Glass fiber and composition for glass fiber

Abstract

To provide a glass composition suitable for glass fibers with a good balance of acid resistance and Young's modulus.SOLUTION: The present disclosure provides a glass composition for glass fibers, which includes, in mass%, SiO2: 50-65%, Al2O3: 10-35%, MgO: 10-20%, CaO: 0-7%, TiO2: 0-5%, and ZrO2: 0-5%. The total content of SiO2, TiO2 and ZrO2 is 58% or more. The total content of TiO2 and ZrO2 is 0.1% or more. In the case of MgO content being 10% or more and less than 16%, 0.1% or more ZrO2 is contained.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to glass fibers and glass compositions suitable for glass fibers. [Background technology]

[0002] Most of the glass fibers in practical use are composed of a glass composition whose Young's modulus is 90 GPa or less. However, glass compositions whose Young's modulus exceeds 90 GPa are also known. For example, Patent Document 1 discloses a glass composition containing a large amount of rare earth oxides. 2 O 3 and La 2 O 3 The total content of these is in the range of 20 to 60% by weight. However, a high content of rare earth oxides increases the manufacturing cost. In consideration of this, Patent Document 2 discloses a technique for improving the Young's modulus of a glass composition without requiring a large amount of rare earth oxides. The glass composition of Patent Document 2 contains 15 to 30% MgO, expressed in mol %, as a component for improving the Young's modulus. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2006 / 057405 [Patent Document 2] Patent No. 6391875 Summary of the Invention [Problem to be solved by the invention]

[0004] Patent Document 2 does not consider the acid resistance of the glass composition. Therefore, an object of the present invention is to provide a glass fiber having a high Young's modulus and excellent acid resistance, and a glass composition suitable for producing such a glass fiber. [Means for solving the problem]

[0005] The present inventors have conducted extensive research into the blending ratio of glass components and have completed a glass composition suitable for glass fibers, which has an excellent balance between acid resistance and Young's modulus.

[0006] The present invention relates to Expressed in mass%, SiO 2 50~65% Al 2 O 3 10~35% MgO 10~20% CaO 0~7% TiO 2 0~5% ZrO 2 0~5% Including, SiO 2 , TiO 2 and ZrO 2 The total content of is 58% or more, TiO 2 and ZrO 2 The total content of is 0.1% or more, If the MgO content is 10% or more but less than 16%, then 0.1% or more ZrO 2 The present invention provides a glass composition for glass fibers, comprising:

[0007] The present invention also provides a glass fiber comprising the glass composition for glass fiber according to the present invention. Effect of the Invention

[0008] According to the present invention, there are provided a glass fiber having an excellent balance between acid resistance and Young's modulus, and a glass composition for glass fiber suitable for such glass fiber. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, an embodiment of the present invention will be described, but the following description is not intended to limit the present invention to a specific embodiment. In this specification, the contents of the components of the glass composition hereinafter are all shown in mass%, and mass% is basically expressed as "%". In this specification, "substantially not contained" and "substantially not contained" mean that the content is less than 0.1 mass%, less than 0.05 mass%, less than 0.01 mass%, less than 0.005 mass%, even less than 0.003 mass%, and in some cases less than 0.001 mass%. "Substantially" is intended to allow the inclusion of trace amounts of impurities derived from glass raw materials, manufacturing equipment, etc. "Alkali metal oxide" refers to Li 2 O, Na 2 O and K 2 O stands for R 2 It may be written as O. The upper and lower limits of the content described below can be arbitrarily combined, both when the upper and lower limits are stated individually and when the upper and lower limits are stated as a range.

[0010] [Glass composition] <Ingredients> Hereinafter, each component that may constitute the glass composition of the present embodiment will be described.

[0011] (SiO 2 ) SiO 2 is a component that forms the skeleton of glass, adjusts the devitrification temperature and viscosity during glass formation, and improves acid resistance. SiO 2 The content of SiO is, for example, 50 to 65%. 2 The lower limit of the SiO content may be 55% or more, 57% or more, 57.5% or more, 58% or more, 59% or more, 59.6% or more, 59.8% or more, or even 60% or more. 2 The upper limit of the SiO content may be 63% or less, 62.3% or less, 62% or less, 61.8%, 61.5% or less, or even 61% or less. 2 The content may be 55 to 62%, or further 57.5 to 61.5%.

[0012] (Al2 O 3 ) Al 2 O 3 Al is a component that adjusts the devitrification temperature and viscosity during glass formation and contributes to improving the water resistance of the glass. 2 O 3 The content of Al is, for example, 10 to 35%. 2 O 3 The lower limit of the Al content may be, for example, 15% or more, 17% or more, 19% or more, 19.5% or more, 19.7% or more, or even 20% or more. 2 O 3 The upper limit of the Al content may be 30% or less, 28% or less, 25% or less, 22% or less, 21% or less, 20.8% or less, or even 20.6% or less. 2 O 3 The content of Al may be 15 to 30%, or further 19.7 to 20.6%. However, as described below, when the content of MgO is in the range of less than 16%, 2 O 3 The content may be 22 to 29%, or further 23.5 to 28%.

[0013] (B 2 O 3 ) B 2 O 3 is an optional component that forms the skeleton of the glass and adjusts the devitrification temperature and viscosity during glass formation. 2 O 3 The content of is, for example, 0 to 1.5%. 2 O 3 The lower limit of the content of may be 0.02% or more. 2 O 3 The upper limit of the content of may be 1.2% or less, 1% or less, 0.5% or less, 0.3% or less, 0.1% or less, or even 0.08% or less. 2 O 3 may not be substantially contained.

[0014] (MgO) MgO is a component that contributes to improving Young's modulus and affects the devitrification temperature, viscosity, etc. The content of MgO is, for example, 10 to 20%. The lower limit of the MgO content may be 12% or more, 14% or more, 16% or more, 16.5% or more, 16.6% or more, 16.8% or more, or even 17% or more. The upper limit of the MgO content may be 19% or less, 18% or less, 17.8% or less, 17.7% or less, or even 17.6% or less. The content of MgO may be 12 to 20%, or even 14 to 19%. When the content of MgO is less than 16%, ZrO 2 The addition of

[0015] (CaO) CaO is an optional component that adjusts the devitrification temperature and viscosity during glass formation. The CaO content is, for example, 0 to 7%. The lower limit of the CaO content may be 0.1% or more, 0.3% or more, 0.5% or more, or even 0.7% or more. The upper limit of the CaO content may be 5% or less, 3% or less, 2% or less, 1.5% or less, 1.4% or less, 1.3% or less, 1.2% or less, or even 1% or less.

[0016] (alkali metal oxides) Alkali metal oxides (R 2 O) is an optional component that adjusts the devitrification temperature and viscosity during glass formation. The total content of alkali metal oxides, specifically [Li 2 O]+[Na 2 O]+[K 2 O] is, for example, 0 to 3%. The lower limit of the content of alkali metal oxides may be 0.05% or more, 0.1% or more, 0.2% or more, or even 0.3% or more. 2 The upper limit of the O content may be 2% or less, 1.5% or less, 1.2% or less, 1.0% or less, 0.9% or less, or even 0.8% or less. 2 If the O content is high, the Young's modulus may not increase sufficiently.

[0017] Li 2 The content of O is, for example, 0 to 1.5%. 2The lower limit of the O content is 0.1% or more, 0.2% or more, 0.3% or more, or even 0.4% or more. 2 The upper limit of the O content may be 1% or less, 0.8% or less, 0.6% or less, or even 0.5% or less. 2 A preferred example of the O content is 0.1 to 0.8%. 2 O has the effect of suppressing the decrease in Young's modulus while adjusting the devitrification temperature and other properties. 2 O and K 2 It is more advantageous than O. 2 The content of O is Na 2 The content of K may be higher than that of O. 2 The content of Na may be higher than that of O. 2 O content and K content 2 The total content of Li may be higher than that of O. 2 O may not be substantially contained.

[0018] Na 2 The content of O is, for example, 0 to 1%. 2 The upper limit of the O content may be 0.5% or less, 0.2% or less, 0.18% or less, 0.15% or less, 0.13% or less, 0.1% or less, or even 0.08% or less. 2 O may not be substantially contained. 2 The content of O is, for example, 0 to 0.5%. 2 The upper limit of the O content may be 0.3% or less, 0.1% or less, 0.08% or less, further 0.06% or less, and further 0.04% or less. 2 O may not be substantially contained.

[0019] Na 2 O content and K content 2 The total content of O may be within the range of 0 to 1%, 0 to 0.5%, or further 0 to 0.3%.

[0020] (TiO 2 and ZrO 2 ) TiO 2 and ZrO2 is an optional component that can contribute to improving acid resistance. However, TiO 2 and ZrO 2 It is preferable to add at least one selected from the following: 2 It was found that TiO is a component that can complement the effect of MgO in improving Young's modulus. 2 Content and ZrO 2 The lower limit of the total content of TiO may be 0.1% or more, 0.3% or more, 0.5% or more, 0.8% or more, 1% or more, or even 1.5% or more. 2 Content and ZrO 2 The upper limit of the total content of may be 5% or less, 4% or less, 3.5% or less, 3% or less, or even 2.5% or less. 2 Content and ZrO 2 The total content of may be in the range of 0.5 to 5%, 0.8 to 4%, or 1 to 3.5%.

[0021] TiO 2 and ZrO 2 are added in the range of, for example, 0 to 5%. 2 Content and ZrO 2 The content of TiO may be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, or even 1.2% or more. 2 Content and ZrO 2 The content of each of these may be 4% or less, 3% or less, 2.5% or less, or even 2% or less, respectively. However, TiO 2 or ZrO 2 may not be substantially contained.

[0022] (ZnO) ZnO is an optional component that may be added. ZnO is added in the range of, for example, 0 to 3%, and further 0 to 1.5%. The upper limit of the ZnO content may be 1.4% or less, 1% or less, and further 0.5% or less. ZnO may not be substantially contained.

[0023] (F 2 ) F 2 F is an optional ingredient that may be added for clarification, etc. 2 is added in the range of, for example, 0 to 0.5%, or further 0 to 0.1%. 2 The upper limit of the content of F may be 0.08% or less. 2 may not be substantially contained.

[0024] (SiO 2 +TiO 2 +ZrO 2 ) SiO 2 , TiO 2 and ZrO 2 The total content of (SiO 2 +TiO 2 +ZrO 2 ) is, for example, 58% or more. SiO 2 , TiO 2 and ZrO 2 The total content of (SiO 2 +TiO 2 +ZrO 2 Glass compositions with high (SiO 2 +TiO 2 +ZrO 2 ) is not particularly limited, but is, for example, 63.5% or less, 63% or less, or further 62.5% or less.

[0025] (SiO 2 +Al 2 O 3 +MgO) SiO 2 , Al 2 O 3 , and the total content of MgO (SiO 2 +Al 2 O 3 +MgO) may be 95% or more, 96% or more, 97% or more, or even 97.5% or more. (SiO 2 +Al 2 O 3+MgO) may be, for example, 99% or less, or even 98.5% or less.

[0026] (CaO+R 2 O) CaO and alkali metal oxides (R 2 The addition of CaO is suitable for adjusting the devitrification temperature of the glass composition. 2 The total content of O (CaO+R 2 O) may be 0 to 2.5%. (CaO+R 2 The lower limit of (CaO+R 2 The upper limit of O) may be, for example, 2.3% or less, 2.2% or less, 2% or less, or even 1.8% or less.

[0027] (Other Ingredients) The glass composition may contain components other than those described above. Other components that the glass composition may contain include Fe. 2 O 3 , Y 2 O 3 , La 2 O 3 , SrO, BaO, Cl 2 , SnO 2 , CEO 2 , P 2 O 5 , S.O. 3 Examples include:

[0028] Fe 2 O 3 For example, Fe is added in the range of 0 to 1%. 2 O 3 The upper limit of the Fe content may be 0.5%, 0.3% or less, 0.2% or less, 0.15% or less, or even 0.1% or less. 2 O 3 It is not necessary that the glass composition contains substantially no iron oxide. The iron oxide is also present in the glass composition as a part of FeO, but the content of FeO is generally defined as Fe 2 O 3 The figures will be converted into the following amounts and shown.

[0029] Y 2 O 3 and La 2 O 3 are optional components that contribute to improving the Young's modulus. However, the raw materials for these components are relatively expensive. 2 O 3 and La 2 O 3 The total content of Y is, for example, 0 to 5%. 2 O 3 and La 2 O 3 The upper limit of the total content of may be 3% or less, 2% or less, 1% or less, or even 0.5% or less. 2 O 3 La may not be substantially contained. 2 O 3 In addition, it is not necessary that the above-mentioned component is substantially contained.

[0030] SrO, BaO, Cl 2 , SnO 2 , CEO 2 , P 2 O 5 , and S.O. 3 The content of each of these components is, for example, 0 to 0.5%. The upper limit of the content of each of these components may be 0.3% or less, 0.2% or less, or even 0.1% or less. Each of these components may not be substantially contained.

[0031] (Example of composition containing 16% or more MgO) The glass composition of the present embodiment may contain the following components. SiO 2 50~65% B 2 O 3 0~1.5% Al 2 O 3 10~35% MgO 16~20% CaO 0~7% Li 2 O 0~1.0% Na 2O 0~0.2% K 2 O 0~0.1% TiO 2 0~5% ZrO 2 0~5% Including, SiO 2 , TiO 2 and ZrO 2 The total content of is 58% or more, TiO 2 and ZrO 2 The total content of is 0.1% or more.

[0032] (MgO content is less than 16% and ZrO 2 (Example of composition including The glass composition of the present embodiment may contain the following components. SiO 2 50~65% B 2 O 3 0~1.5% Al 2 O 3 10~35% MgO 10-16% (except 16%) CaO 0~7% Li 2 O 0~1.0% Na 2 O 0~0.2% K 2 O 0~0.1% TiO 2 0~5% ZrO 2 0.1-5% Including, SiO 2 , TiO 2 and ZrO 2 The total content of is 58% or more.

[0033] The content of MgO is slightly lower, and ZrO 2 In the above composition examples including Al, the content of each component may be appropriately adjusted by referring to the above ranges. 2 O 3The content may be adjusted to be slightly higher, for example, 22 to 29%, or further 23.5 to 28%.

[0034] <Characteristics> (Young's Modulus) The Young's modulus of the glass composition of the present embodiment is, for example, 98 GPa or more. The lower limit of the Young's modulus can be 99 GPa or more, 99.5 GPa or more, or in some cases, 100 GPa or more. The upper limit of the Young's modulus is not particularly limited, but may be, for example, 115 GPa or less, or even 110 GPa or less.

[0035] (acid resistance) The acid resistance can be evaluated by the mass loss rate ΔW (%) obtained by the test described in the Examples section. ΔW of the glass composition of this embodiment is, for example, 0.3 mass% or less. The upper limit of ΔW can be 0.25 mass% or less, and further 0.1 mass% or less.

[0036] [Glass fiber] The glass composition of the present embodiment is suitable for producing glass fibers. The glass fibers may be long glass fibers or short glass fibers. The glass fibers may be in at least one form selected from the group consisting of, for example, strands, rovings, yarns, cloths, chopped strands, glass wool, and milled fibers. The cloths are, for example, roving cloths and yarn cloths.

[0037] However, due to their excellent properties, the glass compositions of the above forms can also be used as glass molded products other than glass fibers. One example of a glass molded product is particulate glass. Particulate glass can be broken finely to such an extent that the external shape of glass fibers is lost, or can be produced using a nozzle according to the desired shape, similar to glass fibers. The glass compositions of the above forms are also suitable for producing particulate glass while avoiding devitrification. In one embodiment of the present invention, the particulate glass includes the glass composition of the above forms or is composed of the glass composition of the above forms.

[0038] The particulate glass may correspond to at least one selected from the group consisting of, for example, glass flakes, glass powder, glass beads, and fine flakes. The particulate glass can be used for FRP, that is, for reinforcing a reinforced object such as a resin.

[0039] Considering that it can also be used for particulate glass, the above-mentioned glass composition can also be understood as a glass composition for glass fibers or particulate glass.

[0040] [Nonwoven fabric, rubber reinforcing cord] Each glass fiber provided by the present invention can be used in the same applications as conventional glass fibers. One embodiment of the present invention provides a glass fiber nonwoven fabric containing glass fibers. Another embodiment of the present invention provides a rubber reinforcing cord containing strands of bundled glass fibers. The glass fibers can also be used in other applications. Other applications include the reinforcement of a reinforced object, typically a resin.

[0041] [Example] Hereinafter, the embodiments of the present invention will be described in more detail with reference to examples and comparative examples. Note that the content of the components in the following tables is also expressed in mass %. <Preparation of Glass Composition> Ordinary glass raw materials such as silica sand were mixed to obtain the compositions shown in Tables 1 and 2, and batches of glass raw materials were prepared for each of the examples and comparative examples. Using an electric furnace, each batch was heated to 1500 to 1600°C to melt, and was maintained as such for about 4 hours until the composition became uniform. After that, a part of the molten glass (glass melt) was poured onto an iron plate and slowly cooled to room temperature in the electric furnace to obtain a bulk glass composition (plate-shaped material, glass sample). The characteristics of these glass compositions were evaluated as follows. The results are also shown in Tables 1 and 2.

[0042] (Young's Modulus) Young's modulus is calculated by measuring the longitudinal wave velocity vl and the transverse wave velocity vt of the elastic wave propagating through the glass using a conventional ultrasonic method, and calculating the density ρ of the glass using the Archimedes method. t 2 ·(v l 2 -4 / 3·v t 2 ) / (v l 2 -v t 2 ) was calculated using the formula:

[0043] (acid resistance) A single glass fiber with a diameter of 15 μm was cut to a length of 20 mm and weighed out in grams equal to the specific gravity of the glass. The glass fiber was immersed in 80 mL of a sulfuric acid solution with a specific gravity of 1.2 at 99°C for 60 minutes to determine the mass loss rate, which was defined as ΔW.

[0044] The mass loss rate was calculated based on the following formula, where Wa is the mass before immersion and Wb is the mass after immersion. Mass reduction rate (%)={(Wa-Wb) / Wa}×100

[0045] [Table 1]

[0046] [Table 2]

[0047] According to each of the examples, a Young's modulus of 98 GPa or more and a ΔW of 0.3 mass % or less were achieved, whereas each of the comparative examples could not satisfy these characteristics.

[0048] As described above, this specification discloses the following techniques.

[0049] (Technology 1) Expressed in mass%, SiO 2 50~65% Al 2 O 3 10~35% MgO 10~20% CaO 0~7% TiO 2 0~5% ZrO 2 0~5% Including, SiO 2 , TiO 2 and ZrO 2 The total content of is 58% or more, TiO 2 and ZrO 2 The total content of is 0.1% or more, If the MgO content is 10% or more but less than 16%, then 0.1% or more ZrO 2 13. A glass composition for glass fibers comprising:

[0050] (Technology 2) Expressed in mass%, SiO 2 55~62% Al 2 O 3 15~30% MgO 12~20% CaO 0~4% TiO 2 0~3% ZrO 2 0~3% The glass composition of technique 1, comprising:

[0051] (Technology 3) Expressed in mass%, TiO 2 and ZrO 2 and the total content of is 0.5% or more and 5% or less.

[0052] (Technology 4) Expressed in mass%, SiO 2 The glass composition according to any one of Techniques 1 to 3, wherein the content of is in the range of 57.5 to 61.5%.

[0053] (Technology 5) Expressed in mass%, Li 2 5. The glass composition according to any one of Techniques 1 to 4, wherein the O content is in the range of 0 to 1.5%.

[0054] (Technology 6) Expressed in mass%, Na 2 O content and K 2 The glass composition according to any one of Techniques 1 to 5, wherein the total content of O is in the range of 0 to 1%.

[0055] (Technology 7) Expressed in mass%, B 2 O 3 The glass composition according to any one of Techniques 1 to 6, wherein the content of is in the range of 0 to 1.5%.

[0056] (Technology 8) Expressed in mass%, Y 2 O 3 and La content 2 O 3 The glass composition according to any one of Techniques 1 to 7, wherein the total content of and is in the range of 0 to 5%.

[0057] (Technology 9) The glass composition according to any one of Techniques 1 to 8, having a Young's modulus of 98 GPa or more.

[0058] (Technology 10) The glass composition according to any one of Techniques 1 to 9, wherein ΔW is 0.3 mass % or less. Here, ΔW is the mass loss rate when the glass composition, whose mass is in grams equal to the specific gravity of the glass composition, is immersed in 80 mL of sulfuric acid solution having a specific gravity of 1.2 and a temperature of 99° C. for 60 minutes.

[0059] (Technology 11) A glass fiber comprising any one of the glass compositions according to any one of claims 1 to 10.

[0060] (Technology 12) The glass fiber according to Technology 11, having a form corresponding to at least one selected from the group consisting of strand, roving, yarn, cloth, chopped strand, glass wool, and milled fiber.

Claims

1. expressed in mass%, SiO 2 50 - 65% Al 2 O 3 10 - 30% MgO 10 - 20% CaO 0 - 7% TiO 2 0 - 5% ZrO 2 0 - 5% containing SiO 2 TiO 2 and ZrO 2 the total content rate of which is 58% or more, TiO 2 and ZrO 2 the total content rate of which is 0.1% or more, when the content rate of MgO is 10% or more and less than 16%, containing 0.1% or more of ZrO 2 glass composition for glass fiber.

2. expressed in mass%, SiO 2 55 - 62% Al 2 O 3 15 - 30% MgO 12 - 20% CaO 0 - 4% TiO 2 0 - 3% ZrO 2 0 - 3% the glass composition according to Claim 1, containing

3. expressed in mass%, the total of the content rate of TiO 2 and the content rate of ZrO 2 is 0.5% or more and 5% or less, the glass composition according to Claim 1.

4. expressed in mass%, the content rate of SiO 2 is in the range of 57.5 - 61.5%, Claim 1 The glass composition described in

5. In terms of mass%, Li 2 The content of O is in the range of 0 to 1.5%, and the glass composition according to claim 1 glass composition.

6. In terms of mass%, Na 2 The content of O and K 2 The total of the content of O is in the range of 0 to 1%, and the glass composition according to claim 1.

7. In terms of mass%, B 2 O 3 The content of is in the range of 0 to 1.5%, and the glass composition according to claim 1.

8. In terms of mass%, Y 2 O 3 The content of and La 2 O 3 The total of the content of is in the range of 0 to 5%, and the glass composition according to claim 1.

9. The Young's modulus is 98 GPa or more, and the glass composition according to claim 1.

10. ΔW is 0.3 mass% or less, and the glass composition according to claim 1. Here, the ΔW is the mass reduction rate when the glass composition with the mass as the number of grams equal to the specific gravity of the glass composition is immersed in 80 mL of sulfuric acid at a specific gravity of 1.2 and a temperature of 99°C for 60 minutes.

11. Glass fiber containing the glass composition according to any one of claims 1 to 10.

12. Having a form corresponding to at least one selected from the group consisting of strand, roving, yarn, cloth, chopped strand, glass wool, and milled fiber, the glass fiber according to claim 11.