WO2014171562A1 - Composition pour produire de la fibre de laine minérale remarquablement soluble dans des fluides corporels et fibre de laine minérale produite à partir de celle-ci - Google Patents

Composition pour produire de la fibre de laine minérale remarquablement soluble dans des fluides corporels et fibre de laine minérale produite à partir de celle-ci Download PDF

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Publication number
WO2014171562A1
WO2014171562A1 PCT/KR2013/003161 KR2013003161W WO2014171562A1 WO 2014171562 A1 WO2014171562 A1 WO 2014171562A1 KR 2013003161 W KR2013003161 W KR 2013003161W WO 2014171562 A1 WO2014171562 A1 WO 2014171562A1
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WIPO (PCT)
Prior art keywords
mineral wool
composition
fiber
fibers
wool fibre
Prior art date
Application number
PCT/KR2013/003161
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English (en)
Korean (ko)
Inventor
우봉기
이병원
이남수
허균용
정원식
주석재
강성호
Original Assignee
주식회사 케이씨씨
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Application filed by 주식회사 케이씨씨 filed Critical 주식회사 케이씨씨
Priority to JP2016507871A priority Critical patent/JP6433981B2/ja
Priority to PCT/KR2013/003161 priority patent/WO2014171562A1/fr
Publication of WO2014171562A1 publication Critical patent/WO2014171562A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2213/00—Glass fibres or filaments
    • C03C2213/02—Biodegradable glass fibres

Definitions

  • the present invention relates to a composition for producing mineral wool fibers excellent in solubility in body fluids and mineral wool fibers prepared therefrom, and more specifically, SiO 2 29-42 wt%, Al 2 O 3 17-23 wt%, FeO 3.6 ⁇ 7.2 wt%, Fe 2 O 3 0.1-4.8 wt%, CaO 18-28 wt%, MgO 7-13 wt%, Na 2 O + K 2 O 1-5 wt%
  • the present invention relates to a composition for preparing a mineral wool fiber and a mineral wool fiber produced therefrom, which can be particularly suitably used as an inorganic fiber thermal insulator as well as having excellent solubility in water) and exhibiting high heat resistance and water resistance, low thermal conductivity, and the like.
  • Mineral wool also called 'rock wool'
  • general mineral wool commonly referred to as stone wool or rock wool
  • ceiling wool mineral wool called bale wool.
  • General mineral wool is produced by processing in various forms such as mat, board, pipe cover, etc. by using an organic binder such as phenolic resin. Used as the main material.
  • Typical characteristics that mineral wool should have include high heat resistance, water resistance, and low thermal conductivity.
  • heat resistance it indicates how much mineral wool maintains its role as a heat insulator under high temperature conditions such as fire.
  • water resistance since the mineral wool fiber has an open-cell shape, external moisture such as rain or snow may penetrate into the mineral wool, or condensation may occur inside the mineral wool due to temperature difference, thereby reducing the thermal conductivity. Therefore, it shows the characteristic of how effectively this moisture is blocked.
  • thermal conductivity the most basic property of a heat insulating material indicates how well the heat is blocked when in contact with the heat insulating material. All three are common requirements for inorganic fiber insulation.
  • Mineral wool is melted by applying high temperature heat to silicate ore and dropping it onto the surface of the spinner, which is centrifugal rotation. It is usually prepared in a fibrous manner.
  • the heat resistance is very excellent compared to other organic insulating materials, and has an advantage of showing excellent safety in an emergency situation such as a fire.
  • the fibrous dust scatters and enters the body through the respiratory tract, which may affect the human body. Therefore, many studies have been conducted on how to efficiently discharge the mineral wool fibers into the body. That is, by designing a specific composition, when the fiber is in contact with human body fluids within the lungs, it can be easily decomposed and dissolved in the body fluids, thereby minimizing the possibility of harmful mineral fibers.
  • This biodegradability is related to how efficiently the inorganic fiber invades the human body through the respiratory tract, so that it can be decomposed and released into the body.
  • the mechanism proceeds differently depending on the pH.
  • Inorganic fibers entering the lungs through the respiratory tract are basically exposed to neutral (pH 7.4) bodily fluids. When contacted with these neutral bodily fluids, the reaction rate is slow, but the dissolution of network formers including SiO 2 The reaction continues and the adsorption of water on the surface of the inorganic fiber becomes easier due to the formation of OH-group on the surface of the fiber.
  • the body fluid inside the macrophage which plays a role in the treatment of external foreign matter inside the alveoli, is weakly acidic (pH 4.5), in which case ion exchange occurs predominantly to make the alkaline earth ions rich in aqueous solution.
  • pH 4.5 weakly acidic
  • fiber weight reduction in this process tends to be controlled by diffusion of ions.
  • in vitro testing that simulates this process is preferably used.
  • the flow-through method is used to reproduce the situation in which the fluid is continuously supplied.
  • the water resistance may also be lowered, and may be vulnerable to the moisture encountered in the general environment, so it is essential to find a composition having both adequate water resistance and biodegradability for the body fluids.
  • high heat resistance and heat insulation which are basic properties of mineral wool fibers, are essential elements.
  • the present invention is to solve the problems of the prior art as described above, not only has excellent solubility in body fluids, but also exhibits high heat resistance and water resistance, low thermal conductivity, and the like, and thus can be particularly suitably used as an inorganic fiber insulation material. It is a technical problem to provide a composition for preparing mineral wool fibers and mineral wool fibers prepared therefrom even when it is necessary to contain Al 2 O 3 essentially.
  • the present invention to achieve the above technical problem, SiO 2 29 ⁇ 42 wt%, Al 2 O 3 17 ⁇ 23 wt%, FeO 3.6 ⁇ 7.2 wt%, Fe 2 O 3 0.1 ⁇ 4.8 wt%, CaO 18 ⁇ 28 wt It provides a composition for producing mineral wool fibers, comprising%, MgO 7 ⁇ 13 wt% and Na 2 O + K 2 O 1 ⁇ 5 wt%.
  • the Redox value [FeO wt% / (FeO wt% + Fe 2 O 3 wt%)] of iron in the composition for producing mineral wool fibers is 0.6 or more.
  • a biodegradable mineral wool fiber for body fluid characterized in that it is prepared from the composition for producing mineral wool fibers of the present invention.
  • an insulation product comprising the mineral wool fibers of the present invention.
  • a raw material configuration phase for a predetermined amount or more of Al 2 O 3 should be essentially free of Even suitable mineral wool fibers can be produced using conventional fiberizers.
  • SiO 2 serves to form a basic skeleton of the glass as a network former oxide.
  • SiO 2 is included 29 to 42 wt% (wt%), more preferably 30 to 38 wt%. If the content of SiO 2 in the composition is less than 29 wt%, the physical properties of the mineral wool fibers prepared from the composition are lowered. If the SiO 2 content is more than 42 wt%, the viscosity of the composition is increased, resulting in a coarse fiber and a large fiber diameter.
  • Al 2 O 3 is an intermediate oxide, the content of which affects the biodegradability of the composition. Depending on the coordination number of Al 3+ , some may replace the role of SiO 2 or may act as a modifier oxide, which may vary depending on the content of other modified oxides.
  • the composition for producing mineral wool fibers of the present invention contains Al 2 O 3 17-23 wt%, more preferably 17-21 wt%. If the Al 2 O 3 content in the composition is less than 17wt% or more than 23wt%, biodegradability may be lowered.
  • the main raw material as Al 2 O 3 content is by using the about 30% for about anorthosite (Anorthite) is more than 35% of the injected raw material mixed-composition in Al 2 O 3 content of the above Can be implemented at the level.
  • iron FeO and Fe 2 O 3
  • the composition for producing mineral wool fibers of the present invention contains FeO of 3.6 to 7.2 wt%, Fe 2 O 3 0.1 to 4.8 wt%, more preferably 4.5 to 7.2 wt% FeO, 0.1 to 4.2 Fe 2 O 3 wt% is included. If the content of FeO and Fe 2 O 3 in the composition is less than the above-mentioned level, there is a problem that the fiber shrinkage is increased or the thermal stability is lowered at high temperatures, and if it exceeds this, it causes an overload of the fiber manufacturing equipment to reduce durability. Occurs.
  • the Redox value [FeO wt% / (FeO wt% + Fe 2 O 3 wt%)] of iron in the composition represents the ratio of FeO content to the total iron content. Therefore, the higher the Redox value, the higher the FeO content, which means that the ratio of Fe 2+ in the total iron in the fiber is higher than Fe 3+ .
  • FeO is oxidized to Fe 2 O 3 (that is, Fe 2+ is oxidized to Fe 3+ ), resulting in crystallization behavior of the fiber surface and the inside.
  • the nanoscale thin periclase (MgO crystal) crystal phase is generated, thereby increasing the physical and chemical durability to improve the heat resistance of the fiber.
  • the Redox value of iron in the composition is particularly preferable in terms of further improving the heat resistance of the fiber.
  • this thermal stability is essential for mineral wool products that can be exposed to high temperatures instantaneously, such as in a fire situation.
  • the Redox value of iron in the composition is at least 0.6 (eg, at least 0.6 and less than 1).
  • High levels of iron Redox can be obtained by melting the raw materials using an electric furnace using a graphite electrode.
  • the continuous oxidation of graphite leads to the formation of a reducing atmosphere in the furnace, which can raise the redox of iron.
  • the existing mineral wool is mainly melted in Cupola (Cupola), which uses a fossil fuel cokes (Cokes) as a fuel has a disadvantage of generating a lot of greenhouse gases such as CO 2 when melting.
  • Cupola Cupola
  • Cokes fossil fuel cokes
  • it is easy to control the temperature in the furnace has a variety of advantages such as to improve the homogeneity of the melt to stabilize the fiber quality.
  • CaO and MgO which are alkaline earth metal oxides, may act as a flux as modifier oxides and increase chemical durability.
  • the composition for producing mineral wool fibers of the present invention contains 18 to 28 wt% of CaO, 7 to 13 wt% of MgO, more preferably 20 to 25 wt% of CaO and 8 to 13 wt% of MgO. If the content of CaO and MgO in the composition is less than the above-mentioned level, there is a problem in that the melting temperature is increased to increase the heat consumption required for melting. This leads to deterioration of fiber quality, such as an increase in shot content.
  • mineral wool fibers for preparing the compositions of the present invention includes the 1 ⁇ 5 wt% to the total amount of Na 2 O + K 2 O, and more preferably contains 1.5 to 4.0 wt% the Na 2 O + K 2 O.
  • the content of each of Na 2 O and K 2 O may be freely selected within a range satisfying the above range of total amounts. That is, the content of each of Na 2 O and K 2 O is in the range of 0 to 5 wt%, with the total amount being 1 to 5 wt%.
  • composition for preparing mineral wool fibers according to the present invention may include components such as TiO 2 , SO 3 , and P 2 O 5 as impurities depending on the raw materials used, but the amount thereof may be 1 wt% or less in the total composition. If so, it does not affect the thermal properties or physical properties of the fiber.
  • the method for producing the composition for producing mineral wool fibers according to the present invention can be prepared by a method for producing a composition for a conventional mineral wool fiber.
  • it may be prepared by the same method as the electric melting method, but is not limited thereto.
  • the raw material may be melted by using an electric furnace of an electric resistance method using a graphite electrode.
  • the viscosity range required for the fiber production composition is preferably 20 to 100 poise.
  • the viscosity of the melt is a function of temperature and the corresponding composition, and the viscosity of the melt having the same composition will depend on the temperature. When the temperature of the melt is high during the fiberization, the viscosity is lowered. On the contrary, when the fiberization temperature is low, the viscosity is increased to affect the fiberization.
  • the length of the fiber produced is short and thin as well as a lot of fine unfiberized particles (shots) to produce a low fiberization yield, even if the viscosity is too high diameter of the fiber The problem arises that this large fiber is formed and the coarse unfiberized shots are increased.
  • a biodegradable mineral wool fiber for body fluid characterized in that it is prepared from the composition for producing mineral wool fibers of the present invention as described above.
  • the mineral wool fiber of the present invention preferably has a dissolution rate constant of 1) at least 300 ng / cm 2 ⁇ hr, more preferably at least 350 ng / cm 2 ⁇ hr, for artificial body fluids having a pH of 4.5; 1,000 ° C / 1 hour retention) is 5% or less, more preferably 4% or less, 3) the water loss test (100 ° C / 5 hour retention) is 1% or less, more preferably 0.7% or less, and 4 ) Satisfies one or more of the conditions that the thermal conductivity is 0.037 W / mK or less, more preferably 0.036 W / mK or less, more preferably two or more, even more preferably three or more, most preferably these Satisfies all conditions
  • an insulation product comprising the mineral wool fibers of the present invention as described above.
  • the specific form of the insulation product for example, plate, board, blanket, pipe cover, or any other form is possible.
  • the heat insulating material product of the present invention can be strengthened between the fibers by spraying the organic binder between the fibers and then cured.
  • the dissolution rate constant (K dis ) value, the Redox value, the heating contraction rate, the loss rate and the thermal conductivity during the water resistance test for the artificial body fluid were measured as follows. It was calculated and shown in Table 3 (Example) and Table 4 (Comparative Example).
  • the solubility in artificial body fluid was obtained by the following method.
  • the biodegradability of the ceramic fiber in the body was evaluated based on the solubility of the fiber in the artificial body fluid, and after comparing the residence time based on the solubility, the dissolution rate constant (K dis ) was calculated using the following equation.
  • d 0 is the initial average fiber diameter ( ⁇ m)
  • ⁇ is the initial density of the fiber (g / cm 3 )
  • M 0 is the mass of the initial fiber (mg)
  • M is the mass of the remaining dissolved fiber (mg)
  • t represents the experiment time (hr).
  • the fiber to be measured was placed between thin layers between 0.2 ⁇ m polycarbonate membrane filters fixed with a plastic filter support, and the dissolution rate was measured by filtering artificial fluid between the filters.
  • the temperature of the artificial fluid was continuously adjusted to 37 ° C. and the flow rate was 135 mL / day, and the pH was maintained at 4.5 ⁇ 0.1 using hydrochloric acid (HCl, 35.0 to 37.0%).
  • the artificial fluids filtered at specific intervals (1, 4, 7, 11, 14, and 21 days) were subjected to inductively coupled plasma analysis (ICP, After dissolving the ions using an Inductively Coupled Plasma Spectrometer, the dissolution rate constant (K dis ) was obtained using the above equation.
  • the content (g) of the composition contained in 1 L of the artificial body fluid used to measure the dissolution rate of the fiber was as follows.
  • the pad was manufactured with the prepared mineral wool and measured by the Hot Furnace Method. After preparing a pad of a predetermined size, it was cut to a size of 50 * 50mm, and the width and length of the cut pad were measured using a vernier caliper. The elevator furnace was then set to 1,000 ° C, and when the elevator furnace reached the set temperature, the pads were placed in the elevator furnace and held for 1 hour. After 1 hour, the pads were removed and the width and length were measured. The bow rate was calculated from the following equation.
  • the prepared mineral wool fibers were molded into a plate to prepare a sample (300 ⁇ 300 ⁇ 20 mm). About this sample, the thermal conductivity which finally converges by the heat flow meter method was measured by making the temperature difference of an average temperature of 20 degreeC, an upper plate, and a lower plate into 28 degreeC.
  • the mineral wool prepared according to the present invention exhibits excellent biodegradability with a K dis value of 300 ng / cm 2 h or more, and at the same time, excellent heat resistance (that is, low shrinkage) and excellent water resistance (ie , Low loss rate) and satisfactory level of thermal conductivity.
  • Comparative Examples 1 and 2 showed poor heat resistance (ie, high heat shrinkage), and Comparative Example 3 showed a high thermal conductivity due to an increase in the shot content with a large diameter inside the fiber due to the increased viscosity, and Comparative Example 4 There was a problem in heat resistance and water resistance, and the viscosity was so low that when the molten metal hit the spinner, it could not be fibrized and splashed, so the content of fine shot increased and the thermal conductivity was increased.
  • Example 6 showed low biodegradability.
  • Comparative Example 7 exhibited problems such as decrease in thermal conductivity, heat resistance, and decrease in water resistance due to a decrease in viscosity.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Glass Compositions (AREA)

Abstract

La présente invention concerne une composition servant à produire des fibres de laine minérale, qui est remarquablement soluble dans des fluides corporels, et une fibre de laine minérale produite à partir de celle-ci, et qui concerne plus précisément : une composition de production de fibre de laine minérale contenant de 29 % à 42 % en poids de SiO2, de 17 % à 23 % en poids d'Al2O3, de 3,6 % à 7,2 % en poids de FeO, de 0,1 % à 4,8 % en poids de Fe2O3, de 18 % à 28 % en poids de CaO, de 7 % à 13 % en poids de MgO et de 1 % à 5 % en poids de Na2O+K2O, et qui non seulement est remarquablement soluble dans des fluides corporels (fluides corporels humains) mais qui montre aussi, entre autres, un niveau élevé de résistance thermique et de résistance à l'eau et une faible conductivité thermique, et qui est particulièrement bien adaptée pour un emploi en tant que matériau inorganique d'isolation thermique par des fibres ; et la fibre de laine minérale produite à partir de la composition.
PCT/KR2013/003161 2013-04-15 2013-04-15 Composition pour produire de la fibre de laine minérale remarquablement soluble dans des fluides corporels et fibre de laine minérale produite à partir de celle-ci WO2014171562A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2016507871A JP6433981B2 (ja) 2013-04-15 2013-04-15 体液に対する溶解性に優れたミネラルウール繊維製造用組成物及びそれにより製造されたミネラルウール繊維
PCT/KR2013/003161 WO2014171562A1 (fr) 2013-04-15 2013-04-15 Composition pour produire de la fibre de laine minérale remarquablement soluble dans des fluides corporels et fibre de laine minérale produite à partir de celle-ci

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/KR2013/003161 WO2014171562A1 (fr) 2013-04-15 2013-04-15 Composition pour produire de la fibre de laine minérale remarquablement soluble dans des fluides corporels et fibre de laine minérale produite à partir de celle-ci

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WO2014171562A1 true WO2014171562A1 (fr) 2014-10-23

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180063280A (ko) * 2015-10-08 2018-06-11 쌩-고벵 이조베르 광물 섬유
WO2018154076A1 (fr) * 2017-02-24 2018-08-30 Knauf Insulation Sprl Laine minérale
CN114174235A (zh) * 2019-07-25 2022-03-11 霓佳斯株式会社 无机纤维、无机纤维制品、无机纤维制品的制造方法、无机纤维制造用组合物和无机纤维的制造方法

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WO1997030002A1 (fr) * 1996-02-16 1997-08-21 Partek Paroc Oy Ab Fibre minerale
US5935886A (en) * 1994-11-08 1999-08-10 Rockwool International A/S Man-made vitreous fibres
US20080277818A1 (en) * 2006-05-19 2008-11-13 Kibol Viktor F Composition and Method for Producing Continuous Basalt Fibre
US20110172077A1 (en) * 2009-11-18 2011-07-14 Albert Lewis High temperature glass fiber insulation
KR20120052288A (ko) * 2009-07-13 2012-05-23 락울 인터내셔날 에이/에스 광물 섬유 및 이의 용도
KR20120116235A (ko) * 2011-04-12 2012-10-22 주식회사 케이씨씨 생용해성 미네랄울 섬유 조성물 및 미네랄울 섬유

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US6067821A (en) * 1996-10-07 2000-05-30 Owens Corning Fiberglas Technology, Inc. Process for making mineral wool fibers from lumps of uncalcined raw bauxite
EP1037861B1 (fr) * 1997-12-02 2007-11-28 Rockwool International A/S Briquettes pour la production de fibres minerales et leur utilisation
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US5935886A (en) * 1994-11-08 1999-08-10 Rockwool International A/S Man-made vitreous fibres
WO1997030002A1 (fr) * 1996-02-16 1997-08-21 Partek Paroc Oy Ab Fibre minerale
US20080277818A1 (en) * 2006-05-19 2008-11-13 Kibol Viktor F Composition and Method for Producing Continuous Basalt Fibre
KR20120052288A (ko) * 2009-07-13 2012-05-23 락울 인터내셔날 에이/에스 광물 섬유 및 이의 용도
US20110172077A1 (en) * 2009-11-18 2011-07-14 Albert Lewis High temperature glass fiber insulation
KR20120116235A (ko) * 2011-04-12 2012-10-22 주식회사 케이씨씨 생용해성 미네랄울 섬유 조성물 및 미네랄울 섬유

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180063280A (ko) * 2015-10-08 2018-06-11 쌩-고벵 이조베르 광물 섬유
JP2018531204A (ja) * 2015-10-08 2018-10-25 サン−ゴバン イゾベール ミネラルファイバー
KR102654081B1 (ko) * 2015-10-08 2024-04-04 쌩-고벵 이조베르 광물 섬유
WO2018154076A1 (fr) * 2017-02-24 2018-08-30 Knauf Insulation Sprl Laine minérale
CN110520388A (zh) * 2017-02-24 2019-11-29 可耐福保温有限公司 矿物棉
US11192819B2 (en) 2017-02-24 2021-12-07 Knauf Insulation Sprl Mineral wool
US11685687B2 (en) 2017-02-24 2023-06-27 Knauf Insulation Sprl Mineral wool
CN114174235A (zh) * 2019-07-25 2022-03-11 霓佳斯株式会社 无机纤维、无机纤维制品、无机纤维制品的制造方法、无机纤维制造用组合物和无机纤维的制造方法
CN114174235B (zh) * 2019-07-25 2023-08-29 霓佳斯株式会社 无机纤维、无机纤维制品、无机纤维制品的制造方法、无机纤维制造用组合物和无机纤维的制造方法

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JP6433981B2 (ja) 2018-12-05

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