WO2014115550A1 - Bio-soluble inorganic fiber and bio-soluble inorganic fiber composition - Google Patents

Abstract

An inorganic fiber composition containing, as principal components, MgO and one or two components selected from Al₂O₃ and CaO.

Description

Biologically soluble inorganic fiber and composition thereof

The present invention relates to a novel biosoluble inorganic fiber and a composition for obtaining the inorganic fiber.

Since asbestos is lightweight, easy to handle and excellent in heat resistance, for example, it has been used as a heat-resistant sealing material. However, asbestos is inhaled by the human body and causes illness in the lungs, so its use is prohibited. Instead, ceramic fibers and the like are used. Ceramic fibers and the like have high heat resistance comparable to that of asbestos. However, since the biosolubility is not sufficient, problems due to being inhaled into the human body and entering the lungs have been pointed out. Therefore, various biosoluble fibers have been developed aiming at biosoluble inorganic fibers that do not cause problems or are unlikely to occur even when inhaled by the human body (for example, Patent Documents 1 and 2).

In the research on conventional biosoluble fibers, fibers that are highly soluble in physiological saline at pH 7.4 have been sought. However, the fiber is inhaled by the lungs and the pH of the lung macrophages is 4.5. Therefore, it is expected that fibers having high solubility in physiological saline having a pH of 4.5 are dissolved and decomposed more effectively in the lung.

In addition, as with asbestos, conventional inorganic fibers are secondary-processed into shaped products and irregular shaped materials, together with various binders and additives, and joint materials in furnaces such as heat treatment equipment, industrial kilns and incinerators, It is used as a joint material, a sealing material, a packing material, a heat insulating material, and the like for filling gaps such as refractory tiles, heat insulating bricks, iron skin, and mortar refractories. Therefore, it is often exposed to high temperatures during use, and preferably has heat resistance. Further, alumina is often used for the wall surface in the furnace, and it is preferable that the fibers contained in the secondary processed product react with the alumina and the secondary processed product and the wall surface do not adhere or melt.

Japanese Patent Publication No. 3753416 Special table 2005-514318

An object of the present invention is to provide a novel biosoluble inorganic fiber and a composition for obtaining the inorganic fiber.

According to the present invention, the following inorganic fiber composition and inorganic fiber are provided.
1. A composition for inorganic fibers containing one or two components selected from Al ₂ O ₃ and CaO, and MgO as main components.
2. 2. Composition for inorganic fiber of 1 containing 3.0 mass% or more of MgO.
3. The composition for inorganic fibers according to 1 or 2 having the following composition.
Al ₂ O ₃ 0.0-97.0 mass%
CaO 0.0-97.0 mass%
MgO 3.0-94.0% by mass
4). 4. The inorganic fiber composition according to any one of 1 to 3, having the following composition.
Al ₂ O ₃ 6.0 to 97.0 mass%
CaO 0.0-72.0 mass%
MgO 3.0-65.0% by mass
5. 5. The inorganic fiber composition according to any one of 1 to 4, having the following composition.
Al ₂ O ₃ 16.0-93.0% by mass
CaO 3.0-62.0 mass%
MgO 4.0-55.0 mass%
6). 5. The inorganic fiber composition according to any one of 1 to 4, having the following composition.
Al ₂ O ₃ 26.0-93.0% by mass
CaO 3.0-52.0 mass%
MgO 4.0 to 45.0 mass%
7). 5. The inorganic fiber composition according to any one of 1 to 4, having the following composition.
Al ₂ O ₃ 31.0-93.0% by mass
CaO 3.0-47.0 mass%
MgO 4.0 to 40.0 mass%
8). 5. The inorganic fiber composition according to any one of 1 to 4, having the following composition.
Al ₂ O ₃ 49.0-93.0 mass%
CaO 3.0-47.0 mass%
MgO 4.0 to 40.0 mass%
9. 5. The inorganic fiber composition according to any one of 1 to 4, having the following composition.
Al ₂ O ₃ 64.0-93.0% by mass
CaO 3.0-36.0 mass%
MgO 4.0-28.0 mass%
10. 5. The inorganic fiber composition according to any one of 1 to 4, having the following composition.
Al ₂ O ₃ 60.0-84.0% by mass
CaO 3.0-36.0 mass%
MgO 4.0-20.0 mass%
11. 5. The inorganic fiber composition according to any one of 1 to 4, having the following composition.
Al ₂ O ₃ 60.0-81.0 mass%
CaO 12.0-33.0 mass%
MgO 7.0-20.0 mass%
12 5. The inorganic fiber composition according to any one of 1 to 4, having the following composition.
Al ₂ O ₃ 60.0-78.0 mass%
CaO 12.0-30.0 mass%
MgO more than 10.0% by mass and 20.0% by mass or less13. The composition for inorganic fibers according to any one of 1 to 5, wherein the total of Al ₂ O ₃ , CaO and MgO is 80.0% by mass or more.
14 The composition for inorganic fibers according to any one of 1 to 6, wherein the total of Al ₂ O ₃ , CaO and MgO is 90.0% by mass or more.
15. The composition for inorganic fibers according to any one of 1 to 6, wherein the total of Al ₂ O ₃ , CaO and MgO is 95.0% by mass or more.
16. Inorganic fibers obtained from the inorganic fiber composition according to any one of 16.1 to 15.
17. The inorganic fiber according to 16, which does not react with Al ₂ O _{3 at} 1200 ° C.
18. 16. The method for producing inorganic fibers according to 16, wherein the melted composition for inorganic fibers according to any one of 1 to 15 is fiberized.
19. A shaped product or an amorphous product obtained using the inorganic fiber described in 19.16.

According to the present invention, a novel biosoluble inorganic fiber and a composition for obtaining the inorganic fiber can be provided. In addition, the biological solubility in this invention says the solubility with respect to the physiological saline of pH4.5.

The fiber composition of the present invention contains one or two components selected from Al ₂ O ₃ and CaO, and MgO as main components.
The main component means that two or three components having the highest content (mass%) among all the components contained in the composition are 1 or 2 selected from Al ₂ O ₃ and CaO, and MgO. means.
Preferably, Al ₂ O ₃ , CaO and MgO are included as main components.
Preferably, 3.0% by mass or more of MgO is included as a viscosity modifier.

The fiber composition of the present invention preferably has the following composition from the viewpoint of biosolubility and heat resistance.
Al ₂ O ₃ 0.0-97.0 mass%
CaO 0.0-97.0 mass%
MgO 3.0-94.0% by mass

The above composition can be further set as the following composition.
Al ₂ O ₃ 6.0 to 97.0 mass%
CaO 0.0-72.0 mass%
MgO 3.0-65.0% by mass

The above composition can be further set as the following composition.
Al ₂ O ₃ 16.0-93.0% by mass
CaO 3.0-62.0 mass%
MgO 4.0-55.0 mass%

The above composition can be further set as the following composition.
Al ₂ O ₃ 26.0-93.0% by mass
CaO 3.0-52.0 mass%
MgO 4.0 to 45.0 mass%

The above composition can be further set as the following composition.
Al ₂ O ₃ 31.0-93.0% by mass
CaO 3.0-47.0 mass%
MgO 4.0 to 40.0 mass%

The above composition can be further set as the following composition.
Al ₂ O ₃ 49.0-93.0 mass%
CaO 3.0-47.0 mass%
MgO 4.0 to 40.0 mass%

The above composition can be further set as the following composition.
Al ₂ O ₃ 64.0-93.0% by mass
CaO 3.0-36.0 mass%
MgO 4.0-28.0 mass%

The above composition can be further set as the following composition.
Al ₂ O ₃ 60.0-84.0% by mass
CaO 3.0-36.0 mass%
MgO 4.0-20.0 mass%

The above composition can be further set as the following composition.
Al ₂ O ₃ 60.0-81.0 mass%
CaO 12.0-33.0 mass%
MgO 7.0-20.0 mass%

The above composition can be further set as the following composition.
Al ₂ O ₃ 60.0-78.0 mass%
CaO 12.0-30.0 mass%
MgO more than 10.0% by mass and 20.0% by mass or less

You may combine the quantity of each component of said composition arbitrarily.
In each of the above compositions, the total of the components to be specified is 80.0% by mass or more, 90.0% by mass or more, 95.0% by mass or more, 97.0% by mass or more, 98.0% by mass or more, 99. It is good also as 0 mass% or more or 100.0 mass%.
The rest other than the specified components is oxides or impurities of other elements.

The composition of the present invention comprises a respective oxide selected from Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or mixtures thereof. May or may not be included. The amount of these oxides is 20.0% by mass or less, 10.0% by mass or less, 5.0% by mass or less, 3.0% by mass or less, 2.0% by mass or less, 1.0% by mass or less, respectively. 0.5% by mass or less, 0.2% by mass or less, or 0.1% by mass or less.

Each of the alkali metal oxides (K ₂ O, Na ₂ O, Li ₂ O, etc.) may or may not be contained, and the alkali metal oxides are each or 20.0% by mass or less in total. 0 mass% or less, 5.0 mass% or less, 3.0 mass% or less, 2.0 mass% or less, 1.0 mass% or less, 0.5 mass% or less, 0.2 mass% or less, or 0.1 It can be made into the mass% or less.

Each of ZrO ₂ , ZnO, B ₂ O ₃ , P ₂ O ₅ , SrO, BaO, Cr ₂ O ₃ , SiO ₂ , Fe ₂ O ₃ , and TiO ₂ may or may not be included, each 20 0.0 mass% or less, 10.0 mass% or less, 5.0 mass% or less, 3.0 mass% or less, 2.0 mass% or less, 1.0 mass% or less, 0.5 mass% or less, It can be 2 mass% or less or 0.1 mass% or less.

The composition of the present invention usually does not contain the following substances, or even if contained, it is 0.2% by mass or less or 0.1% by mass or less, respectively.
Fluorine, calcium sulfate, arsenic oxide, germanium oxide, tellurium oxide, vanadium oxide, sulfur oxide, fluorine molecule, phosphorus compound, tin, cobalt, manganese oxide, fluoride, copper oxide.

Inorganic fibers can be obtained from the composition of the present invention.
The fiber of the present invention can be produced by a known method such as a melting method or a sol-gel method, but the melting method is preferred because of low cost. In the melting method, a raw material melt is produced by a normal method, and the melt is made into a fiber. For example, it can be manufactured by a spinning method in which a melted raw material is poured onto a wheel rotating at high speed, and a blow method in which the melted raw material is fiberized by applying compressed air.

The fiber of the present invention may or may not be coated with a known coating material. The solubility during storage and use can be adjusted by coating.

The fiber of the present invention is the same as the composition of the raw material composition, and has solubility (biological solubility) in physiological saline having a pH of 4.5 by having the above composition.
The solubility in physiological saline of pH 4.5 is preferably 1.0 mg / g or more, more preferably 1.5 mg / g or more, and further preferably 3.0 mg / g or more, according to the measurement method of the example.

Moreover, preferably, it has solubility (biological solubility) in physiological saline having a pH of 7.4.
The solubility in physiological saline at pH 7.4 is preferably 1.0 mg / g or more, more preferably 1.5 mg / g or more, and even more preferably 3.0 mg / g or more, according to the measurement method of the example.

The dissolution rate constant is preferably 10 ng / cm ² · h or more, more preferably 50 ng / cm ² · h or more, still more preferably 100 ng / cm ² · h or more, and particularly preferably 200 ng / cm by the measurement method of the example. ² · h or more.

The fibers of the present invention preferably have low alumina reactivity. The alumina reactivity is preferably not adhered or does not react with the measurement method of the examples.

The fibers of the present invention preferably have heat resistance at 800 ° C or higher, 1000 ° C or higher, 1100 ° C or higher, 1200 ° C or higher, 1300 ° C or higher, 1400 ° C or higher. Specifically, the volume shrinkage (%) is 40% or less, preferably 30% or less at 1400 ° C. for 8 hours by the measurement method of the example. It is 40% or less, preferably 30% or less, more preferably 23% or less, and most preferably 15% or less at 1300 ° C. for 8 hours. It is 40% or less, preferably 30% or less, more preferably 23% or less, and most preferably 15% or less at 1200 ° C. for 8 hours. It is 40% or less, preferably 30% or less, more preferably 23% or less, and most preferably 15% or less at 1100 ° C. for 8 hours. It is 40% or less, preferably 30% or less, more preferably 23% or less, and most preferably 15% or less at 1000 ° C. for 8 hours. It is 40% or less, preferably 30% or less, more preferably 23% or less, most preferably 15% or less at 800 ° C. for 8 hours.

The fiber of the present invention is preferably measured by the measurement method of the Examples, and the linear shrinkage rate is determined at each temperature (600 ° C, 800 ° C, 1000 ° C, 1100 ° C, 1200 ° C, 1300 ° C, 1400 ° C, 1500 ° C, 1600 ° C). ), Preferably 30% or less, more preferably 20% or less, still more preferably 10% or less, and most preferably 5% or less.

The heat shrinkage rate of the fiber can be measured before and after producing a blanket from the fiber and firing it at 1100 ° C. and 1260 ° C. for 24 hours. The tensile strength can be measured with a universal testing machine.

Furthermore, since the fiber of the present invention can reduce the types of essential components, the number of man-hours for the blending process is reduced and the cost is reduced. In addition, the fact that there are few kinds of components for adjusting delicate blending amounts reduces the difficulty of production.

From the fibers of the present invention, bulk products, blankets, blocks, and regular products such as boards, molds, papers, felts and the like manufactured using a solvent such as water can be obtained. Moreover, the amorphous material (mastic, a caster, a coating material, etc.) manufactured using solvents, such as water, is also obtained.

Examples 1-18
The fiber composition shown in Table 1 was examined as follows.
First, the raw materials were mixed so as to have the composition shown in Table 1, and pressed to obtain a molded body. The molded product was melted by heating and rapidly cooled to obtain a sample. Using this sample, the following method was used for evaluation. The results are shown in Table 1.

(1) Biosolubility 1 g of a sample was placed in an Erlenmeyer flask (volume: 300 mL) containing 150 mL of physiological saline having a pH of 4.5 or pH 7.4. This flask was placed in an incubator at 37 ° C., and horizontal vibration at 120 revolutions per minute was continued for 2.5 hours. Thereafter, the amount (mg) of each element contained in the filtrate obtained by filtration was measured with an ICP emission spectrometer, and the total was taken as the elution amount (mg / sample 1 g).

(2) Volume shrinkage The sample was molded to obtain a cylindrical sample having a diameter of about 7 mm and a height of about 15 mm. This columnar sample was heated at 1400 ° C. for 8 hours to determine the volume shrinkage (%).

(3) Alumina reaction resistance A sample was molded to obtain a cylindrical sample having a diameter of about 7 mm and a thickness of about 5 mm. This cylindrical sample was placed on an alumina plate and heated at 1400 ° C. for 8 hours to observe the presence or absence of adhesion or melting. It was 4 when the cylindrical sample was melted, 3 when it was adhered, 2 when it was not adhered but remained, and 1 when it was not adhered and remained.

Comparative Example 1
A ceramic fiber (conventional heat-resistant inorganic fiber) (Comparative Example 1) containing 47.2% by mass of SiO ₂ and 52.7% by mass of Al ₂ O ₃ was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Examples 19-31
Fibers having the compositions shown in Table 2 were produced by a melting method.
The obtained fiber was evaluated by the following method. The results are shown in Table 2.

(1) Linear shrinkage The thermal shrinkage was measured before and after producing a fleece or a blanket from fibers and firing at 1000 ° C. and 1400 ° C. for 8 hours. Two or more platinum pins were driven into the surface of each manufactured sample, the distance between the platinum pins was measured before and after heating, and the dimensional change rate was defined as the linear shrinkage rate (%).

(2) Alumina reaction resistance About 1 g of alumina powder having a purity of 99% or more was press-molded with a mold having a diameter of 17 mm to form pellets. This pellet was placed on a fleece or blanket (50 mm long and 5 to 50 mm thick) sample made from the fiber, and heated at 1000 ° C. to 1400 ° C. for 8 hours in this state, and the reactivity after heating was confirmed. . ○ when there is no reaction with the pellet, light adhesion with the sample (the pellet is easily peeled off by hand, the pellet and the sample are not melted), and there is a reaction (the pellet and the sample are melted and adhered) ) Was marked with x.

(3) Dissolution rate constant The fiber was placed on a membrane filter, physiological saline of pH 4.5 or pH 7.4 was dropped on the fiber with a micropump, and the filtrate passing through the fiber and filter was stored in a container. The accumulated filtrate was taken out after 24 hours, and the eluted components were quantified with an ICP emission spectrometer. The measurement elements were three elements of Mg, Al and Ca which are main elements. The fiber diameter was measured and converted to a dissolution rate constant k (unit: ng / cm ² · h) which is the amount of elution per unit surface area / unit time.

The inorganic fiber of the present invention can be used for various purposes as a heat insulating material or as a substitute for asbestos.

Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The contents of the documents described in this specification and the specification of the Japanese application that is the basis of Paris priority of the present application are all incorporated herein.

Claims (19)

1. A composition for inorganic fibers containing one or two components selected from Al ₂ O ₃ and CaO, and MgO as main components.
2. The composition for inorganic fibers according to claim 1, comprising 3.0% by mass or more of MgO.
3. The composition for inorganic fibers according to claim 1 or 2, having the following composition.
   Al ₂ O ₃ 0.0-97.0 mass%
   CaO 0.0-97.0 mass%
   MgO 3.0-94.0% by mass
4. The composition for inorganic fibers according to any one of claims 1 to 3, which has the following composition.
   Al ₂ O ₃ 6.0 to 97.0 mass%
   CaO 0.0-72.0 mass%
   MgO 3.0-65.0% by mass
5. The composition for inorganic fibers according to any one of claims 1 to 4, which has the following composition.
   Al ₂ O ₃ 16.0-93.0% by mass
   CaO 3.0-62.0 mass%
   MgO 4.0-55.0 mass%
6. The composition for inorganic fibers according to any one of claims 1 to 4, which has the following composition.
   Al ₂ O ₃ 26.0-93.0% by mass
   CaO 3.0-52.0 mass%
   MgO 4.0 to 45.0 mass%
7. The composition for inorganic fibers according to any one of claims 1 to 4, which has the following composition.
   Al ₂ O ₃ 31.0-93.0% by mass
   CaO 3.0-47.0 mass%
   MgO 4.0 to 40.0 mass%
8. The composition for inorganic fibers according to any one of claims 1 to 4, which has the following composition.
   Al ₂ O ₃ 49.0-93.0 mass%
   CaO 3.0-47.0 mass%
   MgO 4.0 to 40.0 mass%
9. The composition for inorganic fibers according to any one of claims 1 to 4, which has the following composition.
   Al ₂ O ₃ 64.0-93.0% by mass
   CaO 3.0-36.0 mass%
   MgO 4.0-28.0 mass%
10. The composition for inorganic fibers according to any one of claims 1 to 4, which has the following composition.
    Al ₂ O ₃ 60.0-84.0% by mass
    CaO 3.0-36.0 mass%
    MgO 4.0-20.0 mass%
11. The composition for inorganic fibers according to any one of claims 1 to 4, which has the following composition.
    Al ₂ O ₃ 60.0-81.0 mass%
    CaO 12.0-33.0 mass%
    MgO 7.0-20.0 mass%
12. The composition for inorganic fibers according to any one of claims 1 to 4, which has the following composition.
    Al ₂ O ₃ 60.0-78.0 mass%
    CaO 12.0-30.0 mass%
    MgO more than 10.0% by mass and 20.0% by mass or less
13. The composition for inorganic fibers according to any one of claims 1 to 5, wherein the total of Al ₂ O ₃ , CaO and MgO is 80.0 mass% or more.
14. The composition for inorganic fibers according to any one of claims 1 to 6, wherein the total of Al ₂ O ₃ , CaO and MgO is 90.0 mass% or more.
15. The composition for inorganic fibers according to any one of claims 1 to 6, wherein the total of Al ₂ O ₃ , CaO and MgO is 95.0 mass% or more.
16. Inorganic fibers obtained from the inorganic fiber composition according to any one of claims 1 to 15.
17. The inorganic fiber according to claim 16, which does not react with Al ₂ O _{3 at} 1200 ° C.
18. The method for producing inorganic fiber according to claim 16, wherein the melted composition for inorganic fiber according to any one of claims 1 to 15 is made into a fiber.
19. A shaped product or an amorphous product obtained using the inorganic fiber according to claim 16.