GLASS COMPOSITION FOR GLASS FIBER, GLASS FIBER, GLASS FIBER WOVEN FABRIC, AND GLASS FIBER REINFORCED RESIN COMPOSITION

Abstract

To provide a glass composition for glass fiber that includes biosolubility and can achieve long fiber formation. The glass composition for glass fiber of the present invention includes SiO.sub.2 in the range of 35.0 to 55.0% by mass, B.sub.2O.sub.3 in the range of 10.0 to 30.0% by mass, Al.sub.2O.sub.3 in the range of 14.5 to 30.0% by mass, and CaO and MgO in the range of 8.7 to 25.0% by mass in total, with respect to the total amount, and the content S of SiO.sub.2, the content B of B.sub.2O.sub.3, the content A of Al.sub.2O.sub.3, the content C of CaO, and the content M of MgO satisfy the following formula (1):

[00001]$\begin{array}{cc}11.3\le \text{S}\times \left(\text{C}+\text{M}\right)/\left(\text{A}+\text{B}\right)\le 20.7& \text{­­­(1)}\end{array}$

Claims

1. A glass composition for glass fiber, comprising: SiO.sub.2 in a range of 35.0 to 55.0% by mass; B.sub.2O.sub.3 in a range of 10.0 to 30.0% by mass; Al.sub.2O.sub.3 in a range of 14.5 to 30.0% by mass; and CaO and MgO in a range of 8.7 to 25.0% by mass in total, with respect to a total amount, wherein a content S of SiO.sub.2, a content B of B.sub.2O.sub.3, a content A of Al.sub.2O.sub.3, a content C of CaO, and a content M of MgO satisfy following formula (1): ##STR00001## .

2. The glass composition for glass fiber according to claim 1, wherein the S, B, A, C, and M satisfy following formula (2): ##STR00002## .

3. The glass composition for glass fiber according to claim 1, wherein the S, B, A, C, and M satisfy following formula (3): ##STR00003## .

4. The glass composition for glass fiber according to claim 1, comprising: SiO.sub.2 in a range of 37.0 to 49.5% by mass; B.sub.2O.sub.3 in a range of 16.5 to 29.0% by mass; Al.sub.2O.sub.3 in a range of 15.0 to 28.0% by mass; CaO in a range of 10.5 to 21.0% by mass; MgO in a range of 0 to 6.5% by mass; and TiO.sub.2 in a range of 0 to 0.4% by mass, with respect to the total amount.

5. The glass composition for glass fiber according to claim 1, wherein the S, B, A, C, and M satisfy following formula (4): ##STR00004## .

6. The glass composition for glass fiber according to claim 1, wherein the S, B, A, C, and M satisfy following formula (5): ##STR00005## .

7. The glass composition for glass fiber according to claim 1, wherein the S, B, A, C, and M satisfy following formula (6): ##STR00006## .

8. Glass fiber comprising glass filaments formed of the glass composition for glass fiber according to claim 1.

9. The glass fiber according to claim 8, wherein a filament diameter of each of the glass filament is less than 3.0 .Math.m.

10. A glass fiber woven fabric comprising the glass fiber according to claim 8.

11. A glass fiber-reinforced resin composition comprising the glass fiber according to claim 8.

Description

EXAMPLES

Examples 1 to 7, Comparative Examples 1 to 3

[0130] At first, glass raw material was mixed to obtain a glass batch so that the glass composition after melt-solidification is the composition of Examples 1 to 7 or Comparative Examples 1 to 3 shown in Tables 2 to 4. Next, the obtained glass batch was placed in a platinum crucible. While this platinum crucible was held in an electric furnace for 4 hours under temperature conditions in the range of 1400 to 1550° C. appropriate for melting of the glass batch of each of Examples and Comparative Examples, the glass batch was melted with stirring to obtain a homogeneous molten glass. Next, the obtained molten glass is poured onto a carbon plate and cooled to obtain bulk glass cullet.

[0131] Next, the obtained glass cullet was used to evaluate the biosolubility and the long fiber forming ability by methods shown below.

Biosolubility

[0132] First, in accordance with K. Sebastian. et al., Glass Science and Technology, Vol. 75, pp. 263-270 (2020), an artificial lung fluid of pH 4.5, which comprises the composition shown in Table 1 and simulates the environment in the lungs, was prepared by sequentially adding Nos. 1 to 12 reagents shown in Table 1 to about 800 mL of distilled water such that the final volume of 1 L was achieved while the pH was adjusted with No. 13 hydrochloric acid so as to reach a pH of 4.5. Then, the prepared artificial lung fluid was allowed to stand for 24 hours. Then, in the artificial lung fluid after the standing, the pH had increased in association with release of carbonic gas, and thus the pH of the artificial lung fluid was adjusted to 4.5 again using hydrochloric acid.

[0133] Fiber taken in the lungs is known to be taken up by macrophages. As the pH around macrophages is 4.5, fiber having high solubility in the artificial lung fluid of pH 4.5 is expected to be dissolved inside the lungs.

TABLE-US-00001 No. Compositional component of artificial lung fluid Content (g/L) 1 Sodium chloride 7.12 2 Sodium hydrogen carbonate 1.95 3 Calcium chloride 0.022 4 Disodium hydrogen phosphate 0.148 5 Sodium sulfate 0.079 6 Magnesium chloride hexahydrate 0.212 7 Glycine 0.118 8 Trisodium citrate dihydrate 0.152 9 Sodium tartrate dihydrate 0.18 10 Sodium pyruvate 0.172 11 90% Lactic acid 0.156 12 Formaldehyde 3 mL 13 Hydrochloric acid (1:1) 4-5 mL

[0134] Next, the glass cullet described above was coarsely pulverized to obtain glass particles having a particle diameter of 0.5 to 1.5 mm. Then, the obtained glass particles were finely pulverized with an automatic mortar and a ball mill-type pulverizer, and particles that had passed through a sieve having a nominal mesh opening of 38 .Math.m in accordance with JIS Z8801-1 were used as a test glass powder sample.

[0135] Next, in accordance with K. Sebastian. et al., Glass Science and Technology, Vol. 75, pp. 263-270 (2020), an elution test was performed in such a manner that the test glass powder sample was packed into a silicone tube having syringe filters attached at the top and bottom, the above artificial lung fluid warmed to 37° C. was pumped into the silicone tube at a flow rate of 140 to 170 mL/day, and the filtrate that passed through the test glass powder sample and the filters was stored in a container. At this time, the mass of the test glass powder sample packed in the silicone tube was adjusted such that the ratio of the flow rate of the artificial lung fluid (unit: .Math.m.sup.3/s) to the sample surface area (unit: .Math.m.sup.2) (flow rate of the artificial lung fluid/sample surface area) was 0.030±0.005 .Math.m/s. After the elapse of 24 hours, the filtrate was recovered from the container, Si and Al were taken as ions to be analyzed, ion components eluted in the filtrate were quantified using inductively coupled plasma mass spectrometry (ICP-MS), and the ICP-MS quantitative results of Si and Al (.Math.g) were divided by 24 hours to calculate the elution rate (.Math.g/h) of each component. The results of Examples 1 to 4 are shown in Table 2, the results of Examples 5 to 7 are shown in Table 3, and the results of Comparative Examples 1 to 3 are shown in Table 4.

Long Fiber Forming Ability

[0136] By use of a high temperature electric furnace equipped with a rotational viscometer (manufactured by Shibaura System Co. Ltd.), the glass cullet described above was melted in a platinum crucible, and the viscosity of the molten glass was continuously measured using the Brookfield rotational viscometer with the melt temperature varied. The temperature at which the rotational viscosity was 1000 poise was measured to determine the 1000 poise temperature.

[0137] Next, 40 g of the glass particles having a particle diameter of 0.5 to 1.5 mm, obtained by pulverizing the glass cullet described above, were placed in a platinum boat of 180 × 20 × 15 mm and heated in a tubular electric furnace provided with a temperature gradient of 900 to 1300° C. for 8 hours or more, then taken out of the tubular electric furnace, and observed with a polarized light microscope to identify the position at which crystals derived from devitrified glass began to precipitate. The temperature inside the tubular electric furnace was measured using a type B thermocouple to determine the temperature of the position at which the precipitation began, which temperature was taken as the liquid phase temperature.

[0138] Next, the working temperature range ΔT (ΔT = 1000 poise temperature - liquid phase temperature) was calculated from the 1000 poise temperature and the liquid phase temperature measured by the above methods. The long fiber forming ability was evaluated as “A” when ΔT was +99° C. or more, the long fiber forming ability was evaluated as “B” when ΔT was -10° C. or more and less than +99° C., and the long fiber forming ability was evaluated as “C” when ΔT was less than -10° C. The results of Examples 1 to 4 are shown in Table 2, the results of Examples 5 to 7 are shown in Table 3, and the results of Comparative Examples 1 to 3 are shown in Table 4.

Example 8

[0139] In the present Example, first, the glass cullet obtained in Example 1 was charged into a platinum container equipped with a nozzle tip at the bottom, and the platinum container was heated to 1150 to 1350° C. to melt the glass cullet to thereby obtain molten glass. Then, the molten glass drawn out through the nozzle tip and wound to a winding apparatus. Then, the heating temperature of the platinum container was adjusted, and the winding apparatus was rotated to wind the glass fiber to the winding apparatus at a spinning temperature in the range of 1150 to 1350° C. appropriate for the glass composition of each Example and at a spinning speed in the range of 800 to 1100 rpm appropriate for the glass composition of each Example to obtain a glass fiber sample having a fiber diameter of 13.0 .Math.m.

[0140] Next, in accordance with K. Sebastian. et al., Glass Science and Technology, Vol. 75, pp. 263-270 (2020), the glass fiber sample was cut to a length of 1 to 3 mm, which length can fit to an in-line filter holder, and used as a glass fiber sample for elution test. An elution test was performed in such a manner that the above glass fiber sample for elution test was mounted on a membrane filter installed in an in-line filter holder, the above artificial lung fluid warmed to 37° C. was pumped into the in-line filter holder at a flow rate of 140 to 170 mL/day, and the filtrate that passed through the test glass powder sample and the filter holder was stored in a container. At this time, the mass of the sample mounted on the membrane filter was adjusted such that the ratio of the flow rate of the artificial lung fluid (unit: .Math.m.sup.3/s) to the sample surface area (unit: .Math.m.sup.2) (flow rate of the artificial lung fluid/sample surface area) was 0.030±0.005 .Math.m/s. After the elapse of 24 hours, the filtrate was recovered from the container, Si and Al were taken as ions to be analyzed, ion components eluted in the filtrate were quantified using inductively coupled plasma mass spectrometry (ICP-MS), and the ICP-MS quantitative results of Si and Al (.Math.g) were divided by 24 hours to calculate the elution rate (.Math.g/h) of each component. The results are shown in Table 5.

Example 9

[0141] In the present Example, a glass fiber sample having a fiber diameter of 13.0 .Math.m in the entirely same manner as in Example 8, except for using the glass cullet obtained in Example 4.

[0142] Next, an elution test was performed entirely in the same manner as in Example 8 except for using the glass fiber sample having a fiber diameter of 13.0 .Math.m obtained in the present Example, and the elution rate (.Math.g/h) of each component was calculated. The results are shown in Table 5.

TABLE-US-00002 Example 1 Example 2 Example 3 Example 4 SiO.sub.2 (wt%) ; S 39.5 46.8 41.4 44.2 B.sub.2O.sub.3 (wt%); B 18.4 24.1 19.3 18.4 Al.sub.2O.sub.3 (wt%) ; A 24.1 15.8 24.4 23.8 CaO (wt%) ; C 18.0 13.3 9.3 13.6 MgO (wt%) ; M 0 0 5.6 0 TiO.sub.2 (wt%) 0 0 0 0 C+M 18.0 13.3 14.9 13.6 S+B+A+C+M 100.0 100.0 100.0 100.0 (A+0.9×B).sup.3×(3×C+2×M)/S.sup.3 58.9 20.5 40.2 31.0 S×(C+M)/(A+B) 16.7 15.6 14.1 14.2 Long fiber formation A A A A Glass biosolubility Amount of SiO.sub.2 eluted (.Math.g/h) 82.2 62.8 52.6 56.3 Amount of Al.sub.2O.sub.3 eluted (.Math.g/h) 60.4 46.1 58.8 52.3 Amount of Al.sub.2O.sub.3 eluted/amount of SiO.sub.2 eluted 0.73 0.73 1.12 0.93 Total amount eluted (.Math.g/h) 142.6 108.9 111.4 108.6

TABLE-US-00003 Example 5 Example 6 Example 7 SiO.sub.2 (wt%) ; S 41.4 44.9 44.0 B.sub.2O.sub.3 (wt%) ; B 24.9 18.8 14.8 Al.sub.2O.sub.3 (wt%) ; A 15.7 24.0 23.6 CaO (wt%) ; C 18.0 10.0 17.6 MgO (wt%) ; M 0 2.3 0 TiO.sub.2 (wt%) 0 0 0 C+M 18.0 12.3 17.6 S+B+A+C+M 100.0 100.0 100.0 (A+0.9×B).sup.3×(3×C+2×M)/S.sup.3 42.1 26.2 31.2 S×(C+M)/(A+B) 18.4 12.9 20.17 Long fiber formation A B B Glass biosolubility Amount of SiO.sub.2 eluted (.Math.g/h) 74.8 51.8 47.4 Amount of Al.sub.2O.sub.3 eluted (.Math.g/h) 34.5 55.8 56.1 Amount of Al.sub.2O.sub.3 eluted/amount of SiO.sub.2 eluted 0.46 1.08 1.18 Total amount eluted (.Math.g/h) 109.3 107.6 103.5

TABLE-US-00004 Comparative Example 1 Comparative Example 2 Comparative Example 3 SiO.sub.2 (wt%) ; S 46.0 41.1 46.0 B.sub.2O.sub.3 (wt%) ; B 21.3 26.5 21.3 Al.sub.2O.sub.3 (wt%) ; A 23.4 23.2 15.6 CaO (wt%) ; C 0 0 17.1 MgO (wt%) ; M 9.3 9.2 0 TiO.sub.2 (wt%) 0 0 0 C+M 9.3 9.2 17.1 S+B+A+C+M 100.0 100.0 100.0 (A+0.9×B).sup.3×(3×C+2×M)/S.sup.3 14.7 27.6 22.2 S×(C+M)/(A+B) 9.6 7.6 21.3 Long fiber formation C C A Glass biosolubility Amount of SiO.sub.2 eluted (.Math.g/h) 85.3 46.6 27.4 Amount of Al.sub.2O.sub.3 eluted (.Math.g/h) 94.9 50.0 14.3 Amount of Al.sub.2O.sub.3 eluted/amount of SiO.sub.2 eluted 1.11 1.07 0.52 Total amount eluted (.Math.g/h) 180.2 96.6 41.7

TABLE-US-00005 Example 8 Example 9 SiO.sub.2 (wt%) ; S 39.5 44.2 B.sub.2O.sub.3 (wt%) ; B 18.4 18.4 Al.sub.2O.sub.3 (wt%) ; A 24.1 23.8 CaO (wt%) ; C 18.0 13.6 MgO (wt%) ; M 0 0 TiO.sub.2 (wt%) 0 0 C+M 18.0 13.6 S+B+A+C+M 100.0 100.0 (A+0.9×B).sup.3×(3×C+2×M)/S.sup.3 58.9 31.0 S×(C+M)/(A+B) 16.7 14.2 Long fiber formation A A Glass long fiber biosolubility Amount of SiO.sub.2 eluted (.Math.g/h) 77.3 54.9 Amount of Al.sub.2O.sub.3 eluted (.Math.g/h) 70.0 57.3 Amount of Al.sub.2O.sub.3 eluted/amount of SiO.sub.2 eluted 0.91 1.04 Total amount eluted (.Math.g/h) 147.3 112.2

[0143] As seen in Table 1 to Table 4, the glass powder samples obtained from the glass compositions for glass fibers of Examples 1 to 7 have a total elution rate of SiO.sub.2 and Al.sub.2O.sub.3 of 103.5 .Math.g/h or more, comprise biosolubility, and additionally can achieve long fiber formation. In contrast, the glass powder of the glass composition for glass fiber of Comparative Example 1 has a total elution rate of SiO.sub.2 and Al.sub.2O.sub.3 of 180.2 .Math.g/h or more and comprises excellent biosolubility, but clearly having poor long fiber forming ability. The glass powder obtained from the glass composition for glass fiber of Comparative Example 2 exhibits a total elution rate of SiO.sub.2 and Al.sub.2O.sub.3 of 96.6 .Math.g/h, which is a relatively high value, but clearly having poor long fiber forming ability. The glass powder obtained from the glass composition for glass fiber of Comparative Example 3, although achieving long fiber formation, has a total elution rate of SiO.sub.2 and Al.sub.2O.sub.3 of 41.7 .Math.g/h, clearly having poor biosolubility.

[0144] As seen in Table 5, the glass fiber samples of Examples 8 and 9 comprise biosolubility equivalent to the glass powder samples of Examples 1 and 4, which have been obtained from the same glass composition for glass fiber. Accordingly, it is considered to be highly probable that the glass fiber samples obtained from the glass compositions for glass fiber of Examples 2, 3, and 5 to 7 also comprise biosolubility equivalent to that of the glass powder samples of Examples 2, 3, and 5 to 7.