JP2015024946A - Composition for glass fiber, glass fiber and method of producing glass fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for glass fiber which causes no problems in production of a glass fiber, meets product characteristics required for e.g. printed wiring boards, is capable especially of emitting a refining gas in an amount required for defoaming and homogenization of a molten glass and is excellent in clarity and a method of producing a glass fiber.SOLUTION: A composition for glass fiber comprises, by mass%, 42-67% SiO, 8-25% AlO, 0-25% BO, 0-15% MgO, 10-35% CaO, 0-2% LiO+NaO+KO, 0-5% PO, 0.003-0.225% Cl and 0.005-0.1% SO.

Description

Glass fiber called E glass is a long glass fiber used as a structural member for printed wiring boards, cars, airplanes, and the like (for example, Patent Document 1). The long glass fiber is produced by continuously forming and spinning using a forming apparatus called a bushing. The bushing device is a device having a substantially rectangular appearance including a large number of nozzle portions (or orifice portions), and the temperature is controlled so that the viscosity of the molten glass is 10 ³ dPa · s at the tip of the bushing nozzle. The molten glass continuously flows out from the tip of the bushing nozzle, is rapidly cooled, and is spun into glass fiber.

  When forming such glass fiber, if bubbles are included in the molten glass, it tends to cause cutting in spinning of the 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. In order to reduce the number of bubbles in the molten glass, it is important to select a refining agent that generates a necessary and sufficient refining gas in a temperature range where the defoaming and homogenization of the glass melt occurs.

JP 2007-39320 A

Conventionally, in the manufacture of E glass, the SO ₃ component is used as a fining agent. However, if SO ₃ is contained in a large amount, a foam layer is formed in the upper layer portion of the molten glass, and heat of the combustion burner is hardly transmitted, so that there is a problem that the melting efficiency is lowered.

Therefore, it is necessary to limit the content of SO ₃ to a certain amount or less. However, in this case, the amount of clarification gas necessary for defoaming and homogenizing the molten glass is not released, and it has been regarded as a problem that clarification becomes insufficient.

  The object of the present invention is to satisfy the product characteristics required for printed wiring boards, etc., without causing problems in the production of glass fibers, and in particular, release the amount of clarified gas necessary for defoaming and homogenizing molten glass. It is an object of the present invention to provide a glass fiber composition excellent in clarity and a method for producing glass fiber.

As a result of various studies, the present inventors have found that the above object can be achieved by using Cl and SO ₃ together as a clarifying agent, and propose the present invention.

That is, the composition for glass fiber of the present invention is SiO ₂ 42-67%, Al ₂ O ₃ 8-25%, B ₂ O ₃ 0-25%, MgO 0-15%, CaO 10-35 by mass%. %, Li ₂ O + Na ₂ O + K ₂ O 0-2%, P ₂ O ₅ 0-5%, Cl 0.003-0.225%, SO ₃ 0.005-0.1% . Here, “Li ₂ O + Na ₂ O + K ₂ O” means the total content of Li ₂ O, Na ₂ O and K ₂ O.

By adopting the above configuration, the number of bubbles in 100 g of glass is 10 or less, the alkali elution amount is 0.1 mg or less, and the difference between the spinning temperature TX and the liquidus temperature TL (hereinafter referred to as TX-TL). It becomes easy to set the melting temperature (temperature at which the viscosity of the glass becomes 10 ^2.0 dPa · s) to 1500 ° C. or higher at 80 ° C. or higher.

In the present invention, _SiO 2 52 - _56% by _{mass%, Al 2 O 3 12~16%} , B 2 O 3 5~10%, 0~5% MgO, CaO 16~25%, Li 2 O + Na 2 O + K _{2 O 0~2%, P 2 O} 5 0~2%, Cl 0.003~0.225%, preferably contains SO 3 0.005 to 0.1%.

  In this invention, it is preferable to contain SrO 0-6% and BaO 0-2% by the mass% further.

In the present invention, preferably contains SnO ₂ 0.001 to 0.06% by further mass%.

  The glass fiber of this invention consists of an above-described composition for glass fibers.

The method of manufacturing glass fibers of the present invention, _SiO 2 _42-67% by _{mass%, Al 2 O 3 8~25%} , B 2 O 3 0~25%, 0~15% MgO, CaO 10~35%, Glass raw material to be a glass containing Li ₂ O + Na ₂ O + K ₂ O 0-2%, P ₂ O ₅ 0-5%, Cl 0.003-0.225%, SO ₃ 0.005-0.1% A batch is prepared, melted, and then spun to form glass fibers.

In the present invention, _SiO 2 52 - _56% by _{mass%, Al 2 O 3 12~16%} , B 2 O 3 5~10%, 0~5% MgO, CaO 16~25%, Li 2 O + Na 2 O + K Preparing glass raw material batch so that it may become glass containing ₂ O 0-2%, P ₂ O ₅ 0-2%, Cl 0.003-0.225%, SO ₃ 0.005-0.1%. Is preferred.

  In the present invention, it is preferable to prepare the raw material batch so that the glass further contains 0 to 6% SrO and 0 to 2% BaO by mass%.

In the present invention, it is preferable to prepare the raw material batch so that the glass further contains 0.001 to 0.06% of SnO ₂ by mass%.

  In the present invention, it is preferable to use glass cullet made of Cl-containing glass as the Cl source.

In the present invention, it is preferable to prepare the batch so that SO ₃ contained in the raw material batch is 0.01 to 0.5% by mass.

The composition for glass fiber of the present invention is characterized by containing a predetermined amount of Cl and SO ₃ as a fining agent. Since both Cl and SO ₃ can release a large amount of clarified gas in a temperature range of 1400 ° C. or higher, a large amount of clarified gas can be generated by using both. Also since the need to use an excess SO ₃ disappears, hardly foam layer is formed on the molten glass, it is possible to efficiently melt the glass.

  Hereinafter, the reason why the composition range of each component is limited as described above for the glass fiber composition of the present invention will be described. In the following description, unless otherwise specified,% display means mass%.

SiO ₂ is one of the elements constituting the glass network. The content is 42 to 67%, preferably 45 to 65%, more preferably 50 to 60%, and particularly preferably 52 to 56%. When the content of SiO ₂ is small, the structural strength of the glass is remarkably deteriorated and the mechanical strength required for the composite member using glass fibers cannot be satisfied. On the other hand, when the content of SiO ₂ is large, the melting temperature of the molten glass rises. As a result, if an attempt is made to produce such a glass composition to be homogeneous with high efficiency by a melting method, expensive equipment is required. Necessary.

Al ₂ O ₃ is a component having an effect of suppressing crystal crystallization and phase separation generation in molten glass. The content of Al ₂ O ₃ is 8 to 25%, preferably 8 to 20%, more preferably 10 to 18%, and particularly preferably 12 to 16%. When the content of Al ₂ O ₃ is less than 8%, TX-TL becomes small and spinnability deteriorates. The spinning temperature is a temperature at which the viscosity of the glass is 10 ³ dPa · s. On the other hand, if the content of Al ₂ O ₃ is more than 25%, the melting temperature of the glass rises and the meltability tends to deteriorate.

B ₂ O ₃ is in the glass network structure similar to the SiO _2, is a component that forms the skeleton, rather than to increase the melting temperature of the molten glass as SiO _2, acts to rather lower the melting temperature is there. The content of B ₂ O ₃ is 0 to 25%, preferably 0 to 20%, more preferably 1 to 10%, and particularly preferably 5 to 10%. When the content of B ₂ O ₃ is large, foreign glass such as scum is likely to be generated in the melting process.

  MgO is a component having a function as a flux that makes it easy to melt glass raw materials, and at the same time, is very effective in lowering the melting temperature. It is a useful ingredient. The content of MgO is 0 to 15%, preferably 0 to 10%, more preferably 0 to 5%, and particularly preferably 0.5 to 4%. When the content of MgO is large, the phase separation of the molten glass becomes high and TL tends to rise, and as a result, TX-TL becomes small, which is not preferable.

  CaO is a component that lowers the melting temperature together with MgO. The content of CaO is 10 to 35%, preferably 15 to 30%, more preferably 16 to 25%. When there is little content of CaO, the melting temperature of glass will rise and meltability will deteriorate easily. On the other hand, when the CaO content is more than 35%, the phase separation of the molten glass is increased, and TX-TL is decreased, which is not preferable.

  The glass composition for glass fiber of the present invention may contain SrO and BaO in order to lower the melting temperature. The SrO content is preferably 0 to 6%, more preferably 0.1 to 2%, and still more preferably 0.1 to 1.5%. Further, the content of BaO is preferably 0 to 2%, more preferably 0.05 to 1%, and still more preferably 0.05% to 0.5%. When the content of SrO or BaO is large, the phase separation of the molten glass is increased and TX-TL is decreased, which is not preferable.

Li 2 _O is an alkali metal _oxide, Na 2 _O or K _{2 O} is, when heating to a glass melt in a state of mixing a plurality of glass raw material, to facilitate the production of the glass melt, a so-called Acts as a flux. It also has the function of lowering the melting temperature. The total content of Li ₂ O, Na ₂ O and K ₂ O is 0 to 2%, preferably 0 to 1%, more preferably 0 to 0.8%. If the total amount of Li ₂ O, Na ₂ O and K ₂ O is large, the amount of alkali elution of the glass increases, and the electrical insulation properties deteriorate. Moreover, since the adhesive strength at the resin / glass interface is lowered and the mechanical strength of the printed wiring board is likely to be lowered, it is not preferable.

P ₂ O ₅ is a component having an effect of preventing the formation of fine crystal nuclei in the molten glass. The content of P ₂ O ₅ is 0 to 5%, preferably 0 to 2%, more preferably 0.1 to 1%. If the content of P ₂ O ₅ is large, TX-TL becomes small, which is not preferable.

  Cl is a component that reacts with components such as alkali metal, alkaline earth metal, and hydrogen in the molten glass to become a clarified gas and is released from the molten glass. For example, Cl releases a clarified gas by the reaction of Na component with the following formula.

Na ₂ O + Cl ₂ → 2NaCl + 1 / 2O ₂

  The Cl content is 0.003 to 0.225%, preferably 0.004 to 0.10%, more preferably 0.005 to 0.08%, and most preferably 0.005 to 0.03. %. If the Cl content is small, the clarity is deteriorated, which is not preferable. On the other hand, when the content of Cl is large, when used for a printed wiring board, the standard of halogen-free printed wiring boards of the Japan Electronic Circuits Association “Copper-clad laminate for halogen-free printed wiring boards-glass cloth / glass Since it becomes easy to deviate from the upper limit (0.09% by mass) of the Cl content of the printed wiring board defined by “nonwoven fabric composite substrate epoxy resin JPCA-ES03-2007”, it is not preferable. For example, assuming that the percentage of glass fiber in the printed wiring board is 40% by mass and the Cl content in the resin is 0% by mass, if the Cl content in the glass fiber exceeds 0.225% by mass, the Cl content in the printed wiring board The quantity deviates from the standard of JPCA-ES03-2007. Moreover, when chlorine is contained in the use of a chlorine-based flame retardant or the resin, the upper limit of the Cl content of the glass fiber is further limited.

SO ₃ causes the following reaction with the glass component in the molten glass, and releases SO ₂ gas and O ₂ .

SO ₄ ²⁻ → SO ₂ + 1 / 2O ₂ + O ²⁻

The SO ₃ content in the glass is 0.005 to 0.1%, preferably 0.01 to 0.08%, more preferably 0.015 to 0.065%. When the content of SO ₃ is small, the clarity is remarkably deteriorated. On the other hand, if the content of SO ₃ is large, a foam layer is formed in the upper part of the molten glass, and the combustion burner heat is hardly transmitted, so that the melting efficiency is lowered.

In the present invention, in addition to Cl and SO ₃ , one or more clarifier components such as Sb ₂ O ₃ , As ₂ O ₃ and SnO ₂ may be contained. In this case, the total amount of standard fining agents added is within 0.5%. However, in consideration of the environment, it is better to avoid using Sb ₂ O ₃ or As ₂ O ₃ . In the case of using SnO _2, although the content can be selected in the range of 0.001 to 0.06%, it is possible to appropriately select a suitable range in terms of devitrification and clarity. That is, when the content of SnO ₂ is small, it becomes difficult to obtain sufficient clarity. On the other hand, devitrification and the content of SnO ₂ is often deteriorated, TX-TL is reduced. Therefore, when priority is given to increasing this difference, the SnO ₂ content is preferably 0.005 to 0.029%, particularly 0.01 to 0.028%. Also in the case where priority is given to clarity, when a content of SnO ₂ 0.031-0.058%, it is preferable to particularly from 0.035 to 0.05 percent.

In addition to the above components, the glass fiber composition of the present invention improves the chemical durability, the melting temperature, etc., in addition to Cr ₂ O ₃ , PbO, La ₂ O ₃ , WO ₃ , Nb ₂ O ₅ , Y Components such as ₂ O ₃ may be contained up to 3% each. However, in consideration of the environment, it is better to avoid using PbO.

Further, the glass fiber composition of the present invention may contain, for example, H ₂ , CO ₂ , CO, H ₂ O, He, Ne, Ar, and N ₂ as impurities up to 0.1%. . Further, Pt, Rh, and Au may be contained up to 0.05% or less as impurities.

The glass fiber composition of the present invention preferably has a melting temperature of 1500 ° C. or lower. The melting temperature is more preferably 1450 ° C. or less, and further preferably 1400 ° C. or less. When the melting temperature is high, expensive equipment is required to melt the glass uniformly. The melting temperature can be lowered by reducing the content of SiO ₂ , Al ₂ O ₃ or the like or increasing the content of B ₂ O ₃ , MgO, CaO or the like.

The glass fiber composition of the present invention preferably has a TX-TL of 80 ° C or higher. TX-TL is more preferably 100 ° C. or higher, and further preferably 115 ° C. or higher. When TX-TL is lower than 80 ° C., crystals are precipitated in the glass at a low temperature portion in the path from the melting furnace to the bushing, which causes cutting during spinning. TX-TL can be increased by decreasing the liquidus temperature TL by increasing the content of P ₂ O ₅ or decreasing the content of MgO, CaO, or the like.

The glass fiber composition of the present invention preferably has an alkali elution amount of 0.1 mg or less. The alkali elution amount is more preferably 0.05 mg or less, still more preferably 0.02 mg or less. When the amount of alkali elution is more than 0.1 mg, the adhesive strength at the resin-glass interface decreases, and the mechanical strength of the printed wiring board tends to decrease. The alkali elution amount can be reduced by reducing the content of the alkali metal oxide or increasing the content of SiO ₂ , Al ₂ O ₃ or the like.

In the composition for glass fiber of the present invention, the number of bubbles in 100 g of glass is preferably 10 or less. The number of bubbles in 100 g of glass is more preferably 5 or less, and still more preferably 2 or less. When the number of bubbles in 100 g of glass is more than 10, cutting during glass fiber spinning tends to occur. The number of bubbles in the glass can be reduced by increasing the content of Cl, SO ₃ or the like.

  Next, the method for producing the glass fiber of the present invention will be described by taking the direct melt method (DM method) as an example. The present invention is not limited to the following method. For example, a so-called indirect molding method (MM method: marble melt method) in which a glass fiber material molded into a marble shape is remelted and spun using a bushing apparatus is employed. You can also. This method is suitable for small-lot, multi-product production.

First, SiO ₂ 42 to 67%, Al ₂ O ₃ 8 to 25%, B ₂ O ₃ 0 to 25%, MgO 0 to 15%, CaO 10 to 35%, Li ₂ O + Na _{2 in} terms of oxide-based mass percentage. O + K ₂ O 0-2%, P ₂ O ₅ 0-5%, SnO ₂ 0.001-0.06%, SO ₃ 0.005-0.1%, preferably SiO ₂ 52-56% by mass Al ₂ O ₃ 12-16%, B ₂ O ₃ 5-10%, MgO 0-5%, CaO 16-25%, Li ₂ O + Na ₂ O + K ₂ O 0-2%, P ₂ O ₅ 0-2 %, Cl 0.003 to 0.225%, SO ₃ 0.005 to 0.1% glass material is prepared. The reason why the content of each component is as described above is as described above, and the description is omitted here.

As the Cl source, chloride raw materials such as NaCl, KCl, BaCl ₂ , and CaCl ₂ can be used. Further, glass cullet containing Cl may be used. Here, the glass cullet refers to defective glass generated in the glass manufacturing process or recycled glass recovered from home appliances. Moreover, you may use the dust containing Cl. Here, dust is dust recovered from exhaust gas generated in a glass melting furnace or the like.

As the SO ₃ source, alkali metal sulfates such as Na ₂ SO ₄ , alkaline earth metal sulfates such as MgSO ₄ , CaSO ₄ , BaSO ₄ , and ZnSO ₄ can be used. The glass cullet consisting SO ₃ containing glass may be used dust, or other glass materials containing SO ₃ component containing SO ₃ component. In addition, it is better not to use metal sulfur or sulfide because it reduces the glass.

The SO ₃ component in the raw material is decomposed during the melting of the glass, and a part of the SO ₃ component is evaporated from the glass as SO ₂ . Therefore, the amount of SO ₃ contained in the obtained glass is smaller than the amount of SO ₃ contained in the raw material batch. Therefore, the glass raw material so that the content of the SO ₃ component in the raw material batch is 0.01 to 0.5%, preferably 0.05 to 0.4%, more preferably 0.1 to 0.4%. Etc. need to be adjusted. If the amount of SO ₃ in the batch is small, the clarity is remarkably deteriorated. On the other hand, if the amount of SO ₃ in the batch is large, a foam layer is formed in the upper layer portion of the molten glass and the combustion burner heat is hardly transmitted, so that the melting efficiency is lowered.

  Subsequently, the prepared glass raw material batch is put into a glass melting furnace, vitrified, melted and homogenized. The melting temperature is preferably about 1400 to 1600 ° C.

  Subsequently, molten glass is spun and formed into glass fibers. More specifically, molten glass is supplied to the bushing device. The molten glass supplied to the bushing device is continuously drawn out in filament form from a number of bushing nozzles provided on the bottom surface. Various processing agents are applied to the monofilaments drawn in this way, and glass fibers are obtained by focusing each monofilament.

  The glass fiber of the present invention thus formed is processed into chopped strands, yarns, rovings, etc. and used for various applications.

  The chopped strand is obtained by cutting glass fibers (strands) obtained by focusing glass monofilaments into a predetermined length. A yarn is a twisted strand. Roving is a combination of a plurality of strands wound in a cylindrical shape.

The present invention will be described below based on examples.
[Example 1]
Tables 1 to 4 show examples (sample Nos. 1 to 19) and comparative examples (samples No. 20 to 222) of the present invention. Moreover, Table 5 has shown the composition (cullet 1-4) of the liquid crystal plate glass cullet used in a present Example.

  Each sample was prepared as follows.

  First, a glass raw material was prepared so as to have the composition in the table, and a 500 g glass raw material batch was prepared. Next, this raw material batch was put into a platinum crucible and melted at 1500 ° C. for 4 hours. The glass was homogenized by stirring twice during melting. Thereafter, molten glass was formed and subjected to various evaluations.

  No. 1-6, 10, 12-16, 19 are magnesium chloride, No. 8, 9, and 11 used calcium chloride as a Cl source. Sample No. 7 is cullet 1; 17 is cullet 2; 18 is cullet 3; 19 used cullet 4 as the source of Sn and Cl, respectively. Sample No. The cullet usage rate of Nos. 7, 18, and 19 was 10% by mass of the entire batch. The cullet usage rate of 17 was 15% by mass of the entire batch.

In the examples of the present invention, the amount of SO ₃ added in the glass batch was adjusted by changing the amount of glass raw material used as the SO ₃ source. The amount of SO ₃ in the glass was determined by fluorescent X-ray analysis.

  For the measurement of the number of bubbles, molten glass was poured onto a carbon plate, slowly cooled to produce an ingot, and the number of bubbles in the ingot was measured. As a result of the measurement, those having more than 31 bubbles in 100 g of glass were indicated by ×, those having 11-30 pieces were indicated by Δ, those having 6-10 pieces were indicated by ○, and those having 5 pieces or less were indicated by ◎. In addition, the measurement observed the center part of the ingot with the optical microscope, and converted into the number per 100g.

The spinning temperature TX (temperature at which the glass viscosity becomes 10 ³ dPa · s) and the melting temperature (temperature at which the glass viscosity becomes 10 ² dPa · s) were measured by a platinum ball pulling method.

  The liquid phase temperature TL was measured as follows. An approximately 120 × 20 × 10 mm platinum boat is filled with the pulverized sample, placed in an electric furnace having a linear temperature gradient for 16 hours, and the temperature of the crystal precipitation determined by a microscope is calculated from the temperature gradient graph of the electric furnace. This temperature was defined as the liquidus temperature TL.

  The alkali elution amount was measured by a method based on JIS R3502.

  Sample No. As is apparent from 1 to 19, the glass of the present invention has 10 or less bubbles in 100 g of glass, an alkali elution amount of 0.1 mg or less, TX-TL of 80 ° C. or higher, 1500 ° C. or lower. And had a melting temperature of

In contrast, Sample No. as a comparative example. Nos. 20 and 21 had more than 10 bubbles in 100 g of glass and poor clarity. Sample No. No. 22 had a large amount of alkali elution.
[Example 2]
Next, the glass fiber realizable by using the composition for glass fibers of this invention is demonstrated.

  For example, sample no. After the glass fiber composition having the glass composition of 1 is melted, the glass fiber composition is supplied to a bushing apparatus having a platinum nozzle, and a monofilament having a diameter of 12 μm is pulled out from the bushing nozzle. The monofilament is coated with a sizing agent and bundled to form a strand.

  Since the glass fiber of the present invention thus obtained has good clarity when the glass is melted, almost no hollow fiber is generated.

The composition for glass fibers of the present invention is suitable as a composition for E glass fibers used as a structural member for printed wiring boards, cars, airplanes and the like.

Claims (11)

_SiO 2 from 42 to _67% by _{mass%, Al 2 O 3 8~25%} , B 2 O 3 0~25%, 0~15% MgO, CaO 10~35%, Li 2 O + Na 2 O + K 2 O 0~2 %, P ₂ O ₅ 0-5%, Cl 0.003-0.225%, SO ₃ 0.005-0.1% _SiO 2 52 - _56% by _{mass%, Al 2 O 3 12~16%} , B 2 O 3 5~10%, 0~5% MgO, CaO 16~25%, Li 2 O + Na 2 O + K 2 O 0~2 _{%, P 2 O 5 0~2%} , Cl 0.003~0.225%, the glass fiber composition according to claim 1, characterized in that it contains SO 3 0.005 to 0.1%.   Furthermore, SrO 0-6% and BaO 0-2% are contained by the mass%, The composition for glass fibers of Claim 1 or 2 characterized by the above-mentioned. Glass fiber composition according to claim 1 further characterized in that it contains SnO ₂ 0.001 to 0.06% in mass%.   A glass fiber comprising the glass fiber composition according to any one of claims 1 to 4. _SiO 2 from 42 to _67% by _{mass%, Al 2 O 3 8~25%} , B 2 O 3 0~25%, 0~15% MgO, CaO 10~35%, Li 2 O + Na 2 O + K 2 O 0~2 %, P ₂ O ₅ 0-5%, Cl 0.003-0.225%, SO ₃ 0.005-0.1% Glass raw material batch was prepared and melted, then spun And then forming the glass fiber. _SiO 2 52 - _56% by _{mass%, Al 2 O 3 12~16%} , B 2 O 3 5~10%, 0~5% MgO, CaO 16~25%, Li 2 O + Na 2 O + K 2 O 0~2 _%, wherein, wherein _{P 2 O 5 0~2%, Cl} 0.003~0.225%, to formulate a glass raw batch so that the glasses containing sO 3 0.005 to 0.1% Item 7. A method for producing a glass fiber according to Item 6.   Furthermore, a raw material batch is prepared so that it may become a glass which contains SrO 0-6% and BaO 0-2% by mass%, The manufacturing method of the glass fiber of Claim 6 or 7 characterized by the above-mentioned. Glass fiber composition according to any one of claims 6-8, characterized in that formulating raw batch so that the glass containing SnO ₂ 0.001 to 0.06% more in mass%.   The glass cullet made of Cl-containing glass is used as a Cl source, The glass fiber manufacturing method according to any one of claims 6 to 9. As SO ₃ contained in the raw batch is 0.01 to 0.5 wt%, the manufacturing method of a glass fiber according to any one of claims 6-10, characterized in that formulating a batch.