JP2020117836A - Mineral wool - Google Patents

Abstract

To provide mineral wool having excellent workability while containing a resin excluding a polycondensate of formaldehyde and other monomers.SOLUTION: Disclosed is mineral wool containing inorganic fibers, and a binder attached to the inorganic fibers. The binder contains a water-soluble resin, and a diol compound represented by the following formula (1), where R is a hydrogen atom or an alkyl group. The water-soluble resin is a resin excluding a polycondensate of formaldehyde and other monomers.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 fibers. For example, Patent Document 1 discloses an aqueous binder for mineral fibers containing a polymer having a carboxyl group, a polyol, a curing catalyst, and water.

JP, 2013-136864, A

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. However, due to concerns about formaldehyde emitted from the polycondensate, it may be desired to use other resins depending on the application. However, the mineral wool using a binder whose main component is a resin other than a polycondensation product of formaldehyde and other monomers, is likely to have uncut residue when cut, and there is room for improvement in processability.

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

で表されるジオール化合物と、を含有する。式（1）中のＲは水素原子又はアルキル基である。前記水溶性樹脂が、ホルムアルデヒドとその他の単量体との重縮合物以外の樹脂である。 One aspect of the present invention relates to mineral wool containing inorganic fibers and a binder attached to the inorganic fibers. The binder is a water-soluble resin and the following formula (1):

And a diol compound represented by R in the formula (1) is a hydrogen atom or an alkyl group. The water-soluble resin is a resin other than a polycondensate of formaldehyde and another monomer.

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.

It is a sectional view showing one embodiment of mineral wool.

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

FIG. 1 is a sectional view showing an embodiment of mineral wool. The mineral wool 1 shown in FIG. 1 is a mat-like material containing inorganic fibers and a binder attached to the inorganic fibers. However, the shape of mineral wool is not limited to this. The binder contains a water-soluble resin and a diol compound having hydroxy groups at the 1-position and 2-position. Since the mineral wool 1 according to the present embodiment is excellent in processability, it can be 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). ..

The mineral wool 1 includes a wool-like fiber aggregate containing inorganic fibers. The inorganic fibers forming the fiber assembly are bound together 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 from 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 and lime as main components, or fibers made from rocks or the like is generally called rock wool. The mineral wool may be glass wool containing glass fibers from the viewpoint of further improving heat insulation and sound absorption.

The density of the mineral wool 1 may be 10 to 250 kg/m ³ . The mineral wool 1 may have a thickness of 10 to 300 mm, for example. The density and thickness of the mineral wool 1 can be measured according to JIS A 9521:2014. The density here is an apparent density based on a volume including void volume.

The fiber diameter of the inorganic fibers constituting the mineral wool 1 (including the thickness of the binder) may be 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 may be 2.0 to 500.0 mm.

The binder of the mineral wool 1 is formed by heating a binder composition containing a water-soluble resin, a diol compound having hydroxy groups at the 1- and 2-positions, and an aqueous medium.

The water-soluble resin is a resin that dissolves in water. The water-soluble resin is usually a resin which dissolves 0.1 g or more in 100 g of water at 25°C. Since the water-soluble resin is a resin other than a polycondensation product of formaldehyde and other monomers, it does not substantially contain a structural unit derived from formaldehyde. Examples of the "other monomer" here include phenol compounds and amine compounds such as urea, melamine and dicyandiamide. Examples of polycondensates of formaldehyde and other monomers include phenol resins, urea resins, and melamine resins (melamine-formaldehyde resin), and the water-soluble resin may be a resin other than these.

The water-soluble resin may be, for example, at least one selected from the group consisting of polyvinyl alcohol resin, (meth)acrylic resin, and polysaccharide. In the present specification, “(meth)acrylic” means “acrylic” or “methacrylic” corresponding thereto. The water-soluble resin may be a polyvinyl alcohol resin or a (meth)acrylic resin from the viewpoint of further improving processability. The water-soluble resin may be a polyvinyl alcohol resin, from the viewpoints that the workability is further improved, the generation of odor in the drying step is further suppressed, and the drying workability is further improved.

At least a part of the water-soluble resin may be crosslinked. In the present specification, a polyvinyl alcohol resin forming a crosslinked body may be referred to as a crosslinked polyvinyl alcohol resin. The crosslinked polyvinyl alcohol resin may be a polyvinyl alcohol resin chemically crosslinked with a crosslinking agent or a polyvinyl alcohol resin 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. Cross-linked polyvinyl alcohol resin means a polyvinyl alcohol resin at least a part of which is chemically or physically cross-linked, and at least because it is excellent in handleability of mineral wool containing inorganic fibers to which the binder according to the present embodiment is attached, It may be a polyvinyl alcohol resin 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, 150 to 3000, 200 to 1500, 220 to 1000, 250 to 800, or 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 defined in JIS K 6726:1994. The saponification degree of the polyvinyl alcohol resin may be, for example, 60 to 100 mol %, or 75 to 99 mol %. The saponification degree of the polyvinyl alcohol resin can be determined by, for example, the method defined 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 by 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 of the polyvinyl alcohol resin is, for example, an aliphatic carboxylic acid, a homopolymer or copolymer containing an aliphatic carboxylic acid as a monomer unit, a boron compound, a reactive group selected from an isocyanate group and a blocked isocyanate group. An isocyanate compound having two or more (hereinafter, also simply referred to as “isocyanate compound”) or a combination of two or more compounds selected from these 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 be a copolymer containing monomeric units derived from maleic acid. Examples of commercially available cross-linking agents include “Gantrenz AN-119” (maleic acid-based copolymer) manufactured by Gokyo Sangyo Co., Ltd.

Examples of boron compounds include borax, boric acid, and boric acid complexes. 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 a group formed by blocking the isocyanate group with a blocking agent. Examples of the blocking agent include methyl ketoxime and caprolactam. The isocyanate compound may be an isocyanate compound having two or more blocked isocyanate groups.

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

Examples of commercially available isocyanate compounds include "Elastron BN11", "Elastron BN77", and "F2462D1" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., and "Meikanate TP10" and "SU268A" of Meisei Chemical Co., Ltd. To be

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 crosslinking agent is not particularly limited, but from the viewpoint of economy, 100 parts by mass or less, 50 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, with respect 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 may be 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. 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 content of the crosslinked polyvinyl alcohol resin means the sum of the mass of the polyvinyl alcohol resin and the mass of the crosslinking agent. The binder may include a cross-linking agent that does not 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 a (meth)acrylic monomer selected from (meth)acrylic acid and a (meth)acrylic acid ester as a main monomer unit. The (meth)acrylic resin may contain a structural unit derived from a monomer other than the (meth)acrylic monomer, but the ratio of the (meth)acrylic monomer is usually 50 with respect to the total mass of the polymer. -100% by mass.

The (meth)acrylic resin may have a carboxyl group. The (meth)acrylic resin having a carboxyl group usually contains a 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 is 50 with respect to the total number of constitutional units constituting the (meth)acrylic resin. It may be less than mol%, less than 30 mol%, less than 10 mol%, or less than 1 mol%. The (meth)acrylic resin having a carboxyl group may be composed only of structural units derived from a monomer having a carboxyl group, and is a poly(meth)acrylic acid composed only of structural units derived from (meth)acrylic acid. It's okay.

The binder may contain a (meth)acrylic resin having a carboxyl group and a metal ion that crosslinks the (meth)acrylic resin. The valence of the metal ion may be 2 or more, or 4 or less. 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 part of the carboxyl group forms an ionic bond with the metal ion, whereby the (meth)acrylic resin is crosslinked. The (meth)acrylic resin 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 ions to carboxyl groups/valence of metal ions) or more with respect to the total amount of carboxyl groups contained in 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 (eg, aqueous ammonia solution) used during the production of mineral wool is Due to the reduction, the production of mineral wool becomes easier.

The polysaccharide as the water-soluble resin is, for example, dextrin, chemically modified starch (for example, hydroxypropylated starch, carboxymethylated starch, phosphate esterified starch), or celluloses (for example, carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose, Hydroxypropyl cellulose, methyl propyl cellulose, etc.).

The number average molecular weight of the water-soluble resin may be 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 binder tends to have appropriate fluidity. In the present specification, the number average molecular weight (Mn) means a value measured by gel permeation chromatography (GPC) and converted into standard polyethylene glycol.

An aqueous solution containing a water-soluble resin and having a concentration of 20% by mass (concentration is a value at which the total amount of the aqueous solution is 100% by mass) is 100 mPa·s or more and 50000 mPa·s or less, or 500 mPa·s or more and 10000 mPa·s at 25°C. It may have a viscosity of s or less.

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% by 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.

At least a part of the diol compound contained in the binder has hydroxy groups bonded to the carbon atoms at the 1-position and the 2-position, respectively. This diol compound is represented by the following formula (1).

R in the formula (1) is a hydrogen atom or an unsubstituted alkyl group. R may be an alkyl group having 1 to 4 carbon atoms. At least the diol compound represented by the formula (1) is selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, and 1,2-hexanediol. One may be included, at least one of ethylene glycol and 1,2-butanediol may be included, and 1,2-butanediol may be included. The binder may further contain a diol compound other than the diol compound represented by the formula (1).

The content of the diol compound of the formula (1) may be 45.0% by mass or less with respect to the mass of the binder, which tends to further improve the processability of the mineral wool. From the same viewpoint, the content of the diol compound of the formula (1) may be 20.0% by mass or less, or 15.0% by mass or less with respect to the mass of the binder, and 0.3% by mass or more, It may be 1.5% by mass or more, or 2.0% by mass or more.

The binder may further contain a dustproofing agent. Examples of the dustproofing agent include oil emulsions. Examples of commercially available dustproofing agents include heavy oil emulsion "Daphne Prosolve 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 the silane coupling agent include aminosilane coupling agents such as 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and aminopropyltriethoxysilane, and 3-glycid. Epoxysilane coupling agents such as xypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane can be mentioned. 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 may be 0.1 to 3.0 parts by mass based on 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 water-soluble 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, the combination of a silane coupling agent and a water repellent such as a silicone-based additive can further improve the water resistance of mineral wool.

The binder composition according to one 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 colorant, 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 less than or equal to 10.0 parts by mass, less than or equal to 6.0 parts by mass, or less than or equal to 5.0 parts by mass. The amount of the binder attached can be measured by the method described in Examples below.

The binder composition is obtained by mixing and stirring a water-soluble resin, a diol compound, and other components added as necessary with an aqueous medium. The crosslinking reaction of the water-soluble resin proceeds during the preparation of the binder composition and/or by heating the binder composition. The aqueous solvent contains, for example, at least one selected from the group consisting of water, methanol, ethanol, ethylene glycol, and glycerin. From the viewpoint of economy and handleability, the aqueous solvent may contain water. Even if the proportion of water in the aqueous solvent is 50 to 100% by mass, 60 to 100% by mass, 70 to 100% by mass, 80 to 100% by mass, or 90 to 100% by mass based on the mass of the aqueous solvent. Good.

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 tends to be short. When the content of the components other than the aqueous solvent is 20.0% by mass or less, the binder composition tends to easily penetrate into the wool-like inorganic fibers. 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 one 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. Examples of the method for fiberizing the inorganic fiber include a flame method, a blowing method, and a centrifugal method (also referred to as a rotary method). Examples of the method of attaching the binder composition to the inorganic fibers include a method of spraying the atomized binder composition onto the inorganic fibers with a spray device or the like.

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, and they form a wool-like morphology. 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 to the inside of the intermediate fiber base material, the binder composition immediately after the formation is formed. A binder composition may be attached to the inorganic fibers, and then a wool-like intermediate fiber base material may be formed.

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 transport 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. May be. When the average heating temperature is within these ranges, generation of an undried portion (water remaining) 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, for example, a mat shape if necessary, and may be 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, and examples thereof include paper (particularly heat-resistant paper, eg glass paper), synthetic resin film, metal foil film, non-woven fabric (eg glass chopped strand mat), woven fabric (eg glass fiber woven fabric). ) Or a combination thereof can be used.

The mineral wool according to this embodiment can be used as a material having a heat insulating/sound absorbing function, for example. The mineral wool according to the present embodiment may be 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 inside a ceiling).

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

1. Glass wool production Example 1
92.5 parts by mass (solid content conversion) of a polyvinyl alcohol resin (“JL-05E” manufactured by Nihon Bibi Poval Co., polymerization degree: 300, number average molecular weight: 13200, saponification degree: 88%), cross-linking agent (Aqueous solution of maleic acid-based copolymer containing maleic acid as a monomer unit ("Gantrenz AN-119" manufactured by Gokyo Sangyo Co., Ltd.)) 7.5 parts by mass (solid content conversion), 10.0 parts by mass of ethylene glycol , Dustproof agent (heavy oil emulsion, "Daphne Prosolvable PF" manufactured by Idemitsu Kosan Co., Ltd.) 15.0 parts by mass (solid content conversion), and silane coupling agent (γ-aminopropyltriethoxysilane) 0.5. Parts by mass were mixed and stirred, and water was added to the resulting mixed liquid to obtain a binder composition having a solid content concentration of 4.0% by mass. Here, "solid content conversion" means the amount of components other than water, and "solid content concentration" means the concentration of components other than water.

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. The binder composition was adhered to the glass fiber by spraying the binder composition in a mist state onto the glass fiber while the formed glass fiber was air-cooled. The glass fibers with the binder composition attached were deposited, thereby forming a wooly 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 glass fibers to which the binder was attached was obtained. The binder after the heat treatment contains a polyvinyl alcohol resin crosslinked with a maleic acid-based copolymer as a crosslinking agent. Moreover, a part of ethylene glycol in the binder composition was volatilized by the heat treatment.

In the obtained glass wool, the amount of the adhered binder was 3.1 parts by mass with respect to 100 parts by mass of the glass wool, and the content of ethylene glycol was 5.2% by mass with respect to the mass of the binder. The residual ratio of the alcohol compound (here, ethylene glycol) calculated by the following formula was 0.65. Also in the following examples and comparative examples, the residual ratio of the alcohol compound was calculated by the following formula. In the formula, “content of alcohol compound in binder (mass %)” is a value measured by a measuring method described later.
Remaining ratio of alcohol compound=(content of alcohol compound in binder (mass %))/(content of alcohol compound relative to mass of all components other than water in binder composition (mass %))

Example 2
A glass wool of Example 2 was obtained in the same manner as in Example 1 except that the amount of ethylene glycol was changed to 30.0 parts by mass. In the obtained glass wool, the adhered amount of the binder was 2.8 parts by mass with respect to 100 parts by mass of the glass wool, and the content of ethylene glycol was 19.0% by mass with respect to the mass of the binder.

Example 3
A glass wool of Example 3 was obtained in the same manner as in Example 1 except that the amount of ethylene glycol was changed to 5.0 parts by mass. In the obtained glass wool, the adhered amount of the binder was 2.6 parts by mass with respect to 100 parts by mass of the glass wool, and the content of ethylene glycol was 2.3% by mass with respect to the mass of the binder.

Example 4
Glass wool of Example 4 was obtained in the same manner as in Example 1 except that the amount of ethylene glycol was changed to 15.0 parts by mass and the heating temperature was changed to 240°C. In the obtained glass wool, the adhered amount of the binder was 2.8 parts by mass with respect to 100 parts by mass of the glass wool, and the content of ethylene glycol was 0.8% 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 ethylene glycol was changed to 40.0 parts by mass. In the obtained glass wool, the adhered 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 ethylene glycol was 30.6% by mass with respect to the mass of the binder.

Example 6
A glass wool of Example 6 was obtained in the same manner as in Example 1 except that 1,2-butanediol was used instead of ethylene glycol. In the obtained glass wool, the amount of the binder attached was 2.7 parts by weight with respect to 100 parts by weight of the glass wool, and the content of 1,2-butanediol was 5.7% by weight based on the weight of the binder. It was The residual ratio of the alcohol compound (here, 1,2-butanediol) was 0.72.

Example 7
An aqueous solution of polymethacrylic acid was prepared by radically polymerizing methacrylic acid using potassium persulfate as a polymerization initiator in deionized water. According to the preparation method described in paragraph 0040 of Japanese Patent No. 3950996, a zinc-containing aqueous ammonia solution was prepared. 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, and zinc was added. 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.

Next, 100 parts by mass of zinc-containing polymethacrylic acid (solid content conversion), 40.0 parts by mass of ethylene glycol, heavy oil emulsion ("Daphne Prosolvable PF" manufactured by Idemitsu Kosan Co., Ltd.) 15.0 parts by mass (solid content conversion). ) And 0.5 part by mass of γ-aminopropyltriethoxysilane were mixed and stirred, and water was added to the obtained mixed liquid to obtain a binder composition having a solid content concentration of 4.0% by mass.

A glass wool of Example 7 was obtained in the same manner as in Example 1 except that this binder composition was used. In the obtained glass wool, the adhered amount of the binder was 3.5 parts by mass based on 100 parts by mass of the glass wool, and the content of ethylene glycol was 18.7% by mass based on the mass of the binder. The binder after the heat treatment contains 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 4 except that the amount of ethylene glycol was changed to 1.0 part by mass. In the obtained glass wool, the adhered amount of the binder was 2.7 parts by mass based on 100 parts by mass of the glass wool, and the content of ethylene glycol was undetectable by HPLC, that is, 0.0 mass% based on the mass of the binder. %Met.

Comparative example 2
A glass wool of Comparative Example 2 was obtained in the same manner as in Example 1 except that ethylene glycol was changed to 1,4-butanediol. In the obtained glass wool, 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 1,4-butanediol was 4.9% by mass with respect to the mass of the binder. It was The residual ratio of the alcohol compound (here, 1,4-butanediol) was 0.61.

Comparative Example 3
A glass wool of Comparative Example 3 was obtained in the same manner as in Example 1 except that ethylene glycol was changed to diethylene glycol. In the obtained glass wool, the adhered amount of the binder was 3.0 parts by mass based on 100 parts by mass of the glass wool, and the content of diethylene glycol was 4.4% by mass based on the mass of the binder. The residual ratio of the alcohol compound (here, diethylene glycol) was 0.55.

Comparative Example 4
A glass wool of Comparative Example 4 was obtained in the same manner as in Example 1 except that ethylene glycol was changed to 2-propanol. In the obtained glass wool, the adhered amount of the binder was 2.9 parts by mass based on 100 parts by mass of the glass wool, and the content of 2-propanol was 3.9% by mass based on the mass of the binder. The residual ratio of the alcohol compound (2-propanol here) was 0.49.

Comparative Example 5
A glass wool of Comparative Example 5 was obtained in the same manner as in Example 1 except that glycerol was used instead of ethylene glycol. In the obtained glass wool, 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 glycerol was 6.5% by mass with respect to the mass of the binder. The residual ratio of the alcohol compound (here, glycerol) was 0.82.

Comparative Example 6
A glass wool of Comparative Example 6 was obtained in the same manner as in Example 7, except that the amount of ethylene glycol (C) was changed to 1.0 part by mass. In the obtained glass wool, the amount of the binder attached was 3.0 parts by mass with respect to 100 parts by mass of the glass wool, and the content of ethylene glycol was undetectable by HPLC, that is, 0.05 parts by mass of the binder. It was mass %.

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

(Amount of binder attached)
The weight (mass before incineration) of the glass wool to which the binder was attached was measured. Then, the glass wool was heated in an air atmosphere at 500° C. for 60 minutes to incinerate the binder. The mass of the remaining glass wool (mass after incineration) was measured, and the adhered amount of the binder was calculated by the following formula.
Adhesion amount of binder (mass %)={(mass before incineration-mass after incineration)/mass before incineration}×100

(Content of alcohol compound)
0.2144 g of a standard product of an alcohol compound (meaning ethylene glycol, 1,2-butanediol, 1,4-butanediol, diethylene glycol, 2-propanol and glycerol) was weighed. The weighed alcohol compound was dissolved in 100 mL of ultrapure water in a volumetric flask, and then diluted 10 times with ultrapure water to prepare 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 analyzed by HPLC (UltraMate 3000 type manufactured by ThermoFisher SCIENTIFIC) to measure the peak area of the alcohol compound. From the measurement results, a calibration curve regarding the concentration of the alcohol compound was created.

Next, 7 g of glass wool having a binder attached thereto and 500 ml of ultrapure water were added to a beaker, and a dispersion treatment by ultrasonic waves (40 kHz) was performed for 30 minutes. Then, the inside of the beaker was well stirred using a spatula. The solution in the beaker was filtered with a 0.45 μm filter to obtain a sample solution. The obtained sample solution was analyzed by HPLC (ThermalMate 3000 type manufactured by ThermoFisher SCIENTIFIC) under the same conditions as when the calibration curve was prepared. The content (unit: mass %) of the alcohol compound in the sample solution was determined from the obtained chromatogram and calibration curve. When the content of alcohols in the sample solution is extremely low and the quantification is difficult by the calibration curve, the sample solution was concentrated to 10 times with a rotary evaporator, and the content of the alcohol compound was measured using the concentrated sample solution. .. From the content of the alcohol compound in the sample solution, the mass of glass wool, and the amount of the binder attached, the content of the alcohol compound in the binder attached to the glass fiber was calculated by the following formula.
Mass of alcohol compound in sample solution (g)=(content of alcohol compound in sample solution (mass %)/100)×mass of sample solution (g)
Content of alcohol compound in binder (mass %)=(mass of alcohol compound in sample solution (g))/{(mass of glass wool (g)×adhesion amount of binder (mass %)/100)}×100

(Processability of glass wool)
The continuously produced glass wool was continuously cut for 10 hours using a slitter (a facility for cutting glass wool with a blade (tip saw) attached to the edge of a disc having a diameter of 405 mm). The slitter was arranged at a position where the width of the glass wool after cutting was 430 mm. The processability of glass wool was evaluated according to the following criteria.
A: The continuous cutting of the glass wool could be carried out for 10 hours without intermittently cutting residue on the lower surface of the glass wool.
B: Intermittent cutting residue (a portion exceeding the specified cutting width of 430 mm of the glass wool product) was formed on the lower surface of the glass wool, but continuous cutting of the glass wool could be carried out for 10 hours.
C: Glass wool cannot be cut continuously.

As shown in Tables 1 and 2, when the binder contains a polyvinyl alcohol resin or a methacrylic resin and the diol compound represented by the formula (1), as compared with the case where the binder contains another alcohol compound. It was confirmed that glass wool having excellent processability was obtained.

1... Mineral wool.

Claims (8)

Inorganic fiber, including a binder attached to the inorganic fiber,
The binder is
A water-soluble resin,
The following formula (1):

And a diol compound in which R is a hydrogen atom or an alkyl group,
The water-soluble resin is a resin other than a polycondensate of formaldehyde and other monomers,
Mineral wool. The mineral wool according to claim 1, wherein the content of the diol compound is 45.0% by mass or less based on the mass of the binder. The mineral wool according to claim 1, wherein the content of the diol compound is 1.5 to 20.0 mass% with respect to the mass of the binder. The mineral wool according to claim 1, wherein the diol compound contains at least one selected from the group consisting of ethylene glycol, 1,2-propanediol and 1,2-butanediol. The mineral wool according to any one of claims 1 to 3, wherein the diol compound is 1,2-butanediol. The mineral wool according to any one of claims 1 to 5, wherein the water-soluble resin is a polyvinyl alcohol resin or a (meth)acrylic resin. The mineral wool according to any one of claims 1 to 5, wherein the water-soluble resin is a polyvinyl alcohol resin. The mineral wool according to any one of claims 1 to 7, wherein an 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.

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