590 μm, the particles were washed with alcohol, weighed precisely with a specific gravity of gram, immersed in a 10% H ₂ SO ₄ solution at 80 ° C., and after 72 hours, the weight loss rate [%] was calculated. The acid resistance shows that the smaller the weight reduction rate is, the better.

The water resistance was examined by measuring the amount of alkali elution by a method based on JIS R3502. The smaller the amount, the better the water resistance.

Each of the samples of Examples 1 to 9 had a weight loss rate of 0.7% or less due to acid resistance and a water resistance of 0.006 or less.
mg or less, and the refractive index was a good value of 1.565 or more.
Further, the temperature corresponding to 1,000 P representing the spinning temperature is also 1,245 ° C. or less, so that the bushing temperature controllability can be easily performed. Furthermore, since the difference ΔT between the spinning temperature and the devitrification temperature is 40 ° C. or more, devitrification hardly occurs during spinning,
High productivity can be maintained.

Comparative Example 1 is a commercially available E glass, which has poor acid resistance and contains B ₂ O ₃ and F ₂ which pollute the environment. Comparative Example 2 is an example (No. 24) described in U.S. Pat. No. 3,847,627, in which ZrO ₂ is contained but Zn is contained.
Although O and TiO ₂ are contained and the spinning temperature is low, the devitrification temperature is high, so that ΔT, which indicates productivity, becomes small, and stable production is difficult. Comparative Example 3 is described in US Pat. No. 5,789,3.
Example having the lowest spinning temperature described in Japanese Patent Publication No. 29 (No. 29).
However, the spinning temperature is as high as 1,248 ° C., and there is a problem in the temperature controllability and life of the bushing.

As described above, the glass fiber of the present invention has excellent productivity, spinnability, excellent chemical durability, and FR
It is useful as a reinforcing material for P and printed wiring boards.

[0033]

According to the first aspect, ZnO, B ₂ O ₃ , F ₂
It does not contain volatile components such as SiO ₂ , Al ₂ O ₃ , ZrO ₂ , MgO,
While limiting the content of CaO, Na ₂ O, K ₂ O, SiO ₂ + ZrO _2-
By limiting the total amount of Al ₂ O ₃ and alkali metal oxide, glass fiber excellent in chemical durability can be obtained.

According to the second aspect, the glass fiber having more excellent spinnability and productivity can be obtained by limiting the spinning temperature and ΔT (spinning temperature−devitrification temperature) even in the range described in the first aspect. can get.

According to the third aspect, particularly, by limiting the composition range of SiO ₂ , Al ₂ O ₃ , and MgO, a glass fiber excellent in spinning temperature and ΔT, and further excellent in acid resistance and water resistance can be obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Nasuhito Nagashima 3-5-1, Doshomachi, Chuo-ku, Osaka-shi, Japan Inside Nippon Sheet Glass Co., Ltd. (72) Inventor Isamu Kuroda 3 Doshucho, Chuo-ku, Osaka-shi, Osaka 5-11, Nippon Sheet Glass Co., Ltd. F-term (reference) 4G062 AA05 BB01 CC10 DA06 DB03 DC01 DD01 DE01 DF01 EA01 EB01 EB02 EB03 EC01 EC02 EC03 ED03 EE04 EF01 EG01 FA01 FB01 FC02 FC03 FD01 FE01 F01 GA01 F01 GB01 GC01 GD01 GE01 HH01 HH03 HH05 HH07 HH09 HH11 HH13 HH15 HH17 HH20 JJ01 JJ03 JJ05 JJ07 JJ10 KK01 KK03 KK05 KK07 KK10 MM15 MM28 NN33 NN34

Claims (3)

[Claims] 1. In mole percent, silicon dioxide (SiO ₂ ): 56-63%, aluminum oxide (Al ₂ O ₃ ): 4-9%, zirconium oxide (ZrO ₂ ): 0.1-3%, , SiO ₂ + ZrO ₂ -Al ₂ O ₃ ≧ 52%, magnesium oxide (MgO): 1 to 7%, calcium oxide (CaO): 21 to 28%, sodium monoxide (Na ₂ O): 0 to 1. 5%, potassium oxide (K ₂ O): 0 to 1.5%, provided that it contains Na ₂ O + K ₂ O ≦ 1.5%, zinc oxide (ZnO), diboron trioxide (B ₂ O ₃ ) Glass fiber substantially free of fluorine (F ₂ ). 2. The glass fiber according to claim 1, wherein the spinning temperature is 1,245 ° C. or lower, and the difference between the spinning temperature and the devitrification temperature is 40 ° C. or higher. 3. SiO ₂ : 58-61 in mole percent.
_{%, Al 2 O 3: 6~7} %, ZrO 2: 0.1~2%, provided that SiO
₂ + ZrO ₂ -Al ₂ O ₃ ≧ 53%, MgO: 3 to 6%, CaO: 23 to 2
7%, Na ₂ O: 0 to 1%, K ₂ O: 0 to 1%, provided that Na ₂ O + K ₂
Glass fiber containing O ≦ 1%, containing substantially no ZnO, B ₂ O ₃ , and F ₂ , having a spinning temperature of 1,235 ° C. or less, and a difference between the spinning temperature and the devitrification temperature of 50 ° C. or more .