CN116670091A - Glass composition for glass fiber, glass fiber, glass fiber fabric, and glass fiber reinforced resin composition - Google Patents

Abstract

The present invention provides a glass composition for glass fibers having a reduced temperature of 1000 poise. Using this glass composition for glass fibers, glass fibers having excellent water resistance and excellent dielectric properties in a high-frequency region can be obtained. The glass composition for glass fibers contains SiO ₂ in the range of 50.00 to 61.00% by mass, B ₂ O ₃ in the range of 16.00 to 27.00% by mass, and Al ₂ in the range of 7.00 to 14.00% by mass, based on the total amount of the glass composition for glass fibers. O ₃ , P ₂ O ₅ in the range of 0.20 to 4.00 mass %, TiO ₂ in the range of 0.50 to 5.00 mass %, CaO in the range of 0.10 to 5.00 mass %, MgO in the range of 0 to 4.00 mass %, and a total of 0 to 2.00 mass % F ₂ and Cl ₂ , SiO ₂ content S, Al ₂ O ₃ content A, P ₂ O ₅ content P, TiO ₂ content T, CaO content C, and MgO content M The following formula (1) is satisfied: 3.65≦(S/A) ² ×(P×T) ^1/2 /(C+M) ^{3 ≦} 8.25...(1).

Description

Glass composition for glass fiber, glass fiber, glass fiber fabric and glass fiber Reinforced resin composition

technical field

The present invention relates to a glass composition for glass fiber, glass fiber, glass fiber fabric and glass fiber reinforced resin composition.

Background technique

Glass fibers are manufactured by the following process: in a glass melting furnace, the glass raw materials prepared into the glass composition for glass fibers with the desired composition are melted to form molten glass (melted product of the glass composition for glass fibers ), the molten glass is ejected from a container (sleeve) having a nozzle plate formed with several to thousands of nozzle chips, and the molten glass is cooled and solidified while being stretched by high-speed coiling It is made into a fiber form (hereinafter, this operation may be referred to as "spinning"). The sleeve is formed of noble metal such as platinum, for example.

Conventionally, glass fiber has been widely used in various applications because it can increase the strength of resin molded products, which are used in casings and components of electronic equipment such as servers, smartphones, and notebook computers.

Generally, glass absorbs energy as heat against alternating current, and therefore, when the above-mentioned resin molded product is used for the case or component of the above-mentioned electronic device, there is a problem that the resin molded product generates heat.

Here, the dielectric loss energy absorbed by the glass is proportional to the dielectric constant and the dielectric loss tangent determined by the composition and structure of the glass, and can be represented by the following formula (A).

W＝kfv ² ×ε ^1/2 ×tanδ...(A)

Here, W represents dielectric loss energy, k represents a constant, f represents frequency, v ² represents a potential gradient, ε represents a dielectric constant, and tan δ represents a dielectric loss tangent. It can be seen from formula (A) that the larger the dielectric constant and the dielectric loss tangent, and the higher the frequency, the larger the dielectric loss, and thus the larger the heat generation of the resin molded product.

In recent years, the frequency of the alternating current (f in the above formula (A)) used in the above-mentioned electronic equipment has become higher. In order to reduce the dielectric loss energy, the glass fiber used in the housing or parts of the above-mentioned electronic equipment has been required to have Lower dielectric constant and dielectric loss tangent. In particular, since the dielectric loss tangent has a greater influence on the above formula (A) than the dielectric constant of the 1/2 power, a low dielectric loss tangent is required.

In view of the above circumstances, the applicant proposed the following glass composition for glass fibers which has a low dielectric constant and a low dielectric loss tangent and which suppresses phase separation and further reduces viscosity at high temperatures. The glass composition for glass fiber contains SiO ₂ in the range of 52.0 to 59.5 mass %, B ₂ O ₃ in the range of 17.5 to 25.5 mass %, Al ₂ O ₃ in the range of 9.0 to 14.0 mass %, relative to the total amount of the glass composition for glass fiber. SrO in the range of 0.5 to 6.0% by mass, MgO in the range of 1.0 to 5.0% by mass, CaO in the range of 1.0 to 5.0% by mass, and a total of _F2 and _Cl2 in the range of 0.1 to 2.5% by mass (see Patent Document 1).

prior art literature

patent documents

Patent Document 1: Japanese Patent No. 6468409

Contents of the invention

The problem to be solved by the invention

On the other hand, there is a particular demand for a glass composition for glass fibers having glass fibers having lower dielectric constant and dielectric loss tangent in the high frequency region around 10 GHz. In order to achieve the above-mentioned problems, it is considered to reduce the Use the content of Al ₂ O ₃ and alkaline earth metal oxides (CaO, MgO, and SrO) in the glass composition relative to the total amount of the glass composition for glass fibers to increase the content of SiO ₂ and B ₂ O ₃ accordingly Rate.

However, when the content of _SiO2 in the above-mentioned glass composition for glass fibers relative to the total amount of the glass composition for glass fibers increases, the 1000 Poise temperature increases and the viscosity of the glass also increases, making it difficult to mix. It is difficult to melt homogeneous glass and the deterioration of the sleeve becomes premature when spinning.

In order to solve the above-mentioned problems, it is conceivable to adopt the following technical solution: In the above-mentioned glass composition for glass fibers, P ₂ O ₅ is used instead of a part of the content of SiO ₂ with respect to the total amount of the glass composition for glass fibers, thereby, While maintaining excellent dielectric properties (low dielectric constant and low dielectric loss tangent) in the high frequency region, the temperature can be reduced by 1000 Poise.

However, in the above-mentioned glass composition for glass fibers, if P ₂ O ₅ is used instead of a part of the content of SiO ₂ relative to the total amount of the glass composition for glass fibers, the glass fibers obtained from the glass composition for glass fibers will be There is a problem that the water resistance of the glass is lowered, and the dielectric properties are deteriorated due to the foreign matter deposited on the surface of the glass fiber due to the hydrolysis of the glass, and the strength of the glass fiber is greatly reduced.

The present invention solves the above-mentioned problems, and aims to provide a glass composition for glass fibers having its own lowered temperature of 1000 poise, and by using the glass composition for glass fibers, it is possible to obtain a Excellent dielectric properties.

means to solve the problem

In order to achieve the above object, the glass composition for glass fibers of the present invention is characterized in that the glass composition for glass fibers contains SiO ₂ in the range of 50.00 to 61.00% by mass relative to the total amount of the glass composition for glass fibers, 16.00 to B ₂ O ₃ in the range of 27.00 mass %, Al 2 O ₃ in the range of 7.00 to 14.00 mass _{%, P 2 O 5} in the range of 0.20 to 4.00 mass %, TiO ₂ in the range of 0.50 to 5.00 mass %, and in the range of 0.10 to 5.00 mass % CaO in the range of 0-4.00% by mass, MgO in the range of 0-4.00% by mass, and F ₂ and Cl ₂ in the range of 0-2.00% by mass in total, the content (mass %) of the SiO ₂ S, the content of the Al ₂ O ₃ ( mass %) A, the P ₂ O content (mass %) P, the TiO ₂ content (mass %) _T , the CaO content (mass %) C, and the MgO content The ratio (mass %) M satisfies the following formula (1),

3.65≤(S/A) ² ×(P×T) ^1/2 /(C+M) ³ ≤8.25…(1)

The glass composition for glass fibers of the present invention contains SiO ₂ , B ₂ O ₃ , Al ₂ O ₃ , P ₂ O ₅ , TiO ₂ , CaO, MgO, F ₂ and Cl ₂ in the above range, and the content of SiO ₂ ( Mass %) S, Al ₂ O ₃ content (mass %) A, P ₂ O ₅ content (mass %) P, TiO ₂ content (mass %) T, CaO content (mass %) The content rate (mass %) M of C and MgO satisfies formula (1), thereby, can have the 1000 poise temperature that itself is lowered, and utilize this glass composition for glass fiber to obtain excellent water resistance and high frequency Glass fibers with excellent dielectric properties such as low dielectric constant and low dielectric loss tangent under the region.

It should be noted that the glass fiber obtained by using the glass composition for glass fiber of the present invention has a low dielectric constant means that the dielectric constant is 4.1 or less at a measurement frequency of 10 GHz, and having a low dielectric loss tangent means that the glass fiber has a low dielectric constant. The loss tangent is 0.0011 or less at a measurement frequency of 10 GHz.

In addition, the glass fiber obtained by using the glass composition for glass fiber of the present invention exhibits excellent water resistance means that when evaluated by the following water resistance evaluation method, the mass loss rate is 2.0% or less, and there is almost no water resistance in water. Dissolution of glass fiber components.

In the evaluation method of water resistance, first, the glass batch material obtained by mixing glass raw materials to have a predetermined glass composition for glass fibers is placed in a platinum crucible with a diameter of 80 mm, and heated at a temperature of 1550 ° C. After heating for 4 hours, it was further melted by heating at a temperature of 1650°C for 2 hours. Next, the homogeneous glass chips taken out from the crucible were put into a small cylindrical platinum sleeve having one circular nozzle tip at the bottom of the container, heated to a predetermined temperature, and melted. Then, the molten glass discharged from the nozzle head is wound around a stainless steel collet at a predetermined speed, thereby cooling and solidifying the molten glass while stretching it, and obtaining a fiber diameter having a circular cross section in a perfect circle shape. 13μm glass fiber. Next, about 1 g (glass fiber for test) of the above-obtained glass fiber was collected from the collet, dried at a temperature of 120° C. for 1 hour, and the mass (mass before operation) was measured. Next, the test glass fiber was placed in 100 ml of distilled water at a temperature of 80°C for 24 hours, and then the test glass fiber was obtained using a metal mesh with an opening of about 150 μm, washed with distilled water, and dried at a temperature of 120°C. After 1 hour, the mass (mass after operation) was measured. Then, the mass reduction rate (100×(1−(mass after operation/mass before operation))) was calculated from the above-mentioned mass before operation and mass after operation.

In addition, that the glass composition for glass fibers of the present invention has a reduced 1000 poise temperature means that the 1000 poise temperature is 1500° C. or lower.

In addition, in the glass composition for glass fibers of the present invention, the above-mentioned S, A, P, T, C and M preferably satisfy the following formula (2), more preferably satisfy the following formula (3), and further preferably satisfy the following Formula (4).

4.51≤(S/A) ² ×(P×T) ^1/2 /(C+M) ³ ≤7.32…(2)

4.87≤(S/A) ² ×(P×T) ^1/2 /(C+M) ³ ≤7.20…(3)

5.96≤(S/A) ² ×(P×T) ^1/2 /(C+M) ³ ≤7.16…(4)

In addition, the present invention is also a glass fiber characterized by being composed of any one of the above-mentioned glass compositions for glass fibers. In addition, the present invention is also a glass fiber fabric characterized by containing the glass fiber. Furthermore, the present invention is also a glass fiber-reinforced resin composition characterized by containing the glass fiber.

The glass fiber of the present invention can be obtained, for example, by melting the above-mentioned glass composition for glass fiber of the present invention, and spraying the obtained melt from a sleeve having a nozzle plate having 1 to 8,000 nozzle tips or holes formed therein. , and coiled at a high speed, thereby cooling and solidifying the molten material while stretching it, and forming it into a fibrous shape. Therefore, the glass fiber of this invention has the same glass composition as the glass composition for glass fibers of this invention mentioned above.

Detailed ways

Next, embodiments of the present invention will be described in more detail.

The glass composition for glass fibers according to this embodiment contains SiO ₂ in the range of 50.00 to 61.00 mass %, B ₂ O ₃ in the range of 16.00 to 27.00 mass %, and 7.00 to 14.00 mass % with respect to the total amount of the glass composition for glass fibers. Al ₂ O ₃ in the range of 0.20 to 4.00 mass %, P ₂ O ₅ in the range of 0.20 to 4.00 mass %, TiO ₂ in the range of 0.50 to 5.00 mass %, CaO in the range of 0.10 to 5.00 mass %, MgO in the range of 0 to 4.00 mass %, and a total of 0 ~2.00% by mass of _F2 and _Cl2 , _the content of _SiO2 (mass%) S, _the content of _Al2O3 (mass%)A, the content of _P2O5 ( Mass %) P, the TiO ₂ content (mass %) T, the CaO content (mass %) C, and the MgO content (mass %) M satisfy the following formula (1).

3.65≤(S/A) ² ×(P×T) ^1/2 /(C+M) ³ ≤8.25…(1)

The glass composition for glass fibers according to the present embodiment contains SiO ₂ , B ₂ O ₃ , Al ₂ O ₃ , P ₂ O ₅ , TiO ₂ , CaO, MgO, F ₂ , and Cl ₂ within the above range, and the content of SiO ₂ (mass %) S, Al ₂ O ₃ content (mass %) A, P ₂ O ₅ content (mass %) P, TiO ₂ content (mass %) T, CaO content (mass %) ) C and MgO content rate (mass %) M satisfies the formula (1), thereby, can have the lowered 1000 poise temperature of less than 1500 ℃ itself, and can use the glass composition for glass fibers to obtain excellent Glass fiber with excellent dielectric properties such as water resistance, low dielectric constant of 4.1 or less and low dielectric loss tangent of 0.0011 or less in the high-frequency region of the measurement frequency of 10 GHz.

Here, in the formula (1), "S/A" is the ratio of the content of SiO ₂ to the content of Al ₂ O ₃ , and the smaller the value, the higher the content of Al ₂ O ₃ is. In this case, the dielectric properties of the glass fibers tend to deteriorate. On the other hand, a larger "S/A" means that the content of _SiO2 is relatively higher, which contributes to the improvement of the dielectric properties of the glass fiber, but has the disadvantage that the 1000 Poise temperature of the glass composition for glass fiber becomes higher. tendency.

"P×T" is the product of P ₂ O ₅ and TiO ₂ as an intermediate oxide. The larger the value, the better the dielectric properties of the glass fiber, but the water resistance of the glass fiber tends to deteriorate. On the other hand, the smaller "PxT" is, the higher the viscosity of the molten glass tends to be, and the 1000 poise temperature of the glass composition for glass fibers tends to be higher.

"C+M" is the total content of CaO and MgO, which are alkaline earth metal oxides that greatly affect the dielectric properties of glass fibers, and the larger the value, the lower the dielectric properties of glass fibers tend to be. On the other hand, the smaller the "C+M", the higher the 1000 Poise temperature of the glass composition for glass fibers tends to be.

Therefore, formula (1) synthesizes these tendencies, and it can be inferred that it reflects the balance of the dielectric properties of glass fibers, the water resistance of glass fibers, and the 1000-poise temperature of the glass composition for glass fibers.

In the glass composition for glass fibers of this embodiment, if the content of SiO ₂ relative to the total amount of the glass composition for glass fibers is less than 50.00% by mass, the mechanical properties of the glass fibers obtained from the glass composition for glass fibers will be reduced. The strength is greatly reduced, and the function of the glass fiber as a reinforcing material in the glass fiber reinforced resin composition is impaired. In addition, the glass fibers tend to deteriorate when placed in an acidic environment. On the other hand, if the content of _SiO2 with respect to the total amount of the glass composition for glass fibers exceeds 61.00% by mass, the viscosity at high temperature becomes high, so the temperature at which the glass raw material is melted becomes high, and from the viewpoint of production cost Starting, not suitable for industrial glass fiber manufacturing.

In the glass composition for glass fibers according to this embodiment, the content of _SiO2 relative to the total amount of the glass composition for glass fibers is preferably in the range of 52.10 to 59.90% by mass, more preferably in the range of 54.10 to 59.70% by mass, and even more preferably 56.10-59.60 mass % range, especially preferably 57.60-59.50 mass % range, most preferably 58.10-59.40 mass % range.

In the glass composition for glass fibers according to this embodiment, if the content of B ₂ O ₃ with respect to the total amount of the glass composition for glass fibers is less than 16.00% by mass, the amount obtained by using the glass composition for glass fibers cannot be sufficiently reduced. The dielectric loss tangent of the glass fiber. On the other hand, if the content of _B2O3 with respect to the total amount of the glass composition for glass fibers exceeds 27.00% _by mass, the glass fibers obtained from the glass composition for glass fibers will undergo phase separation, and the chemical durability of the glass fibers will be reduced. Sexuality may decrease.

In the glass composition for glass fibers according to this embodiment, the content of B ₂ O ₃ with respect to the total amount of the glass composition for glass fibers is preferably in the range of 19.60 to 24.90% by mass, more preferably in the range of 20.10 to 24.50% by mass, and further It is preferably in the range of 20.60 to 24.00 mass %, particularly preferably in the range of 21.10 to 23.50 mass %, and most preferably in the range of 21.50 to 23.00 mass %.

In the glass composition for glass fibers of the present embodiment, by making the content of _B2O3 to be 19.60% by mass or more relative to the total amount of _the glass composition for glass fibers, the molten glass obtained by using the glass composition for glass fibers The viscosity is kept at a low level, and the manufacturing cost is reduced, so it is suitable for industrial glass fiber manufacturing.

In the glass composition for glass fibers of the present embodiment, the content of B ₂ O ₃ is 24.90% by mass or less with respect to the total amount of the glass composition for glass fibers, and the glass composition for glass fibers by melting glass can be reduced. Volatile components in the manufacture of glass fibers. In addition, the loss of the furnace body of the glass melting furnace for melting the glass composition for glass fibers can be reduced, and the life of the furnace body becomes longer, so that the production cost can be reduced.

In the glass composition for glass fibers of the present embodiment, if the content of Al ₂ O ₃ with respect to the total amount of the glass composition for glass fibers is less than 7.00% by mass, the glass fibers obtained from the glass composition for glass fibers will be Phase separation may reduce the chemical durability of glass fibers. On the other hand, when the content of Al ₂ O ₃ with respect to the total amount of the glass composition for glass fibers exceeds 14.00% by mass, the dielectric loss tangent of glass fibers obtained from the glass composition for glass fibers cannot be sufficiently reduced.

In the glass composition for glass fibers of the present embodiment, the content of Al ₂ O ₃ to the total amount of the glass composition for glass fibers is preferably in the range of 8.00 to 13.50% by mass, more preferably in the range of 9.00 to 13.00% by mass , more preferably in the range of 9.60 to 12.80% by mass, especially preferably in the range of 10.10 to 12.40% by mass, particularly preferably in the range of 10.30 to 11.90% by mass, extremely preferably in the range of 10.50 to 11.50% by mass, most preferably in the range of 10.60 to 11.90% by mass 10.90% by mass range.

In the glass composition for glass fibers of the present embodiment, by making the content of Al ₂ O ₃ relative to the total amount of the glass composition for glass fibers 13.00% by mass or less, the liquidus temperature is greatly reduced, and the working temperature range is widened. Therefore, stable spinning can be performed.

In the glass composition for glass fibers of the present embodiment, if the content of _P2O5 with respect to the total amount of the glass composition for glass fibers is less than 0.20% by _mass , it will be difficult to balance the quality of the glass obtained from the glass composition for glass fibers. A reduction in the dielectric loss tangent of the fibers and a reduction in the 1000 Poise temperature of the glass composition for glass fibers. On the other hand, if the content of _P2O5 with respect to the _total amount of the glass composition for glass fibers exceeds 4.00% by mass, phase separation of the glass fibers obtained by using the glass composition for glass fibers cannot be suppressed, and the water resistance will deteriorate. .

In the glass composition for glass fibers according to this embodiment, the content of P ₂ O ₅ with respect to the total amount of the glass composition for glass fibers is preferably in the range of 0.30 to 3.50% by mass, and more preferably in the range of 0.50 to 3.20% by mass. , more preferably in the range of 0.70 to 2.90 mass%, particularly preferably in the range of 0.90 to 2.70 mass%, most preferably in the range of 1.00 to 2.50 mass%.

In the glass composition for glass fibers according to the present embodiment, when the content of _TiO2 is less than 0.50% by mass relative to the total amount of the glass composition for glass fibers, the viscosity at high temperature becomes high, so the temperature at which the glass raw material is melted becomes low. High, from the viewpoint of manufacturing cost, it is not suitable for industrial glass fiber manufacturing. On the other hand, when the content of _TiO2 with respect to the total amount of the glass composition for glass fibers exceeds 5.00% by mass, the dielectric loss tangent of the glass fibers obtained by using the glass composition for glass fibers cannot be sufficiently reduced. , since the liquidus temperature of the glass composition for glass fibers increases significantly, stable glass fibers cannot be produced.

In the glass composition for glass fibers of the present embodiment, the content of _TiO2 relative to the total amount of the glass composition for glass fibers is preferably in the range of 0.60 to 4.90% by mass, more preferably in the range of 1.00 to 4.50% by mass, and furthermore Preferably it is in the range of 1.50 to 4.00 mass %, especially preferably in the range of 1.60 to 3.50 mass %, particularly preferably in the range of 1.70 to 3.40 mass %, particularly preferably in the range of 1.80 to 3.30 mass %, most preferably in the range of 2.10 to 3.20 mass % % range.

In the glass composition for glass fibers of this embodiment, if the content of CaO is less than 0.10% by mass relative to the total amount of the glass composition for glass fibers, it is difficult to suppress the crystallization of glass, and the liquid phase of the glass composition for glass fibers The temperature increases significantly, and therefore, the operating temperature range cannot be sufficiently ensured. On the other hand, when the content of CaO exceeds 5.00 mass % with respect to the whole glass composition for glass fibers, the dielectric loss tangent of the glass fiber obtained using this glass composition for glass fibers cannot fully be reduced.

In the glass composition for glass fibers according to the present embodiment, the content of CaO relative to the total amount of the glass composition for glass fibers is preferably in the range of 0.50 to 4.50% by mass, more preferably in the range of 0.70 to 4.00% by mass, and even more preferably It is in the range of 0.90 to 3.50% by mass, particularly preferably in the range of 1.10 to 3.00% by mass, extremely preferably in the range of 1.30 to 2.70% by mass, and most preferably in the range of 1.50 to 2.50% by mass.

In the glass composition for glass fibers of this embodiment, if the content of MgO exceeds 4.00% by mass relative to the total amount of the glass composition for glass fibers, striae will be generated in the melt of the glass composition for glass fibers, There is a possibility that breakage of the glass fiber is likely to occur during spinning.

In the glass composition for glass fibers according to this embodiment, the content of MgO relative to the total amount of the glass composition for glass fibers is preferably less than 3.00% by mass, more preferably less than 2.00% by mass, even more preferably less than 2.00% by mass. The range of 1.50 mass % is particularly preferably less than 1.00 mass %, especially preferably less than 0.95 mass %, most preferably less than 0.50 mass %.

In the glass composition for glass fibers of this embodiment, if the total content of _F2 and _Cl2 with respect to the total amount of the glass composition for glass fibers exceeds 2.00% by mass, the glass obtained by using the glass composition for glass fibers The chemical durability of the fiber is reduced.

In the glass composition for glass fibers according to this embodiment, the total content of _F2 and _Cl2 with respect to the total amount of the glass composition for glass fibers is preferably in the range of 0.10 to 1.80% by mass, more preferably 0.30 to 1.60% by mass The range of 0.50-1.50 mass % is more preferable.

In the glass composition for glass fibers of the present embodiment, the total content of _F2 and _Cl2 with respect to the total amount of the glass composition for glass fibers is 0.30% by mass or more, thereby further reducing the amount of the glass composition used for glass fibers. The dielectric constant of the obtained glass fiber.

In the glass composition for glass fibers of this embodiment, the total content of _F2 and _Cl2 with respect to the total amount of the glass composition for glass fibers is 1.60% by mass or less. In the case of glass fibers, the generation of volatiles derived from _F2 and Cl2 can be suppressed, and the deterioration of the environment around the furnace body of the glass melting furnace that melts the glass composition for glass fibers can be prevented.

Moreover, the glass composition for glass fibers of this embodiment can contain SrO in the range of 0-6.00 mass % with respect to the glass composition total amount for glass fibers. When the glass composition for glass fibers of this embodiment contains SrO, if the content of SrO exceeds 6.00% by mass, the dielectric properties of the glass fibers obtained from the glass composition for glass fibers deteriorate and cannot satisfy the target dielectric properties. electrical characteristics.

When the glass composition for glass fibers of the present embodiment contains SrO, the content of SrO relative to the total amount of the glass composition for glass fibers is preferably in the range of 4.00% by mass or less, more preferably in the range of 3.00% by mass or less, It is more preferably in the range of 2.00% by mass or less, particularly preferably in the range of less than 1.00% by mass, extremely preferably in the range of less than 0.50% by mass, and most preferably in the range of less than 0.45% by mass.

Moreover, the glass composition for glass fibers of this embodiment may contain _Na2O , _K2O , and _Li2O in the range whose total content rate is less than 1.00 mass % with respect to the glass composition whole quantity for glass fibers. When the glass composition for glass fibers according to this embodiment contains Na ₂ O, K ₂ O, and Li ₂ O, if their total content exceeds 1.00% by mass, the glass obtained from the glass composition for glass fibers will The dielectric properties of the fibers deteriorated significantly, and the target dielectric properties could not be achieved.

When the glass composition for glass fibers of this embodiment contains Na ₂ O, K ₂ O, and Li ₂ O, the total of Na ₂ O, K ₂ O, and Li ₂ O relative to the total amount of the glass composition for glass fibers The content is preferably less than 0.80% by mass, more preferably less than 0.50% by mass, still more preferably less than 0.20% by mass, particularly preferably less than 0.10% by mass, most preferably less than 0.05% by mass .

Moreover, the glass composition for glass fibers of this embodiment may contain ZnO in the range of 0-3.00 mass % of content rate with respect to the glass composition whole quantity for glass fibers. When the glass composition for glass fibers of the present embodiment contains ZnO, if the content of ZnO exceeds 3.00% by mass, the glass fibers obtained by using the glass composition for glass fibers tend to generate devitrified matter during spinning, and cannot While stable glass fiber production is performed, the dielectric properties of the glass fiber deteriorate.

When the glass composition for glass fibers according to this embodiment contains ZnO, the content of ZnO relative to the total amount of the glass composition for glass fibers is preferably in the range of 2.50% by mass or less, more preferably in the range of 1.50% by mass or less, even more preferably It is in the range of 0.50% by mass or less.

Moreover, the glass composition for glass fibers of this embodiment can contain _MnO2 in the range of 0-3.00 mass % with respect to the glass composition total amount for glass fibers. When the glass composition for glass fibers of the present embodiment contains MnO ₂ , if the content of MnO ₂ exceeds 3.00% by mass, the dielectric properties of the glass fibers obtained from the glass composition for glass fibers will deteriorate, and the desired dielectric properties.

When the glass composition for glass fibers according to the present embodiment contains MnO ₂ , the content of MnO ₂ with respect to the total amount of the glass composition for glass fibers is preferably 2.50% by mass or less, more preferably 1.50% by mass or less. range, more preferably a range of 0.50% by mass or less.

Moreover, the glass composition for glass fibers _of this embodiment may contain _Fe2O3 in the range of 0 mass % or more and 1.00 mass % or less with respect to the glass composition total amount for glass fibers. When the glass composition for glass fibers according to _the present embodiment contains _Fe2O3 , it is effective from the _viewpoint of suppressing air bubbles contained in the glass fibers that the content of _Fe2O3 is 0.10% by mass or more and The range of 0.60 mass % or less.

Moreover, the glass composition for glass fibers of this embodiment may contain _SnO2 in the range of 0 mass % or more and 1.00 mass % or less with respect to the glass composition total amount for glass fibers. When the glass composition for glass fibers according to the present embodiment contains SnO ₂ , from the viewpoint of suppressing air bubbles contained in the glass fibers, it is effective that the content of SnO ₂ is not less than 0.10% by mass and not more than 0.60% by mass. range.

Moreover, the glass composition for glass fibers of this embodiment may contain _ZrO2 as long as the content rate of ZrO2 with respect to the glass composition whole quantity for glass fibers is less _than 0.50 mass %. When the glass composition for glass fibers according to this embodiment contains ZrO ₂ , if the content of ZrO ₂ relative to the total amount of the glass composition for glass fibers is 0.50% by mass or more, the glass composition for glass fibers obtained by using the glass composition for glass fibers Glass fibers are prone to devitrification during spinning, and stable glass fiber production cannot be performed.

When the glass composition for glass fibers according to this embodiment contains ZrO ₂ , the content of ZrO ₂ with respect to the total amount of the glass composition for glass fibers is preferably less than 0.45% by mass, more preferably less than 0.40% by mass. , more preferably less than 0.20% by mass, particularly preferably less than 0.10% by mass, and most preferably less than 0.05% by mass.

Moreover, the glass composition for glass fibers _of this embodiment may contain _Cr2O3 as long as the content rate of _Cr2O3 with respect to the glass composition whole quantity for glass fibers is less than _0.05 mass %. When the glass composition for glass fibers of this embodiment contains Cr ₂ O ₃ , if the content of Cr ₂ O ₃ relative to the total amount of the glass composition for glass fibers is 0.05% by mass or more, the glass for glass fibers The glass fiber obtained from the composition tends to generate devitrified matter during spinning, and stable glass fiber production cannot be performed.

In addition, in the glass composition for glass fibers of the present embodiment, as impurities derived from raw materials, Ba and Co may be contained in a total content rate of less than 1.00% by mass relative to the total amount of the glass composition for glass fibers. , Ni, Cu, Mo, W, Ce, Y, La, Bi, Gd, Pr, Sc or Yb oxides. In particular, the glass composition for glass fibers of this embodiment contains BaO, CeO ₂ , Y ₂ O ₃ , La ₂ O ₃ , Bi ₂ O ₃ , Gd ₂ O ₃ , Pr ₂ O ₃ , Sc ₂ O ₃ or Yb When ₂ O ₃ is used as an impurity, the content thereof is preferably less than 0.40% by mass, more preferably less than 0.20% by mass, still more preferably less than 0.10% by mass, and particularly preferably less than 0.05% by mass. , most preferably less than 0.01% by mass.

In addition, in the glass composition for glass fibers of the present embodiment, the aforementioned S, A, P, T, C, and M preferably satisfy the following formula (1-1), more preferably satisfy the following formula (1-2), It is more preferable to satisfy the following formula (1-3), particularly preferably to satisfy the following formula (2), extremely preferably to satisfy the following formula (3), and most preferably to satisfy the following formula (4).

3.86≤(S/A) ² ×(P×T) ^1/2 /(C+M) ³ ≤7.32…(1-1)

4.00≤(S/A) ² ×(P×T) ^1/2 /(C+M) ³ ≤7.32…(1-2)

4.25≤(S/A) ² ×(P×T) ^1/2 /(C+M) ³ ≤7.32…(1-3)

4.51≤(S/A) ² ×(P×T) ^1/2 /(C+M) ³ ≤7.32…(2)

4.87≤(S/A) ² ×(P×T) ^1/2 /(C+M) ³ ≤7.20…(3)

5.96≤(S/A) ² ×(P×T) ^1/2 /(C+M) ³ ≤7.16…(4)

By making the glass composition for glass fibers of the present embodiment satisfy the formula (2), it is possible to have a lower 1000 poise temperature lower than 1500° C., and the glass composition for glass fibers with excellent water resistance can be obtained. It is a glass fiber having extremely excellent dielectric properties such as a low dielectric constant of 4.0 or less and a low dielectric loss tangent of 0.0010 or less in the high-frequency region of the measurement frequency of 10 GHz.

In addition, by making the glass composition for glass fibers of the present embodiment satisfy the formula (3), it is possible to have excellent glass fiber manufacturability with a reduced 1000 poise temperature below 1500°C and an operating temperature range of 150°C or higher. , and the glass composition for glass fibers can be used to obtain an extremely excellent dielectric material having excellent water resistance and a low dielectric constant of 4.0 or less and a low dielectric loss tangent of 0.0010 or less in the high-frequency region of the measurement frequency of 10 GHz. Electrical properties of glass fibers.

In addition, by making the glass composition for glass fiber according to the present embodiment satisfy the formula (4), it is possible to have an extremely excellent glass fiber having a reduced 1000 poise temperature below 1500°C and an operating temperature range of 200°C or higher. Manufacturability, and the use of the glass composition for glass fibers can obtain excellent water resistance and a low dielectric constant of 4.0 or less and a low dielectric loss tangent of 0.0010 or less in the high-frequency region of the measurement frequency of 10 GHz. Dielectric properties of glass fibers.

In addition, in the glass composition for glass fibers of this embodiment, regarding the content rate of each said component, Li which is a light element can be measured using an ICP emission spectrometer, and a wavelength dispersion type fluorescent X-ray analyzer can be used. Determination of other elements.

The measurement method is as follows: First, put the glass batch prepared by mixing glass raw materials into a platinum crucible, keep it at 1550°C for 4 hours in an electric furnace, and then keep it at 1650°C for 2 hours while stirring While melting, a homogeneous molten glass is obtained. Alternatively, glass fibers were put in a platinum crucible, kept in an electric furnace at a temperature of 1550° C. for 6 hours, and melted while stirring to obtain a homogeneous molten glass.

When organic matter is attached to the surface of glass fiber, or when glass fiber is mainly contained in organic matter (resin) as a reinforcing material, heating in a muffle furnace at a temperature of 300 to 650°C for about 0.5 to 24 hours, etc. , Remove the organic matter and then use the above-mentioned glass fiber.

Next, the obtained molten glass was flowed out onto a carbon plate to form glass shavings, which were pulverized and powdered. Li, which is a light element, was quantitatively analyzed using an ICP emission spectrometer after thermally decomposing the glass powder obtained above with an acid. After molding the above-mentioned glass powder into a disc shape with a press, quantitative analysis of other elements was carried out using a wavelength dispersive fluorescent X-ray analyzer. Specifically, the quantitative analysis using a wavelength dispersive fluorescent X-ray analyzer prepared samples for a calibration curve based on the results measured by the fundamental parameter method, and analyzed by the calibration curve method. It should be noted that the content of each component in the sample for the calibration curve can be quantitatively analyzed by an ICP emission spectrometer. These quantitative analysis results can be converted into oxides to calculate the content and total amount of each component, and the content rate of each of the above-mentioned components can be calculated from these numerical values.

The glass composition for glass fibers of this embodiment can be obtained by cooling and solidifying the glass raw material (glass batch material) prepared so that it may become the said composition after melting and solidification.

When forming the glass fiber of the present embodiment using the glass composition for glass fiber of the present embodiment, first, the glass raw material prepared as described above is supplied to a glass melting furnace, and the glass is heated in the temperature region above the above-mentioned 1000 poise temperature, specifically Specifically, it is melted at a temperature in the range of 1400°C to 1700°C. Then, the molten glass melted to the temperature is ejected from 1 to 8,000 nozzle heads or holes controlled to a predetermined temperature, and is cooled while stretching by high-speed coiling, and solidified to form a glass. fiber.

Here, the cooled and solidified glass single fiber (glass filament) ejected from one nozzle head or hole usually has a perfect circular cross-sectional shape and a diameter in the range of 3.0 to 35.0 μm. In applications requiring low dielectric properties, the glass filaments preferably have a diameter in the range of 3.0 to 6.0 μm, and more preferably have a diameter in the range of 3.0 to 4.5 μm.

On the other hand, in the case where the above-mentioned nozzle head has a non-circular shape and has a protrusion or a notch for quenching the molten glass, by controlling the temperature conditions, it is possible to obtain a non-circular (for example, oval, oblong shape) cross-sectional shape of glass filaments. When the glass filament has an elliptical or oblong cross-sectional shape, the ratio of the major diameter to the minor diameter (major diameter/short diameter) of the cross-sectional shape is, for example, in the range of 2.0 to 10.0, when the cross-sectional area is converted into a perfect circle The fiber diameter (converted fiber diameter) is in the range of 3.0 to 35.0 μm.

The glass fiber of this embodiment takes the shape of the glass fiber bundle (glass strand) which bundled the said glass filament in the range of 10-8000 normally, and has the weight in the range of 1-10000 tex (g/km). It should be noted that glass filaments ejected from a plurality of nozzle heads or holes may be bundled into one glass fiber bundle, or may be bundled into a plurality of glass fiber bundles.

The glass fiber of this embodiment can take the following various forms: yarn, fabric, braided fabric, non-woven fabric (including chopped strand mat, multiaxial non-woven fabric) obtained by further processing the above-mentioned glass strands. ), chopped strands, rovings, powders, etc.

From the purpose of improving the bundling of glass filaments, improving the adhesion between glass fibers and resins, and improving the uniform dispersion of glass fibers in the mixture of glass fibers and resins or inorganic materials, the glass fibers of this embodiment can be made The surface is coated with organic matter. Examples of such organic substances include starch, polyurethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene (especially carboxylic acid-modified polypropylene), (poly)carboxylic acid (especially Copolymers of acid) and unsaturated monomers, etc.

In addition, the glass fiber of the present embodiment may be coated with a resin composition containing a silane coupling agent, a lubricant, a surfactant, and the like in addition to these resins. In addition, the glass fiber of this embodiment may not contain the said resin, but may be coated with the processing agent composition containing a silane coupling agent, a surfactant, etc. Based on the mass of the glass fiber of this embodiment in the state not covered by the resin composition or the treatment agent composition, such a resin composition or treatment agent composition coats the glass in a ratio in the range of 0.03 to 2.0% by mass. fiber.

It should be noted that the coating of glass fibers with organic substances can be carried out, for example, by applying a resin solution or a resin composition solution to the glass fibers in a glass fiber manufacturing process using a known method such as a roll coater. , and then dry the glass fibers to which the resin solution or the resin composition solution has been applied. In addition, the coating of glass fibers with organic substances can also be carried out by immersing the glass fibers of this embodiment in the form of fabrics in a treatment agent composition solution, and then applying the treatment agent composition to the glass fibers. dry.

Here, examples of the silane coupling agent include aminosilane, chlorosilane, mercaptosilane, vinylsilane, (meth)acrylic silane, and the like.

Examples of aminosilanes include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-N' -β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane and the like.

Examples of the chlorosilane include γ-chloropropyltrimethoxysilane and the like.

Examples of epoxysilane include (β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and the like.

Examples of the mercaptosilane include γ-mercaptotrimethoxysilane and the like.

Examples of vinylsilane include vinyltrimethoxysilane and N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane.

Examples of (meth)acrylic silanes include γ-methacryloxypropyltrimethoxysilane and the like.

In this embodiment, the above-mentioned silane coupling agents may be used alone, or two or more of the above-mentioned silane coupling agents may be used in combination.

Examples of lubricants include modified silicone oils, animal oils and their hydrogenated products, vegetable oils and their hydrogenated products, animal waxes, vegetable waxes, mineral waxes, condensates of higher saturated fatty acids and higher saturated alcohols, polyethylene glycol Amines, polyalkylpolyamine alkyllinoside derivatives, fatty acid amides, quaternary ammonium salts, etc.

Examples of animal oil include beef tallow and the like.

Examples of vegetable oils include soybean oil, coconut oil, rapeseed oil, palm oil, and castor oil.

Examples of animal waxes include beeswax, wool, and the like.

Examples of vegetable waxes include candelilla wax, carnauba wax, and the like.

Examples of mineral waxes include paraffin wax, montan wax, and the like.

Stearic acid esters, such as lauryl stearate, etc. are mentioned as a condensate of a higher saturated fatty acid and a higher saturated alcohol.

Examples of fatty acid amides include dehydration condensation of polyethylene polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine with fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid. things etc.

Examples of the quaternary ammonium salt include alkyltrimethylammonium salts such as lauryltrimethylammonium chloride and the like.

In this embodiment, the above-mentioned lubricants may be used alone, or two or more of the above-mentioned lubricants may be used in combination.

Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. In this embodiment, the above-mentioned surfactants may be used alone, or two or more of the above-mentioned surfactants may be used in combination.

Examples of nonionic surfactants include ethylene oxide oxypropylene alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene-polyoxypropylene-block copolymers, alkylpolyoxyethylene-polyoxypropylene- Block copolymer ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid monoester, polyoxyethylene fatty acid diester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester ethylene oxide adduct, Polyoxyethylene stearyl ether, hydrogenated castor oil ethylene oxide adduct, alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, glycerin fatty acid ester, polyglycerol fatty acid ester , pentaerythritol fatty acid esters, sorbitol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyol alkyl ethers, fatty acid alkanolamides, acetylene glycols, acetylene alcohols, acetylene glycol epoxy Ethane adducts, ethylene oxide adducts of acetylenic alcohols.

As cationic surfactant, can enumerate: Chloride alkyl dimethyl benzyl ammonium, chloride alkyl trimethyl ammonium, alkyl dimethyl ethyl ammonium ethyl sulfate, higher alkyl amine salt ( Acetate or hydrochloride, etc.), ethylene oxide adducts to higher alkylamines, condensation products of higher fatty acids and polyalkylene polyamines, ester salts of higher fatty acids and alkanolamines, higher fatty acid amides Salts, imidazoline cationic surfactants, alkylpyridinium salts.

Examples of anionic surfactants include higher alcohol sulfates, higher alkyl ether sulfates, α-olefin sulfates, alkylbenzene sulfonates, α-olefin sulfonates, fatty acid halides, and N - Reaction products of methyl taurine, dialkyl sulfosuccinate salts, higher alcohol phosphate ester salts, phosphate ester salts of higher alcohol ethylene oxide adducts.

Amphoteric surfactants include amino acid-type amphoteric surfactants such as alkylalanine alkali metal salts, betaine-type amphoteric surfactants such as alkyldimethylbetaine, and imidazoline-type amphoteric surfactants.

The glass fiber fabric of this embodiment contains the glass fiber of this embodiment mentioned above. Specifically, the glass fiber fabric of this embodiment can be produced by weaving the above-mentioned glass fiber of this embodiment as at least a part of warp or weft with a loom known per se. As said loom, jet looms, such as an air jet loom and a water jet loom, a shuttle loom, a rapier loom, etc. are mentioned, for example.

In addition, as the weaving method of the above-mentioned loom, plain weave, satin weave, square weave, twill weave, etc. are mentioned, for example, but the plain weave is preferably used from the viewpoint of production efficiency. In the glass fiber fabric of this embodiment, it is preferable to use the above-mentioned glass fiber of this embodiment as a warp and a weft.

In the glass fiber fabric of this embodiment, it is preferable that the aforementioned glass fibers of this embodiment are bundled with 35 to 400 glass filaments with a diameter in the range of 3.0 to 9.0 μm and applied 0 to 1.0 times/25 mm. The quality of the twisted 0.9 ~ 69.0tex (g/km) range.

In the glass fiber fabric of this embodiment, when using the above-mentioned glass fiber of this embodiment as warp or weft, it is preferable that the weaving density of the warp is in the range of 40 to 120/25mm, and the weaving density of the weft is 40~120 pieces/25mm range.

The glass fiber fabric of this embodiment may be subjected to deoiling treatment, surface treatment and fiber opening treatment after weaving.

As the deoiling treatment, the following treatment can be mentioned: placing the glass fiber fabric in a heating furnace with an atmosphere temperature in the range of 350°C to 400°C for 40 to 80 hours, and thermally decomposing the organic matter attached to the glass fiber .

As surface treatment, can enumerate following treatment: in the solution that contains above-mentioned silane coupling agent or in the solution that contains above-mentioned silane coupling agent and above-mentioned surfactant, immerse glass fiber fabric, and after removing excess water, after 80 ~ Heat drying at a temperature in the range of 180°C for a time in the range of 1 to 30 minutes.

As the fiber opening treatment, for example, the following treatments can be mentioned: fiber opening using hydraulic pressure while applying a tension in the range of 30 to 200 N to the warp yarns of the glass fiber fabric, fiber opening using high frequency vibration using a liquid as a medium, and using The line widths of the warp and weft are widened by spreading by fluid pressure with surface pressure, by pressing by rollers, or the like.

The glass fiber fabric of this embodiment preferably has a mass per unit area in the range of 7.0 to 190.0 g/m ² and a thickness in the range of 8.0 to 200.0 μm.

In the glass fiber fabric of the present embodiment, the warp yarn width is preferably in the range of 110 to 600 μm, and the weft yarn width is preferably in the range of 110 to 600 μm.

The glass fiber fabric of this embodiment may be equipped with the surfactant containing the said silane coupling agent, or the surface treatment layer containing the said silane coupling agent and the said surfactant. When the glass fiber fabric of this embodiment contains this surface treatment layer, this surface treatment layer may have mass in the range of 0.03-1.50 mass % with respect to the glass fiber fabric whole quantity containing a surface treatment layer, for example.

The glass fiber-reinforced resin composition of this embodiment contains the above-mentioned glass fiber of this embodiment. Specifically, in the glass fiber reinforced resin composition containing thermoplastic resin or thermosetting resin, glass fiber, and other additives, the glass fiber reinforced resin composition of this embodiment contains 10 Glass fibers in the range of ~90% by mass. Moreover, the glass fiber-reinforced resin composition of this embodiment contains resin in the range of 90-10 mass % with respect to the whole glass fiber-reinforced resin composition, and contains other additives in the range of 0-40 mass %.

Here, examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, styrene/maleic anhydride resin, styrene/maleimide resin, polyacrylonitrile, acrylonitrile/styrene (AS ) resin, acrylonitrile/butadiene/styrene (ABS) resin, chlorinated polyethylene/acrylonitrile/styrene (ACS) resin, acrylonitrile/ethylene/styrene (AES) resin, acrylonitrile/styrene/ Methyl acrylate (ASA) resin, styrene/acrylonitrile (SAN) resin, methacrylic resin, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyamide, polyacetal, polyethylene terephthalate Ethylene Formate (PET), Polybutylene Terephthalate (PBT), Polytrimethylene Terephthalate (PTT), Polycarbonate, Polysulfide, Polyethersulfone (PES), Polyethylene Phenylsulfone (PPSU), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyaryl ether ketone, liquid crystal polymer (LCP), fluororesin, polyetherimide (PEI), Polyarylate (PAR), polysulfone (PSF), polyamideimide (PAI), polyaminobismaleimide (PABM), thermoplastic polyimide (TPI), polyethylene naphthalate Ester (PEN), Ethylene/Vinyl Acetate (EVA) Resin, Ionomer (IO) Resin, Polybutadiene, Styrene/Butadiene Resin, Polybutene, Polymethylpentene, Olefin/Vinyl Alcohol resin, cyclic olefin resin, cellulose resin, polylactic acid, etc.

Specifically, examples of polyethylene include high-density polyethylene (HDPE), medium-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-high molecular weight polyethylene. .

Examples of polypropylene include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures of the above polypropylenes.

Examples of polystyrene include general-purpose polystyrene (GPPS) which is an atactic polystyrene having an atactic structure, high-impact polystyrene (HIPS) in which a rubber component is added to GPPS, and Syndiotactic polystyrene with isotactic structure, etc.

Examples of the methacrylic resin include one of acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and fatty acid vinyl ester. A polymer obtained by polymerizing one kind of methacrylic resin alone, or a polymer obtained by copolymerizing two or more of the above-mentioned methacrylic resins.

Examples of polyvinyl chloride include vinyl chloride homopolymers polymerized by known methods such as emulsion polymerization, suspension polymerization, microsuspension polymerization, and bulk polymerization, or polyvinyl chloride copolymers that can be copolymerized with vinyl chloride monomers. A copolymer of monomers, or a graft copolymer obtained by graft-polymerizing vinyl chloride monomer to a polymer, etc.

Examples of polyamides include polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 410), polypentamethylene adipamide (nylon 56), polypentamethylene sebacamide (nylon 510), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodeca Amide (nylon 612), polydecamethylene adipamide (nylon 106), polysebacylmethyl sebacic acid amide (nylon 1010), polydecamethylene dodecamide (nylon 1012), polyundecylamide Alkylamide (nylon 11), polyhexamethylene adipamide (nylon 116), polydodecylamide (nylon 12), polyxylylene adipamide (nylon D6), polyxylylene adipamide (nylon MXD10), polym-xylylene adipamide (nylon MXD6), polyparaxylylene adipamide (nylon PXD6), polyterephthalamide (nylon 4T), polypentamethylene terephthalamide (Nylon 5T), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polynonamethylene terephthalamide (nylon 9T) , polyterephthalamide terephthalamide (nylon 10T), polyhexamethylene terephthalamide (nylon 11T), polydodecamethylene terephthalamide (nylon 12T), Polytetramethylene polyphthalamide (nylon 4I), polybis(3-methyl-4-aminohexyl)methane terephthalamide (nylon PACMT), polybis(3-methyl-4- Aminohexyl)methane isophthalamide (nylon PACMI), polybis(3-methyl-4-aminohexyl)methane dodecamide (nylon PACM12), polybis(3-methyl-4-aminohexyl) One of the components such as methane tetradecylamide (nylon PACM14), or a copolymer combining two or more of the above components, or a mixture of the above components and the above copolymer, etc.

Examples of polyacetals include: homopolymers mainly composed of oxymethylene units as repeating units, and oxygen compounds having 2 to 8 adjacent carbon atoms in the main chain. Copolymers of alkylene units, etc.

Examples of polyethylene terephthalate include polymers obtained by polycondensing ethylene glycol, terephthalic acid or derivatives thereof, and the like.

Examples of polybutylene terephthalate include polymers obtained by polycondensing 1,4-butanediol and terephthalic acid or derivatives thereof.

As polytrimethylene terephthalate, the polymer etc. which polycondensed 1, 3- propanediol, terephthalic acid, or its derivative(s) are mentioned.

Examples of the polycarbonate include: polymers obtained by utilizing a transesterification method in which a dihydroxydiaryl compound reacts with a carbonate such as diphenyl carbonate in a molten state, or a polymer obtained by utilizing a dihydroxyaryl compound and A polymer obtained by the phosgene reaction of phosgene.

Examples of polyarylene sulfide include linear polyphenylene sulfide, cross-linked polyphenylene sulfide obtained by curing reaction after polymerization, polyphenylene sulfide sulfone, polyphenylene sulfide ether, polyphenylene sulfide Phenylsulfide ketone, etc.

Examples of polyphenylene ethers include poly(2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-chloromethyl-1,4 -phenylene ether), poly(2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly(2-methyl-6-n-butyl-1,4-phenylene ether), poly(2-ethyl-6-isopropyl-1,4-phenylene ether), poly(2-ethyl-6-n-propyl-1,4-phenylene ether), poly (2,3,6-trimethyl-1,4-phenylene ether), poly[2-(4'-methylphenyl)-1,4-phenylene ether], poly(2-bromo -6-phenyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2-phenyl-1,4-phenylene phenylene ether), poly(2-chloro-1,4-phenylene ether), poly(2-methyl-1,4-phenylene ether), poly(2-chloro-6-ethyl-1 , 4-phenylene ether), poly(2-chloro-6-bromo-1,4-phenylene ether), poly(2,6-di-n-propyl-1,4-phenylene ether), Poly(2-methyl-6-isopropyl-1,4-phenylene ether), poly(2-chloro-6-methyl-1,4-phenylene ether), poly(2-methyl -6-ethyl-1,4-phenylene ether), poly(2,6-dibromo-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene base ether), poly(2,6-diethyl-1,4-phenylene ether), poly(2,6-dimethyl-1,4-phenylene ether), etc.

Examples of modified polyphenylene ethers include polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and polystyrene, poly(2,6-dimethyl-1 , Polymer alloy of 4-phenylene) ether and styrene/butadiene copolymer, poly(2,6-dimethyl-1,4-phenylene) ether and styrene/maleic anhydride copolymer Polymer alloy of poly(2,6-dimethyl-1,4-phenylene) ether and polyamide polymer alloy, poly(2,6-dimethyl-1,4-phenylene) Polymer alloys of ether and styrene/butadiene/acrylonitrile copolymers, modified polyphenylene ethers with functional groups such as amino groups, epoxy groups, carboxyl groups, and styrene groups introduced into the polymer chain ends of the above-mentioned polyphenylene ethers A modified polyphenylene ether having functional groups such as amino groups, epoxy groups, carboxyl groups, styryl groups, and methacryloyl groups introduced into the side chains of the polymer chains of the polyphenylene ethers.

Examples of the polyaryl ether ketone include polyether ketone (PEK), polyetheretherketone (PEEK), polyether ketone ketone (PEKK), polyetherether ketone ketone (PEEKK), and the like.

Examples of liquid crystal polymers (LCP) include (co)polymers composed of structural units of one or more components selected from the following components: aromatic hydroxyl groups as thermotropic liquid crystal polyesters, etc. Carbonyl unit, aromatic dihydroxy unit, aromatic dicarbonyl unit, aliphatic dihydroxy unit, aliphatic dicarbonyl unit, etc.

Examples of fluororesins include: polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene resin (FEP), fluorinated ethylene tetrafluoroethylene resin (ETFE), polyethylene fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene/chlorotrifluoroethylene resin (ECTFE), etc.

Examples of the ionomer (IO) resin include a copolymer of olefin or styrene and an unsaturated carboxylic acid, and a polymer obtained by neutralizing a part of carboxyl groups with metal ions.

Examples of the olefin/vinyl alcohol resin include ethylene/vinyl alcohol copolymers, propylene/vinyl alcohol copolymers, ethylene/vinyl acetate copolymer saponified products, propylene/vinyl acetate copolymer saponified products, and the like.

Examples of the cyclic olefin resin include monocyclic bodies such as cyclohexene, polycyclic bodies such as tetracyclic cycloolefins, polymers of cyclic olefin monomers, and the like.

Examples of polylactic acid include poly-L-lactic acid which is a homopolymer of L-form, poly-D-lactic acid which is a homopolymer of D-form, and stereocomplex polylactic acid which is a mixture thereof.

Examples of cellulose resins include methylcellulose, ethylcellulose, hydroxycellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, and hydroxypropylmethylcellulose , cellulose acetate, cellulose propionate, cellulose butyrate, etc.

In addition, examples of the above-mentioned thermosetting resins include unsaturated polyester resins, vinyl ester resins, epoxy (EP) resins, melamine (MF) resins, phenolic resins (PF), polyurethane resins (PU), poly Isocyanate, polyisocyanurate, polyimide (PI), urea (UF) resin, silicon (SI) resin, furan (FR) resin, benzoguanamine (BR) resin, alkyd resin, xylene resin, bismaleimide triazine (BT) resin, diallyl phthalate resin (PDAP), etc.

Specifically, as an unsaturated polyester resin, the resin obtained by esterifying an aliphatic unsaturated dicarboxylic acid and an aliphatic diol is mentioned.

Examples of vinyl ester resins include bisvinyl ester resins and novolak-based vinyl ester resins.

Examples of epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol E epoxy resins, bisphenol S epoxy resins, and bisphenol M epoxy resins (4 , 4'-(1,3-phenylene diisopropylidene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylene diisopropylidene) Propyl) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexylene diphenol type epoxy resin), phenol novolak type epoxy resin, cresol novolak type epoxy resin Resin, tetraphenol ethane type novolak type epoxy resin, novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure, biphenyl type epoxy resin, xylylene type epoxy resin or phenylarane Aralkyl type epoxy resins such as base type epoxy resins, naphthylene ether type epoxy resins, naphthol type epoxy resins, naphthalene diol type epoxy resins, 2 or 4 functional epoxy naphthalene resins, Naphthyl type epoxy resin, naphthalene aralkyl type epoxy resin, anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane Type epoxy resin, fluorene type epoxy resin, etc.

Examples of the melamine resin include polymers formed by polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.

Examples of the phenolic resin include novolak-type phenolic resins such as phenol novolac resins, cresol novolac resins, and bisphenol A-type novolac resins, methylol-type resole phenolic resins, and dimethylene ether-type resole resins. Resole-type phenolic resins such as phenolic resins, or arylalkylene-type phenolic resins, etc., are one type of resin or a combination of two or more types of resins.

Examples of the urea resin include resins obtained by condensation of urea and formaldehyde.

The above-mentioned thermoplastic resin or the above-mentioned thermosetting resin may be used alone, or two or more resins may be used in combination.

The glass fiber-reinforced resin composition of this embodiment is used in applications requiring low dielectric properties, and therefore, epoxy resins, modified polyphenylene ethers, polybutylene terephthalate, polypropylene, and fluororesins are preferred. , Liquid crystal polymer (LCP) as the aforementioned resin.

Examples of the above-mentioned other additives include reinforcing fibers other than glass fibers, fillers other than glass fibers, flame retardants, ultraviolet absorbers, heat stabilizers, antioxidants, antistatic agents, fluidity improvers, and antiblocking agents. , lubricants, nucleating agents, antibacterial agents, pigments, etc.

Examples of reinforcing fibers other than glass fibers include carbon fibers and metal fibers.

Examples of fillers other than glass fibers include glass powder, talc, and mica.

The glass fiber-reinforced resin composition of the present embodiment may be a prepreg obtained by impregnating the above-mentioned resin with the above-mentioned glass fiber fabric of the present embodiment and semi-curing it by a method known per se.

The glass fiber reinforced resin composition of the present embodiment can be molded by injection molding, injection compression molding, two-color molding, hollow molding, foam molding (including supercritical fluid), insert molding, and in-mold coating. Molding, extrusion, sheet molding, thermoforming, rotational molding, lamination molding, compression molding, blow molding, stamping, melting, hand lay-up, spraying, resin transfer Various glass fiber-reinforced resin moldings can be obtained by molding by known molding methods such as sheet molding compound molding, bulk molding compound molding, pultrusion molding, and filament winding. In addition, a glass fiber reinforced resin molded article can also be obtained by curing the above-mentioned prepreg.

Examples of uses of such molded products include electronic device housings, electronic components, vehicle exterior parts, vehicle interior parts, vehicle engine peripheral parts, muffler-related parts, high-pressure tanks, and the like.

As an electronic component, a printed wiring board etc. are mentioned.

Examples of vehicle exterior parts include bumpers, fenders, engine covers, air dams, wheel houses, and the like.

Examples of vehicle interior parts include door trims, roof materials, and the like.

Examples of the vehicle engine peripheral parts include an oil pan, a hood, an intake manifold, an exhaust manifold, and the like.

Examples of components related to the silencer include noise reduction components and the like.

In addition, the glass fiber of this embodiment can be used not only for the glass fiber reinforced resin composition of this embodiment, but also for the reinforcing material of inorganic materials, such as gypsum and cement. For example, when used as a reinforcing material for gypsum, especially gypsum boards with a thickness ranging from 4 to 60 mm, the gypsum contains glass fibers having the above composition range in an amount of 0.1 to 4.0% by mass relative to the total mass of the gypsum.

Next, examples and comparative examples of the present invention are shown.

Example

First, glass batch materials were obtained by mixing glass raw materials so that the glass compositions after melting and solidification would be the respective compositions of Examples 1-8 and Comparative Examples 1-5 shown in Table 1.

Next, the glass batches corresponding to the glass compositions for glass fibers of Examples 1 to 8 or Comparative Examples 1 to 5 were put into a platinum crucible with a diameter of 80 mm, heated at 1550° C. for 4 hours, and further heated at 1650° C. Heating at a certain temperature for 2 hours to melt the batch of glass, and then taking it out from the crucible to obtain homogeneous glass block and glass shavings. Next, the obtained glass block and glass cullet were annealed at a temperature of 620° C. for 8 hours to obtain test pieces.

Then, the dielectric constant and dielectric loss tangent of the test piece obtained above were evaluated by the method shown below. Moreover, water resistance was evaluated by the method shown below using the glass cullet obtained in the test piece preparation process. In addition, the 1000 Poise temperature and the liquidus temperature were measured by the method shown below using the glass cullet obtained in the preparation of the test piece, and the operating temperature range was calculated using these values. The results are shown in Table 1.

〔Evaluation method of water resistance〕

Put the glass cullet obtained in the above way into a small cylindrical platinum sleeve with a circular nozzle head at the bottom of the container, and heat it to a predetermined temperature to melt it, and then melt the molten glass ejected from the nozzle head. The glass was wound around a stainless steel collet at a predetermined speed, cooled and solidified while being stretched, and a glass fiber having a perfectly circular circular cross section and a fiber diameter of 13 μm was obtained. About 1 g of the above-obtained glass fiber (glass fiber for test) was collected from a collet, dried at a temperature of 120° C. for 1 hour, and the mass (mass before operation) was measured. Next, the test glass fiber was left still at a temperature of 80° C. for 24 hours in 100 ml of distilled water. Then, the test glass fibers were obtained using a metal mesh having openings of about 150 μm, washed with distilled water, dried at a temperature of 120° C. for 1 hour, and the mass (mass after handling) was measured.

The mass reduction rate (100×(1-(mass after operation/mass before operation))) was calculated from the above-mentioned mass before operation and mass after operation. The case where the mass loss rate was 2.0% or less and the glass fiber component was hardly eluted in water was set as OK; the case where the mass loss rate exceeded 2.0% and the glass fiber component was largely eluted in water was set as NG.

[Measurement method of dielectric constant and dielectric loss tangent]

The test piece was ground to prepare a ground test piece of 80 mm×3 mm (thickness 1 mm). Next, after drying the obtained polishing test piece, it was stored in a room at a temperature of 23° C. and a humidity of 60% for 24 hours. Next, according to JIS C 2565: 1992, the dielectric constant (dielectric constant Dk ) and dielectric loss tangent (dissipation rate Df).

〔Measurement method of 1000 Poise temperature〕

The 1000 Poise temperature was measured by melting glass shavings in a platinum crucible using a high-temperature electric furnace with a rotary viscometer (manufactured by Shibaura System Co., Ltd.), and using a rotary Brookfield viscometer while changing the melting temperature. The meter continuously measures the viscosity of the molten glass, and measures the corresponding temperature when the rotational viscosity is 1000 poise.

〔Measuring method of liquidus temperature〕

Crush glass shavings, put 40 g of glass particles with a particle size in the range of 0.5 to 1.5 mm into a platinum vessel of 180 mm × 20 mm × 15 mm, and heat in a tubular electric furnace with a temperature gradient in the range of 1000 to 1550 ° C for more than 8 hours Thereafter, it was taken out from the tubular electric furnace, observed with a polarizing microscope, and the position where glass-derived crystals (devitrification) started to precipitate was identified. The temperature in the tubular electric furnace was actually measured using a B-type thermocouple, and the temperature at the position where the above-mentioned crystals started to precipitate was determined, and this was taken as the liquidus temperature.

[Calculation method of operating temperature range]

Using the difference between the 1000 Poise temperature and the liquidus temperature, the operating temperature range is calculated.

[Table 1]

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 SiO ₂ (mass%: S) 58.90 56.30 56.20 57.30 56.90 56.60 56.40 56.90 B ₂ O ₃ (mass%) 22.20 22.80 22.90 22.50 22.90 22.80 22.90 22.90 Al ₂ O ₃ (mass%: A) 10.80 12.00 12.00 11.90 12.00 11.40 12.00 12.00 P ₂ O ₅ (mass%: P) 2.10 2.10 3.60 2.20 1.60 2.10 1.00 1.60 TiO ₂ (mass%: T) 3.10 3.10 1.60 3.20 3.10 3.60 4.20 2.60 CaO (mass%: C) 2.20 2.20 2.20 2.20 2.20 2.60 2.20 2.20 MgO (mass%: M) 0 0 0 0 0 0 0 0 _F2 (mass%) 0.70 1.50 1.50 0.70 1.30 0.90 1.30 1.30 Cl ₂ (mass%) 0 0 0 0 0 0 0 0 F ₂ +Cl ₂ (mass%) 0.70 1.50 1.50 0.70 1.30 0.90 1.30 1.30 _Na2O + _K2O + _Li2O 0 0 0 0 0 0 0 0 SrO (mass%) 0 0 0 0 0 0 0 0 MnO ₂ (mass%) 0 0 0 0 0 0 0 0.50 ZrO ₂ (mass%) 0 0 0 0 0 0 0 0.0 total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 (S/A) ² ×(P×T)(1 ²⁾ /(C+M) ³ 7.13 5.27 4.94 5.78 4.70 3.86 4.25 4.31 water resistance OK OK OK OK OK OK OK OK 1000 Poise Temperature(℃) 1463 1424 1446 1449 1416 1436 1395 1414 Liquidus temperature (°C) 1208 1270 1275 1270 1300 1289 1332 1292 Operating temperature range (°C) 255 154 171 179 116 147 63 122 Dielectric constant 4.0 4.0 4.0 4.0 4.0 4.1 4.1 4.1 Dielectric loss tangent 0.0010 0.0010 0.0010 0.0010 0.0010 0.0011 0.0011 0.0011

[Table 2]

Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 SiO ₂ (mass%: S) 60.10 55.30 52.50 59.60 62.20 B ₂ O ₃ (mass%) 22.30 22.90 26.20 20.20 22.30 Al ₂ O ₃ (mass%: A) 8.40 13.00 1210 11.60 8.30 P ₂ O ₅ (mass%: P) 2.00 1.00 3.40 0.30 0 TiO ₂ (mass%: T) 2.90 4.20 3.40 4.10 3.10 CaO (mass%: C) 3.30 2.30 1.90 3.70 3.10 MgO (mass%: M) 0 0 0 0 0 _F2 (mass%) 1.00 1.30 0.50 0.50 1.00 Cl ₂ (mass%) 0 0 0 0 0 F ₂ +Cl ₂ (mass%) 1.00 1.30 0.50 0.50 1.00 _Na2O + _K2O + _Li2O 0 0 0 0 0 SrO (mass%) 0 0 0 0 0 MnO ₂ (mass%) 0 0 0 0 0 ZrO ₂ (mass%) 0 0 0 0 0 total 100.00 100.00 100.00 100.00 100.00 (S/A) ² ×(P×T) ^(1/2) /(C+M) ³ 3.43 3.05 9.33 0.58 0.00 water resistance OK OK NG OK OK 1000 Poise Temperature(℃) 1507 1376 1414 1443 1504 Liquidus temperature (°C) 1100 1334 1239 1215 1120 Operating temperature range (°C) 407 42 175 228 384 Dielectric constant 4.0 4.2 4.0 4.1 4.0 Dielectric loss tangent 0.0010 0.0011 0.0010 0.0012 0.0009

As can be seen from Table 1, according to the glass compositions for glass fibers of the following Examples 1 to 8, the 1000 Poise temperature of itself can be lowered to less than 1500°C, and the glass composition for glass fibers can be used to obtain excellent water resistance. And a glass fiber having excellent dielectric properties with a dielectric constant of 4.1 or less and a dielectric loss tangent of 0.0011 or less in a high-frequency region of a measurement frequency of 10 GHz. In Examples 1 to 8, SiO ₂ in the range of 50.00 to 61.00 mass %, B ₂ O ₃ in the range of 16.00 to 27.00 mass %, and Al in the range of 7.00 to 14.00 mass % were contained with respect to the total amount of the glass composition for glass fibers. ₂ O ₃ , P ₂ O ₅ in the range of 0.20 to 4.00 mass %, TiO ₂ in the range of 0.50 to 5.00 mass %, CaO in the range of 0.10 to 5.00 mass %, MgO in the range of 0 to 4.00 mass %, and a total of 0 to 2.00 mass % _F2 and _Cl2 in the range, the content of _SiO2 (mass% _{) S} , the content of _Al2O3 (mass%)A, the content of _P2O5 (mass%)P , the TiO ₂ content (mass %) T, the CaO content (mass %) C, and the MgO content (mass %) M satisfy the formula (1).

On the other hand, as is evident from Table 2, the glass compositions for glass fibers of Comparative Examples 1, 2, and 4 below have a 1000-poise temperature of more than 1500° C., or the glass obtained by using the glass compositions for glass fibers The dielectric constant of the fiber exceeds 4.1, or the dielectric loss tangent exceeds 0.0011; according to the glass composition for glass fibers of Comparative Example 3 in which the S, A, P, T, C and M exceed the range of formula (1), it is impossible to Get full water resistance. In Comparative Examples 1, 2, and 4, although SiO ₂ in the range of 50.00 to 61.00 mass %, B ₂ O ₃ in the range of 16.00 to 27.00 mass %, 7.00 to 14.00 mass % of Al ₂ O ₃ in the range of 0.20 to 4.00 mass %, P ₂ O ₅ in the range of 0.20 to 4.00 mass %, TiO ₂ in the range of 0.50 to 5.00 mass %, CaO in the range of 0.10 to 5.00 mass %, MgO in the range of 0 to 4.00 mass %, and a total of 0 F ₂ and Cl ₂ in the range of ~2.00% by mass, but the S, A, P, T, C and M are less than the range of formula (1).

Furthermore, it is clear that the glass composition for glass fibers according to Comparative Example 5 below has a 1000 poise temperature of itself exceeding 1500°C. In Comparative Example 5, SiO ₂ was contained exceeding 61.00% by mass relative to the total amount of the glass composition for glass fibers, the content of P ₂ O ₅ was less than 0.20% by mass, and the above-mentioned S, A, P, T, C, and M smaller than the range of formula (1).

Claims (7)

1. A glass composition for glass fibers, characterized in that, Contains SiO ₂ in the range of 50.00% by mass to 61.00% by mass, B ₂ O ₃ in the range of 16.00% by mass to 27.00% by mass, and Al ₂ O in the range of 7.00% by mass to 14.00% by mass relative to the total amount of the glass composition for glass fibers _3. P ₂ O ₅ in the range of 0.20 mass % to 4.00 mass %, TiO ₂ in the range of 0.50 mass % to 5.00 mass %, CaO in the range of 0.10 mass % to 5.00 mass %, MgO in the range of 0 mass % to 4.00 mass %, and A total of _F2 and _Cl2 in the range of 0 mass % to 2.00 mass %, The _SiO2 content (mass%) S, the _Al2O3 content (mass%)A, _{the P2O5} content ( _mass %)P, the _TiO2 content (mass %) T, the content rate (mass %) C of the said CaO and the content rate (mass %) M of the said MgO satisfy the following formula (1): 3.65≤(S/A) ² ×(P×T) ^1/2 /(C+M) ³ ≤8.25...(1). 2. The glass composition for glass fibers according to claim 1, wherein The S, the A, the P, the T, the C and the M satisfy the following formula (2): 4.51≤(S/A) ² ×(P×T) ^1/2 /(C+M) ³ ≤7.32...(2). 3. The glass composition for glass fibers according to claim 1 or 2, characterized in that, The S, the A, the P, the T, the C and the M satisfy the following formula (3): 4.87≤(S/A) ² ×(P×T) ^1/2 /(C+M) ³ ≤7.20...(3). 4. The glass composition for glass fibers according to any one of claims 1 to 3, characterized in that, The S, the A, the P, the T, the C and the M satisfy the following formula (4): 5.96≤(S/A) ² ×(P×T) ^1/2 /(C+M) ^3≤7.16 ...(4). 5. A glass fiber, characterized in that, It consists of the glass composition for glass fibers as described in any one of Claims 1-4. 6. A glass fiber fabric, characterized in that, It comprises glass fibers as claimed in claim 5 . 7. A glass fiber reinforced resin composition, characterized in that it comprises the glass fiber according to claim 5.