TWI474988B - Glass composition for glass fiber, glass fiber and sheet-shaped glass fiber object - Google Patents

Description

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

The present invention relates to a glass composition for glass fibers which is excellent in meltability and spinnability used in a printed wiring board or the like which is required for high-density packaging used in electronic parts and the like, and is composed of the glass. A glass fiber formed of the object, and a glass fiber sheet composed of the glass fiber.

With the development of various information equipment such as mobile phones or personal digital assistants (PDAs), a large number of electronic components such as resistors, condensers, and integrated circuits In the trend of high-density packaging technology, it is packaged on a printed wiring board (also called a printed circuit board, a rigid substrate, a printed substrate, or a printed wiring board) at a high density that was not previously available. There are more cases on the top. The printed wiring board is a sheet-like composite material in which a resin is mixed with an appropriate amount of a glass fiber or a modifying agent, and has a form in which a through hole for mounting various electronic components is provided. It is also represented by an alias such as a module, a board, a unit, or a package depending on its function or use.

For the glass fiber used for the use of the printed wiring board, a glass composition called E glass which is composed of nonalkali glass has been previously used. The E glass is excellent in electrical insulating properties, excellent in spinnability when glass fibers are produced in a molten state, and excellent in workability such as cutting processing. Therefore, it has many uses and is the most well-known glass fiberglass. Material. Further, for example, in terms of weight percentage in terms of oxide, the E glass contains 52% to 56% of SiO ₂ , 12% to 16% of Al ₂ O ₃ , 5% to 10% of B ₂ O ₃ , and 16%. 25% CaO, 0% to 5% MgO, 0% to 2% alkali metal oxide (R ₂ O), 0.05% to 0.4% Fe ₂ O ₃ , 0% to 1.0% F ₂ glass Material.

On the other hand, in recent years, in order to realize the use of a printed wiring board, it is necessary to use a high-frequency wave in order to realize a high-speed electronic circuit. However, the electrical characteristics of the printed wiring board are emphasized at this time. The transfer speed is inversely proportional to the square root of the permittivity, so it is necessary to have a low dielectric constant in order to increase the transfer speed. Moreover, the dielectric loss is required to be small, so the dielectric dissipation factor must be small. That is, the dielectric constant (ε) of the present invention represents a dimensionless number, which is the ratio of the dielectric constant of the medium to the dielectric constant of the vacuum, that is, the relative dielectric constant. It is conventionally expressed as a dielectric constant (ε). In general, if an alternating current flows into the glass, the glass absorbs energy from the alternating current and absorbs it as heat. The absorbed dielectric loss energy is proportional to the dielectric constant and dielectric loss factor determined by the composition and structure of the glass, and is expressed by W = kfv ² × ε tan δ. Here, W represents dielectric loss energy, k represents a constant, f represents a frequency, v ² represents an electric potential gradient, ε represents a dielectric constant, and tan δ represents a dielectric loss factor. From this equation, it is understood that the dielectric constant and the dielectric loss factor are larger, and the higher the frequency, the larger the dielectric loss becomes. Therefore, in order to reduce the dielectric loss, it is required to reduce the dielectric constant and the dielectric loss factor.

Therefore, for a glass fiber used for a printed wiring board, a material for a glass fiber having a low dielectric constant and a dielectric loss factor is required, and a room temperature is disclosed in Japanese Patent Laid-Open Publication No. SHO 63-2831. A glass material having a dielectric constant of 6.7 at a lower frequency of 1 GHz and a lower dielectric constant and dielectric loss factor of E glass having a dielectric loss factor of 12 × 10 ^-4 is called a glass material of D glass. For example, in terms of weight percentage in terms of oxide, the D glass contains 74.5% SiO ₂ , 0.3% Al ₂ O ₃ , 21.7% B ₂ O ₃ , 0.5% CaO, 0.5% Li ₂ O, A glass material of 1.0% Na ₂ O and 1.5% K ₂ O. The glass has a dielectric constant of about 4.3 at 1 MHz and a dielectric loss factor of about 10 to 20 × 10 ^-4 .

However, although the electrical properties of the D glass are excellent, it has been pointed out that there are various problems in the process of printing a wiring board or a glass fiber. For example, D glass is inferior in meltability to glass compared with E glass, and it is easy to cause end breakage or the like at the time of spinning, and manufacturing of glass fiber is not easy. Further, since the D glass is structurally weak, the weaving property in the weaving process for forming the cloth form for obtaining the printed wiring board is poor, and as a result, the product yield is lowered. Further, in the printed wiring board using the D glass, there is also a problem that the wear of the drill in the drilling process becomes large, the positional accuracy of the via hole becomes low, and the like. The process is a process of forming a via hole, that is, a via hole for the purpose of not interposing the interlayer of the electronic component lead.

In order to solve the problems as described above, many inventions have been made so far. A low dielectric constant glass fiber characterized by containing a glass composition of 50% to 60% SiO ₂ , 10% to 18% by weight, is disclosed, for example, in Japanese Laid-Open Patent Publication No. Hei 10-167759. Al ₂ O ₃ , 18% to 25% B ₂ O ₃ , 0% to 10% CaO, 1% to 10% MgO, 0% to 1.0% Li ₂ O+Na ₂ O+K ₂ O 0.1%~1% Fe ₂ O ₃ .

A low dielectric constant glass fiber is disclosed in Japanese Laid-Open Patent Publication No. Hei 8-333137, which is characterized by containing a composition of 50% to 60% SiO ₂ and 10% to 20% Al by weight. ₂ O ₃ , 20% to 30% B ₂ O ₃ , 0% to 5% CaO, 0% to 4% MgO, 0% to 0.5% Li ₂ O+Na ₂ O+K ₂ O, 0.5 %~5% TiO ₂ .

Further, a low dielectric constant low dielectric loss factor glass is disclosed in Japanese Laid-Open Patent Publication No. 2003-137590, which is characterized by containing a composition of 48% to 80% by weight of SiO ₂ , 0. %~18% Al ₂ O ₃ , 11%~35% B ₂ O ₃ , 0%~10% MgO, 0%~10% CaO, 0%~7% Li ₂ O+Na ₂ O +K ₂ O, less than 3% TiO ₂ ; and H ₂ O < 800 ppm, a dielectric constant of 5.0 or less at 1 MHz, and a dielectric loss factor of 7 × 10 ^{-4 or} less.

However, as far as the invention disclosed so far is concerned, in order to realize the generation of glass defects having sufficient mechanical properties and easy control of devitrification and the like, a glass material having a low dielectric constant and a low dielectric loss factor is further obtained. For glass fibers with a low dielectric constant and a low dielectric loss factor, there are still problems that need to be further solved.

For example, the glass composition of Japanese Laid-Open Patent Publication No. Hei 10-167759 Although it is successful in lowering the dielectric constant and the dielectric loss factor of the glass fiber, there is a problem in the meltability at the initial stage of glass melting, and bubbles are likely to remain in the molten glass during melting of the glass, and the molten glass cannot be sufficiently homogenized.

Further, the printed wiring board is mounted on a large number of electronic devices, but the environment surrounding the mounted electronic devices is diverse. For example, in today's automobiles, a large number of integrated circuits are mounted, which are densely packaged on printed wiring boards, but the parts used in automobiles are required to ensure the road from the hot summer days to the extreme north. Driving reliability. In addition, in order to sufficiently secure the passenger space in the passenger car in recent years, the electronic circuit or the like is disposed in an environment in which the ambient temperature of the engine room and the engine room is high, and the temperature change is more severe than before. The situation has increased. In addition, there is a demand for miniaturization of the size of the mounted substrate.

Due to various changes in such conditions, printed wiring boards for automotive use are more resistant to heat resistance and high through-hole reliability than before. The reason for this is that it is absolutely necessary to avoid the occurrence of a large fault: due to the difference in the thermal expansion coefficient of the printed wiring board and the packaged part, heat stress is generated at the solder joint portion in the high temperature environment to cause soldering. Crack, so that electrical connections and the like cannot be obtained. That is, electronic parts for in-vehicle use are not allowed to malfunction in an electronic circuit due to a large temperature change, and the reliability of the electronic parts is required to be long. Therefore, in order to satisfy such a requirement, the difference in linear thermal expansion coefficient between the printed wiring board and the packaged component used in the environment for in-vehicle use is reduced, so that it is required to reduce the linear thermal expansion coefficient. Therefore, a glass formed of a glass material having a lower coefficient of linear thermal expansion than that of the E glass is required. fiber.

In addition, as the thickness of the printed circuit board which is required to reduce the size and thickness of the electronic device is reduced, there is a tendency for the glass fiber used for the printed wiring board to be a type of glass fiber having a smaller fiber diameter. In the case of so-called "long" glass in which the spinning temperature of D glass is high and the viscosity of the glass does not become large due to temperature change, it is difficult to produce a fiber diameter with no defect and stable quality in a limited manufacturing environment. The high-quality glass fiber is required to be a so-called "short" glass in which the viscosity of the glass changes rapidly due to temperature changes. The glass composition in Japanese Laid-Open Patent Publication No. Hei 8-333137 has a tendency to have a high spinning temperature of 10 ^3.0 dPa·s, and is a "long" glass having a small temperature dependence of viscosity, and is not suitable for producing a fiber having a small diameter. Fiberglass. Further, there is a problem in that when the spinning temperature is high, a large load is imposed on the manufacturing equipment, and thus the service life of the manufacturing equipment such as a bushing used when the glass fiber is taken out is shortened. The glass composition in Japanese Laid-Open Patent Publication No. 2003-137590 has a problem that the spinning temperature is as high as 1300 ° C or higher, which shortens the service life of the spinning device.

Further, in the case of producing a glass fiber having a small fiber diameter, bubbles contained in the molten glass as defects are likely to cause the glass fibers to be cut when the glass fiber is spun. In addition, when glass fibers containing bubbles in the printed wiring board are mixed as hollow fibers, through-hole plating intrudes into the hollow fibers, thereby causing a risk of poor conduction and printing wiring. The reliability of the board is lowered, which is a problem. When the temperature of 10 ^2.0 dPa ‧ which is the standard of the melting temperature as in D glass is high, it is necessary to apply a large amount of energy at the time of melting, and it is often the case that a large amount of hollow fibers are generated when the bubbles are not completely floated at the time of melting. In order to reduce the number of bubbles in the molten glass, it is effective to use a clarificant such as arsenious acid or antimony trioxide. However, these clarifying agents are also environmentally hazardous substances, and the inclusion of these elemental components in the components used in the electronic machine is regarded as a problem.

An object of the present invention is to provide a printed wiring which can solve the above various problems, can easily obtain a homogeneous molten glass, has excellent spinnability of glass fibers, has high chemical durability, and realizes high-density packaging. a glass fiber composition having a low dielectric constant and a low dielectric loss factor required for a sheet and further having a low coefficient of linear thermal expansion, and a glass fiber obtained by spinning the glass composition of the glass fiber And a glass fiber sheet composed of the glass fiber.

The inventors of the present invention have repeatedly conducted a large number of studies relating to the number of difficult problems required to reliably overcome the use of a printed wiring board capable of high-density packaging, and to stably produce a glass fiber composition of glass fibers having a small fiber diameter. In particular, regarding the action of the alkaline earth metal element in the glass composition, the above various problems are solved by adding the components in a predetermined amount, and it is possible to realize a glass fiber composition which exhibits excellent properties which have not been hitherto and which can be used. Since the glass fiber composition is formed into a glass fiber having a small fiber diameter, the glass fiber composition of the present invention is disclosed herein.

The glass composition for glass fibers of the present invention is characterized by containing 45% to 65% of SiO ₂ , 10% to 20% of Al ₂ O ₃ , and 13% to 25% of B by weight percentage in terms of oxide. ₂ O ₃ , 5.5% to 9% of MgO, 0% to 10% of CaO, 0% to 1% of Li ₂ O+Na ₂ O+K ₂ O, SrO, and BaO.

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

In other words, when the elemental components constituting the glass are expressed in terms of oxide by various analytical methods such as chemical analysis and machine analysis, the glass composition is expressed as a range of 45 to 65 weight percent of the SiO ₂ component, and Al _{2 .} The O ₃ component is in the range of 10 weight percent to 20 weight percent, the B ₂ O ₃ component is in the range of 13 weight percent to 25 weight percent, the MgO component is in the range of 5.5 weight percent to 9 weight percent, and the CaO component is 10 weight percent 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 weight or less, and further contains a SrO component and a BaO component.

Further, in the glass composition for glass fiber of the present invention, in addition to the above components, in terms of weight percentage of oxide, when CeO ₂ is 0.01% to 5.0%, the number of bubbles in the molten glass can be reduced to make the hollow The generation of fibers is reduced, so that glass fibers having higher homogeneity can be obtained.

Further, in the glass composition for glass fibers of the present invention, in addition to the above components, SrO is 0.1% by weight in terms of oxide. When the amount of BaO is from 0.1% to 10%, the glass composition in the case where the glass is melted and the so-called devitrification property is low, the glass composition is easily melted and the water resistance of the glass is improved. And the acid resistance does not become low, so it is better.

In other words, in the same manner as the above, the weight percentage of the oxide is 0.1% to 10%, and the BaO is 0.1% to 10%, which means that the elemental composition of the glass is expressed in terms of oxide. In addition to the composition of the above glass composition, the SrO component is from 0.1% by weight to 10% by weight, and the BaO component is from 0.1% by weight to 10% by weight.

Hereinafter, the reason for limiting the content ratio of each component constituting the glass composition for glass fibers of the present invention will be specifically described.

The SiO ₂ component is a component of the skeleton of the network structure in the glass structure, and is a main component of the glass composition of the present invention. When the content of the SiO ₂ component in the glass composition increases, the structural strength of the glass becomes The bigger the tendency. When the structural strength of the glass is increased, the glass composition for glass fibers having a high degree of chemical durability, particularly high acid resistance, is obtained. 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 must be at least 45 wt% or more, more preferably 48 wt% or more. On the other hand, when the content of the SiO ₂ component in the glass composition is increased, the high-temperature viscosity value of the molten glass is increased, and as a result, if the glass composition is to be produced efficiently and homogeneously by the melting method, Need to have expensive equipment. Moreover, the molding temperature at the time of forming into a glass fiber also becomes high. Therefore, there are cases where there are restrictions on equipment management at the time of manufacture. In order to obtain a homogeneous molten glass which does not remain in the vitrification reaction or the like during the glass melting, it is not necessary to have excess heat energy in the melting of the glass, and to ensure high spinnability in the production of the glass fiber. Then, the content of the SiO ₂ component must be 65% or less.

The Al ₂ O ₃ component is an active component for realizing chemical stability and mechanical stability of the glass, and may have an effect of suppressing crystallization and phase separation of crystals in the molten glass by being contained only in an appropriate amount in the glass. However, if it is contained in a large amount, the viscosity of the molten glass is increased. When the content of the Al ₂ O ₃ component in the glass composition is less than 10% by weight, the phase separation property at the time of melting is deteriorated, which is not preferable. The deterioration of the phase separation property in the molten glass causes deterioration of the acid resistance of the obtained glass fiber, and is therefore unsatisfactory. Here, the phase separation means a phenomenon in which the molten glass is separated into a plurality of glass phases of 2 or more. On the other hand, when 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 small, and the acid resistance is adversely affected. Therefore, Al ₂ O _{3 is present.} The content of the component must be 20% by weight or less, preferably 18% by weight or less, more preferably 17% by weight or less, still more preferably 16% by weight or less, and most preferably 15% by weight or less. .

The B ₂ O ₃ component is a component which becomes a skeleton in the glass network structure similarly to the SiO ₂ component, and does not increase the high-temperature viscosity of the molten glass as in the SiO ₂ component, but has a function of lowering the high-temperature viscosity. . Therefore, the B ₂ O ₃ component has two effects of lowering the dielectric constant of the formed glass and suppressing an increase in the high-temperature viscosity of the molten glass. When the content of the glass composition of B ₂ O ₃ component is less than 13 percent by weight, there is the following situation: the glass is difficult to maintain the dielectric constant of 6.0 or less, i.e., a spinning temperature of the molten glass and at 10 ^3.0 dPa‧s The temperature is difficult to be a temperature of less than 1300 ° C which can ensure sufficient spinnability. On the other hand, when the content of the B ₂ O ₃ component in the glass composition is too large, the amount of evaporation of the B ₂ O ₃ component in the melt increases, and it is difficult to maintain the molten glass in a homogeneous state. Further, when the content of the B ₂ O ₃ component is too large, the acid resistance is likely to be deteriorated, and the phase separation property in the molten glass is deteriorated. From such a viewpoint, when the B ₂ O ₃ component in the glass composition exceeds 25 weight%, the acid resistance and the phase separation property of the glass are deteriorated, which is not preferable.

The MgO component is a component having a function as a fusing agent for easily melting the glass raw material, and is very effective for lowering the viscosity at a high temperature equivalent to a temperature of 10 ^2.0 dPa ‧ s, and defoaming the glass at the time of melting , which helps to make a homogeneous glass. Further, it has a function of lowering the temperature of 10 ^3.0 dPa‧s and shortening the glass, so that the productivity is very good, and it is possible to efficiently produce glass fibers having a small fiber diameter. However, this glass composition in a state of MgO in order to function effectively so that the spinning temperature i.e. temperature near 10 ^3.0 dPa‧s viscosity decreases, the MgO component is necessary to be larger than 5.5 percent by weight. On the other hand, when the content of the MgO component in the glass composition is too large, the phase separation property of the molten glass becomes high, and the acid resistance is deteriorated. Further, the dielectric constant also rises, so from this point of view, it is not preferable that the MgO component exceeds 9 weight%.

The CaO component is a component that acts to lower the viscosity of the molten glass corresponding to a temperature of 10 ^2.0 dPa ‧ in the same manner as the MgO component, and has a minimum dielectric constant increase ratio in the component containing an alkaline earth metal element. However, when a large amount of CaO component is contained in the glass composition, the phase separation property becomes high and the acid resistance of the glass is lowered. Moreover, the dielectric constant of the glass also increases as the CaO component increases. Therefore, it is not good if the CaO component exceeds 10% by weight.

In the glass composition represented by the Li ₂ O component, the Na ₂ O component, or the K ₂ O component, the alkali metal oxide component expressed in terms of oxide is heated in a state in which a plurality of glass raw materials are mixed. In the case of the glass melt, it functions as a so-called flux which facilitates the formation of the glass melt, and also has a function of lowering the high-temperature viscosity. However, when the content of any of the Li ₂ O component, the Na ₂ O component, or the K ₂ O component in the glass composition increases, the value of the dielectric loss factor of the glass increases, so the upper limit of the total amount of the total is the largest. It is 1 weight percent.

SrO is a component and serves to considerable temperature 10 ^2.0 dPa‧s molten glass viscosity decreases, so the spinning temperature is further close to the molten glass 10 ^3.0 dPa‧s action of lowering a component, but its role not as MgO or The role of the CaO component. However, the SrO component is a component which has an action of suppressing the deterioration of the phase separation property at the time of glass melting and the subsequent deterioration of the acid resistance of the glass due to an increase in the MgO or CaO component, and is therefore an essential component in the present invention. The various effects of containing such a SrO component become more pronounced in the case where the glass composition contains 0.1% by weight or more. On the other hand, when the SrO component is used as a glass composition for glass fibers, if the content is too large, it becomes a long glass, and it becomes difficult to produce a glass fiber having a small fiber diameter. From this point of view, the upper limit of the SrO component is preferably at most 10% by weight. When the glass is melted, if the phase separation property is deteriorated, the molten glass is separated into an acid-rich phase and a poor acid-resistant phase. In this case, the acid-resistant phase determines the acid resistance of the glass fiber, so that the acid resistance of the glass fiber is deteriorated. It is not good.

In the same manner as the SrO component, the BaO component has a function of lowering the viscosity of the molten glass corresponding to a temperature of 10 ^2.0 dPa ‧ and further reducing the spinning temperature in the vicinity of 10 ^3.0 dPa ‧ of the molten glass, but It is not as effective as MgO or CaO. However, the BaO component is a component which has a function of suppressing the deterioration of the phase separation property due to an increase in the MgO or CaO component and the subsequent deterioration of the acid resistance of the glass, and is an essential component for achieving the object of the present invention in the same manner as the SrO component. . The BaO component is also the same as the SrO component, and the effect of the inclusion is more remarkable in the case where the glass composition contains 0.1% by weight or more. On the other hand, when the BaO component is used as a glass composition for glass fibers, if the content is too large, the liquidus temperature is deteriorated and the glass becomes long, and it becomes difficult to produce a glass fiber having a small fiber diameter. From this point of view, it is preferred to contain the BaO component in a range of up to 10% by weight. The term "long glass" refers to a glass having a small viscosity dependence on temperature change, and it is difficult to solidify into a fiber by cooling.

In addition, the SrO component and the BaO component are likely to form a crystal with SiO ₂ , and if the SrO component is contained in the glass composition containing SiO ₂ , the SrO ‧ SiO ₂ crystal is easily precipitated, and if the BaO component is contained, BaO‧2 SiO is easily precipitated. ₂ crystals, and as a result, the liquidus temperature of the glass tends to increase. When the liquidus temperature is high when the glass fiber is spun, the bushing nozzle is clogged with the precipitated crystal due to the precipitated crystal, and the glass fiber is cut during the spinning, which is a problem. However, if the SrO component and the BaO component coexist in the glass composition, the glass composition enters into the eutectic region of SrO‧SiO ₂ and BaO‧2SiO ₂ , thereby causing a decrease in the liquidus temperature of the glass, which is difficult to precipitate in the spinning. Since crystallization is preferred, it is preferable to contain both the SrO component and the BaO component in the glass composition, that is, the SrO component and the BaO component.

The CeO ₂ component acts to clarify the bubbles which are present as defects in the molten glass, and the CeO ₂ component can be added as a clarifying agent which is not an environmentally-charged substance, but the clarification effect of the CeO ₂ component is exhibited. More specifically, it is assumed to be 0.01% by weight or more in terms of weight percentage in terms of oxide, and more preferably 0.02% or more. However, if the CeO ₂ component is added in an excessively large amount, there is a case where the devitrification property of the molten glass is affected. In this regard, the weight percentage in terms of oxide should not exceed 5%. In order to achieve a more stable quality, the upper limit is preferably at most 4%, more preferably at most 2%. If it is the best addition amount, the non-hollow of the glass fiber can be achieved by this.

In addition to the above components, the glass composition for glass fibers of the present invention may contain various components in a range that does not greatly affect the performance of the glass composition for glass fibers of the present invention as needed. When a component which can be used as a constituent component of the glass composition for glass fibers of the present invention is specifically exemplified, ZrO ₂ , P ₂ O ₅ , Fe may be contained in a percentage by weight or less. ₂ , such as rare earth oxides such as O ₃ , SO ₂ , Cl ₂ , F ₂ , La ₂ O ₃ , WO ₃ , Nb ₂ O ₅ and Y ₂ O ₃ , or MoO ₃ .

Further, in addition to the above components, a trace component of up to 0.1% by weight may be contained. 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 suitable.

Further, in the glass composition for glass fibers of the present invention, if the glass composition for glass fibers is not greatly affected, the glass may contain a trace amount of a precious metal element. For example, it may contain a platinum metal element such as Pt, Rh, and Os of at most 1000 ppm, that is, a content of a metal element in terms of a weight percentage, and a platinum metal element such as Pt, Rh, and Os having a maximum of 0.1%.

Further, in the glass composition for glass fiber of the present invention, in addition to the above components, the total amount of the alkaline earth metal oxides of MgO, CaO, SrO, and BaO is 10% to 25 in terms of weight percentage in terms of oxide. %, the total amount of SrO and BaO divided by the total amount of the alkaline earth metal oxide is in the range of 0.15 to 0.50, thereby suppressing the phase separation of the glass during melting and avoiding the acid resistance caused by the phase separation. Since the spinning temperature is lowered and the spinning temperature is lowered to become a short glass, productivity of non-hollow glass can be improved, which is preferable. In addition, it is a glass fiber which has a small risk of being in a state in which the molten glass is heterogeneous due to precipitation and phase separation of crystals at the time of melting of the glass, and has a high viscosity dependency in the vicinity of the spinning temperature and has a short viscosity. It is preferable to use a glass composition and obtain a predetermined dielectric constant and dielectric loss factor.

The weight percentage in terms of oxides indicates that the total amount of alkaline earth metal oxides of MgO, CaO, SrO, and BaO is 10% to 25%, and the total amount of SrO and BaO is divided by the ratio of alkaline earth metal oxides. The measured value is in the range of 0.15 to 0.50, which is a total value expressed by the weight percentage of the oxides of Sr and Ba divided by the oxides of Mg, Ca, Sr, and Ba which are alkaline earth oxide elements. The value obtained by the weight percentage indicates a value ranging from 0.15 to 0.50.

When the total amount of the alkaline earth metal oxides of MgO, CaO, SrO, and BaO is less than 10% by weight, it is difficult to obtain a sufficient homogeneous state at the initial stage of glass melting, and the molten glass is obtained. Since the viscosity is high, the molding temperature is too high, and the spinnability of the glass fiber is lowered. On the other hand, when the total amount of the alkaline earth metal oxides of MgO, CaO, SrO, and BaO exceeds 25% in terms of weight percentage in terms of oxide, there is a problem in acid resistance and phase separation.

In addition, when the value obtained by dividing the total amount of SrO and BaO by the total amount of the alkaline earth metal oxide is less than 0.15, the content ratio of MgO and CaO increases, and the phase separation property of the molten glass tends to increase. And the dielectric constant also becomes high, so it is not good. On the other hand, when the value obtained by dividing the total amount of SrO and BaO by the total amount of the alkaline earth metal oxide is more than 0.50, the dielectric constant becomes too high. Further, the spinning temperature, that is, Ty becomes high, and the glass develops in a long direction, so that the spinnability is lowered, and it becomes difficult to produce a glass fiber having a small fiber diameter.

In the glass composition for glass fibers of the present invention, if the dielectric constant at a frequency of 1 MHz is 6.0 or less and the dielectric loss factor is 20 × 10 ^-4 or less, the dielectric loss of the printed wiring board becomes Small, so better.

Further, in the glass composition for glass fibers of the present invention, in addition to the above, if the dielectric constant at a frequency of 10 GHz is 6.0 or less and the dielectric loss factor is 100 × 10 ^-4 or less, high-frequency printing is used. It is preferable that the dielectric loss of the wiring board is further reduced.

In the glass composition for glass fiber of the present invention, when the volume resistivity ρ at 150 ° C is equal to or greater than 13 Ω ‧ cm, the electric resistance is sufficiently large, so that it is stable when used as a printed wiring board or the like. .

Further, in the glass composition for glass fibers of the present invention, the temperature Ty of 10 ^3.0 dPa ‧ is less than 1300 ° C except for the above, and the value obtained by subtracting the temperature Tx of 10 ^7.6 dPa ‧ from Ty is 300 ° C In the range of -450 ° C, it is preferred to produce the glass fiber efficiently without greatly changing the spinning device and the spinning method of the glass fiber.

If the temperature Tx of 10 ^7.6 dPa ‧ is subtracted from the temperature Tx of 10 ^3.0 dPa ‧ and the value obtained by the temperature Tx is 450 ° C or more, the viscosity of the glass becomes long, so that the glass fiber having a small fiber diameter is to be spun. Then, the meniscus which is a curved surface shape formed under the nozzle from the molten glass which is disposed at the tip end of the nozzle is unstable, and there is a problem in that stable spinnability in which the fiber diameters are uniform cannot be obtained. On the other hand, if the value obtained by subtracting the temperature Tx of 10 ^7.6 dPa ‧ from the temperature Ty of 10 ^3.0 dPa ‧ is 300 ° C or less, the viscosity of the glass becomes too short, and thus the following problems occur: A reasonable range for setting other manufacturing conditions for obtaining a predetermined fiber diameter, such as a drawing speed and a cooling condition, is small, and management of the fiber diameter becomes difficult.

The glass fiber of the present invention is composed of the glass fiber of the present invention. Since the average value of the diameter of the glass fiber is from 3 μm to 7.2 μm, the glass fiber of the fiber having a small diameter is greatly improved, particularly when it is applied to a printed wiring board which is required to have a high density and a thin thickness. The performance of the composite material used for the printed wiring board.

When the average value of the diameters of the glass fibers is less than 3 μm, there is also a case where the production yield of the glass fibers is lowered because the fiber diameter becomes too small. In addition, in terms of environmental problems and recycling, such as the glass fiber which deteriorates with time in the environment in which the glass fiber to be produced is used, it is necessary to construct the human body. A high-priced processing environment with adverse effects. This leads to various environmental problems and is therefore not good.

On the other hand, when the average value of the diameters of the glass fibers exceeds 7.2 μm, even if the glass fiber formed of the glass composition of the present invention is not used, it is possible to use a glass composition of low dielectric constant which has been used since the beginning. The glass fiber is formed to obtain a glass fiber having less stable quality such as glass defects, and thus has an economical advantage.

From the above viewpoints, the glass fiber of the present invention is formed of the glass composition for glass fiber of the present invention, and the average diameter thereof is preferably in the range of 3.1 μm to 6.5 μm, more preferably in the range of 3.2 μm to 6.2 μm. Further preferably, it is in the range of 3.3 μm to 5.5 μm, further preferably 3.4 μm to 5.2 μm, and most preferably 3.8 μm to 4.8 μm.

Further, in the glass fiber of the present invention, in addition to the above, if the hollow fiber is less than or equal to 2/100,000 filaments, the composition is printed. When used in the use of a wiring board, a highly reliable printed wiring board can be obtained.

The hollow fiber is equal to or less than 2 per 100,000 filaments, which means that the number of hollow fibers per 100,000 filaments is 2 or less. The number of hollow fibers was measured by immersing glass cloth in an immersion liquid adjusted to have a refractive index equal to that of glass fibers, and observed under a microscope (50 times) of transmitted light, and a warp of glass cloth. The number of hollow fibers in the measurement was measured, and the value was divided by the number of filaments observed and increased by 100,000 times, thereby being easily obtained.

Further, in addition to the above, the glass fiber of the present invention has a bubble content of 0.01 or less, particularly 0.001 or less, and when used in an application constituting a printed wiring board, it is possible to obtain a uniformity in which defects have been reduced. The high-complexity composite structure is a glass fiber that performs according to the design specifications of the printed wiring board.

The bubble content rate is 0.001/m or less, which means that the number of bubbles per 1000 m glass filament is less than or equal to one, and the count of the number of bubbles is for all the cells having a bubble length of 1 mm or more. The counting of the number of bubbles can be easily measured by immersing the glass fibers in an immersion liquid adjusted to have a refractive index equal to that of the glass in the microscope.

Further, in the glass fiber of the present invention, in addition to the above, if the bubble content ratio is 50/100 g or less, higher quality can be achieved, more preferably 20/100 g of glass or less, and even more preferably less than Equal to 5 / 100g glass. The bubble content ratio indicates the number of bubbles in the glass having a weight of 100 g.

Glass fiber can also impart the required physical chemistry to the surface coating Performance of the coating glass fiber. Specifically, it may be a glass fiber coated with a sizing agent, an antistatic agent, a surfactant, an antioxidant, a film forming agent, a coupling agent or a lubricant.

If a silane coupling agent which can be used in the surface treatment is exemplified, there are: γ-aminopropyl triethoxysilane, N-phenyl-γ-aminopropyl N-phenyl-γ-aminopropyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-methylpropenyloxypropyltrimethoxysilane (γ-glycidoxypropyl trimethoxysilane) Γ-methacryloxypropyl trimethoxysilane), γ-(2-aminoethyl)aminopropyl trimethoxysilane, β-(3,4-epoxycyclohexyl)B Β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxydecane ‧ hydrochloride (N -β-((N-vinylbenzylaminoethyl)-γ-aminopropyl trimethoxysilane), γ-chloropropyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane, vinyl Triethoxysilane (vinyl triethoxysilane), etc., may also be used according to And glass fiber composite of the type of resin selected appropriately.

Regarding the glass fiber of the present invention, in addition to the above, the coefficient of variation (CV) of the glass fiber diameter obtained by multiplying the standard deviation of the fiber diameter by the average value of the fiber diameter by 100 is multiplied by 100. More than 10% of the glass filaments are cut (chopped) In the form of strand, yarn, or roving, it can be used for various applications requiring a glass fiber having a small fiber diameter, in addition to the use of a printed wiring board, even for applications other than a printed wiring board. When the CV value of the glass fiber exceeds 10%, a trouble occurs in formability or the like which requires a precise shape, which is not preferable.

The plurality of glass filaments having a CV value of glass fiber diameter of 10% or less is in the form of a tang, a spun yarn or a roving, and is a glass strand obtained by spinning the glass fiber of the present invention from molten glass ( The diameter of each filament in the glass strand is measured, and each condition of the glass fiber manufacturing apparatus is adjusted so that the standard deviation is divided by the average value and multiplied by 100 to obtain a value of 10 or less, thereby performing spinning. Thus, a glass entanglement obtained by cutting the obtained glass fiber is produced, or a spun yarn as a crepe yarn or a roving yarn in which a plurality of glass filaments are wound and wound in a rewinding state is prepared. Incidentally, the standard deviation and average value of the fiber diameter were calculated from the measured values of 200 glass fibers.

The control is performed so that the CV value of the glass fiber diameter is 10% or less, for example, in the case of a glass forming apparatus in which a plurality of heat-resistant nozzles are disposed on the bushing, the nozzle hole diameter and the nozzle are determined. The conditions of the length, the nozzle temperature, the atmospheric temperature around the nozzle, the nozzle head pressure, the blowing speed, and the glass filament drawing speed may be selected to be optimum conditions suitable for the composition for glass fibers of the present invention.

In the glass fiber of the present invention, if a plurality of glass filaments having a glass fiber diameter of 10% or less of a CV value is in the form of a tang, a spun yarn or a roving, a glass fiber having a uniform diameter can be formed in various forms, and In the use of the printed wiring board, the glass cloth which has been subjected to the weaving and the stretching treatment is used to suppress the fluctuation of the position of the hole due to the deviation of the tip end of the drill during the drilling process for forming the through hole, thereby increasing the position of the hole. Accuracy, so it is better.

Further, the glass fiber of the present invention can be produced by any production method if desired properties can be achieved. 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) can be employed depending on the application and the amount of production. In other words, the glass fiber of the present invention may be a glass fiber obtained by drawing a glass fiber from a bush including a heat-resistant nozzle to obtain a glass fiber having a predetermined diameter.

The glass fiber of the present invention is a glass fiber used for the purpose of forming an organic resin composite material by combining with an organic resin material after forming a glass cloth or a glass paper, in addition to the above, and forming a high-density fiberglass. It is preferable to print a wiring board and to be the most suitable glass fiber.

In other words, the glass fiber used in the use of a glass cloth or a glass paper and composited with an organic resin material to form an organic resin composite material means a glass fiber used in the following applications: As a warp yarn and a weft yarn, a woven fabric woven by various weaving methods used in a glass cloth for a printed wiring board, or a diced strand is formed into a cellophane by a wet method or a dry method, and then It is combined with an organic resin material to form an organic resin composite material.

The glass fiber constituting the glass cloth obtained by using the glass fiber of the present invention is, for example, 1 tex to 50 tex, preferably 1.5 tex to 23 tex, more preferably 1.5 tex to 15 tex, and constitutes a bundled glass original. Silk glass filament The cross-sectional shape and the like are not particularly limited. The cross-sectional shape of the glass filaments may be circular, elliptical or oblong. The twist number of the glass fiber bundle is more preferably equal to or less than 2 times / 25 mm.

Further, the glass cloth obtained by using the glass fiber of the present invention is more suitably a glass cloth having the following structure: the number of the warp yarns and the weft yarns per 25 mm is 30 to 100, respectively, and preferably the warp yarn is 45. The roots are ~90 and the weft yarns are 35 to 90.

When the woven fabric obtained by using the glass fiber of the present invention is used as a constituent material of a printed wiring board, the process is specifically as follows. That is, the glass spun yarn and the glass spun yarn of the glass spun yarn rewinding body or the glass spun yarn crepe rewinding body formed of the composition for glass fiber of the present invention are warped by a warper (warper). Warping), a sizing machine is used to impart a secondary dimension, and a beam is wound on a loom beam of a shuttle machine to form a warp yarn. The package of the glass spun yarn rewinding body and the glass spun yarn crepe rewinding body is unwound, and it is used for the weft yarn, and the glass cloth is woven by a jet jet weaving machine (Air Jet Loom) or the like. The organic component adhered to the woven glass cloth is removed by heating incineration (heating and deoiling), immersed in a treatment liquid containing a decane coupling agent, dried (surface-treated), and then impregnated with a resin. After laminating, the resin is cured to produce a laminate for a printed wiring board.

Further, when the cellophane obtained by using the glass fiber of the present invention is a cell paper using diced strands, the length dimension of the strand is not limited. In terms of the length dimension of the fiber, a size suitable for the use can be selected. Moreover, in terms of the manufacturing method of the strand, any size can be employed. Can be melted in a pair The spun strands are subjected to cutting immediately after spinning, and may be formed into a continuous fiber at a time and wound, and then cut by a cutting device depending on the application. At this time, any method can be employed as the cutting method. For example, a peripheral blade cutting device, an inner peripheral blade cutting device, a hammer mill, or the like can be used. Further, the form of aggregation of the strands is not particularly limited.

Further, for the glass cloth and the cellophane obtained by using the glass fiber of the present invention, a fiber material other than the glass fiber of the present invention, a solid additive, or a liquid additive may be used in combination according to the use. Further, when the glass cloth and the cellophane are used, as the fiber material other than the glass fiber of the present invention used in combination with the glass fiber material of the present invention, glass fiber of D glass fiber or other composition, organic fiber material, or ceramic fiber may be used ( Ceramic fiber), carbon fiber, etc., as a solid addition material, ceramics powder, organic resin powder, silicone powder, etc., as a liquid additive, a polymerization accelerator can also be used in an appropriate amount (polymerization) Promoter), polymerization inhibitor, antioxidant, decomposition reaction inhibitor, diluent, antistatic agent, anti-agglomerating agent, modifier, wetting agent, desiccant, anti-fungal agent, dispersant, hardening accelerator (hardening accelerator), thickening agent or reaction accelerator.

The glass fiber sheet of the present invention is characterized by being used for forming an organic resin composite material by combining the glass fiber of the present invention with an organic resin material.

Here, the use of the glass fiber of the present invention in combination with an organic resin material to form an organic resin composite material means that it is expressed by weight percentage in terms of oxide, and contains 45% to 65% of SiO _{2 .} 10%~20% Al ₂ O ₃ , 13%~25% B ₂ O ₃ , 5.5%~9% MgO, 0%~10% CaO, 0%~1% Li ₂ O+Na The glass fiber of ₂ O+K ₂ O, SrO, and BaO is formed into a glass fiber sheet having a thickness of 1 mm or less, and is impregnated with a thermosetting organic resin material to obtain an organic resin composite 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 can be used.

Further, in the glass fiber sheet of the present invention, in addition to the above, when the glass sheet is glass cloth or cellophane, a printed wiring board which exhibits various properties depending on the use can be produced.

As the glass cloth, a woven fabric of various structures can be used. For example, a woven fabric of a woven fabric structure such as a plain woven fabric or a twill fabric can be used for a woven fabric having a more complicated structure. Further, the cellophane may be a cellophane obtained by dispersing a strand into a monofilament in white water, then weaving and forming the sheet into a sheet using an organic binder. For example, in the case of using a dicing, the molten glass obtained by melting the composition for glass fibers of the present invention is continuously extracted from a heat-resistant nozzle disposed on a molding apparatus such as a bushing, and a sizing agent is coated around the same. Wait for the formation of long glass fibers. Next, the obtained glass long fiber is wound around a paper tube or the like to form a cake (or called a cheese). Thereafter, the number of necessary roots is extracted from the cheese cake, and the glass fiber cutting device is cut into a predetermined length. A glass fiber sheet composed of glass strands is obtained by the following joining process: after the thus obtained strands are dispersed in white water, they are woven on a mesh and randomly stacked on the mesh. On the conveyor, a liquid adhesive is sprayed from above in a sheet form, and the glass strands are joined to each other by hardening the adhesive.

(1) The glass fiber composition of the present invention is expressed by weight percentage in terms of oxide, and contains: 45% to 65% of SiO ₂ , 10% to 20% of Al ₂ O ₃ , and 13% to 25% of B _{2 .} O ₃ , 5% to 9% of MgO, 0% to 10% of CaO, 0% to 1% of Li ₂ O+Na ₂ O+K ₂ O, SrO, and BaO, so it is made into glass fiber In the case of the glass fiber having a small fiber diameter, it is easy to form a glass fiber having a small fiber diameter, and the obtained glass fiber is excellent in electrical properties such as a dielectric constant and a dielectric loss factor.

(2) When the composition of the glass fiber of the present invention has a CeO _{2 content} of 0.01% to 5.0% by weight in terms of an oxide, a glass fiber having high homogeneity can be obtained from the molten glass in which the number of bubbles is suppressed. It is preferred to improve the manufacturing efficiency or the performance of the produced glass fiber.

(3) When the composition of the glass fiber of the present invention has an SrO of 0.1% to 10% by weight and a BaO of 0.1% to 10% by weight, the phase separation property at the time of glass melting and precipitation by crystallization can be avoided. And the resulting devitrification.

(4) The composition for glass fibers of the present invention, in terms of oxide The weight percentage indicates that the total amount of the alkaline earth metal oxides of MgO, CaO, SrO, and BaO is 10% to 25%, and the total amount of SrO and BaO divided by the total amount of alkaline earth metal oxides is 0.15. In the range of up to 0.50, temperature dependence of high-temperature viscosity and high-temperature viscosity suitable for the spinning operation can be achieved, and it is suitable for obtaining a glass fiber having excellent quality of acid resistance or devitrification of glass.

(5) The glass fiber composition of the present invention has a dielectric constant of 6.0 or less and a dielectric loss factor of 20 × 10 ^-4 when the frequency is 1 MHz, so that the electrical signal can be speeded up. A printed wiring board having a small electrical loss has a good performance for a printed wiring board. Further, if the dielectric constant at a frequency of 10 GHz is 6.0 or less and the dielectric loss factor is 100 × 10 ^-4 or less, it is more suitable for a printed wiring board using high-frequency waves.

(6) The glass fiber of the present invention is formed of the glass composition for glass fiber of the present invention, and the average diameter of the glass fiber is from 3 μm to 7.2 μm, which is particularly preferable for a printed wiring board which is made into a high-density package.

(7) When the glass fiber of the present invention is used for forming a glass cloth or a cellophane and then compounding with an organic resin material to form an organic resin composite material, it is possible to supply a glass fiber having high performance in accordance with an optimum form of use. The dielectric characteristics and heat resistance of a printed wiring board suitable for various electronic circuits can be improved.

(8) When the glass fiber sheet of the present invention is used for the composite of the glass fiber of the present invention and an organic resin material to form an organic resin composite material, the production is performed without changing the prior process to produce high quality and stability. A good performance printed wiring board is preferred.

(9) The glass fiber sheet material of the present invention is a glass cloth or a cellophane. Therefore, when a prepreg used in a process for producing a printed wiring board is manufactured, it may be manufactured without changing the manufacturing conditions. It is preferable to obtain a printed wiring board which can be used in an environment which does not interfere with the process of the printed wiring board and which can be used in an environment where the temperature changes drastically.

The above described features and advantages of the present invention will be more apparent from the following description.

Hereinafter, the glass fiber composition, the glass fiber, and the method for producing the same according to the present invention will be specifically described based on examples.

[Example]

The composition and evaluation results of the composition for glass fibers of the examples of the present invention are shown in Table 1. The composition of the glass represented by the oxide conversion shown in Table 1 is expressed by weight percentage.

For each of the glass samples of Sample No. 1 to Sample No. 10 of the example, the glass sample was prepared in the following order.

First, a predetermined amount of various types of glass raw materials such as natural mineral glass raw materials and chemically synthesized glass raw materials are weighed in g units of three decimal places to form the respective glass compositions of Table 1. Next, a batch of glass raw material mixed in such a manner that the plurality of raw materials were in a homogeneous state was prepared, and this glass raw material mixed batch was placed in a crucible having a volume of 500 cc made of platinum rhodium. Next, the platinum crucible to which the raw material mixed batch was charged was placed in an indirect heating electric furnace, and heated in an air atmosphere at 1550 ° C for 5 hours to chemically react the glass raw material mixed batch at a high temperature to become molten glass. In order to make the molten glass a homogeneous state, the molten glass is stirred by a heat-resistant stirring bar during heating and melting.

In this manner, the molten glass in a homogeneous state is discharged into a predetermined fire-resistant template, and slip-casting is performed into a predetermined shape, and an annealing treatment is performed in the slow cooling furnace to room temperature. A glass molded body used in a test or the like is obtained.

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

Regarding the measurement of the linear thermal expansion coefficient, SRM-731 and SRM-738 of the National Institute of Standards and Technology (NIST) are used as standard samples for which the coefficient of linear thermal expansion is known, and by using The average linear thermal expansion system measured by a well-known linear thermal expansion measuring machine that has been calibrated in a temperature range of 30 ° C to 380 ° C number. The lower the value of the linear thermal expansion coefficient, the smaller the expansion of the glass fiber is when the temperature changes greatly, and as a result, the temperature variation in the case where the printed wiring board using the glass fiber is mounted on the electronic device is involved. Increased reliability.

For measuring the temperature (Ty) of 10 ^3.0 dPa ‧ which indicates the high-temperature viscosity of the molten glass, each glass sample crushed in such a manner as to be appropriately sized is put into an alumina crucible for further After heating, after heating to the molten state, each value was calculated by interpolation of a viscosity curve obtained by multiple measurement of each viscosity value measured by the platinum ball pulling method. Further, the value of Ty-Tx in the table is a value obtained by subtracting a temperature corresponding to 10 ^7.6 dPa ‧ s, that is, a softening point, from a value corresponding to a temperature of 10 ^3.0 dPa ‧ s. Further, the measurement of the softening point means a value measured by a method according to ASTM C338. The smaller the value of Ty-Tx, the greater the temperature dependence of viscosity and the shorter the glass. The shorter the glass, the easier it is to be solidified from the molten state due to cooling. Therefore, even after the same cooling conditions, the meniscus is stable, and the molten glass is spun from the nozzle attached to the liner. The glass fiber is produced by cutting off. The longer the temperature dependence of the viscosity of the glass fiber, the longer and the unstable the meniscus. Therefore, it is necessary to equip the equipment for the production of the glass fiber such as the enhanced cooling condition.

Further, in the liquidus temperature T _L , each glass molded body is cut into a predetermined shape and pulverized into a predetermined particle size, and the finely pulverized material is removed to have a surface area of a predetermined range, so that the particle size is 300 μm to 500 μm. In this state, it is filled in a platinum container in a state of having an appropriate bulk density, and placed in an indirect heating type temperature gradient furnace having a maximum temperature of 1,250 ° C, and allowed to stand in an atmosphere. 16 hours of heating operation. Thereafter, the test body was taken out together with a platinum container, and after standing to cool to room temperature, the liquidus temperature T _{L was} determined by a polarizing microscope. The value of Ty-T _L in the table is obtained by subtracting the value of the liquidus temperature T _L from the value corresponding to the temperature of 10 ^3.0 dPa ‧ s. The larger the value of Ty-T _L is, the more the crystal which hinders the spinning operation is precipitated in the vicinity of the spinning temperature, and a stable spinning state can be ensured. In order to increase the value of this Ty-T _L , it is sufficient to increase the temperature Ty corresponding to the spinning temperature of 10 ^3.0 dPa ‧ s, but if so, the energy required for melting the glass becomes large, resulting in an increase The manufacturing cost rises and the service life of the attached equipment such as the bushing device is shortened.

The volume resistivity at 150 ° C is a value measured at 150 ° C according to ASTM C657-78. The higher the value of the volume resistance, the stable electrical insulation performance can be exhibited even for a printed wiring board that is subjected to high-density packaging.

For the measurement of the dielectric constant (ε) and the dielectric loss factor (tan δ) at a frequency of 1 MHz, a glass coupon of a size of 50 mm × 50 mm × 3 mm was processed using a 1200-gauge sand paper. A sample having two surfaces having a thickness of 3 mm was ground. The measurement was carried out by measuring at room temperature according to ASTM D150-87 by using a 4192A impedance analyzer manufactured by Yokogawa Hewlett-Packard. For the measurement of the dielectric constant (ε) and the dielectric loss factor (tan δ) at a frequency of 10 GHz, the short-circuit dielectric resonator method according to JIS R1627:1996 is used, by using Agilent (Aglient). ) manufactured network analyzer (network Analyzer), obtained by measurement at room temperature. When the dielectric constant and the dielectric loss factor are smaller, the dielectric loss of the printed wiring board becomes smaller as the glass fiber is used in the application constituting the printed wiring board.

In terms of acid resistance, the finely pulverized material is removed so as to have a surface area of a predetermined range, so that the particle size is in the range of 300 μm to 500 μm, and in this state, the pulverized material corresponding to 1 cm ³ is expressed by weight percentage. 50 cc of a 10% aqueous hydrochloric acid solution was placed in an acid-resistant sealed container, and in this state, it was kept in a constant temperature oscillator set at 80 ° C for 16 hours, and the liquid portion was removed by filtration and dried in a dryer at 110 ° C. A constant value of the weight of the glass is obtained. Then, the weight value after the acid treatment was measured with respect to the reduction rate of the weight value of the glass initially charged. The measured value of the reduction rate obtained by this is 30% or more, and it has been confirmed that the acid resistance of the glass is lowered in the sample in which the reaction product is formed in the middle of the corrosion reaction on the glass surface due to hydrochloric acid in the acid resistance test. Therefore, it is judged as ×, and as for other samples, it is judged as ○. The reason for this is that when a reaction product is formed by a corrosion reaction, in the plating treatment or the like performed in the process of producing a printed wiring board using glass fibers, it is hindered to ensure a homogeneous processing state during the acid treatment. The risk of lower yield is higher.

According to the above test, the following can be clarified. That is, in the samples of Test No. 1 to Test No. 12 of the examples of the present invention, the glass composition of the sample is expressed by weight percentage in terms of oxide, and SiO _{2 is} in the range of 47.4% to 54.5%, Al ₂ O. _{3 is} in the range of 11.7% to 18.7%, B ₂ O _{3 is} in the range of 14.0% to 20.0%, MgO is in the range of 5.5% to 8.7%, CaO is 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%~0.4%, SrO is in the range of 1.1%~8.8%, BaO is in the range of 0.8%~5.0%, and alkaline earth of MgO, CaO, SrO and BaO The total amount of metal oxide conversion is in the range of 15.2% to 21.4%, and the total amount of SrO and BaO divided by the total amount of alkaline earth metal oxide is 0.20 to 0.45, and CeO ₂ is 0.1%. ~0.9% range.

Further, as shown in the items in Table 1, the average coefficient of linear thermal expansion in the temperature range of 30 ° C to 380 ° C of the example of the present invention is at 39.2 × 10 ^{-7 /} ° C to 49.0 × 10 ^-7 In the range of / ° C, the temperature corresponding to the spinning temperature of 10 ^3.0 dPa ‧ is in the range of 1194 ° C ~ 1298 ° C, and the temperature Tx of 10 ^7.6 dPa ‧ is in the range of 828 ° C ~ 880 ° C, indicating viscosity The temperature dependence of the value of Ty-Tx is in the range of 364 ° C to 426 ° C. Further, the liquidus temperature T _L of the example of the present invention is in the range of a value of 1000 ° C or less to 1095 ° C, and thus the value of Ty-T _L is in the range of 162 ° C to 251 ° C. Further, the temperature Tw of 10 ^2.0 dPa ‧ which is a standard of the melting temperature is in the range of 1384 ° C to 150 2 ° C, and becomes a lower temperature than D glass. Further, regarding the electrical properties, the volume resistivity log ρ at 150 ° C of 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 5.36 to 5.82 In the range of the present invention, the dielectric loss factor (tan δ) at a frequency of 1 MHz is in the range of 0.0008 to 0.0014, and the dielectric loss factor is less than or equal to 20×10. ^-4 necessary conditions. Further, the dielectric constant (ε) at a frequency of 10 GHz is in the range of 5.4 to 5.9, and satisfies the requirements of the present invention having a dielectric constant of 6.0 or less, and the dielectric loss factor (tan δ) at a frequency of 10 GHz is 0.0038. In the range of ~0.0096, the necessary condition that the dielectric loss factor is less than or equal to 100×10 ^-4 is also satisfied. Further, it has an excellent quality of a number of hollow fibers of 1.5 or more per 100,000 filaments. That is, Sample No. 1 to Sample No. 10 of the examples of the present invention have preferable properties as the glass fiber composition of the present invention.

Hereinafter, samples having special features in the examples of the present invention will be described.

Regarding the glass composition of sample No. 1 of the example, SiO ₂ was 47.4%, which was the lowest content rate, but was compensated for the maximum content of B ₂ O ₃ of 20.0%, and the expansion coefficient was 44.7×10. ^-7 / ° C, is a sufficiently low value, the value of Ty-Tx indicating the temperature dependence of viscosity is 364 ° C, at a level of no problem, and the Ty corresponding to the spinning temperature is 1194 ° C, which becomes the melting temperature. The standard 10 ^2.0 dPa‧s temperature Tw is 1384 ° C, which is a sufficiently low value. Further, as the T _{L of the} liquidus temperature is 1020 ° C or less, the value of Ty-T _L is 190 ° C or more even if it is underestimated, so the value of the Ty-T _L is a sufficient value. In addition, the volume resistivity is 17.5 Ω ‧ cm, which is a sufficiently large value, and the dielectric constant ε at a frequency of 1 MHz is 5.50, the dielectric loss factor is 0.0010, and the dielectric constant ε at a frequency of 10 GHz is 5.6. The electrical loss factor is 0.0042, both of which show smaller values without any drawbacks. Further, regarding the acid resistance, the weight reduction rate was low and the formation of the reaction product was not confirmed, and therefore it was judged as "○". Further, the glass composition of the sample No. 1 of this example contained CeO ₂ in order to promote clarification of the molten glass without generating hollow fibers. Thus, the glass composition of the sample No. 1 of the example corresponds to the present invention. Therefore, by evaluating the glass fiber by the glass molded body, it was found that the problem of devitrification and the like can be prevented from being spun, and that no bubbles remain in the glass fiber, and the number of hollow fibers in the glass fiber is calculated and measured. A homogeneous glass fiber satisfying less than or equal to 2/100,000 filaments.

The glass composition of the sample No. 2 of the example had a characteristic that Al ₂ O ₃ was 11.7% and had a minimum content ratio, and the glass composition of the sample No. 2 of this example contained CeO ₂ . This sample No. 2 is a typical sample of the present invention, and has a coefficient of expansion of 44.4 × 10 ^-7 / ° C, which is also a low value without any disadvantage, and the value of Ty-Tx indicating the temperature dependence of viscosity is 391 ° C, with a short enough viscosity. The temperature of 10 ^2.0 dPa ‧ which is the standard of the melting temperature is as low as 1436 ° C, and the T _L as the liquidus temperature is a value as low as 1054 ° C, and the value of Ty-T _L shows a sufficiently large value of 180 ° C. Moreover, the volume resistivity is sufficiently large to be 17.0 Ω ‧ cm, the dielectric constant (ε) at a frequency of 1 MHz is 5.49, the dielectric loss factor (tan δ) is 0.0014, and the dielectric constant ε at a frequency of 10 GHz is 5.6. The dielectric loss factor is 0.0056, and any value is a small value. Further, the acid resistance was also the same as that of the sample No. 1, and the weight reduction rate was low, and the formation of the reaction product was not confirmed, so it was judged as "○". In the sample No. 2, spinning was performed by using 200 nozzles to have an average fiber diameter of 5.0 μm, and evaluation of glass fiberization was carried out, and it was found that the glass manufacturing apparatus can be stabilized without a large change. In the spinning operation, the obtained glass fiber can be spun out without causing problems such as devitrification, and bubbles are not left in the glass fiber, and the number of hollow fibers in the glass fiber is calculated to satisfy 2 or less. Hundreds of thousands of filaments of homogeneous glass fiber. Further, the average fiber diameter of the 200 glass fibers was 5.0 μm, the standard deviation was 0.40 μm, and the value obtained by dividing the standard deviation of the fiber diameter by the average value of the fiber diameters by 100 was obtained, and the CV value was 8%. Has good quality. From this, it is clear that it has excellent quality and performance as a glass fiber used for a printed wiring board. Therefore, the glass fiber is woven flat to produce a prepreg, and the printed wiring board obtained thereby can be a printed wiring board that fully exhibits design performance.

The glass composition of the sample No. 4 of the example is the glass composition having the largest BaO content in the example, but the average linear thermal expansion coefficient is 40.4×10 ^-7 /° C., and also has a very small value, in addition, 10 ^2.0 dPa. The temperature Tw of ‧ s is 1491 ° C, the temperature of 10 ^3.0 dPa ‧ is 1284 ° C, and the value of Ty-Tx indicating the temperature dependence of viscosity is 409 ° C, which is a very short glass. Moreover, in terms of electrical properties, the dielectric constant (ε) at a frequency of 1 MHz is 5.46, the dielectric loss factor (tan δ) is 0.0012, the dielectric constant ε at a frequency of 10 GHz is 5.6, and the dielectric loss factor is 0.0038, which satisfies the requirements of the present invention. In addition, as for the acid resistance, the weight reduction rate is low as in the case of the sample No. 1 and the like, and the formation of the reaction product is not confirmed. Therefore, it is judged as "○", and when the evaluation of the glass fiber is performed, the previous glass may not be produced. The equipment is subjected to a large change to perform a stable spinning operation. It can be understood that the glass fiber having the glass composition of Sample No. 4 thus obtained does not cause problems such as phase separation and devitrification, and bubbles do not remain in the glass fiber, and the measurement glass can be spun out. The number of hollow fibers in the fiber can satisfy a homogenous glass fiber of 2 or 100,000 filaments.

The glass composition of sample No. 2 obtained as described above was used. A glass cloth of a plain woven fabric can obtain a glass cloth having a small number of hollow fibers and a low dielectric constant and a dielectric loss factor, and can exhibit good performance as a printed wiring board.

[Comparative Example] Next, in Table 2, the results of investigations relating to the samples corresponding to the comparative examples are shown in the same manner as the examples, and the samples were prepared in the same order as the examples of the present invention. The results of the various measurements shown in Table 2 are the same as in the examples.

The glass composition of the sample No. 101 of the comparative example had a composition similar to that of a glass generally called E glass, but the linear thermal expansion coefficient was as high as 62.5 × 10 ^-7 / ° C, and the dielectric constant was as high as 1 MHz. 7.00, and the dielectric constant at a frequency of 10 GHz is also as high as 6.8, and thus is completely different from the present invention.

In Comparative Example No. 102, the glass composition contained no SrO or BaO, but the content of SiO ₂ was as high as 76.1%, so that the acid resistance did not deteriorate. However, since the content of SiO ₂ is high, the temperature of 10 ^3.0 dPa ‧ which is equivalent to the spinning temperature becomes a value of up to 1336 ° C. When the glass fiber is spun for a long period of time, it causes deterioration of the manufacturing equipment, which is economically problematic. Further, the temperature Tw of 10 ^2.0 dPa ‧ which is a standard of the melting temperature is 1600 ° C or more, which is extremely high. Therefore, bubbles are likely to remain in the glass when the glass is melted, and the value of Ty-Tx is 526 ° C, which is a long glass and has a problem in spinnability.

Regarding the glass composition of sample No. 103 of the comparative example, the ratio of the total amount of SrO to BaO to the total amount of the alkaline earth metal oxide exceeded 0.5. The temperature of 10 ^3.0 dPa ‧ exceeded 1400 ° C, and the value of Ty-Tx Since it is a long glass at 536 ° C, it is difficult to produce a glass fiber having a small fiber diameter, and there is a problem in the meltability and spinnability of the molten glass. 10 ^2.0 dPa‧s has a high temperature Tw and does not contain CeO ₂ , so bubbles are easily left in the glass when the glass melts. Therefore, the glass fiber which satisfies the required number of hollow fibers of 2 or 100,000 filaments is not required. Moreover, the dielectric loss factor at a frequency of 1 MHz is as high as 0.0025, and the dielectric loss factor at a frequency of 10 GHz is also as high as 0.0108, so that there is a problem that the dielectric loss becomes large and the transmission speed becomes slow.

The glass composition of the sample No. 104 of the comparative example was a glass composition containing no SrO and BaO, and the ratio of the total amount of SrO to BaO to the total amount of the alkaline earth metal oxide was as low as 0.00. Therefore, the temperature of 10 ^3.0 dPa‧s is as high as 1332 °C. The temperature Tw of 10 ^2.0 dPa ‧ which is the standard of the melting temperature is also as high as 1568 ° C or 1568 ° C or more, and many bubbles remain in the glass melting. When the glass was melted, the phase separation property was confirmed, and in the acid resistance test, the reaction product which reacted with hydrochloric acid was confirmed. Therefore, there was a concern that an etching process or the like was performed in the process of printing a wiring board. The volume resistivity log ρ is 12.7 Ω ‧ cm, which is low in electrical reliability as a printed wiring board.

Regarding the glass composition of sample No. 105 of the comparative example, the ratio of the total amount of SrO to BaO to the total amount of the alkaline earth metal oxide was as low as 0.05. The glass of the sample No. 105 was a glass composition having a dielectric constant of 6.10 at a frequency of 1 MHz and a dielectric constant of 6.2 at a frequency of 10 GHz. Further, the dielectric loss factor of the sample at a frequency of 1 MHz is also as high as 0.0025, and the dielectric loss factor at a frequency of 10 GHz is also as high as 0.0127, so that there is a problem that the dielectric loss becomes large and the transmission speed becomes slow. Further, a remarkable phase separation property was observed when the glass was melted, and this remarkable phase separation property resulted in a bad influence on the acid resistance, and was a glass composition in which the problem was confirmed.

According to the series of evaluations performed in the examples and comparative examples shown above, it is clear that the glass composition for glass fibers of the present invention is made into a glass fiber having a small fiber diameter for use in a printed wiring board for realizing high-density packaging. Preferably, it is excellent in spinnability in the production of glass fibers, and can provide stable quality glass fibers with high production efficiency.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

Claims (9)

A glass composition for glass fibers, characterized by containing 45% to 65% of SiO ₂ , 10% to 20% of Al ₂ O ₃ , and 13% to 25% of B ₂ by weight percentage in terms of oxide. O ₃ , 5.5% to 9% of MgO, 0% to 10% of CaO, 0% to 1% of Li ₂ O+Na ₂ O+K ₂ O, SrO, BaO, and 0.01% to 5.0% of CeO ₂ . The glass composition for glass fibers according to claim 1, wherein the SrO is 0.1% to 10% and the BaO is 0.1% to 10% by weight percentage in terms of oxide. The glass composition for glass fibers according to the first aspect of the invention, wherein the total amount of the alkaline earth metal oxides of MgO, CaO, SrO, and BaO is 10 to 25%, SrO. The total amount of the total amount of BaO divided by the alkaline earth metal oxide is in the range of 0.15 to 0.50. The glass composition for glass fibers according to any one of claims 1 to 3, wherein a dielectric constant at a frequency of 1 MHz is 6.0 or less, and a dielectric loss factor is 20 × 10 ^{-4 or} less. . The glass composition for glass fibers according to any one of claims 1 to 3, wherein a dielectric constant at a frequency of 10 GHz is 6.0 or less, and a dielectric loss factor is 100 × 10 ^{-4 or} less. . A glass fiber formed of a glass composition for glass fibers according to any one of claims 1 to 5, wherein an average diameter of the glass fibers is 3 μm to 7.2 μm. The glass fiber according to claim 6, wherein the glass fiber is used as a glass cloth or a non-woven fabric and an organic resin material to form an organic resin composite material. A glass fiber sheet characterized by using the glass fiber according to claim 6 or 7 to be composited with an organic resin material to form an organic resin composite material. The glass fiber sheet according to claim 8, wherein the glass fiber sheet is glass cloth or cellophane.