JP2020059955A - Mineral wool - Google Patents

Abstract

To provide mineral wool excellent in processability while including a resin other than a polycondensation product of formaldehyde and a monomer different therefrom.SOLUTION: Mineral wool includes inorganic fibers and a binder adhered onto the inorganic fibers. The binder includes a water-soluble resin and urea. The water-soluble resin is a resin other than a polycondensation product of formaldehyde and a monomer different therefrom. A content of the urea is 0.3-50.0 mass% based on a mass of the binder.SELECTED DRAWING: None

Description

  The present invention relates to mineral wool.

  In mineral wool such as glass wool or rock wool, a binder (binder for mineral wool) is used to bond the fibers. For example, Patent Document 1 discloses a mineral fiber, particularly a rock or a glass, which contains a phenol resin, urea, a resin crosslinking catalyst and, if necessary, an additive, and the catalyst is a mixture of ammonium sulfamate and ammonium sulfate. A sizing composition for fibers is disclosed. Further, Patent Document 2 discloses a flame-retardant heat and / or acoustic insulation product based on mineral wool, particularly rock wool or glass wool, and an organic binder, and contains a carboxylic acid metal salt as a flame retardant. A product characterized by the above is disclosed.

Japanese Patent Publication No. 2010-513736 Special table 2012-514141 gazette

  Conventionally, a binder containing a polycondensation product of formaldehyde and another monomer (for example, a phenol resin) as a main component has been used for mineral wool. Due to concerns about formaldehyde emitted from the polycondensate, it may be desired to use other resins depending on the application. However, mineral wool using a binder whose main component is a resin other than a polycondensation product of formaldehyde and other monomers has a room for improvement in processability such that uncut residue easily occurs when cut. .

  Therefore, a main object of the present invention is to provide a mineral wool having excellent processability while containing a resin other than a polycondensate of formaldehyde and another monomer.

  One aspect of the present invention includes an inorganic fiber and a binder attached to the inorganic fiber, the binder includes a water-soluble resin and urea, and the water-soluble resin is polycondensable with formaldehyde and formaldehyde. The present invention relates to a mineral wool which is a resin other than a polycondensate of a raw material containing a different monomer. The content of urea may be 0.3 to 50.0 mass% with respect to the mass of the binder.

  The water-soluble resin may be a polyvinyl alcohol resin, a (meth) acrylic resin, or a polyvinyl alcohol resin.

  The content of urea may be 3.0 to 15.0 mass% with respect to the mass of the binder.

  The amount of the adhered binder may be 1.0 to 15.0 parts by mass with respect to 100 parts by mass of mineral wool.

  According to one aspect of the present invention, it is possible to provide a mineral wool having excellent processability while containing a resin other than a polycondensate of formaldehyde and another monomer.

  Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  The mineral wool according to the present embodiment includes inorganic fibers and a binder attached to the inorganic fibers, and the binder contains a water-soluble resin and urea. The water-soluble resin is a resin other than a polycondensate of formaldehyde and other monomers. In the mineral wool, the content of urea may be 0.3 to 50.0 mass% with respect to the mass of the binder. The mineral wool according to the present embodiment is excellent in processability, and thus can be used as a heat insulating material for building materials (particularly, a heat insulating material arranged inside a building material such as inside a wall or ceiling).

  Mineral wool is a wool-like fiber aggregate containing inorganic fibers, and the inorganic fibers are bound to each other via a binder. The inorganic fiber may be glass fiber, blast furnace slag containing silicic acid content and lime content as main components, or fiber made of rock or the like. Mineral wool containing glass fibers as inorganic fibers is generally called glass wool. Mineral wool containing, as inorganic fibers, blast furnace slag containing silicic acid content and lime content as main components, or fibers made from rocks or the like is generally called rock wool. The mineral wool is preferably glass wool containing glass fibers from the viewpoint of further excellent heat insulation and sound absorption.

The density of mineral wool may be 10 to 250 kg / m ³ . The density and thickness of mineral wool can be measured according to JIS A 9521: 2014. The density here is an apparent density based on a volume including a void volume. The mineral wool may be mat-shaped, and the thickness of the mat-shaped mineral wool may be, for example, 10 to 300 mm.

  The fiber diameter of the inorganic fibers constituting the mineral wool (including the thickness of the binder) is preferably 3.0 to 10.0 μm, 3.5 to 8.0 μm, or 4.0 to 7.0 μm. The fiber diameter here is a value measured by the micronaire method. The fiber length of the inorganic fibers constituting the mineral wool is preferably 2.0 to 500.0 mm.

  In the mineral wool according to this embodiment, the binder contains a water-soluble resin. The binder is formed by heating a composition (binder composition) containing at least a water-soluble resin and an aqueous medium. Here, water-soluble is defined as a substance that dissolves 0.1 g or more in 100 g of water at 25 ° C.

  The water-soluble resin is a resin other than a polycondensate of formaldehyde and another monomer. That is, the water-soluble resin does not contain a structural unit derived from formaldehyde. Examples of other monomers include phenol compounds and amine compounds such as urea, melamine and dicyandiamide. Examples of polycondensates of formaldehyde and other monomers include polycondensates of phenol compounds or amine compounds (for example, urea, melamine, dicyandiamide). Specific examples of the polycondensate include phenol resin, urea resin, and melamine resin (melamine-formaldehyde resin).

  Specific examples of the water-soluble resin include polyvinyl alcohol resin, (meth) acrylic resin, and polysaccharides. In the present specification, “(meth) acryl” means “acryl” or “methacryl” corresponding thereto.

  The water-soluble resin may be a polyvinyl alcohol resin or a (meth) acrylic resin from the viewpoint that the workability is further improved, and the workability is further improved, and odor is generated in the drying step. The polyvinyl alcohol resin may be used from the standpoint that the above is further suppressed and the drying workability is further improved. At least a part of the water-soluble resin may be crosslinked.

  When the binder contains a polyvinyl alcohol resin as the water-soluble resin, the binder may contain a cross-linked polyvinyl alcohol resin which is a cross-linked body of the polyvinyl alcohol resin. The crosslinked polyvinyl alcohol resin may be a polyvinyl alcohol resin that is chemically crosslinked with a crosslinking agent or a polyvinyl alcohol resin that is physically crosslinked with the crystal structure or the like in the resin without depending on the crosslinking agent. . When the binder does not contain a crosslinking agent, the binder usually contains a component for promoting physical crosslinking of the polyvinyl alcohol resin, such as a crystallization accelerator described below. The cross-linked polyvinyl alcohol resin means a polyvinyl alcohol resin that is at least partially chemically or physically cross-linked, and is excellent in handleability of mineral wool containing inorganic fibers to which the binder according to the present embodiment is attached. It is preferable that the polyvinyl alcohol resin is at least partially chemically crosslinked.

  Polyvinyl alcohol resin is a saponified product of polyvinyl acetate. The polyvinyl alcohol resin may include a structural unit having an ester group derived from vinyl acetate. The degree of polymerization of the polyvinyl alcohol resin may be, for example, in the range of 150 to 3000, preferably in the range of 200 to 1500, more preferably in the range of 220 to 1000, and further preferably in the range of 250 to 800. The range is from 280 to 500, particularly preferably from 280 to 500. The degree of polymerization of the polyvinyl alcohol resin is, for example, the value of the average degree of polymerization obtained by the method specified in JIS K 6726: 1994. The saponification degree of the polyvinyl alcohol resin may be, for example, in the range of 60 to 100 (mol%), and preferably in the range of 75 to 99 (mol%). The saponification degree of the polyvinyl alcohol resin can be determined by, for example, the method specified in JIS K 6726: 1994. Examples of commercially available polyvinyl alcohol resins include "JL-05E" (polymerization degree: 500, saponification degree: 80 to 84 (mol%)) manufactured by Nippon Vinegar Poval Co., Ltd.

  When the cross-linked polyvinyl alcohol resin is a polyvinyl alcohol resin chemically cross-linked with a cross-linking agent, the cross-linking agent forms a covalent bond or a non-covalent bond with a hydroxyl group of the polyvinyl alcohol resin, thereby forming a molecular chain of the polyvinyl alcohol resin. Is composed of one or more compounds that crosslink. The crosslinking agent may contain a compound having two or more functional groups capable of reacting with a hydroxyl group to form a covalent bond. An example of a functional group capable of reacting with a hydroxyl group to form a covalent bond is a carboxyl group.

  The cross-linking agent has, for example, two or more reactive groups selected from aliphatic carboxylic acids, homopolymers or copolymers containing aliphatic carboxylic acids as monomer units, boron compounds, isocyanate groups and blocked isocyanate groups. An isocyanate compound (hereinafter, also simply referred to as “isocyanate compound”) or a combination thereof can be included.

  Examples of the polymer or copolymer containing an aliphatic carboxylic acid as a monomer unit include maleic acid homopolymers or copolymers, (meth) acrylic acid homopolymers or copolymers, and fumaric acid homopolymers. Examples thereof include a polymer and a copolymer. The cross-linking agent may in particular be a copolymer containing monomer units derived from maleic acid, which has two carboxyl groups. The crosslinking agent may be a commercially available product. Examples of commercially available cross-linking agents include "Gantrenz AN-119" (maleic acid-based copolymer) manufactured by Gokyo Sangyo Co., Ltd.

  Examples of the boron compound include borax, boric acid, boric acid complex and the like. The boron compound can advance the crosslinking reaction of the polyvinyl alcohol resin in the step of preparing a binder composition containing the same. Therefore, from the viewpoint of suppressing an excessive increase in viscosity of the binder composition, the boron compound may be used in the preparation of the binder composition in the state of a low concentration aqueous solution. For example, an aqueous solution having a concentration of 4.0% prepared by dissolving commercially available borax in water is used.

  The isocyanate compound has two or more reactive groups selected from an isocyanate group and a blocked isocyanate group. The blocked isocyanate group is obtained by blocking the isocyanate group with a blocking agent. Examples of the blocking agent include methyl ketoxime and caprolactam. The isocyanate compound is preferably an isocyanate compound having two or more blocked isocyanate groups.

  As the isocyanate compound, a hexamethylene diisocyanate (HDI) type isocyanate compound, a diphenylmethane diisocyanate (MDI) type isocyanate compound, a toluene diisocyanate (TDI) type isocyanate compound, a blocked HDI type isocyanate compound, a blocked MDI type isocyanate compound, or Examples thereof include blocked TDI isocyanate compounds, preferably HDI isocyanate compounds, MDI isocyanate compounds, blocked HDI isocyanate compounds, or blocked MDI isocyanate compounds, more preferably HDI isocyanate compounds. It is an isocyanate compound or a blocked HDI-based isocyanate compound. Here, the HDI-based isocyanate compound means hexamethylene diisocyanate or an oligomer of hexamethylene diisocyanate (for example, 2 to 10 mer), and preferably hexamethylene diisocyanate. Further, the MDI-based isocyanate compound means diphenylmethane diisocyanate or an oligomer of diphenylmethane diisocyanate (for example, a dimer to dimer), and preferably diphenylmethane diisocyanate. The TDI-based isocyanate compound means toluene diisocyanate or an oligomer of toluene diisocyanate (for example, a dimer to dimer), and preferably toluene diisocyanate.

  The isocyanate compound may be a commercially available product. Examples of commercially available isocyanate compounds include "Elastron BN11", "Elastron BN77", and "F2462D1" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., "Meicanate TP10" and "SU268A" manufactured by Meisei Chemical Co., Ltd., and the like. .

  The content of the cross-linking agent may be 1.0 part by mass or more based on 100 parts by mass of the polyvinyl alcohol resin. When the content of the cross-linking agent is 4.0 parts by mass or more, the water resistance of the binder tends to be further improved. From the same viewpoint, the content of the crosslinking agent may be 2.0 parts by mass or more, 6.0 parts by mass or more, or 7.0 parts by mass or more with respect to 100 parts by mass of the polyvinyl alcohol resin. The upper limit of the content of the cross-linking agent is not particularly limited, but from the viewpoint of economic efficiency, 100 parts by mass or less, 50 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, relative to 100 parts by mass of the polyvinyl alcohol resin. Alternatively, it may be 10 parts by mass or less.

  When the crosslinking agent contains an isocyanate compound, the content of the isocyanate compound is preferably 12 to 90 parts by mass with respect to 100 parts by mass of the polyvinyl alcohol resin. When the content of the isocyanate compound is 12 parts by mass or more, generation of odor will be further suppressed. Moreover, when the content of the isocyanate compound is 90 parts by mass or less, the hardness during heating is further improved. The content of the isocyanate compound may be 14 to 70 parts by mass, 16 to 50 parts by mass, 18 to 40 parts by mass, or 20 to 30 parts by mass with respect to 100 parts by mass of the polyvinyl alcohol resin.

  When the binder containing a polyvinyl alcohol resin contains a crosslinking agent, the mass of the crosslinked polyvinyl alcohol resin means the total of the mass of the polyvinyl alcohol resin and the mass of the crosslinking agent. In the binder, not all of the cross-linking agent may necessarily form a covalent bond or a non-covalent bond with the hydroxyl group of the polyvinyl alcohol resin.

  The binder containing the polyvinyl alcohol resin may further contain a crystallization accelerator. The polyvinyl alcohol resin physically crosslinked by the crystal structure in the resin can be obtained by increasing the crystallinity of the polyvinyl alcohol resin with a crystallization accelerator. As the crystallization accelerator, inorganic particles having a particle diameter of 1 μm or less (for example, talc or the like), crystalline organic substances (for example, carboxylic acid amide or the like), and the like can be used. The content of the crystallization accelerator may be 0.1 to 10 parts by mass with respect to 100 parts by mass of the crosslinked polyvinyl alcohol resin (or polyvinyl alcohol resin).

  The (meth) acrylic resin is a polymer containing (meth) acrylic acid and / or (meth) acrylic acid ester as a main monomer unit. That is, the (meth) acrylic resin contains a structural unit derived from (meth) acrylic acid and / or (meth) acrylic acid ester as a main component. The (meth) acrylic resin may include a structural unit derived from another monomer (a monomer other than (meth) acrylic acid and (meth) acrylic acid ester). Here, the "main component" refers to a structural unit occupying 50% by mass or more with respect to the total mass of the polymer.

  When the binder contains a (meth) acrylic resin as the water-soluble resin, the binder may contain a (meth) acrylic resin having a carboxyl group. The (meth) acrylic resin having a carboxyl group contains a structural unit (monomer unit) derived from a monomer having a carboxyl group. Examples of the monomer having a carboxyl group include (meth) acrylic acid (acrylic acid or methacrylic acid).

  The (meth) acrylic resin having a carboxyl group may include a structural unit derived from a monomer other than the monomer having a carboxyl group. In the (meth) acrylic resin having a carboxyl group, the ratio of the number of constitutional units derived from a monomer other than the monomer having a carboxyl group, relative to the total number of constitutional units constituting the polymer or copolymer, It is less than 50%, preferably less than 30%, more preferably less than 10%, still more preferably less than 1%, and most preferably not containing a constitutional unit derived from a monomer other than a monomer having a carboxyl group. . The (meth) acrylic resin having a carboxyl group may be composed only of a structural unit derived from a monomer having a carboxyl group, or may be composed only of a structural unit derived from (meth) acrylic acid.

When the binder contains a (meth) acrylic resin having a carboxyl group, the binder may contain a metal ion. The valence of the metal ion is 2 or more, for example, 4 or less, and may be 2. Examples of metal ions include zinc ions, zirconium ions, titanium ions, aluminum ions, iron ions, magnesium ions, beryllium ions, bismuth ions, and cobalt ions. The metal ion may be at least one selected from the group consisting of zinc ion (Zn ²⁺ ) and zirconium ion (Zr ⁴⁺ ) and may be zinc ion (Zn ²⁺ ) or zirconium ion (Zr ⁴⁺ ), It may be zinc ion (Zn ²⁺ ).

  In a binder containing a (meth) acrylic resin having a carboxyl group and a metal ion, at least a part of the carboxyl group is crosslinked via the metal ion. The (meth) acrylic resin in which at least a part of the carboxyl groups is crosslinked via metal ions can also be referred to as a metal crosslinked (meth) acrylic resin.

  The content of metal ions may be 0.03 chemical equivalents (molar ratio of metal ion to carboxyl group / valence of metal ion) or more with respect to the total amount of carboxyl groups of the (meth) acrylic resin, and minerals. From the viewpoint of further improving the hardness of wool, it may be 0.07 chemical equivalent or more, 0.20 chemical equivalent or more, or 0.30 chemical equivalent or more, and 1.00 chemical equivalent or less, 0.90 chemical equivalent or less. , 0.80 chemical equivalents or less, 0.70 chemical equivalents or less, or 0.60 chemical equivalents or less. From the viewpoint of further improving the hardness of mineral wool, the content of metal ions is 0.03 to 0.80 chemical equivalents, 0.07 to 0. 0, based on the total amount of carboxyl groups in the (meth) acrylic resin. It may be 70 chemical equivalents, 0.20 to 0.60 chemical equivalents, or 0.30 to 0.50 chemical equivalents. When the content of metal ions is 0.80 chemical equivalent or less with respect to the total amount of carboxyl groups contained in the (meth) acrylic resin, the amount of the dispersion aid (for example, aqueous ammonia solution) used during the production of mineral wool is The reduction makes the mineral wool easier to manufacture (more manufacturable).

  Examples of the polysaccharides include dextrin, chemically modified starch (eg, hydroxypropylated starch, carboxymethylated starch, phosphate esterified starch, etc.), and celluloses (eg, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, hydroxypropylcellulose, methylpropyl). Cellulose etc.) and the like can be used.

  The number average molecular weight of the water-soluble resin may be, for example, more than 1000, 1100 or more, 3000 or more, 5000 or more, 7000 or more, or 9000 or more, and 100,000 or less, 50,000 or less, 30,000 or less, or 20,000 or less. When the number average molecular weight of the water-soluble resin is within the above range, the fluidity of the binder becomes appropriate. In the present specification, the number average molecular weight (Mn) is a value measured by gel permeation chromatography (GPC) and converted into standard polystyrene.

  The water-soluble resin may have a viscosity of 100 mPa · s or more and 50000 mPa · s or less, or 500 mPa · s or more and 10000 mPa · s or less in an aqueous solution having a concentration of 20% by mass (the total amount of the aqueous solution is 100% by mass).

  The content of the water-soluble resin is 40% by mass or more, 50% by mass or more, 60% by mass, 70% by mass, 80% by mass or more, 90% by mass or more, and 95% by mass or more with respect to the mass of the binder. Well, it may be 100 mass% or less. The content of the water-soluble resin may be 40 to 100% by mass, 60 to 100% by mass, 70 to 100% by mass, 80 to 100% by mass, or 100% by mass with respect to the mass of the binder.

  In the mineral wool according to this embodiment, the binder may contain urea. In the mineral wool according to the present embodiment, the content of urea (after a part of the urea contained in the binder composition is volatilized by heating, remains in the binder in a state not covalently bonded to the cured water-soluble resin). The amount of urea to be used) may be 0.3 to 50.0 mass% with respect to the mass of the binder. The content of urea is 0.3 to 40.0% by mass, and 0.5 to 35.% with respect to the mass of the binder, from the viewpoint that the workability is further improved and the drying workability is more excellent. It may be 0% by mass or 3.0 to 15.0% by mass. From the same viewpoint, the content of urea is 0.3 mass% or more, 0.5 mass% or more, 1.0 mass% or more, 1.5 mass% or more, 2.0 mass% with respect to the mass of the binder. % Or more, 2.5% by mass or more, 3.0% by mass or more, 3.5% by mass or more or 4.0% by mass or more, 40.0% by mass or less, 35.0% by mass or less, 30 It may be 0.0 mass% or less, 25.0 mass% or less, 20.0 mass% or less, 18.0 mass% or less, 15.0 mass% or less, or 14.0 mass% or less.

  The content of urea with respect to the mass of the binder is specifically measured by the method described in Examples below.

  The binder may further contain a dustproofing agent. Examples of the dustproof agent include oil emulsions. Examples of commercially available dustproofing agents include heavy oil emulsion "Daphne Prosolvable PF" manufactured by Idemitsu Kosan Co., Ltd. The content of the dustproofing agent may be 1 to 30 parts by mass with respect to 100 parts by mass of the water-soluble resin.

  The binder may further contain a water repellent. Examples of the water repellent include silicone-based additives such as silicone oil emulsion, and fluorine-based additives. Examples of commercially available water repellents include silicone oil emulsion "Polon MR" manufactured by Shin-Etsu Chemical Co., Ltd. The content of the water repellent may be 0.05 to 20 parts by mass with respect to 100 parts by mass of the water-soluble resin.

  The binder may further contain a silane coupling agent. The silane coupling agent contributes to the interfacial adhesion between the water-soluble resin and the inorganic fiber. Examples of silane coupling agents include aminosilane coupling agents such as 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, aminopropyltriethoxysilane, and 3-glycidoxypropyl. Examples thereof include epoxysilane coupling agents such as trimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane. Examples of commercially available silane coupling agents include aminopropyltrimethoxysilane "KBE903" manufactured by Shin-Etsu Chemical Co., Ltd. The silane coupling agent may be used alone or in combination of two or more. The content of the silane coupling agent is preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the water-soluble resin, from the viewpoint of water solubility and reactivity of the water-soluble resin and manufacturing cost. When the content of the silane coupling agent is 0.1 part by mass or more, sufficient interfacial adhesion between the crosslinked polyvinyl alcohol resin and the inorganic fiber can be easily obtained. The silane coupling agent also contributes to fixing the silicone-based additive on the surface of the inorganic fiber. Therefore, by using the silane coupling agent in combination with a water repellent such as a silicone-based additive, the water resistance of mineral wool can be further improved.

  The binder composition according to the present embodiment may further contain other components, if necessary, in addition to the components exemplified above. Examples of other components include an adhesion suppressant, a release agent, a coloring agent, and dihydrazides that contribute to shape retention of mineral wool.

  The amount of the binder attached may be 0.5 to 15.0 parts by mass, 1.0 to 15.0 parts by mass, or 1.0 to 6.0 parts by mass with respect to 100 parts by mass of mineral wool. The amount of the binder attached may be 1.0 part by mass or more, 1.5 parts by mass or more, 2.0 parts by mass or more, or 2.5 parts by mass or more with respect to 100 parts by mass of mineral wool. It may be not more than 10 parts by mass, not more than 10.0 parts by mass, not more than 6.0 parts by mass or not more than 5.0 parts by mass. The amount of the binder attached can be measured by the method described in Examples below.

  The binder composition that forms a binder by heating is a water-soluble resin, urea, and, if necessary, a silane coupling agent, mineral oil, an antifoaming agent, a surfactant, a dustproofing agent, a water repellent, and an adhesive. Inhibitors, release agents, components such as colorants are mixed and stirred with an aqueous medium, and, if necessary, the aqueous medium is added, and the content of the above components, as the amount in the binder, falls within the above range. It is obtained by adjusting so that The crosslinking reaction of the water-soluble resin proceeds during the preparation of the binder composition and / or by heating the binder composition. Examples of the aqueous solvent include water, methanol, ethanol, ethylene glycol, glycerin and the like, and may be water from the viewpoint of economy and handleability. The aqueous solvent may be used alone or in combination of two or more.

  The solid content concentration in the binder composition, that is, the content of components other than the aqueous solvent may be 2.0 to 20 mass% with respect to the total amount of the binder composition. When the content of the components other than the aqueous solvent is 2.0% by mass or more, the time required for the heat treatment for drying the mineral wool is shortened, and the productivity tends to be improved. When the content of the components other than the aqueous solvent is 20.0% by mass or less, the viscosity of the solution (binder composition) is sufficiently reduced and the permeability to the wool-like inorganic fiber is improved. From the same viewpoint, the content of components other than the aqueous solvent may be 2.0 to 10.0% by mass.

  Mineral wool according to the present embodiment, for example, a step of attaching the binder composition to the inorganic fiber, a step of forming a wool-like intermediate fiber substrate containing the inorganic fiber and the binder composition attached to the inorganic fiber, And a step of heating the fiber base material.

  In the step of adhering the binder composition to the inorganic fiber, for example, while the inorganic raw material such as heat-melted glass or minerals such as rock is fibrous to form the inorganic fiber, the binder composition is formed on the formed inorganic fiber. May be attached. As a method for fiberizing the inorganic fiber, for example, a usual method such as a flame method, a blowing method, a centrifugal method (also referred to as a rotary method) or the like can be used. In the case of producing glass wool, a centrifugal method is preferably used as a method for making fibers. As a method of attaching the binder composition to the inorganic fibers, for example, a method of spraying the atomized binder composition onto the inorganic fibers with a spray device or the like can be used.

  By adhering the binder composition to the inorganic fibers and depositing the inorganic fibers to which the binder composition is attached, a wool-like intermediate fiber base material can be formed. The deposited inorganic fibers are gradually intertwined with each other to form a wool-like form. The binder composition may be attached to the inorganic fibers at any time after the inorganic fibers are formed, but since the binder composition is easily attached inside the intermediate fiber base material, the binder composition immediately after being formed may be used. It is preferable to attach the binder composition to the inorganic fibers and then form the wool-like intermediate fiber base material.

  By heating the intermediate fiber base material, the binder composition attached to the inorganic fibers is heat-cured to form a binder, and mineral wool containing the inorganic fibers and the binder attached to the inorganic fibers is obtained. The method of heating the intermediate fiber base material is not particularly limited. For example, the intermediate fiber base material can be heated by passing through one or a plurality of heating zones set to a predetermined heating temperature. The plurality of heating zones may be installed in series along the transportation direction of the intermediate fiber base material. The heating temperature may be set so as to remove the aqueous solvent from the binder composition, and for example, the average heating temperature may be 200 ° C or higher, 200 ° C or higher and 250 ° C or lower, or 210 ° C or higher and 240 ° C or lower. It is preferable. When the average heating temperature is within these ranges, generation of an undried portion (remaining water) in the mineral wool can be prevented or suppressed, and as a result, the resilience of the mineral wool is secured.

When the intermediate fiber base material is heated by passing through n heating zones each of which can be set to a predetermined heating temperature, the average heating temperature T _ave is a value calculated by the following formula (1). In the formula (1), L _i represents the distance that the intermediate fiber base material is transported in each heating zone, and T _i represents the set temperature of each heating zone. i indicates the number of heating zones, which is an integer of 1 or more.

  The heating time of the intermediate fiber base material is appropriately adjusted depending on the density and thickness of the inorganic fiber to which the binder composition is attached. The heating time may be, for example, 30 seconds to 10 minutes, or 2 minutes to 10 minutes.

  The intermediate fiber base material after the heating step, that is, mineral wool may be formed into a mat shape, for example, if necessary, and may be further cut into a desired width and length.

  The mineral wool may be used as it is, or the surface of the mineral wool may be covered with a skin material to produce a member such as a panel having the mineral wool and the skin material. The skin material is not particularly limited, but includes, for example, paper (particularly heat resistant paper, for example, glass paper), synthetic resin film, metal foil film, non-woven fabric (for example, glass chopped strand mat), woven fabric (for example, glass fiber woven fabric). ) Or a combination thereof.

  The mineral wool according to this embodiment can be preferably used as a material having a heat insulating / sound absorbing function, for example. In particular, the mineral wool according to the present embodiment can be particularly suitably used as a heat insulating material for building materials (in particular, a heat insulating material arranged inside a building material such as inside a wall or ceiling).

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

<Production of glass wool with binder>
Example 1
(A) Polyvinyl alcohol resin having a degree of polymerization of 300 (number average molecular weight 13200) and a degree of saponification of 88% (“JL-05E” manufactured by Nippon Vine-Poval Co., Ltd .; aqueous solution) 92.5 parts by mass (solid content) 7.5 parts by mass (converted to solid content), maleic acid-based copolymer containing maleic acid as a monomer unit (“Gantrenz AN-119” manufactured by Gokyo Sangyo Co., Ltd .; aqueous solution) which is (B) a crosslinking agent. ), (C) 10.0 parts by mass of urea (in terms of solid content), (D) 15.0 parts by mass (solid content of heavy oil emulsion (“Daphne Prosolve PF” manufactured by Idemitsu Kosan Co., Ltd.) which is a dustproofing agent). (Converted) and (E) 0.5 parts by mass (converted to solid content) of γ-aminopropyltriethoxysilane which is a silane coupling agent are mixed and stirred, and the solid content concentration of the obtained mixed liquid is 4.0. Adjust with water so that the mass% is It was obtained Indah composition. The “solid content” here is the amount of solid components remaining after volatilization and drying of the aqueous solvent (content of components other than the aqueous solvent).

  The heat-melted raw material glass was introduced into a fiberizing device, and the heat-melted raw material glass was ejected into a fibrous state by a centrifugal method to form glass fibers. When the formed glass fiber was air-cooled, the binder composition obtained was atomized and sprayed to adhere the binder composition to the glass fiber. The glass fibers with the binder composition attached were deposited to form a wool-like intermediate fiber substrate.

  The obtained intermediate fiber base material was dried under the conditions of a heating temperature of 220 ° C. and a heating time of 3 minutes. As a result, matte glass wool of Example 1 containing the glass fiber to which the binder was attached was obtained. By the heat treatment, a polyvinyl alcohol resin cross-linked with the maleic acid-based copolymer as a cross-linking agent is produced, and on the other hand, part of the urea in the binder composition is volatilized to give the binder of Example 1. Been formed.

  In the obtained glass wool of Example 1, the adhered amount of the binder was 3.0 parts by mass with respect to 100 parts by mass of the glass wool, and the content of urea was 4.5% by mass with respect to the mass of the binder. It was

Example 2
A glass wool of Example 2 was obtained in the same manner as in Example 1 except that the amount of (C) urea was changed to 20.0 parts by mass. In the obtained glass wool of Example 2, the adhered amount of the binder was 3.1 parts by mass with respect to 100 parts by mass of the glass wool, and the content of urea was 13.3% by mass with respect to the mass of the binder. It was

Example 3
Glass wool of Example 3 was obtained in the same manner as in Example 1 except that the amount of (C) urea was changed to 15.0 parts by mass and the drying temperature was set to 240 ° C. In the obtained glass wool of Example 3, the amount of the adhered binder was 2.8 parts by mass with respect to 100 parts by mass of the glass wool, and the content of urea was 0.5% by mass with respect to the mass of the binder. It was

Example 4
A glass wool of Example 4 was obtained in the same manner as in Example 1 except that the amount of (C) urea was changed to 50.0 parts by mass. In the obtained glass wool of Example 4, the adhesion amount of the binder was 3.3 parts by mass with respect to 100 parts by mass of the glass wool, and the content of urea was 28.1% by mass with respect to the mass of the binder. .

Example 5
A glass wool of Example 5 was obtained in the same manner as in Example 1 except that the amount of (C) urea was changed to 100.0 parts by mass. In the obtained glass wool of Example 5, the binder adhesion amount was 3.4% by mass, and the urea content was 43.7% by mass based on the mass of the binder.

Example 6
An aqueous solution of polymethacrylic acid was prepared by radically polymerizing methacrylic acid in deionized water using potassium persulfate as a polymerization initiator. Then, a zinc-containing aqueous ammonia solution was prepared according to the preparation method described in paragraph 0040 of Japanese Patent No. 3950996. This zinc-containing ammonia aqueous solution was added to the polymethacrylic acid aqueous solution so that the content of metal ions (Zn ²⁺ ) was 0.4 chemical equivalent to the total amount of carboxyl groups contained in polymethacrylic acid. An aqueous solution containing polymethacrylic acid was obtained. The viscosity of this zinc-containing polymethacrylic acid aqueous solution was 24 mPa · s at 25 ° C. The viscosity of the zinc-containing polymethacrylic acid aqueous solution was measured using a B-type viscometer in accordance with JIS K6833-1: 2008.

  Then, (A-2) 100 parts by mass of zinc-containing polymethacrylic acid (as solid content), (C) 40.0 parts by mass of urea (as solid content), and (D) a heavy oil emulsion as a dustproof agent (Idemitsu Kosan). "Daphne Prosolvable PF" manufactured by K.K.) 15.0 parts by mass (solid content conversion), and (E) silane coupling agent γ-aminopropyltriethoxysilane 0.5 parts by mass (solid content conversion). Were mixed and stirred, and water was adjusted so that the solid content concentration of the obtained mixed liquid was 4.0% by mass to obtain a binder composition.

  A glass wool of Example 6 was obtained in the same manner as in Example 2 except that this binder composition was used. In the glass wool of Example 6, the adhesion amount of the binder was 3.5 parts by mass with respect to 100 parts by mass of the glass wool, and the content of urea was 18.5% by mass with respect to the mass of the binder. The heat treatment produced a polymethacrylic resin crosslinked with zinc ions.

Comparative Example 1
A glass wool of Comparative Example 1 was obtained in the same manner as in Example 3 except that the amount of (C) urea was changed to 1.0 part by mass. In the obtained glass wool of Comparative Example 1, the amount of the attached binder was 2.9 parts by mass with respect to 100 parts by mass of the glass wool, and the content of urea was 0.0% by mass (HPLC Was not detected).

Comparative Example 2
A glass wool of Comparative Example 2 was obtained in the same manner as in Example 6 except that the amount of (C) urea was changed to 1.0 part by mass. In the obtained glass wool of Comparative Example 2, the amount of the attached binder was 3.0 parts by mass with respect to 100 parts by mass of the glass wool, and the content of urea was 0.0% by mass (HPLC Was not detected).

Reference example 1
A glass wool of Reference Example 1 was obtained in the same manner as Comparative Example 1 except that 100 parts by mass of a phenol resin (manufactured by Gunei Chemical Co., Ltd.) was used in place of the polyvinyl alcohol resin (A) and the crosslinking agent (B). . In the obtained glass wool of Reference Example 1, the adhered amount of the binder was 2.7 parts by mass with respect to 100 parts by mass of the glass wool, and the content of urea was 0.0% by mass based on the mass of the binder (detected by HPLC). It was impossible).

Reference example 2
A glass wool of Reference Example 1 was obtained in the same manner as in Example 2 except that 100 parts by mass of a phenol resin (manufactured by Gunei Chemical Co., Ltd.) was used instead of the polyvinyl alcohol resin (A) and the crosslinking agent (B). . In the obtained glass wool of Reference Example 1, the adhered amount of the binder was 2.9 parts by mass with respect to 100 parts by mass of the glass wool, and the content of urea was 4.8% by mass with respect to the mass of the binder. A part of urea in the binder composition reacts with formaldehyde in the phenol resin, and such urea is not measured by the method for measuring the content of urea described below.

(Fiber diameter, density, width, length, thickness and thermal performance λ)
When the density, width, length, thickness and thermal performance λ of the mineral wool were measured according to JIS A 9521: 2014, the mineral wool of Examples 1-6 and Comparative Examples 1-2 had a density of 10 kg / m ³ , width 430 mm, length 2350 mm, thickness 100 mm, thermal performance λ was 0.0446 W / m · K. The density here is an apparent density based on a volume including a void volume.

(Measurement of binder adhesion amount)
First, the weight of the glass wool to which the binder was attached (weight before incineration) was measured, and then the binder was incinerated by heating in an air atmosphere at 500 ° C. for 60 minutes. The weight of the remaining glass wool (weight after incineration) was measured, and the adhered amount of the binder was calculated by the following formula.
Binder adhesion amount = (weight before incineration-weight after incineration) / weight before incineration x 100

(Measurement of urea content)
First, 0.2144 g of a urea standard product was weighed, dissolved in 100 ml of ultrapure water in a measuring flask, and then diluted 10 times with ultrapure water to prepare a standard solution 1. Then, the standard solution 1 was diluted 2-fold, 10-fold, 20-fold, 50-fold or 100-fold with ultrapure water to prepare standard solutions 2 to 6. The obtained standard solutions 1 to 6 were subjected to HPLC (UltraMate 3000 type manufactured by ThermoFisher SCIENTIFIC) measurement to prepare a calibration curve for the urea concentration.

Next, in a beaker, 7 g of a glass wool sample to which a binder was attached and 500 ml of ultrapure water were added, and ultrasonic (40 kHz) dispersion was performed for 30 minutes. The beaker was then well stirred using a spatula. Next, the solution in the beaker was filtered with a 0.45 μm filter to obtain a sample solution. Then, for the obtained sample solution, HPLC (ThermoMate 3000 type manufactured by ThermoFisher SCIENTIFIC) measurement was carried out under the same conditions as when the calibration curve was prepared, and the urea content (unit: mass%) was determined from the measurement results and the calibration curve. It was calculated and calculated from the following formula. In addition, when the content of urea in the sample solution is extremely low and it is difficult to quantify it by the calibration curve, the sample solution is distilled by a rotary evaporator, concentrated to 10 times, readjusted the sample solution, and again urea Was measured.
Urea content = ((urea content determined by calibration curve / 100 × sample solution amount (unit: g)) / (glass wool sample weight (7 g) × binder adhesion amount / 100)) × 100

(Evaluation of glass wool processability)
To evaluate the workability (cuttability), continuously cut glass wool using a slitter (equipment for cutting glass wool with a blade (chip saw) attached to the edge of a disc having a diameter of 405 mm) for 10 hours. It was carried out by. The slitter was arranged so that the cutting width was 430 mm (the specified cutting width for glass wool products).

  In the evaluation of workability, when continuous cutting of the glass wool was impossible, “x”, intermittent cutting residue (a portion exceeding the specified cutting width 430 mm of the glass wool product) occurs on the lower surface of the glass wool, When the continuous cutting of the glass wool was able to be performed for 10 hours, it was evaluated as “◯”, and when the continuous cutting of the glass wool was able to be performed for 10 hours neatly (without cutting residue), it was evaluated as “⊚”.

(Workability evaluation of the drying process)
In the process of drying the intermediate fiber base material, "x" was given when 3 or more of the 5 workers felt an ammonia odor, and "○" was given when 1 or 2 of the 5 workers felt an ammonia odor. When 0 out of 5 workers felt an ammonia odor, it was evaluated as “⊚”. The ammonia odor is caused by the ammonia produced by heating and decomposing urea in the dryer, or the aqueous ammonia solution contained in the binder.

  When the phenol resin was used, the workability was good regardless of the presence or absence of urea (Reference Examples 1 and 2). On the other hand, when polyvinyl alcohol resin and zinc-containing polymethacrylic acid (methacrylic resin) were used as the binder component, there was room for improvement in processability (Comparative Examples 1-2 and Reference Examples 1-2). Contrast with).

  As shown in Table 1, a polyvinyl alcohol resin or a zinc-containing polymethacrylic acid (methacrylic resin) and urea are contained, and the content of urea is 0.3 to 50.0 mass% with respect to the mass of the binder. In this case, it was shown that the workability was excellent.

Claims (5)

Inorganic fiber, including a binder attached to the inorganic fiber,
The binder contains a water-soluble resin and urea,
The water-soluble resin is a resin other than a polycondensate of formaldehyde and other monomers,
Mineral wool whose content of the said urea is 0.3-50.0 mass% with respect to the mass of the said binder.   The mineral wool according to claim 1, wherein the water-soluble resin is a polyvinyl alcohol resin or a (meth) acrylic resin.   The mineral wool according to claim 1, wherein the water-soluble resin is a polyvinyl alcohol resin.   The mineral wool according to any one of claims 1 to 3, wherein the content of the urea is 3.0 to 15.0 mass% with respect to the mass of the binder.   The mineral wool according to any one of claims 1 to 4, wherein the amount of the binder attached is 1.0 to 15.0 parts by mass with respect to 100 parts by mass of the mineral wool.