JP2014511820A - Bio-soluble mineral wool fiber composition and mineral wool fiber - Google Patents

Abstract

A biosoluble mineral wool fiber composition and a biosoluble mineral wool fiber that can be further dissolved in a physiological medium.
The present invention provides a total content of SiO ₂ and Al ₂ O ₃ of 45 to 67% by weight, a total content of CaO, MgO, Na ₂ O and K ₂ O of 20.1 to 50% by weight, and others. A biosoluble mineral wool fiber composition having a higher biosolubility, while maintaining the thermal properties and physical properties of existing products, and a biodissolvable mineral produced using the same Provide wool fiber.
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Description

  The present invention relates to a biosoluble mineral wool fiber composition and mineral wool fibers.

Ceramic fibers, especially mineral wool (Mineral Wool / Rock Wool / asbestos), melt silicate ores such as basalt and andesite with high heat of 1,500 to 1,700 ° C., and high-speed air flow or high-speed rotation of spinner It is an artificial mineral fiber that is made into fiber using force. In general, widespread conventional mineral _wool, SiO 2 30 to 50 _{wt%, Al} 2 O 3 5 to 20 _{wt%, FeO + Fe 2 O 3} 1~15 wt%, CaO15～45 wt%, and MgO1~20 weight Is a product with excellent heat insulation, nonflammability and heat resistance, and is used for various purposes such as heat insulation, heat insulation, sound absorbing material, soundproofing material. Conventionally, most of the researches for producing mineral wool products with higher heat resistance by increasing MgO and Fe ₂ O ₃ and minimizing alkali metals with the above composition have recently been conducted. Then, discussion began about the possibility that the fine fibers of MMVF (Man-Made Vitreous Fibers) products could cause disease in the lungs if accumulated in the lungs for a long time via the respiratory organs.

  In general, although there is no direct evidence that ceramic fibers are associated with human illness, if crushed fibers are inhaled and accumulated in the lungs by respiration, they can cause harm to the human body. However, the potential for harm can be minimized by increasing solubility in physiological media and draining the accumulated fibers out of the body. At the same time as improving the biosolubility, the basic characteristics of the existing mineral wool composition, that is, fiberization must be possible, and the heat-resistant temperature reaches 1000-1100 ° C. during use. There has been extensive research on mineral wool compositions that have improved heat resistance and sufficient durability and thermal insulation properties.

On the other hand, it is known that by reducing the content of Al ₂ O ₃ , the KI (Numerical Index) value can be increased and the biosolubility can be enhanced.

However, there is a limit to increasing the KI value in the cupola (Cupola Furnace) melting process that uses silicate-based ores containing the composition of Al ₂ O ₃ unavoidably as a lump. Is only a difficult condition. Accordingly, there is a demand for the production of ceramic fibers having excellent biosolubility and water resistance even when the content of Al ₂ O ₃ is increased and the KI (Numerical Index) value is less than 30, and in some cases less than 20.

  Accordingly, an object of the present invention is to develop a mineral wool fiber composition and mineral wool fiber having characteristics that can be more effectively dissolved in a body fluid and easily discharged outside the body during absorption in the body, and the human body Is to minimize the impact on

Another object of the present invention is to provide a mineral wool fiber composition and mineral wool fiber that are excellent in raw solubility even when the content of Al ₂ O ₃ is increased and the KI value is low.

Another object of the present invention is to modify the composition of an existing mineral wool fiber to maintain the heat resistance, water resistance, thermal conductivity and restoring force, while maintaining the level of conventional mineral wool fibers, while maintaining a dissolution rate constant. An object of the present invention is to provide a mineral wool fiber composition that is 300 ng / cm ² · hr or more and has excellent biosolubility.

In order to achieve the above object, according to an aspect of the present invention, the total content of SiO ₂ and Al ₂ O ₃ is 45 to 67% by weight, and the total content of CaO, MgO, Na ₂ O and K ₂ O is 20 A biodissolvable mineral wool fiber composition comprising 1 to 50% by weight as well as other ingredients is provided.

Here, soluble mineral wool fiber composition of the present _invention, SiO 2 30-45 _{wt%, Al} 2 O 3 15 to 22 wt%, of iron oxide (FeO and _Fe 2 _{O 3,} comprising at least one ) 8-12 wt%, CaO 15-30 wt%, MgO 5-15 wt%, R ₂ O (including at least one of Na ₂ O and K ₂ O) 0.1-5 wt% Features.

Moreover, the biosoluble mineral wool fiber composition of the present invention comprises 17 to 20% by weight of Al ₂ O ₃ and 1 to ₂ % by weight of R ₂ O (including at least one of Na ₂ O and K ₂ O). It is characterized by including.

Further, the biosoluble mineral wool fiber composition of the present invention has a weight ratio of R ₂ O (including at least one of Na ₂ O and K ₂ O) / Al ₂ O ₃ of less than 0.5. Features.

The biosoluble mineral wool fiber composition of the present invention contains SiO ₂ and Al ₂ O ₃ as essential components, and contains three or more of Fe ₂ O ₃ , CaO, MgO, Na ₂ O and K ₂ O. A biosoluble mineral wool fiber composition comprising a dissolution rate constant for an artificial body fluid of 300 ng / cm ² · hr or more.

  The biosoluble mineral wool fiber composition of the present invention is characterized in that the difference between the fiber drawing viscosity temperature and the liquidus temperature is 80 ° C. or more.

  The biosoluble mineral wool fiber composition of the present invention is characterized in that the water resistance is 0.8% or less.

According to another aspect of the present invention, biodissolution containing SiO ₂ and Al ₂ O ₃ as essential, and including three or more of Fe ₂ O ₃ , FeO, CaO, MgO, Na ₂ O and K ₂ O. Mineral wool fiber composition, the content of Al ₂ O ₃ is 10% by weight or more, and the value of the formula [(Na ₂ O + K ₂ O + CaO + MgO) -2 × Al ₂ O ₃ ] (calculated in weight%) Is 20 or less, and a biosoluble mineral wool fiber composition having a dissolution rate constant with respect to an artificial body fluid of 300 ng / cm ² · hr or more is provided.

  According to another aspect of the present invention, a biosoluble mineral wool fiber produced using the biosoluble mineral wool fiber composition is provided.

  The biosoluble mineral wool fiber composition according to the present invention and the biosoluble mineral wool fiber produced by using the composition are significantly improved in the biosolubility in artificial body fluids by the modification and optimization of the composition, and are applied to the human lungs. Because it can be easily dissolved and removed during inhalation, it can greatly reduce the harmfulness to the human body, has excellent water resistance, and can be applied to existing Rotary processes. There is.

In addition, existing ceramic fibers exhibiting biodegradation performance have been artificially lowered in Al ₂ O ₃ content to increase the KI value and used relatively expensive raw materials with high purity. The composition of the invention exhibits a biodegradation performance equivalent to or better than that of existing products while using inexpensive raw materials containing some low-purity Al ₂ O _{3, so} that the range of raw materials used can be widened. There is an advantage that raw material costs can be reduced. Furthermore, it has excellent durability against moisture and exhibits a liquidus temperature and a fiber drawing viscosity temperature (log η3.0) lower than those of existing compositions, so that it can reduce costs by omitting energy required for fiberization. it can.

  Hereinafter, the biosoluble mineral wool fiber composition according to the present invention will be described in detail.

The present invention includes a biosoluble mineral wool fiber composition containing SiO ₂ and Al ₂ O ₃ as essential components, and containing three or more of Fe ₂ O ₃ , FeO, CaO, MgO, Na ₂ O and K ₂ O. I will provide a.

The biosoluble mineral wool fiber composition has a total content of SiO ₂ and Al ₂ O ₃ of 45 to 67% by weight, and a total content of CaO, MgO, Na ₂ O and K ₂ O of 20.1 to 50% by weight. As well as other residual components.

The raw soluble mineral wool fibers _composition, SiO 2 30-45 _{wt%, Al} 2 O 3 15 to 22 wt%, (including at least one FeO and _Fe 2 _{O 3)} iron oxide 8-12 wt%, CaO15~30 wt%, MgO5～15 wt%, and (at least one of Na ₂ O and _{K 2} O) _{R 2} O may include 0.1 to 5 wt%.

The present invention improves the biosolubility, but may cause other problems such as processability in the process, and does not add other oxides such as P ₂ O ₅ , SO _{3 and the} like. The present invention relates to a new biodissolvable mineral wool fiber composition in which the alumina content in the composition of the wool fiber is increased and the biosolubility is increased without a decrease in physical properties such as heat resistance through the combination of other oxides. The biosoluble mineral wool fiber composition according to the present invention will be described in more detail by the constituent components.

First, SiO ₂ which is the main component of mineral wool fiber plays the role of a network former that forms the basic structure of glass, and is contained at 30 to 45% by weight based on the total fiber composition. However, if the content is less than 30% by weight, the raw material cost is increased due to the relative increase of Al ₂ O ₃ and alkaline earth metal oxides or alkali metal oxides. The produced fiber is inferior in mechanical properties such as water resistance, and if the content exceeds 45% by weight, the melting temperature and the fiber drawing viscosity temperature of the molten composition increase. Is large, and fiberization is difficult.

Based on the network-forming oxide SiO ₂ , the water-resistant intermediate oxide Al ₂ O ₃ is added to lower the melting temperature and enter the network formed by the network-forming oxide, affecting the properties of the glass R ₂ O (Na ₂ O, K ₂ O), RO (CaO, MgO) or the like can be added as a modified oxide capable of exerting the following.

Al ₂ O ₃ which is an intermediate forming oxide can be contained in an amount of 10 wt% or more and 30 wt% or less, preferably 15 to 22 wt%. Particularly, the Al ₂ O ₃ may be contained at 17 to 20% by weight. Al ₂ O ₃ increases the viscosity of the glass melt near the liquidus, controls the crystallization of the glass, and improves the water resistance of the fiber. In particular, since an appropriate content of Al ₂ O _{3 has} a great influence on biosolubility and heat resistance, an appropriate composition with other compositions is required.

R ₂ O, which is a modified oxide in the fiber composition, acts as a melting agent that smoothly melts the glass by generating non-crosslinked oxygen in the glass. Here, R ₂ O may be an alkali metal oxide. For _example, Na 2 O, etc. _{K 2} O and the like. These two types of alkali metal oxides are components that greatly increase the biosolubility but adversely affect the water resistance of the fiber and also affect the collapse and restoration rate of the fiber. Therefore, in consideration of such biosolubility, water resistance and economical aspects, the content of Na ₂ O + K ₂ O in the fiber composition is preferably 0.1 to 5% by weight. In particular, it may be 1 to 2% by weight. Further, the weight ratio of R ₂ O (including at least one of Na ₂ O and K ₂ O) / Al ₂ O ₃ may be less than 0.5. If the weight ratio is 0.5 or more, the water resistance may decrease.

  RO, another modified oxide in the fiber composition, has the effect of increasing the biosolubility of the manufactured fiber and reducing the viscosity of the glass melt to aid fiberization. Here, RO may be an alkaline earth metal oxide. For example, CaO and MgO can be mentioned. Furthermore, there is an effect of improving the chemical durability which is lowered by the introduction of the alkali metal oxide. MgO is a composition that can reduce the temperature at which crystallization occurs and can provide more effects on biosolubility than CaO. Such CaO and MgO can be used in an amount of 15 to 30% by weight and 5 to 15% by weight, respectively, based on the fiber composition. In particular, the mixed usage amount of CaO and MgO is preferably 20 to 45% by weight with respect to the entire composition. If the content is less than 20% by weight, the melting temperature is rapidly increased. If the content exceeds 45% by weight, the difference between the fiberizing temperature and the crystallization temperature decreases, and the possibility of forming crystals increases during the fiberizing operation. The problem of difficulty can arise.

The biosoluble mineral wool fiber composition satisfying the above composition can be provided as a biosoluble mineral wool fiber having a dissolution rate constant with respect to an artificial body fluid of 300 ng / cm ² · hr or more.

  Further, the difference between the fiber drawing viscosity temperature and the liquidus temperature is 80 ° C. or more, and stable fiber production is possible without problems in the process such as spinner crystallization during fiberization.

Further, the content of Al ₂ O ₃ is 10% by weight or more, the value of the formula [(Na ₂ O + K ₂ O + CaO + MgO) −2 × Al ₂ O ₃ ] (calculated by weight%) is 20 or less, and artificial The dissolution rate constant for the body fluid may be 300 ng / cm ² · hr or more.

  The glass fiber according to the present invention can be manufactured by applying to a normal rotary process. The biodissolvable glass fiber according to the present invention thus manufactured has a fiber average diameter of 3 to 10 μm, modified without greatly changing the existing composition, has high solubility in artificial body fluids, and is water resistant. It is characterized by excellent properties.

  Hereinafter, the present invention will be described in more detail with reference to experimental examples and comparative experimental examples. However, these experimental examples and comparative experimental examples are illustrated to facilitate the understanding of the present invention, and do not limit the scope of the present invention.

Experimental Examples 1-6 and Comparative Experimental Examples 1-7
A mineral wool fiber composition having the components and contents shown in Table 2 (Experimental Example) and Table 3 (Comparative Experimental Example) below is manufactured, and the mineral wool fiber composition is melted in a smelter, Glass fibers were produced by a rotary process in which fibers were produced using a centrifugal force by dropping them on a spinner having a small hole in the spinner. Then, the physical property of the obtained glass fiber was measured with the following method. The results are shown in Table 2 and Table 3 below.

1. Dissolution rate constant ( _Kdis )
In order to evaluate the solubility of the fibers produced in the experimental example and the comparative experimental example in the body fluid, the dissolution rate constant of the artificial body fluid was determined by the following method. The in-vivo solubility of glass fiber is evaluated based on the solubility of the fiber in the artificial body fluid. After comparing the residual time in the body based on the solubility, the dissolution rate constant (K _dis ) is calculated using the following formula 1. Calculated. The results are shown in Tables 1 and 2 below.

In the formula, d ₀ is the initial average fiber diameter, ρ is the initial density of the fiber, M ₀ is the mass of the initial fiber, M is the mass of the fiber remaining after dissolution, and t is the experimental time.

  Table 1 below shows the content (g) of the composition components contained in 1 L of the artificial body fluid (Gamble solution) used for measuring the dissolution rate of the fiber.

The glass fibers of the experimental example and the comparative experimental example are placed between thin layers of a 0.2 μm polycarbonate membrane filter fixed on a plastic filter support, and the artificial body fluid is filtered through the filter. The dissolution rate was measured. During the experiment, the temperature of the artificial body fluid was continuously adjusted to 37 ° C., the flow rate was adjusted to 135 mL / day, and the pH was maintained at 4.5 ± 0.1 using HCl. In order to accurately measure fiber solubility over a long period of time, induced artificial body fluids filtered at specific intervals (1, 4, 7, 11, 14, 21 days) while the fibers are leaching for 21 days The dissolved ions were analyzed using coupled plasma spectroscopy (ICP, Inductively Coupled Plasma Spectrometer), and then the dissolution rate constant (K _dis ) was determined using Equation 1 using the results.

2. Hot load temperature A mineral wool pad of a certain standard is put in a heating vessel, and a load plate and a measuring rod adjusted so that the weight per unit cm ² is 5 g are installed on the heating pad. Read the height on a scale and record it. Next, the heating furnace is heated, and the temperature in the furnace is measured by a thermocouple. The position of the thermocouple is assumed to be 20 mm away from the center of the heating container in the vertical direction and 20 mm from the outer surface of the heating container in the horizontal direction. The heating and heating rate is about 5 ° C./min from the assumed value of the hot shrinkage temperature of the sample to a temperature lower by about 200 ° C., and thereafter about 3 ° C./min. The temperature inside the furnace and the height of the tip of the measuring rod are measured and recorded at intervals of 10 minutes from the start of heating. This is measured at 3 minute intervals near the assumed hot shrink temperature of the sample. In order to correct the extension of the measuring rod itself due to thermal expansion, the extension of the measuring rod with respect to the furnace temperature is measured in advance to create a correction curve, and based on this, the tip position of the measuring rod is corrected.

  The thickness shrinkage rate is obtained using the following formula 2.

A: Thickness (mm) of the sample when the load plate and the measuring rod are placed at room temperature
B: Thickness of the sample during heating (mm)

  The temperature at which the measured thickness shrinkage rate is 10% is measured to determine the hot load temperature.

3. Hot line shrinkage rate (1) Slow heating method
In order to measure the hot linear shrinkage of mineral wool fibers, the fibers were made into pad specimens, which were used in the experiments. First, 220g of fiber is sufficiently defibrated with 0.2% starch solution, then cast into a 300 / 300nm mold, the defibrated fibers are aligned to reduce surface deviation, and then drained from the bottom of the mold. Thus, a pad was manufactured. The pad is sufficiently dried in an oven at 100 ° C. for 24 hours or more, then cut into a size of 100 × 100 × 25 mm to produce a specimen, and a material having sufficient heat resistance such as platinum or ceramic is used. After the measurement points are displayed, the distance between the measurement points is carefully measured using vernier calipers, and then the pads are placed in a furnace and heated at 1000 ° C. for 24 hours, respectively. Allowed to cool slowly. The distance between the measurement points of the cooled specimen was measured, and the measurement results before and after the heat treatment were compared. The linear shrinkage rate was calculated using Equation 3 below.

Here, l ₀ represents the initial distance (mm) between the test piece marks, and l ₁ represents the length (mm) between the test piece marks after heating.

(2) Hot Surface method
In order to measure the hot-line shrinkage of mineral wool fibers, the fibers were produced in a pad-shaped specimen and then used in the experiment. First, 220g of fiber is sufficiently defibrated with 0.2% starch solution, then cast into a 300 / 300mm mold, the defibrated fibers are aligned to reduce surface deviation, and then drained from the bottom of the mold. Thus, a pad was manufactured. The pad is sufficiently dried in an oven at 100 ° C. for 24 hours or more, then cut into a size of 100 × 100 × 25 mm to produce a specimen, and a material having sufficient heat resistance such as platinum or ceramic is used. After the measurement points are displayed, the distance between the measurement points is carefully measured using a caliper, and then the pads are placed in a furnace heated at 1000 ° C. and heated for 1 hour, respectively. And cooled at room temperature. The distance between the measurement points of the cooled specimen was measured, and the measurement results before and after the heat treatment were compared. The linear shrinkage rate was calculated using Equation 3 above.

4). water resistant(%)
The DGG weight loss method was used. In this method, about 10 g of glass (360 to 400 μm) is boiled with 100 mL of distilled water for 5 hours, rapidly cooled and filtered, and then the filtrate is dried at 150 ° C., and the weight reduced is measured as a percentage. It is a method represented by.

5. Liquidus temperature (Liquidus temperature, ° C)
The liquidus temperature can be defined as the maximum temperature at which crystals in the glass can be produced, and was measured according to ASTM C829-81.

6). Fiber draw viscosity temperature (log η3.0, ° C)
The fiber drawing viscosity temperature is obtained by measuring a temperature at which the viscosity of the glass melt becomes approximately 1000 poise. The fiberizing operation is performed near this temperature.

As shown in Experimental Examples 1 to 6 in Table 2, in the composition region of the present invention, although the KI value is as low as 20 or less due to the high content of aluminum oxide, the dissolution rate constant value is 300 ng / cm ² ···. More than hr, specifically, since the dissolution rate constant value shows a value of 305 to 417 ng / cm ² · hr, it can be seen that the raw solubility is excellent. This means the collapse of common sense that the biosolubility is excellent when the value of KI is 30 or more.

In the case of Comparative Experimental Example 1, it can be seen that the content of SiO ₂ is slightly high, the content of MgO is low, and the biosolubility is relatively inferior.

In the case of Comparative Example 2, high and the content of SiO _2, relative dissolution rate helps constant value indicates a relatively low dissolution rate constant value by content reduction such as CaO, fiber draw viscosity by high SiO ₂ content It can be seen that the temperature increases. This can extend the life of the spinner with a low fiber drawing viscosity temperature, and lower the possibility of precipitation of crystals, which is a problem during the fiber production process, to enable stable fiber production. From the point of view, it acts as a drawback.

Comparative Experimental Examples 3 and 4 are mineral wool fiber compositions having a low content of SiO ₂ and Al ₂ O ₃ and have relatively high dissolution rate constant values, but high values of RO and R ₂ O. The water resistance decreases depending on the content, which causes an increase in raw material costs.

In Comparative Example 5, the content of Al ₂ O ₃ is 23.42% by weight, and it can be seen that the content is significantly increased and the solubility is rapidly deteriorated. In addition, the difference between the fiber drawing viscosity temperature (log η3.0) and the liquidus temperature is less than 80 ° C., that is, 8 ° C., and the glass composition may crystallize in the spinner, which may adversely affect the fiber process. is there.

In Comparative Experimental Example 6, it is presumed that the solubility rapidly deteriorates due to special conditions in which the content of Fe ₂ O ₃ is small and the content of R ₂ O exceeds 5% by weight.

In Comparative Experimental Example 7, it can be seen that R ₂ O / Al ₂ O ₃ > 0.5 or more in the mineral wool fiber composition and the water resistance sharply decreases.

  Although the mineral wool fiber composition according to the present invention does not give a large change in physical properties by appropriately changing the content of each oxide, a fiber excellent in biosolubility and water resistance can be produced. It shows the characteristics that the drawing viscosity temperature (log η3.0) and the liquid phase temperature are low, and the difference between the log η 3.0 and the liquid phase temperature is 80 ° C. or more in the fiberizing temperature region, and the spinner is used during fiberization. Stable fiber production is possible without any problems in the process such as crystallization of the material.

  Features, structures, effects, and the like described in the above-described embodiments are included in at least one embodiment of the present invention, and are not necessarily limited to only one embodiment. As a result, the features, structures, effects, etc., exemplified in each embodiment can be combined or modified with respect to another embodiment by a person having ordinary knowledge in the field to which the embodiment belongs. Therefore, the contents relating to the combinations and modifications should be construed as being included in the scope of the present invention.

  The biodissolvable mineral wool fiber composition according to the present invention and the biodissolvable mineral wool fiber produced using the composition are significantly improved in biosolubility in artificial body fluids by modification and optimization of the composition to the lungs of the human body. It can be easily dissolved and removed even when inhaled, so it can greatly reduce the harmfulness to the human body and has excellent water resistance and can be applied to the existing rotary process. It has advantages and is industrially useful because it can reduce raw material costs and save energy.

Claims (9)

The total content of 45-67 wt% of SiO ₂ and _Al 2 _{O 3,} including CaO, MgO, the total content of 20.1 to 50 wt% of Na ₂ O and _{K 2} O, as well as other components, raw solubility Mineral wool fiber composition. SiO ₂ 30-45 _{wt%, Al} 2 O 3 15 to 22 wt%, iron oxide (including at least one FeO and _Fe 2 _{O 3) 8~12} wt%, CaO15～30 wt%, MgO5～15 weight %, and _R (at least one of Na ₂ O and _{K 2} O) ₂ O _0.1~5% by weight of the total composition, raw soluble mineral wool fiber composition of claim 1. The _Al 2 _O 3 17 to 20 wt%, and _R 2 O (Na ₂ comprising at least one O and _{K 2} O) containing 1 to 2 wt%, raw soluble mineral wool fibers according to claim 1 Composition. R ₂ (including Na least one ₂ O and _{K 2} O) O / weight ratio of _Al 2 _{O 3} is less than 0.5, Raw soluble mineral wool fiber composition of claim 1. The biosoluble mineral wool fiber composition according to claim 1, wherein the dissolution rate constant for the artificial body fluid is 300 ng / cm ² · hr or more.   The biosoluble mineral wool fiber composition according to claim 1, wherein the difference between the fiber drawing viscosity temperature and the liquidus temperature is 80 ° C or higher.   The biosoluble mineral wool fiber composition according to claim 1, wherein the water resistance is 0.8% or less. A biosoluble mineral wool fiber composition comprising SiO ₂ and Al ₂ O ₃ as essential, and comprising three or more of Fe ₂ O ₃ , FeO, CaO, MgO, Na ₂ O and K ₂ O,
The content of Al ₂ O ₃ is 10% by weight or more, the value of the formula [(Na ₂ O + K ₂ O + CaO + MgO) −2 × Al ₂ O ₃ ] (calculated by weight%) is 20 or less, and dissolution in artificial body fluids A biosoluble mineral wool fiber composition having a rate constant of 300 ng / cm ² · hr or more. The biosoluble mineral wool fiber manufactured using the biosoluble mineral wool fiber composition of any one of Claims 1-8.