JPH0419175B2 - - Google Patents

Description

[Detailed description of the invention]

<Field of Application> The present invention relates to rock wool that is colored (designable) and has excellent heat resistance, mechanical properties (fiber tensile strength and flexibility), and water erosion resistance.
More specifically, it is made from ferrochrome slag, silica stone, and iron ore slag, has a fiberization temperature similar to that of ordinary rock wool, is colored (designable),
It relates to rock wool that has excellent heat resistance, mechanical properties, and water erosion resistance. This rock wool has made it possible to expand conventional uses, such as mineral fiber boards with design features (ceiling boards), asbestos substitutes, inorganic fibers to replace ceramic wool, and the agricultural field (agricultural pine), as well as to develop new uses. <Prior art> Conventionally, slag-based rock wool using iron ore slag was produced by adding natural stone such as silica stone as a component adjustment material to iron ore slag, melting it in a cupola furnace or electric furnace, and using the centrifugal force of the molten product. Fibers are produced using a high-speed rotating body, by blowing with compressed air, or by using a combination of centrifugal force and compressed air. Such slag wool-based rock wool has a grayish-white appearance and lacks design, has higher heat resistance than glass wool but lower than ceramic wool, and has lower fiber tensile strength than glass wool, and is less flexible than glass wool or ceramic wool. Furthermore, it has performance problems that are common to inorganic fibers, such as a tendency to be easily eroded by water. Reflecting the performance of slag wool-based rock wool and the advantage that it can be manufactured at low cost, it is currently being used as a non-combustible sound-absorbing mineral fiber board (ceiling board), mainly as an industrial insulation material for medium to high temperatures (500 to 600 degrees Celsius), Although it is used in large quantities as a fireproof coating material, the current situation is that it has not been possible to expand its use in conventional product fields or develop new uses. <Problems to be Solved by the Present Invention> The present invention is capable of producing fibers using the same fiberizing temperature as conventional slag wool-based rock wool, and using the same fiberizing method, that is, centrifugal force or compressed air, or a combination of both. Rock wool can be manufactured using a fiberization method, and as a result of inexpensive raw materials and low melting energy, it can be produced at low cost, and has excellent coloring (design), heat resistance, mechanical properties, and water erosion resistance. It was done for the purpose of obtaining. many kinds,
As a result of investigation, it was found that it was a mixture of ferrochrome slag 5-90wt%, silica stone 5-30wt%, iron ore slag 0-90wt%, SiO ₂ 35-50wt%,
_{Al2O3 10} ~25wt%, CaO2~20wt%, MgO5~
Rock wool whose main components are 30 wt% and 0.2 to 10 wt% Cr ₂ O ₃ has excellent properties such as coloring (design), heat resistance, mechanical properties, and water erosion resistance.
As a result, conventional slag wool-based rock wool related products (mineral ceiling panels, insulation materials, fireproof coating materials)
In addition, it has enabled the development of new uses such as asbestos fibers, inorganic fibers to replace ceramic wool, and the agricultural field (agricultural pine). <Method for Solving Problems> As a method of imparting color (design), which is the first objective of the present invention, a method of coloring fibers by adding a colored ionic substance can be used. However, there are limits to the coloring of fibers with colored ionic substances.
Also, it depends on the composition (relative to the degree of coloring), whether the atmosphere at the time of melting the raw material composition is oxidizing or reducing.
If the valence of the added colored ionic substance changes, not only will it be impossible to obtain the desired coloring of the fiber, but even if the colored raw material composition is made into a final fiber, the fiber shape will change. Please note that there will be differences in the degree of coloring, reflecting this. Generally, SiO ₂ −Al ₂ O ₃ −CaO
- In MgO-based rock wool compositions, as a method for coloring fibers by adding colored ionic substances,
Fe ⁺⁺ ...dark green, Mn ⁺⁺ ...reddish-purple, Cu ⁺⁺ ...green-yellow, Cr ⁺⁺⁺ ...dark blue are available, but 1~
Cr ⁺⁺⁺ ionic substances are excellent as effective coloring agents that give a colored design to fibers with a fiber diameter of 10μ, and other ionic substances cannot produce clear coloring, so they are difficult to color even when actually used. No benefits can be expected. Coloring with the Cr ⁺⁺⁺ ion substance according to the present invention colors the finally obtained fibers with a diameter of 1 to 10μ as light blue, and mineral fiber boards (ceiling boards) using these fibers can be produced even in an unpainted state. It has an excellent design. Cr ⁺⁺⁺ as a specific coloring method
Ionic substances are added in the form of Cr ₂ O ₃ , but from the perspective of the degree of coloration of the fibers, the upper limit is 0.2wt% or more, and the upper limit is 10wt% or less from the perspective of the blending ratio of other components and the heat resistance of the fibers. The range is appropriate. Regarding the improvement of heat resistance and mechanical properties, which is the second and third objective of the present invention, SiO ₂ 37 to 42 wt%,
_{Al2O3 10} ~15wt%, CaO35~40wt%, MgO5~
10wt%, trace components such as FeO + MnO + TiO ₂ + S
In slag-based rock wool with a composition of 5wt% or less, CaO is the main component of alkaline earth metals.
An inexpensive method is to reduce the amount of FeO and increase the amount of SiO ₂ , Al ₂ O ₃ , FeO, Cr ₂ O ₃ , etc.; Therefore, it is important to increase the amount of MgO.
SiO ₂ is required in an amount of 35 to 50 wt% to obtain high-quality fibers, and if SiO ₂ is less than 35 wt%, it is difficult to obtain high-quality fibers with a diameter of 2 to 10 μm.
This is because if the temperature exceeds 100%, the viscosity of the melt increases, making it difficult to form fibers at the same fiberizing temperature as in the past. Al ₂ O ₃ combines with SiO ₂ and improves the heat resistance of fibers, but as the amount added increases, the appropriate fiberization temperature increases due to increased viscosity and devitrification temperature.
Must be 25wt% or less. Also, 10wt%
If it is less than 10~ _25wt %, especially 15~25wt% as _Al2O3 , it will be difficult to obtain heat resistance and high quality fiber.
A blending range of 20 wt% is preferred. It is preferable to reduce the amount of alkaline earth metal CaO as much as possible for the purpose of improving the heat resistance of the fiber, but from the viewpoint of preventing an increase in the viscosity of the melt, it is mainly
By increasing the amount of MgO (which, like CaO, has the effect of reducing viscosity, it does not become a negative factor for the heat resistance of the fibers, especially the dimensional stability of the fibers at high temperatures).
It is important that the total content of +CaO is 30wt% or more. In addition, since the CaO component does not have a positive effect on water erosion resistance and flexibility of the obtained fiber, the amount of CaO added must be 20 wt% or less. On the other hand, MgO is the opposite of CaO,
In order to improve the erosion resistance against water and the flexibility of the obtained fibers, it is necessary to incorporate 10 wt% or more, and it is a good idea to actively increase the amount of SiO ₂ and Al ₂ O ₃ . To ensure the required amount,
The upper limit is limited to 30wt% or less. In addition to coloring the fibers, Cr ₂ O ₃ has the function of improving the heat resistance of the fibers. as coloring
The amount of Cr ₂ O ₃ blended is 0.2wt% to 5wt%, but
In order to improve the heat resistance of the fiber in the form of a composite with SiO ₂ and Al ₂ O ₃ , it is preferable to mix it in an amount of 1 wt % or more. The upper limit of 10wt% is due to limitations caused by the raw materials used and by maintaining the blending amount of other necessary ingredients. The main components of rock wool, which is the object of the present invention and is excellent in color (design), heat resistance, mechanical properties, and water erosion resistance, have been described above, but FeO, S, and Na ₂ are unavoidable components. O,
The total content of K ₂ O and the like is preferably kept at 5 wt% or less in order not to impair the properties aimed at by the present invention. Furthermore, TiO ₂ and MnO as unavoidable trace components
has a slightly positive effect on the above-mentioned desired properties, so there is no problem in adding an appropriate amount. As the raw material whose composition can be adjusted at low cost within the composition range to obtain the target fiber of the present invention,
It is advisable to use ferrochrome slag, silica, and iron ore slag. Next, the raw materials and blending amounts will be explained in detail. The main component of ferrochrome slag, which is produced as a by-product when producing ferroalloy, is SiO ₂ 30~
35wt%, _{Al2O3 20} ~25wt%, MgO30~35wt%,
It can be obtained as a dark blue crushed stone block containing 0 to 5 wt% CaO, ₄ to 9 wt% _Cr2O3 , and 3 wt% or less of trace components (FeO, MnO, etc.). Silica is SiO ₂ 98
It is available as a natural crushed stone containing % or more. or,
Iron ore slag, which is the main raw material for conventional slag-based rock wool, is a by-product when producing pig iron, and its main components are SiO ₂ 30-35wt% and Al ₂ O ₃ 10-15wt%.
%, MgO 5-10 wt%, CaO 35-40 wt%, trace components (TiO ₂ , MnO, FeO, S, etc.) 5 wt% or less, and can be obtained as gray-black crushed stone blocks.
The fiber composition of the present invention can be obtained by mixing the raw material ore in a range of 5 to 90 wt% of chromium slag, 5 to 30 wt% of silica stone, and 0 to 90 wt% of iron ore slag. In addition, silicon manganese slag, basalt, diabase,
It is possible to incorporate small amounts of peridotite, dolomite, pyrite, silica brick, manganese silicate, and manganese oxide. When the above raw material composition is melted in a cupora furnace,
The size is 10 to 100 mm, when melted in an electric furnace,
A suitable size is 1-5 mm, and it can be melted at 1400-1600°C using coke fuel, carbon or molybdenum electrodes. Examples of the present invention will be described below. Example 1 Particle sizes 1 to 3 of the present invention shown as examples in Table 1
A raw material mixture (wt%) of mm is heated and melted in an electric furnace using a carbon electrode, and the melt is transferred to a plurality of internally cooled high-speed rotating bodies (φ=
10 inches, φ = 14 inches, rotation speed approximately 4000 rpm) and in a compressed air flow (approximately 100 m/sec), the fibers were collected. In addition, comparative examples (Comparative Example 1: Conventional slag-based rock wool, Comparative Example 2: Natural stone-based rock wool) are also shown in Table 1.
The raw material compositions shown in Table 2 were fiberized and collected in the same manner as in the example except that they were melted at the fiberization temperatures shown in Table 2. Table 2 shows the composition and properties of the rock wool of the present invention obtained as described above.

【table】

【table】

[Table] Example 2 Solid component consisting of each composition listed in Table 3
An aqueous slurry is prepared using 1000 g of a 4% by weight aqueous dispersion, the resulting aqueous slurry is made into paper using a last paper making machine in a laboratory, and dehydrated.The obtained paper board is then dehydrated and press-molded using a press forming machine. The obtained press molded product was dried at 230℃ using a hot air dryer.
time, followed by 2 hours drying at 150℃, specific gravity approximately 0.4,
A mineral fiberboard with a thickness of 12 mm was obtained. The obtained specific gravity,
Table 4 shows the bending strength, combustibility, and appearance.

【table】

【table】

[Table] Example 3 In an oxygen-blown Cupora furnace, the raw material compositions of Comparative Example 1 and Example 1-1 with a size of 10 to 100 mm were melted,
Multiple internally cooled high-speed rotating bodies (φ = 10 inches, φ
= 14 inches, approx. 4000 rpm) and in compressed air flow (approx.
Fiberization was performed at a speed of 100 m/sec). At this time, while spraying a water-soluble phenolic resin binder at a concentration of 20 wt% onto the fibers from around the high-speed rotating body, the resulting uncured phenolic resin binder (approximately 1.5 wt% attached in solid content) was collected. After pre-compression, the binder is cured in a caterpillar double conveyor thermosetting furnace (temperature 250℃, 10 minutes) to a bulk density of approximately 40Kg/m ³ and a thickness of 100mm.
We obtained lightweight rock wool products. Cut the above lightweight product into a size of length x width = 10 x 10 (cm), compress it to 50 mm using a Tensilon at a crosshead speed of 50 mm/min, leave it at 50 mm compression for 10 minutes, and then remove the weight. , thickness restoration rate=
h/h ₀ ×100 (%) was calculated (h: thickness after test,
h ₀ : Thickness before test), the obtained results are shown in Table 5.

[Table] From the above results, the lightweight product according to the present invention has a better recovery rate than the conventional product. <Effects> As described above in Examples 1 to 4, it is understood that the rock wool of the present invention has excellent performance in coloration (design), heat resistance, mechanical properties, and water erosion resistance. Ru. In addition, since inexpensive ferrochrome slag can be used, it can be produced industrially at low cost, which will expand the use of conventional rock wool-related products (ceiling panels, insulation materials, fireproof coatings), and new applications (asbestos substitutes). , ceramic wool substitute, agricultural field, etc.).

Claims (1)

[Claims] 1 Ferrochrome slag 5~90wt%, silica stone 5~
30wt%, iron ore slag 0-90wt%, SiO ₂ 35-50wt%, Al ₂ O ₃ 10-25wt%,
CaO2~20wt%, MgO5~30wt%, _{Cr2O30.2 ~}
10wt% as the main component and TiO ₂ as a trace component,
K ₂ O, Na ₂ O, MnO, FeO and S have a total maximum
Rock wool characterized by up to 5wt%.