WO2010109721A1 - Glass composition for glass fiber, glass fiber, and sheet-shaped material of glass fiber - Google Patents

Abstract

A glass composition for glass fiber, characterized by comprising, in terms of oxide contents by mass, 45 to 65% of SiO₂, 10 to 20% of Al₂O₃, 13 to 25% of B₂O₃, 5.5 to 9% of MgO, 0 to 10% of CaO, 0 to 1% of (Li₂O+Na₂O+K₂O), SrO, and BaO; a glass fiber which consists of the glass composition and which has an average fiber diameter of 3 to 7.2μm; and a sheet-shaped material of the glass fiber, which is to be combined with an organic resin and thus form an organic resin composite material.

Description

Glass composition for glass fiber, glass fiber and glass fiber sheet

The present invention relates to a glass composition for glass fibers excellent in meltability and spinnability used for printed wiring boards and the like that require high-density mounting used in electronic parts and the like, and a glass comprising the glass composition The present invention relates to a fiber and a glass fiber sheet composed of the glass fiber.

With the development of various information devices such as cellular phones and personal digital assistants (PDAs), many electronic components such as resistors, capacitors, and integrated circuits are not in the past due to the trend of high-density mounting technology. It is often mounted on a printed wiring board (also called a printed circuit board, a rigid board, a printed board or a printed wiring board) at a high density. A printed wiring board is a sheet-shaped composite material in which an appropriate amount of resin, glass fiber, modifier, etc. are mixed, and has a form with through-holes for mounting various electronic components, and its functions and uses Depending on the case, it may be expressed using an alias such as a module, a board, a unit, or a package.

Conventionally, a glass composition called E glass, which is a non-alkali glass composition, has been used for the glass fiber used in this printed wiring board application. This E-glass is a material with excellent electrical insulation, excellent spinnability when manufactured as a glass fiber from a melted state, and excellent workability such as cutting. It is the glass material for obtained glass fibers. The E glass is, for example, expressed in terms of a mass percentage in terms of oxide, SiO ₂ 52 to 56%, Al ₂ O ₃ 12 to 16%, B ₂ O ₃ 5 to 10%, CaO 16 to 25%, MgO 0 to It is a glass material composed of 5%, alkali metal oxide (R ₂ O) 0 to 2%, Fe ₂ O ₃ 0.05 to 0.4%, F ₂ 0 to 1.0%.

On the other hand, in the use of printed wiring boards, the use of high frequency has become necessary in recent years in order to realize high-speed electronic circuits. It is. Since the transmission speed is inversely proportional to the square root of the dielectric constant, a low dielectric constant is necessary to improve the transmission speed. In addition, the dielectric loss is required to be small. For this purpose, it is necessary that the dielectric loss tangent is small. Incidentally, in the present invention, the dielectric constant (ε) is a dimensionless number that means a relative dielectric constant that is a ratio of a dielectric constant of a medium and a vacuum dielectric constant. ε). Generally, when an alternating current is passed through the glass, the glass absorbs energy with respect to the alternating current and absorbs it as heat. The absorbed dielectric loss energy is proportional to the dielectric constant and dielectric loss tangent determined by the composition and structure of the glass, and is expressed as W = kfv ² × εtan δ. Here, W is dielectric loss energy, k is a constant, f is frequency, v ² is a potential gradient, ε is a dielectric constant, and tan δ is a dielectric loss tangent. From this equation, it can be seen that the larger the dielectric constant and dielectric loss tangent, and the higher the frequency, the greater the dielectric loss. Therefore, in order to reduce the dielectric loss, it is required to reduce the dielectric constant and the dielectric loss tangent.

For this reason, a glass fiber material having a low dielectric constant and dielectric loss tangent is required for the glass fiber used for the printed wiring board. Patent Document 1 discloses that the dielectric constant at a frequency of 1 MHz at room temperature is 6.7, A glass material called D glass is disclosed in order to achieve a lower dielectric constant and dielectric loss tangent than E glass having a dielectric loss tangent of 12 × 10 ⁻⁴ . This D glass is, for example, expressed in oxide-based mass percentage, SiO ₂ 74.5%, Al ₂ O ₃ 0.3%, B ₂ O ₃ 21.7%, CaO 0.5%, Li ₂ O. This glass material is composed of 0.5%, Na ₂ O 1.0%, K ₂ O 1.5%. The glass has a dielectric constant of about 4.3 MHz and a dielectric loss tangent of about 10 to 20 × 10 ^{− 4} .

However, although D glass is excellent in terms of electrical performance, various problems have been pointed out in the manufacturing process of printed wiring boards and glass fibers. For example, D glass is inferior to E glass in terms of glass meltability, and yarn breakage and the like are likely to occur frequently during spinning, making it difficult to produce glass fibers. Moreover, since D glass becomes structurally brittle, it has poor weaving properties in the weaving process performed to form a cloth form used to obtain a printed wiring board, resulting in a decrease in the yield rate of products. It leads to. Furthermore, in the printed wiring board using D glass, wear of the drill in the drilling process for forming a via hole (via hole) that is a through hole for the purpose of interlayer conduction without inserting an electronic component lead is increased, and the position accuracy of the via hole is increased. There was also a problem that became low.

In order to solve the above problems, many inventions have been made so far. For example, in Patent Document 2, SiO ₂ 50 to 60%, Al ₂ O ₃ 10 to 18%, B ₂ O ₃ 18 to 25%, CaO 0 to 10%, MgO 1 to 10%, Li ₂ by mass%. A low dielectric constant glass fiber characterized by having a glass composition of O + Na ₂ O + K ₂ O 0 to 1.0% and Fe ₂ O ₃ 0.1 to 1% is disclosed.

Patent Document 3 discloses, in mass%, SiO ₂ 50 to 60%, Al ₂ O ₃ 10 to 20%, B ₂ O ₃ 20 to 30%, CaO 0 to 5%, MgO 0 to 4%, Li ₂ O + Na. A low dielectric constant glass fiber having a composition of ₂ O + K ₂ O 0 to 0.5% and TiO ₂ 0.5 to 5% is disclosed.

Further, in Patent Document 4, by mass%, SiO ₂ 48 to 80%, Al ₂ O ₃ 0 to 18%, B ₂ O ₃ 11 to 35%, MgO 0 to 10%, CaO 0 to 10%, Li ₂ O + Na ₂ O + K ₂ O 0-7%, TiO ₂ less than 3% composition, H ₂ O <800 ppm, 1 MHz, dielectric constant 5.0 or less, dielectric loss tangent 7 × 10 ⁻⁴ or less A low dielectric constant, low dielectric loss tangent glass characterized in that is disclosed.

JP-A-63-2831 Japanese Patent Laid-Open No. 10-167759 JP-A-8-333137 JP 2003-137590 A

However, the inventions disclosed up to now have sufficient mechanical performance and can easily suppress the occurrence of glass defects such as devitrification, and further achieve a low dielectric constant and a low dielectric loss tangent. In order to realize a glass material and to obtain a glass fiber having a low dielectric constant and a low dielectric loss tangent, there are further problems to be solved.

For example, the glass composition of Patent Document 2 has succeeded in reducing the dielectric constant and dielectric loss tangent of glass fiber, but there is a problem in meltability at the initial stage of glass melting, and bubbles are formed in the molten glass during glass melting. It cannot be said that it is sufficient to make the molten glass uniform and easily remain.

Also, printed wiring boards are mounted on many electronic devices, but the environment surrounding the mounted electronic devices is diverse. For example, many integrated circuits are installed in current automobiles, and these electronic components are mounted on printed wiring boards at high density, but the parts used in automobiles are on the streets from the hot summer to the far north. It is required to be able to ensure reliability up to running. Also, in recent passenger cars, electronic circuits, etc. are often installed in environments where the ambient temperature around the engine room and the engine room is high and the temperature changes more severely than in the past in order to ensure sufficient boarding space. It has become. Furthermore, there is a demand to reduce the size of the board to be mounted.

Due to such changes in various situations, printed circuit boards for in-vehicle use are required to have higher heat resistance and higher through-hole reliability than ever before. Since there is a difference in the coefficient of linear thermal expansion between the printed wiring board and the mounted parts, thermal stress is generated at the solder joints in a high-temperature environment, causing solder cracks and causing major failures such as inability to obtain electrical connections. This is because it must be avoided. That is, an electronic component used in an on-vehicle application is not allowed to fail in an electronic circuit due to a large temperature change, and its reliability is required to be long-term. Therefore, in order to satisfy such requirements, printed wiring boards used in the environment for in-vehicle use are required to have a low coefficient of linear thermal expansion in order to reduce the difference in coefficient of linear thermal expansion from the mounted components. . For this reason, the glass fiber which consists of a glass material which has a lower linear thermal expansion coefficient than E glass is requested | required.

Furthermore, with the progress of thinner printed circuit boards reflecting the demand for lighter, thinner and smaller electronic devices, glass fibers used for printed wiring boards tend to require glass fiber varieties with smaller fiber diameters. In the case of so-called “long” glass, which has a high spinning temperature like glass and the viscosity of the glass does not change greatly due to temperature changes, it is a high quality with a small fiber diameter in a limited production environment. Since it becomes difficult to produce glass fibers with a stable quality without defects, there is a demand for so-called “short” glass in which the viscosity of the glass rapidly changes due to temperature changes. The glass composition of Patent Document 3 tends to have a high spinning temperature of 10 ^3.0 dPa · s, and is a “long” glass having a small temperature dependency of viscosity, and is used to produce glass fibers having a small fiber diameter. Is not suitable. In addition, when the spinning temperature is high, a large load is imposed on the manufacturing equipment, so that there is a problem of shortening the service life of the manufacturing equipment such as a bushing used for drawing out the glass fiber. The glass composition of Patent Document 4 has a problem that the spinning temperature is as high as 1300 ° C. or more, and the service life of the spinning device is shortened.

Moreover, when manufacturing glass fiber with a small fiber diameter, the bubble which may be contained as a defect in molten glass tends to cause the cutting | disconnection of glass fiber in spinning of glass fiber. In addition, when glass fibers containing bubbles are mixed into the printed wiring board as hollow fibers, there is a risk that through-hole plating will enter the hollow fibers, resulting in poor conduction, reducing the reliability of the printed wiring board. Therefore, it is a problem. When the temperature of 10 ^2.0 dPa · s, which is the standard of melting temperature as in D glass, is high, it is necessary to apply a great deal of energy at the time of melting. There are many things to do. In order to reduce the number of bubbles in the molten glass, it is effective to use a clarifying agent such as arsenous acid or antimony trioxide. However, these fining agents are also environmentally hazardous substances, and it is regarded as a problem that these elements are contained in members used in electronic equipment.

The present invention solves the above-mentioned various problems, and since the melting temperature is low, it is easy to obtain a homogeneous molten glass, excellent spinnability of glass fibers, high chemical durability, and high-density mounting. A glass fiber composition that achieves a low dielectric constant and a low dielectric loss tangent required for printed wiring boards and a glass fiber composition having a low coefficient of linear thermal expansion, and glass obtained by spinning the glass of the glass fiber composition It aims at providing the glass fiber sheet-like thing comprised from fiber and this glass fiber.

The present inventors can surely overcome many difficult problems required from the use of a printed wiring board that enables high-density mounting, and can stably produce glass fibers having a small fiber diameter. Many researches on glass fiber compositions have been conducted. In particular, focusing on the role of alkaline earth metal elements in glass compositions, the above-mentioned various problems have been solved by adding predetermined amounts of these components. The present invention is presented here because it has been found that a glass fiber composition exhibiting unprecedented performance and that the glass fiber composition can be molded as a glass fiber having a small fiber diameter.

The glass composition for glass fiber according to the present invention has a SiO ₂ 45 to 65%, Al ₂ O ₃ 10 to 20%, B ₂ O ₃ 13 to 25%, MgO 5.5 to 9 in terms of mass percentage in terms of oxide. %, CaO 0 to 10%, Li ₂ O + Na ₂ O + K ₂ O 0 to 1%, SrO, BaO.

Here, SiO ₂ 45 to 65%, Al ₂ O ₃ 10 to 20%, B ₂ O ₃ 13 to 25%, MgO 5.5 to 9%, CaO 0 to 10% in terms of mass percentage in terms of oxides, The content of Li ₂ O + Na ₂ O + K ₂ O 0 to 1%, SrO, and BaO is as follows.

That is, when the elemental components constituting the glass are expressed in terms of oxides by using various analytical means such as chemical analysis and instrumental analysis, the glass composition has a SiO ₂ component in the range of 45 mass% to 65 mass%, Al ₂ O ₃ component is in the range of 10% to 20% by mass, B ₂ O ₃ component is in the range of 13% to 25% by mass, and MgO component is in the range of 5.5% to 9% by mass. The CaO component is 10% by mass or less, the total amount of the Li ₂ O component, the Na ₂ O component and the K ₂ O component is 1% by mass or less, and further contains the SrO component and the BaO component. Represents.

Further, in the glass composition for glass fiber of the present invention, in addition to the above, if the CeO _{2 is} 0.01 to 5.0% in terms of mass percentage in terms of oxide, the number of bubbles in the molten glass can be reduced. The generation of hollow fibers is reduced, and highly homogenous glass fibers can be obtained.

Further, in the glass composition for glass fiber of the present invention, in addition to the above, if SrO 0.1 to 10% and BaO 0.1 to 10% are expressed in terms of mass percentage in terms of oxide, crystal precipitation during glass melting Therefore, it is preferable because the glass composition can be easily melted and the water resistance and acid resistance of the glass are not lowered.

That is, similarly to the above, this is SrO 0.1 to 10% and BaO 0.1 to 10% in terms of oxide in terms of the mass. This means that the SrO component is 0.1% by mass to 10% by mass and the BaO component is 0.1% by mass to 10% by mass in addition to the composition of the glass composition.

The reasons for limiting the content of each component constituting the glass composition for glass fiber of the present invention will be specifically described below.

The SiO ₂ component is a component that forms a skeleton of the network structure in the glass structure and is the main component of the glass composition of the present invention. The glass structure increases as the content of the SiO ₂ component in the glass composition increases. The strength tends to increase. As the structural strength of the glass increases, the chemical durability also increases, and in particular, the acid resistance has high performance. In order to maintain the strength of the glass structure in a sufficient state and have a stable quality, the content of the SiO ₂ component needs to be at least 45% by mass, more preferably 48%. It is to be at least mass%. On the other hand, when the content of the SiO ₂ component in the glass composition increases, the high-temperature viscosity value of the molten glass increases, and as a result, an attempt is made to produce such a glass composition with high efficiency and homogeneity by the melting method. If so, expensive equipment is required. Moreover, the molding temperature at the time of shaping | molding as glass fiber becomes high. Therefore, there may be restrictions in terms of equipment management during manufacturing. In addition, it is easy to obtain a homogeneous molten glass that does not retain bubbles generated during the vitrification reaction at the time of glass melting, and does not require excessive heat energy for melting the glass. In order to ensure spinnability, the content of the SiO ₂ component needs to be 65% or less.

The Al ₂ O ₃ component is an effective component for realizing the chemical and mechanical stability of the glass. By containing an appropriate amount in the glass, crystallization and phase separation in the molten glass can be achieved. Although it may have an effect of suppressing the formation, when it is contained in a large amount, the viscosity of the molten glass is increased. It is not preferable because the content of the Al ₂ O ₃ component in the glass composition is deteriorated phase separation property at the time of melting and less than 10 wt%. Deterioration of phase separation in the molten glass is not preferable because it leads to deterioration of acid resistance of the obtained glass fiber. Here, the phase separation means a phenomenon in which the molten glass is separated into two or more glass phases. On the other hand, if the content of the Al ₂ O ₃ component in the glass composition is excessively increased, the content of other components, particularly the SiO ₂ component, is relatively reduced, and the above-described acid resistance is adversely affected. The content of ₂ O ₃ component needs to be 20% by mass or less, more preferably 18% by mass or less, further preferably 17% by mass or less, more preferably 16% by mass or less, and most preferably 15% by mass or less. It is to be.

In B ₂ O ₃ component is a glass network structure like the SiO ₂ component is a component forming the skeleton, rather than to increase the high temperature viscosity of the molten glass as SiO ₂ component, to lower the high temperature viscosity rather There is work. Therefore, the B ₂ O ₃ component has both the role of keeping the dielectric constant of the molded glass low and suppressing the increase in the high temperature viscosity of the molten glass. When the content of the B ₂ O ₃ component in the glass composition is less than 13% by mass, the dielectric constant of the glass is maintained at 6.0 or less, and the molten glass at a spinning temperature of 10 ^3.0 dPa · s is used. It may be difficult for the temperature to be less than 1300 ° C. at which sufficient spinnability can be ensured. On the other hand, when the content of the B ₂ O ₃ component in the glass composition is excessive, the amount of evaporation of the B ₂ O ₃ component increases during melting, making it difficult to maintain the molten glass in a homogeneous state. There is also. The B ₂ O ₃ easily when the content is too high acid resistance is deteriorated components, phase separation in the molten glass will be lead to deterioration. From such a viewpoint, if the B ₂ O ₃ component in the glass composition exceeds 25% by mass, the acid resistance and phase separation of the glass deteriorate, which is not preferable.

The MgO component is a component having a function as a flux that makes it easy to melt the glass raw material, and at the same time, is very effective in reducing the high temperature viscosity corresponding to a temperature of 10 ^2.0 dPa · s. Helps to make bubbles out of foam and make homogeneous glass. Further, it has the function of lowering the temperature of 10 ^3.0 dPa · s to make the glass short, so that the productivity is greatly improved, and it is useful for efficiently producing glass fibers having a small fiber diameter. However, the MgO component needs to be 5.5% by mass or more in order to make the glass composition work effectively in order to lower the high temperature viscosity around 10 ^3.0 dPa · s, which is the spinning temperature. It is. On the other hand, when the content of the MgO component in the glass composition is excessive, the phase separation of the molten glass is increased and the acid resistance is deteriorated. In addition, since the dielectric constant also increases, it is not preferable to exceed 9% by mass from such a viewpoint.

The CaO component, like the MgO component, is a component that acts to lower the viscosity of the molten glass corresponding to a temperature of 10 ^2.0 dPa · s, and has the highest dielectric constant among the components made of alkaline earth metal elements. The increase rate is small. However, when a large amount of CaO component is contained in the glass composition, the phase separation is increased and the acid resistance of the glass is lowered. Further, the dielectric constant of the glass increases as the CaO component increases. For this reason, it is not preferable that the CaO component exceeds 10% by mass.

Li 2 _O component, the alkali metal oxide component oxides conversion display in the glass composition, expressed as Na 2 _O component or K _{2 O} component, the glass melt is heated in a state of mixing a plurality of glass raw material In this case, it functions as a so-called flux that facilitates the production of a glass melt, and also has a function of lowering the high-temperature viscosity. However, the Li ₂ O component, the Na ₂ O component, or the K ₂ O component all increase the value of the dielectric loss tangent of the glass when the content in the glass composition increases, so the upper limit of the total amount is 1 Up to mass%.

The SrO component is a component that functions to lower the viscosity of the molten glass corresponding to a temperature of 10 ^2.0 dPa · s, and further lower the spinning temperature in the vicinity of 10 ^3.0 dPa · s of the molten glass. Its function is not as good as MgO and CaO components. However, the SrO component is an essential component in the present invention because it has a function of suppressing deterioration of phase separation at the time of glass melting caused by an increase in the MgO and CaO components and the accompanying acid resistance reduction of the glass. It is. The various functions containing the SrO component become clearer when the glass composition contains 0.1% by mass or more. On the other hand, when the SrO component is used as a glass composition for glass fibers, if its content is too large, it becomes long glass and it becomes difficult to produce glass fibers having a small fiber diameter. From such a viewpoint, the upper limit of the SrO component content is preferably up to 10% by mass. At the time of glass melting, if the phase separation deteriorates, the molten glass will be separated into a phase rich in acid resistance and a phase poor in acid resistance, in which case the phase poor in acid resistance determines the acid resistance of the glass fiber. Therefore, the acid resistance as a glass fiber is poor, which is not preferable.

Similar to the SrO component, the BaO component lowers the viscosity of the molten glass corresponding to a temperature of 10 ^2.0 dPa · s, and further reduces the spinning temperature of the molten glass near 10 ^3.0 dPa · s. Although it is a component, its function is not as good as that of the MgO or CaO component. However, the BaO component is a component that has the function of suppressing the deterioration of phase separation caused by the increase in MgO and CaO components and the accompanying decrease in acid resistance of the glass, and achieves the object of the present invention in the same manner as the SrO component. It is an indispensable ingredient. Similarly to the SrO component, the inclusion effect of the BaO component is further clarified when the content is 0.1% by mass or more in the glass composition. On the other hand, when the BaO component is used as a glass composition for glass fibers, if its content is too large, the liquidus temperature is deteriorated and it becomes long glass, making it difficult to produce glass fibers having a small fiber diameter. From such a viewpoint, it is preferable that the BaO component is contained in a range of up to 10% by mass. A long glass is a glass having a small viscosity dependency with respect to a temperature change, and is not easily solidified as a fiber by cooling.

Further, SrO component and BaO components is easy to form crystals with SiO _2, if SrO component is contained in the glass composition, tends to precipitate SrO · SiO ₂ crystal and the BaO component-containing containing SiO ₂ If so, BaO.2SiO ₂ crystals are likely to precipitate, and as a result, the liquidus temperature of the glass tends to increase. If the liquidus temperature is high during glass fiber spinning, the bushing nozzle is clogged with crystals precipitated by the bushing nozzle, and the glass fiber is cut during spinning. However, in the glass composition and SrO component and BaO components are coexisting, a liquid phase temperature of the glass is lowered by the glass composition enters the eutectic region of SrO · SiO ₂ and BaO · 2SiO _2, during the spinning Since it is difficult for crystals to precipitate, it is desirable that both the SrO component and the BaO component are contained in the glass composition, that is, the SrO component and the BaO component coexist.

CeO ₂ component, by floating the air bubbles present as defects in the molten glass is intended to serve to facilitate fining, but in which an appropriate amount as is not fining agent in environmental substances, the CeO ₂ component fining The effect appears more clearly when it is 0.01% or more, more preferably 0.02% or more, in terms of mass percentage in terms of oxide. However, if the CeO ₂ component is added in a large amount, it may affect the devitrification of the molten glass. From this point of view, it should not exceed 5% in terms of oxide-based mass percentage. This upper limit value is preferably up to 4%, more preferably up to 2%, in order to achieve more stable quality. If the addition amount is optimum, the glass fiber can be made non-hollow.

The glass composition for glass fibers of the present invention may contain various components as necessary in addition to the above within a range that does not significantly affect the performance of the glass composition for glass fibers of the present invention. _If specifically exemplified what can be used as a constituent of glass composition for glass fiber of the present _{invention, ZrO 2, P 2 O 5} , Fe 2 O 3, SO 2, Cl 2, F 2, La 2 O ₃ , WO ₃ , rare earth oxides such as Nb ₂ O ₅ and Y ₂ O ₃ , or MoO ₃ can be contained as long as the content is 3% or less in terms of mass%.

In addition to the above, trace components can be contained up to 0.1% in terms of mass%. For example, various trace components such as Cr ₂ O ₃ , H ₂ O, OH, H ₂ , CO ₂ , CO, He, Ne, Ar, and N ₂ are applicable.

Further, in the glass composition for glass fiber of the present invention, a small amount of noble metal element may be contained in the glass as long as the performance of the glass composition for glass fiber is not greatly affected. For example, a white metal element such as Pt, Rh, and Os may be contained up to 1000 ppm, that is, the content of the metal element expressed as a mass percentage up to 0.1%.

In addition, in the glass composition for glass fiber of the present invention, the total amount of MgO, CaO, SrO and BaO in terms of alkaline earth metal oxide in terms of oxide percentage in addition to the above is 10 to 25%, If the value obtained by dividing the total amount of SrO and BaO by the total amount in terms of alkaline earth metal oxide is within the range of 0.15 to 0.50, the phase separation of the glass during melting is suppressed, The decrease in acid resistance caused by the above is avoided, the spinning temperature is low, and the glass becomes short, which is preferable because the productivity of non-hollow glass is increased. In addition, there is a small risk of the molten glass becoming inhomogeneous due to crystal precipitation or phase separation during glass melting, and the viscosity depends on the temperature near the spinning temperature, and has a short viscosity. Since a dielectric constant and a dielectric loss tangent can be obtained, it is preferable.

The total amount of MgO, CaO, SrO and BaO in terms of alkaline earth metal oxides expressed in terms of mass percentage in terms of oxide is 10 to 25%, and the total amount of SrO and BaO is the total amount in terms of alkaline earth metal oxides. The value divided by the amount is within the range of 0.15 to 0.50 means that the Sr is expressed by the total value of the oxide-converted mass percentage of the alkaline earth oxide elements Mg, Ca, Sr, and Ba. It means that the value obtained by dividing the total value of the mass percentage in terms of oxide of Ba and Ba falls within the range of 0.15 to 0.50.

When the total amount of MgO, CaO, SrO, and BaO in terms of the oxide-based mass percentage in terms of alkaline earth metal oxides is less than 10% by mass, it is difficult to obtain a sufficiently homogeneous state at the beginning of glass melting, and the glass in the molten state Since the viscosity of the glass fiber increases, the molding temperature rises too much and the spinnability of the glass fiber decreases. On the other hand, when the total amount of MgO, CaO, SrO, and BaO in terms of oxides in terms of mass percentage in terms of oxides exceeds 25%, problems arise in acid resistance and phase separation.

And if the value which remove | divided the total amount of SrO and BaO by the total amount of alkaline-earth metal oxide is less than 0.15, the phase separation property of molten glass will become high because the content ratio of MgO and CaO increases. This is not preferable because the tendency increases and the dielectric constant also increases. On the other hand, if the value obtained by dividing the total amount of SrO and BaO by the total amount in terms of alkaline earth metal oxide exceeds 0.50, the dielectric constant may be too high. In addition, the spinning temperature Ty is increased, and the glass is in a long direction, so that the spinnability is lowered and it is difficult to produce glass fibers having a small fiber diameter.

In addition to the above, the glass composition for glass fiber of the present invention has a low dielectric loss of the printed wiring board if the dielectric constant at a frequency of 1 MHz is 6.0 or less and the dielectric loss tangent is 20 × 10 ⁻⁴ or less. This is preferable.

In addition to the above, the glass composition for glass fiber of the present invention is a printed wiring using a high frequency if the dielectric constant at a frequency of 10 GHz is 6.0 or less and the dielectric loss tangent is 100 × 10 ⁻⁴ or less. A plate is preferable because the dielectric loss is further reduced.

In addition to the above, the glass composition for glass fiber of the present invention is stable when used as a printed wiring board because the electrical resistance is sufficiently large if the volume electrical resistivity logρ at 150 ° C. is 13 Ω · cm or more. Performance.

In addition to the above, the glass composition for glass fiber of the present invention has a temperature Ty of 10 ^3.0 dPa · s less than 1300 ° C., and a value obtained by subtracting the temperature Tx of 10 ^7.6 dPa · s from Ty is 300. If it is in the range of -450 ° C., it is preferable because the glass fiber can be efficiently produced without greatly changing the spinning device and spinning method of the glass fiber.

When the value obtained by subtracting the temperature Tx of 10 ^7.6 dPa · s from the temperature Ty of 10 ^3.0 dPa · s is 450 ° C. or more, the glass has a long viscosity. When trying to spin fibers, the curved shape formed by the molten glass drawn from the tip of the nozzle arranged in the bushing below the nozzle, that is, the meniscus becomes unstable, and stable spinning properties with a uniform fiber diameter cannot be obtained. The problem occurs. On the other hand, if the value obtained by subtracting the temperature Tx of 10 ^7.6 dPa · s from the temperature Ty of 10 ^3.0 dPa · s is 300 ° C. or less, the glass viscosity becomes too short, and a predetermined fiber diameter is obtained. For this reason, the appropriate range for setting other manufacturing conditions, for example, the yarn drawing speed and the cooling condition is narrowed, and there is a problem that it becomes difficult to manage the fiber diameter.

The glass fiber of the present invention comprises the glass composition for glass fiber of the present invention, and the average value of the diameter of the glass fiber is 3 to 7.2 μm. When applied to the above-mentioned uses, the performance of the composite material for printed wiring board applications constituted by using such glass fibers having a small fiber diameter is greatly improved.

When the average value of the glass fiber diameter is less than 3 μm, the fiber diameter is too small, and the production yield of the glass fiber may be lowered. In addition, depending on the environment in which the manufactured glass fiber is used, there is an environmental problem when the glass fiber deteriorated over time is scattered in the atmosphere, etc., or an expensive processing environment that does not adversely affect the human body etc. in recycling etc. It will be necessary to build. This leads to various environmental problems, which is not preferable.

On the other hand, when the average value of the glass fiber diameter exceeds 7.2 μm, a glass fiber made of a glass composition having a low dielectric constant, which has been used conventionally, is used without using the glass fiber made of the glass composition of the present invention. Even if it is used, it is possible to obtain a glass fiber having a stable quality with few glass defects and the like, which is not economical.

From the above viewpoints, the glass fiber of the present invention comprises the glass composition for glass fiber of the present invention, and the average value of its diameter is more preferably in the range of 3.1 to 6.5 μm, still more preferably. Is in the range of 3.2 to 6.2 μm, more preferably in the range of 3.3 to 5.5 μm, and still more preferably in the range of 3.4 to 5.2 μm. Most preferably, the thickness is 3.8 to 4.8 μm.

In addition to the above, the glass fiber of the present invention can provide a highly reliable printed wiring board when used in applications constituting a printed wiring board, if the number of hollow fibers is 2 / 100,000 filaments or less. Can do.

That the number of hollow fibers is 2 / 100,000 filaments or less means that the number of hollow fibers per 100,000 filaments is 2 or less. The number of hollow fibers is measured by immersing the glass cloth in an immersion liquid adjusted to have the same refractive index as that of the glass fiber, and observing it under a microscope (50 times) of the transmitted light. It can be easily obtained by measuring the number of fibers and dividing the value by the number of observed filaments and multiplying by 100,000.

In addition to the above, the glass fiber of the present invention has a bubble content of 0.01 or less, particularly 0.001 / m or less. A reduced composite structure with high homogeneity can be obtained, and the performance according to the design specifications of the printed wiring board can be exhibited.

The bubble content of 0.001 / m or less means that the number of bubbles per 1000 m of the glass filament is 1 or less, and the bubble count has a bubble length of 1 mm or more. For all bubbles. The bubble count can be easily measured by immersing the glass fiber in an immersion liquid adjusted to have the same refractive index as that of the glass in a microscope.

In addition to the above, the glass fiber of the present invention can achieve higher quality if the bubble content is 50/100 g glass or less, more preferably 20/100 g glass or less, and further preferably 5/100 g. It should be below glass. The bubble content ratio represents the number of bubbles in 100 g of glass.

The glass fiber may have a surface coated with a coating agent that imparts desired physicochemical performance. Specifically, a sizing agent, an antistatic agent, a surfactant, an antioxidant, a film forming agent, a coupling agent or a lubricant may be coated.

Examples of silane coupling agents that can be used for surface treatment include γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltri Methoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltri There are methoxysilane / hydrochloride, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriethoxysilane, and the like, which may be appropriately selected depending on the type of resin to be combined with the glass fiber used.

In addition to the above, the glass fiber of the present invention is obtained by dividing the standard deviation of the fiber diameter by the average value of the fiber diameters and multiplying the value by 100 to obtain a plurality of glass fibers having a CV value of 10% or less. As long as the glass filament is in the form of chopped strand, yarn, or roving, in addition to the printed wiring board application, various applications that require glass fibers with a small fiber diameter, even for other applications other than the printed wiring board It can be used in any case. If the CV value of the glass fiber exceeds 10%, it is not preferable because a problem occurs in formability that requires a precise shape.

A glass strand obtained by spinning the glass fiber of the present invention described above from a molten glass means that a plurality of glass filaments having a CV value of glass fiber diameter of 10% or less are in the form of chopped strand, yarn or roving. Spinning was carried out by measuring the diameter of each filament therein, adjusting the various conditions of the glass fiber production apparatus so that the value obtained by dividing the standard deviation by the average value and multiplying by 100 was 10 or less. It indicates that the glass fiber is cut glass chopped strand or twisted yarn, or a roving obtained by winding a plurality of glass filaments in a wound state. Incidentally, the standard deviation and average value of the fiber diameter are calculated from the measured values of 200 glass fibers.

In order to control the CV value of the glass fiber diameter to be 10% or less, for example, when using a glass forming apparatus in which a number of heat-resistant nozzles are provided in the bushing, the nozzle hole diameter, nozzle length, nozzle Each condition of the temperature, the ambient air temperature around the nozzle, the nozzle head pressure, the air blowing speed, and the glass filament drawing speed may be determined so as to be optimal for the glass fiber composition of the present invention.

If the glass fiber of the present invention is a glass fiber having a CV value of 10% or less in the form of chopped strand, yarn or roving, a plurality of glass filaments having a CV value of 10% or less can be used. Hole position generated by misalignment of the drill tip in the drilling process to form a through hole by using a glass cloth that is opened and widened when used in printed wiring board applications. It is preferable because the hole position accuracy can be improved by suppressing the fluctuations.

Further, the glass fiber of the present invention may be manufactured by any manufacturing method as long as the desired performance can be realized. For example, various production methods such as a direct molding method (DM method: direct melt method) and an indirect molding method (MM method: marble melt method) may be employed depending on the application and production amount. That is, the glass fiber of the present invention may be any glass fiber that has been spun by obtaining a glass fiber having a predetermined diameter by drawing the glass fiber from a bushing having a heat-resistant nozzle in addition to the above.

In addition to the above, the glass fiber of the present invention is made of glass cloth or glass paper, and then combined with an organic resin material to form an organic resin composite material. It is preferable because the glass fiber is optimal for constituting the plate.

In other words, after being made into glass cloth or glass paper, it is used in applications where it is combined with an organic resin material to form an organic resin composite material. Glass fiber for printed wiring boards using glass fibers as warps and wefts Use as a woven fabric by various weaving methods used in, or to form an organic resin composite by forming chopped strands into glass paper by a wet method or a dry method and combining them with an organic resin material It is used in.

The glass fiber constituting the glass cloth obtained by using the glass fiber of the present invention is, for example, 1 to 50 tex, preferably 1.5 to 23 tex, more preferably 1.5 to 15 tex. There is no special limitation on the cross-sectional shape of the glass filament constituting the strand. The cross-sectional shape of the glass filament may be circular, elliptical, or oval. The twist number of the glass fiber bundle is more preferably 2 times / 25 mm or less.

The glass cloth obtained by using the glass fiber of the present invention has 30 to 100 warps per warm and 25 mm of wefts, preferably 45 to 90 warps and 35 to 90 wefts. A glass cloth having a structure is more preferable.

When the woven product obtained by using the glass fiber of the present invention is used as a constituent material of a printed wiring board, the manufacturing process is specifically as follows. That is, a glass yarn or glass yarn twisted yarn unwound from a package of a glass yarn wound body or a glass yarn twisted yarn wound body made of the glass fiber composition of the present invention is warped with a warper, and then used with a gluing machine. The next size is taken up from the beam to the room beam, and this is used as the warp. The package of the glass yarn winding body or the glass yarn twisted yarn winding body is unwound, this is used for the weft, and the glass cloth is woven using an air jet loom or the like. Organic components adhering to the woven glass cloth are removed by incineration by heating (heat deoiling), immersed in a treatment solution containing a silane coupling agent and dried (surface treatment), and then impregnated with resin. A laminated board for a printed wiring board is manufactured by laminating and curing the resin.

Further, when the glass paper obtained using the glass fiber of the present invention uses chopped strands, the length dimension of the chopped strands is not limited. About the length dimension of a fiber, what was suitable for a use can be selected. Further, any method for producing chopped strands can be adopted. The strand spun from the melt process can be cut immediately after spinning, or once wound as a continuous fiber, it may be cut by a cutting device according to the application. In this case, any method can be adopted as a cutting method. For example, an outer peripheral blade cutting device, an inner peripheral blade cutting device, a hammer mill, or the like can be used. Moreover, it does not specifically limit about the aggregate form of a chopped strand.

In addition, a glass cloth or glass paper obtained using the glass fiber of the present invention may be used in combination with a fiber material other than the glass fiber of the present invention, a solid additive, or a liquid additive depending on the application. In addition, when constituting a glass cloth or glass paper, the fiber material other than the glass fiber of the present invention used in combination with the glass fiber material of the present invention includes D glass fiber, glass fiber of other composition, organic fiber material, ceramic fiber And carbon fibers may be used. Examples of solid additives include ceramic powder, organic resin powder, and silicone powder. Examples of liquid additives include polymerization accelerators, polymerization inhibitors, antioxidants, and decomposition reactions. Use appropriate amounts of inhibitors, diluents, antistatic agents, anti-aggregation agents, modifiers, wetting agents, drying agents, antifungal agents, dispersants, curing accelerators, reaction accelerators, thickeners or reaction accelerators May be.

The glass fiber sheet of the present invention is characterized in that it is used in applications where the glass fiber of the present invention is combined with an organic resin material to form an organic resin composite material.

Here, the glass fiber of the present invention is used in an application in which an organic resin composite is formed by combining with an organic resin material to mean that SiO _{2 is} 45 to 65% in terms of oxide mass, Al ₂ O ₃ Glass fiber containing 10 to 20%, B ₂ O ₃ 13 to 25%, MgO 5.5 to 9%, CaO 0 to 10%, Li ₂ O + Na ₂ O + K ₂ O 0 to 1%, SrO, BaO It means that the glass fiber sheet is 1 mm or less in thickness and is used in an application in which an organic resin composite material is obtained by impregnating a thermosetting organic resin material.

As the thermosetting organic resin material, for example, a resin such as a phenol resin, an epoxy resin, a polyimide resin, or a bismaleimide resin may be used.

If the glass fiber sheet of the present invention is a glass cloth or glass paper in addition to the above, a printed wiring board that exhibits various performances can be produced depending on the application.

As the glass cloth, woven fabrics with various structures can be used. For example, it is possible to use a woven structure such as a plain weave or a twill weave to a more complicated structure. Further, the glass paper may be any glass paper as long as it is chopped strands, dispersed as a monofilament in white water, and then formed into a sheet using an organic binder. For example, in the case of using chopped strands, the molten glass obtained by melting the glass fiber composition of the present invention described above is continuously drawn out from a heat-resistant nozzle provided in a molding apparatus such as a bushing and focused around it. A glass long fiber is formed by coating with an agent. Next, the obtained long glass fiber is wound around a paper tube or the like to make a cake (also called cheese), and then the necessary number is pulled out from the cake and cut to a predetermined length by a glass fiber cutting device. To do. After the chopped strands thus obtained are dispersed in white water, they are picked up on a mesh, randomly deposited on a conveyor to form a sheet, and a liquid binder is sprayed from above to bond this By curing the agent, a glass fiber sheet-like material constituted by the glass chopped strands is obtained through a step of bonding the glass chopped strands to each other.

(1) glass fiber composition of the present invention, _SiO 2 ₄₅ ~ _65% in mass percentage terms of _{oxides, Al 2 O 3 10 ~ 20} %, B 2 O 3 13 ~ 25%, MgO 5 ~ 9 %, CaO 0 to 10%, Li ₂ O + Na ₂ O + K ₂ O 0 to 1%, SrO, BaO, glass fiber having a small fiber diameter and excellent spinnability when spinning glass fiber. Molding can be easily performed, and the obtained glass fiber has excellent electrical performance such as dielectric constant and dielectric loss tangent.

(2) If the composition for glass fiber of the present invention is CeO ₂ 0.01 to 5.0% in terms of mass percentage in terms of oxide, a glass with high homogeneity is obtained from a molten glass in which the number of bubbles is suppressed. Since fibers can be obtained, the production efficiency and the performance of the produced glass fibers are improved, which is preferable.

(3) If the composition for glass fiber of the present invention is SrO 0.1 to 10% and BaO 0.1 to 10% in terms of mass percentage in terms of oxide, phase separation during glass melting and crystal precipitation It is possible to avoid the devitrification caused by.

(4) The composition for glass fiber of the present invention is expressed in mass percentage in terms of oxide, and the total amount of MgO, CaO, SrO and BaO in terms of alkaline earth metal oxide is 10 to 25%, and SrO and BaO If the value obtained by dividing the total amount by the total amount in terms of alkaline earth metal oxides is in the range of 0.15 to 0.50, the high temperature viscosity suitable for performing the spinning operation and the temperature dependence of the high temperature viscosity are It is suitable for obtaining a glass fiber of a quality that can be realized and is excellent in acid resistance and devitrification of glass.

(5) The composition for glass fiber of the present invention can cope with an increase in the speed of an electric signal as long as the dielectric constant at a frequency of 1 MHz is 6.0 or less and the dielectric loss tangent is 20 × 10 ⁻⁴ or less. Since a printed wiring board with a small loss can be obtained, it has performance suitable for application to a printed wiring board. Further, when the dielectric constant at a frequency of 10 GHz is 6.0 or less and the dielectric loss tangent is 100 × 10 ⁻⁴ or less, it has more suitable properties for application to a printed wiring board using a high frequency.

(6) The glass fiber of the present invention comprises the glass composition for glass fiber of the present invention, and the average value of the glass fiber diameter is 3 to 7.2 μm. Is preferred.

(7) The glass fiber of the present invention is a glass having high performance if it is used for the purpose of forming an organic resin composite material after being formed into a glass cloth or glass paper and then being combined with an organic resin material. The fibers can be supplied in an optimum form according to the application, and the dielectric properties and heat resistance of the printed wiring board applied to various electronic circuits can be improved.

(8) If the glass fiber sheet-like material of the present invention is used for the purpose of forming the organic resin composite material by combining the glass fiber of the present invention with the organic resin material, the conventional process is not changed. It is suitable for manufacturing a printed wiring board that exhibits high quality and stable performance.

(9) Since the glass fiber sheet-like material of the present invention is a glass cloth or glass paper, it is manufactured without changing manufacturing conditions when manufacturing a prepreg used in a process of manufacturing a printed wiring board. Therefore, the present invention is suitable for obtaining a printed wiring board that can be used even in an environment where the temperature changes rapidly without hindering the manufacturing process of the printed wiring board.

Hereinafter, the composition for glass fiber, the glass fiber and the production method thereof of the present invention will be specifically described based on examples.

Table 1 shows the compositions and evaluation results of the glass fiber compositions according to the examples of the present invention. The glass compositions in oxide conversion shown in Table 1 are all expressed in mass%.

Example sample No. 1 to sample no. For each glass sample up to 10, glass samples were prepared according to the procedure shown below.

First, a predetermined amount of a plurality of glass raw material species such as natural mineral glass raw materials and chemical glass raw materials is weighed in units of g with three decimal points so that the glass composition of Table 1 is obtained. Next, a glass raw material mixing batch in which these plural raw materials are mixed so as to be in a homogeneous state is prepared, and this glass raw material mixing batch is put into a crucible made of platinum rhodium having a volume of 500 cc. Next, the platinum rhodium crucible charged with this raw material mixing batch is heated in an indirect heating electric furnace at 1550 ° C. for 5 hours in an air atmosphere to chemically react the glass raw material mixing batch at a high temperature to obtain molten glass and did. In order to make this molten glass into a homogeneous state, the molten glass was stirred using a heat-resistant stirring rod in the middle of heating and melting.

Thus, the molten glass in a homogeneous state was poured into a predetermined refractory mold, cast into a predetermined shape, and annealed to room temperature in a slow cooling furnace to obtain a glass molded body used for testing and the like.

Using the glass molded body thus obtained, various physical properties and the like of each glass composition of the examples of the present invention were measured by the following procedure. The measurement results are summarized in Table 1.

Regarding the measurement of the linear thermal expansion coefficient, a temperature of 30 ° C. to 380 ° C. was measured with a known linear thermal expansion measuring instrument that was calibrated using NIST's SRM-731 and SRM-738 as standard samples with known linear thermal expansion coefficients. It is the average linear thermal expansion coefficient measured for the range. The lower the value of this linear thermal expansion coefficient, the smaller the expansion of the glass fiber, even when the temperature change is large. As a result, the temperature fluctuation when a printed wiring board using the glass fiber is mounted on an electronic device. It leads to increase the reliability related to.

In order to measure the temperature (Ty) of 10 ^3.0 dPa · s, which indicates the high temperature viscosity of the molten glass, each glass sample crushed to an appropriate size in advance is put into an alumina crucible and reheated. Each value is calculated by interpolation of viscosity curves obtained by a plurality of measurements of each viscosity value measured based on the platinum ball pulling method after heating to the melt state. The value of Ty−Tx in the table is obtained by subtracting the value of the softening point, which is the temperature corresponding to 10 ^7.6 dPa · s, from the value of the temperature corresponding to 10 ^3.0 dPa · s. In addition, the measurement of a softening point points out the value measured by the method based on ASTMC338. The smaller the value of Ty−Tx, the greater the temperature dependency of the viscosity, and the glass is short-circuited. The shorter the glass, the more likely it will be solidified by cooling from the molten state, so even if the molten glass is spun from the nozzle attached to the bushing, the meniscus is stable and without cutting Glass fiber can be produced. The longer the temperature dependency of the viscosity of the glass fiber, the longer the meniscus becomes and the more unstable it becomes. Therefore, it is necessary to make heavy equipment for incidental equipment when manufacturing the glass fiber, such as strengthening the cooling conditions.

Also, for the liquidus temperature _TL , each glass molded body is cut into a predetermined shape and pulverized to a predetermined particle size, and the finely pulverized product is removed to obtain a particle size in the range of 300 μm to 500 μm so as to have a predetermined surface area. In a state adjusted so as to be filled in a platinum container having an appropriate bulk density, it is placed in an indirect heating type temperature gradient furnace whose maximum temperature is set to 1250 ° C. and left to stand for 16 hours in the atmosphere. A heating operation was performed in an atmosphere. Thereafter, the test specimen was taken out together with the platinum container, allowed to cool to room temperature, and then the liquidus temperature _TL was specified by a polarizing microscope. The value of Ty− _TL in the table is obtained by subtracting the value of the liquidus temperature _TL from the value of temperature corresponding to 10 ^3.0 dPa · s. As the value of Ty- _TL is larger, crystals that hinder the spinning operation in the vicinity of the spinning temperature are not easily precipitated, and a stable spinning state can be secured. In order to increase the value of Ty- _TL , it is only necessary to increase the temperature Ty of 10 ^3.0 dPa · s, which corresponds to the spinning temperature, but this increases the energy required for melting the glass and increases the manufacturing cost. Leading to a problem of reducing the service life of incidental equipment such as a bushing device.

The volume electrical resistivity at 150 ° C. is a value measured at 150 ° C. based on ASTM C657-78. The higher the value of the volume electrical resistance, the more stable electrical insulation performance can be achieved even with a printed wiring board on which high-density mounting is performed.

For the measurement of dielectric constant (ε) and dielectric loss tangent (tan δ) at a frequency of 1 MHz, a glass sample piece processed to a size of 50 mm × 50 mm × 3 mm was polished on both surfaces with a thickness of 3 mm with No. 1200 sandpaper. used. The measurement was obtained by measuring at room temperature according to ASTM D150-87 and using a 4192A impedance analyzer made by Yokogawa Hewlett-Packard. For measurement of dielectric constant (ε) and dielectric loss tangent (tan δ) at a frequency of 10 GHz, measurement is performed at room temperature by using an Agilent network analyzer by a double-end short-circuited dielectric resonator method according to JIS R1627: 1996. Was obtained. The smaller the dielectric constant and the dielectric loss tangent are, the smaller the dielectric loss of the printed wiring board is when glass fiber is used for the purpose of forming the printed wiring board.

With respect to acid resistance, 10% hydrochloric acid is expressed as a percentage by weight with a pulverized product equivalent to 1 cm ³ in a state in which the finely pulverized product is removed and adjusted to have a particle size in the range of 300 μm to 500 μm so as to have a surface area in a predetermined range. The solution was put into an acid-resistant sealed container together with 50 cc of aqueous solution, kept in a constant temperature shaker set at 80 ° C. for 16 hours in this state, filtered to remove the liquid, and dried in a 110 ° C. dryer to dry the glass. Get the constant mass value. And the decreasing rate of the mass value after the acid treatment with respect to the mass value of the initially added glass is measured. With respect to the sample in which the measured decrease rate obtained in this way is 30% or more and the reaction product was confirmed to be formed during the corrosion reaction of the glass surface with hydrochloric acid during the acid resistance test, Acid resistance has fallen and it was set as x determination, and it was set as (circle) determination about the other sample. If a reaction product is formed by a corrosion reaction, it may prevent a homogeneous treatment state from being secured when an acid treatment is performed in a plating process or the like performed in a process of manufacturing a printed wiring board using glass fibers. This is because there is a high risk of reducing the yield rate.

From the above tests, the following became clear. That is, test No. which is an example of the present invention. 1 to test no. For up to 12 samples, the glass composition is expressed in mass% in terms of oxide, with SiO _{2 in} the range of 47.4% to 54.5%, and Al ₂ O ₃ of 11.7% to 18.7%. B ₂ O ₃ in the range of 14.0% to 20.0%, MgO in the range of 5.5 to 8.7%, CaO in the range of 3.5 to 8.8%, Li ₂ O + Na ₂ O + K ₂ O is in the range of 0.1 to 0.4%, SrO is in the range of 1.1 to 8.8%, BaO is in the range of 0.8 to 5.0%, and MgO, The total amount of CaO, SrO and BaO in terms of alkaline earth metal oxides is in the range of 15.2 to 21.4%, and the total amount of SrO and BaO is divided by the total amount in terms of alkaline earth metal oxides. a value in the range from 0.20 to 0.45, der what CeO ₂ is in the range from 0.1 to 0.9% .

Further, as shown in Table 1, the average linear expansion coefficient in the temperature range from 30 ° C. to 380 ° C. of the examples of the present invention is 39.2 × 10 ⁻⁷ to 49.0 × 10 ⁻⁷ / ° C. The temperature of 10 ^3.0 dPa · s corresponding to the spinning temperature is in the range of 1194 ° C to 1298 ° C, and the temperature Tx of 10 ^7.6 dPa · s is in the range of 828 ° C to 880 ° C. Thus, the value of Ty−Tx indicating the temperature dependence of the viscosity is in the range of 364 ° C. to 426 ° C. Furthermore, the liquidus temperature _{TL in the} examples of the present invention is in the range of 1000 ° C. or less to 1095 ° C., and therefore the value of Ty− _TL is in the range of 162 ° C. to 251 ° C. Furthermore, the temperature Tw of 10 ^2.0 dPa · s, which is a measure of the melting temperature, is in the range of 1384 ° C. to 1502 ° C., which is lower than that of D glass. Regarding the electrical properties, the volume electrical resistivity logρ at 150 ° C. in the example of the present invention is in the range of 13.3 Ω · cm to 17.9 Ω · cm, and the dielectric constant (ε) at a frequency of 1 MHz is 5 Satisfying the requirement of the present invention that the dielectric constant is 6.0 or less within the range of .36 to 5.82, and the dielectric loss tangent (tan δ) at the frequency of 1 MHz is within the range of 0.0008 to 0.0014. Therefore, the requirement that the dielectric loss tangent is 20 × 10 ⁻⁴ or less is also satisfied. Further, the dielectric constant (ε) at the frequency of 10 GHz satisfies the requirement of the present invention that the dielectric constant is in the range of 5.4 to 5.9 and the dielectric constant is 6.0 or less, and the dielectric loss tangent at the frequency of 10 GHz ( tan δ) is in the range of 0.0038 to 0.0096 and satisfies the requirement that the dielectric loss tangent is 100 × 10 ⁻⁴ or less. Further, the number of hollow fibers has an excellent quality of 1.5 filaments / 100,000 filaments or less. That is, sample No. which is an example of the present invention. 1 to sample no. No. 10 had properties suitable as the glass fiber composition of the present invention.

A particularly characteristic sample among the embodiments of the present invention will be described below.

Sample No. of Example The glass composition of No. 1 has the smallest SiO ₂ content of 47.74%, which is compensated by making the B ₂ O ₃ content the maximum 20.0%, and has an expansion coefficient of Is 44.7 × 10 ⁻⁷ / ° C., which is a sufficiently low value, and the value of Ty-Tx indicating the temperature dependence of viscosity is 364 ° C., which is at a satisfactory level and corresponds to the spinning temperature. Ty is 1194 ° C., and the temperature Tw of 10 ^2.0 dPa · s, which is a standard of the melting temperature, is 1384 ° C., which is a sufficiently low value. Furthermore, _TL , which is the liquidus temperature, is 1020 ° C. or lower, and the value of Ty− _TL is sufficiently large because it is 190 ° C. or higher at least. Furthermore, the volume resistivity is 17.5 Ω · cm, which is a sufficiently large value. The dielectric constant ε at a frequency of 1 MHz is 5.50, the dielectric loss tangent is 0.0010, and the dielectric constant ε at a frequency of 10 GHz is 5. 6. The dielectric loss tangent is 0.0042, which is a very small value. And regarding acid resistance, since the mass decreasing rate was low and formation of the reaction product was not recognized, it was determined as “◯”. Further, it contains CeO ₂ and is considered so as to promote the clarification of the molten glass so that no hollow fiber is generated. Thus, sample No. One glass composition is suitable for the present invention. Then, when glass fiber formation was evaluated using this glass molded body, the number of hollow fibers in the glass fiber was measured without causing problems such as devitrification and without bubbles remaining in the glass fiber. It has been found that a homogeneous glass fiber satisfying a ratio of 100 / 100,000 filaments or less can be spun.

Sample No. of Example The glass composition of No. ₂ has a feature that Al ₂ O ₃ has the lowest content of 11.7%, and contains CeO ₂ . This sample No. 2 is a typical sample of the present invention, the expansion coefficient is 44.4 × 10 ⁻⁷ / ° C., which is a sufficiently low value, and the Ty-Tx value indicating the temperature dependence of viscosity is 391 ° C. It has a sufficiently short viscosity. The temperature of 10 ^2.0 dPa · s, which is a standard for the melting temperature, is as low as 1436 ° C, and the liquid phase temperature _TL is as low as 1054 ° C. The value of Ty- _TL is sufficiently high at 180 ° C. Indicates a large value. The volume resistivity is sufficiently large at 17.0 Ω · cm, the dielectric constant (ε) at a frequency of 1 MHz is 5.49, the dielectric loss tangent (tan δ) is 0.0014, and the dielectric constant ε at a frequency of 10 GHz is 5. 6. The dielectric loss tangent is 0.0056, both of which are small values. As for acid resistance, sample No. As in the case of No. 1, the mass reduction rate was low, and formation of a reaction product was not recognized. This sample No. Regarding No. 2, when spinning was performed with 200 nozzles so as to have an average fiber diameter of 5.0 μm and evaluation of glass fiber formation was performed, stable spinning operation could be performed without major changes to conventional glass production equipment. When the number of hollow fibers in the glass fiber was measured without causing any problems such as devitrification or the like and without bubbles remaining in the glass fiber. It was found that homogeneous glass fibers satisfying 10,000 filaments or less can be spun. The average diameter of the 200 glass fibers is 5.0 μm and the standard deviation is 0.40 μm. The standard deviation of the fiber diameter is divided by the average value of the fiber diameters, and the value is multiplied by 100. The CV value obtained was 8%, which was a good quality. From this, it became clear that it has excellent quality and performance as glass fiber for printed wiring board applications. Therefore, a prepreg is produced by plain weaving this glass fiber, and the printed wiring board obtained thereby can sufficiently exhibit design performance.

Sample No. of Example The glass composition of No. 4 is the glass composition having the highest BaO content in the examples, but the average linear expansion coefficient is 40.4 × 10 ⁻⁷ / ° C. and has a very small value. Furthermore, the temperature Tw of 10 ^2.0 dPa · s is 1491 ° C., the temperature of 10 ^3.0 dPa · s is 1284 ° C., and the value of Ty−Tx indicating the temperature dependence of viscosity is The glass is sufficiently short at 409 ° C. In terms of electrical performance, the dielectric constant (ε) at a frequency of 1 MHz is 5.46, the dielectric loss tangent (tan δ) is 0.0012, the dielectric constant ε at a frequency of 10 GHz is 5.6, and the dielectric loss tangent is 0.0038. Yes, it satisfies the requirements of the present invention. Further, regarding the acid resistance, sample No. As with No. 1 etc., the mass reduction rate is low, and no reaction product is formed, so it is judged as “◯”, and when glass fiber evaluation is performed, it is stable without major changes to conventional glass production equipment. The spinning operation could be performed. Sample No. obtained in this way. Glass fiber having a glass composition of 4 has no problems such as phase separation or devitrification, and no bubbles remain in the glass fiber, and the number of hollow fibers in the glass fiber is measured. As a result, it was found that glass fibers satisfying 2 filaments / 100,000 filaments or less can be spun.

Sample No. obtained as described above. A glass cloth made of plain weave using the glass composition of No. 2 can be used to obtain a glass cloth with low hollow fiber, low dielectric constant and low dielectric loss tangent, and exhibiting suitable performance as a printed wiring board application Met.

[Comparative Example] Next, Table 2 shows the results of the investigation related to the sample corresponding to the comparative example prepared in the same procedure as that of the example of the present invention. Regarding the results of various measurements shown in Table 2, the method and apparatus used were the same as those in the examples.

Sample No. of Comparative Example The glass composition of 101 has a composition similar to a glass composition generally called E glass, but has a high linear thermal expansion coefficient of 62.5 × 10 ⁻⁷ / ° C. and a dielectric constant of 7 MHz at a frequency of 1 MHz. Since it is as high as 00 and the dielectric constant at a frequency of 10 GHz is as high as 6.8, it is completely different from the present invention.

Sample No. of Comparative Example The glass composition 102 does not contain SrO or BaO, but the acid resistance is not deteriorated because the content of SiO ₂ is as high as 76.1%. However, since the content of SiO ₂ is high, the temperature of 10 ^3.0 dPa · s corresponding to the spinning temperature is as high as 1336 ° C. This glass fiber causes deterioration of production-related equipment when spinning over a long period of time, and is also economically problematic. Further, the temperature Tw of 10 ^{2 · 0} dPa · s, which is a standard of the melting temperature, was as high as 1600 ° C. or higher. For this reason, bubbles are likely to remain in the glass even when the glass is melted, and the glass has a long Ty-Tx value of 526 ° C., which has a problem in spinnability.

Sample No. of Comparative Example In the glass composition of 103, the ratio of the total amount of SrO and BaO to the total amount of alkaline earth metal oxide exceeds 0.5. 10 ^3.0 dPa · s temperature exceeds 1400 ° C, Ty-Tx value is 536 ° C and long glass, so it is difficult to produce glass fiber with small fiber diameter. There was a problem with sex. Since the temperature Tw of 10 ^2.0 dPa · s was also high and CeO ₂ was not contained, bubbles were likely to remain in the glass even when the glass was melted. For this reason, with this glass composition, the required number of hollow fibers cannot be 2 / 100,000 filaments or less. In addition, since the dielectric loss tangent at a frequency of 1 MHz is as high as 0.0025 and the dielectric loss tangent at a frequency of 10 GHz is also high as 0.0108, there is a problem that the dielectric loss increases and the transmission speed becomes slow.

Sample No. of Comparative Example The glass composition 104 is a glass composition containing no SrO or BaO, and the ratio of the total amount of SrO and BaO to the total amount of alkaline earth metal oxide is as low as 0.00. For this reason, the temperature of 10 ^3.0 dPa · s was as high as 1332 ° C. The temperature Tw of 10 ^{2 · 0} dPa · s ^{, which} is a measure of the melting temperature, was also as high as 1568 ° C., and many bubbles remained during glass melting. Phase separation was observed when the glass was melted, and reaction products that reacted with hydrochloric acid were observed in the acid resistance test, so there was a concern that problems would occur during the etching process performed in the printed wiring board manufacturing process. . The volume electrical resistivity logρ is 12.7 Ω · cm, and the electrical reliability as a printed wiring board is low.

Sample No. of comparative example In the glass composition of 105, the ratio of the total amount of SrO and BaO to the total amount of alkaline earth metal oxide is as low as 0.05. This sample No. Glass No. 105 had a high dielectric constant of 6.10 at a frequency of 1 MHz, and a high dielectric constant of 6.2 at a frequency of 10 GHz. Further, this sample has a problem that the dielectric loss tangent at a frequency of 1 MHz is as high as 0.0025 and the dielectric loss tangent at a frequency of 10 GHz is as high as 0.0127, so that the dielectric loss increases and the transmission speed is slow. In addition, a remarkable phase separation property was observed when the glass was melted, which led to a negative effect on acid resistance, and was a glass composition in which problems were recognized.

Through a series of evaluations performed in the examples and comparative examples shown above, the glass composition for glass fibers of the present invention is suitable as a glass fiber having a small fiber diameter used for a printed wiring board realizing high-density mounting. It has become clear that it is excellent in spinnability in the production of glass fibers and can provide stable quality glass fibers with high production efficiency.

Claims (10)

SiO ₂ 45 to 65%, Al ₂ O ₃ 10 to 20%, B ₂ O ₃ 13 to 25%, MgO 5.5 to 9%, CaO 0 to 10%, Li ₂ O + Na in terms of oxide-based mass percentage _{2. A} glass composition for glass fiber, which contains ₂ O + K ₂ O 0 to 1%, SrO, BaO. The glass composition for glass fibers according to claim 1, wherein CeO _{2 is} 0.01 to 5.0% in terms of mass percentage in terms of oxide. The glass composition for glass fibers according to claim 1 or 2, wherein SrO is 0.1 to 10% and BaO is 0.1 to 10% in terms of mass percentage in terms of oxide. The total amount of MgO, CaO, SrO and BaO in terms of alkaline earth metal oxides expressed in terms of mass percentage in terms of oxide is 10 to 25%, and the total amount of SrO and BaO is the total amount in terms of alkaline earth metal oxides. The glass composition for glass fibers according to any one of claims 1 to 3, wherein the value divided by the amount is in the range of 0.15 to 0.50. 5. The glass composition for glass fibers according to claim 1, wherein a dielectric constant at a frequency of 1 MHz is 6.0 or less and a dielectric loss tangent is 20 × 10 ⁻⁴ or less. . 6. The glass composition for glass fiber according to claim 1, wherein a dielectric constant at a frequency of 10 GHz is 6.0 or less and a dielectric loss tangent is 100 × 10 ⁻⁴ or less. . A glass fiber comprising the glass composition for glass fiber according to any one of claims 1 to 6, wherein an average value of the diameter of the glass fiber is 3 to 7.2 µm. The glass fiber according to claim 7, wherein the glass fiber is used for a purpose of forming an organic resin composite material by being combined with an organic resin material as a glass cloth or a nonwoven fabric. A glass fiber sheet-like material, characterized in that the glass fiber sheet according to claim 7 or 8 is used in an application in which an organic resin composite material is formed by combining the glass fiber with an organic resin material. The glass fiber sheet material according to claim 9, wherein the glass fiber sheet material is glass cloth or glass paper.