JP7138282B2 - mineral wool - Google Patents

Description

The present invention relates to mineral wool.

In glass wool or mineral wool such as rock wool, a binder (binder for mineral wool) is used for bonding between fibers. For example, Patent Document 1 discloses an aqueous binder for mineral fibers containing a polymer having carboxyl groups, a polyol, a curing catalyst, and water.

JP 2013-136864 A

Conventionally, a binder containing a polycondensate (eg, phenolic resin) of formaldehyde and other monomers as a main component has been used for mineral wool. However, due to concerns over formaldehyde emitted from the polycondensate, the use of other resins may be desired depending on the application. However, mineral wool using a binder containing a resin other than a polycondensate of formaldehyde and other monomers as a main component tends to leave uncut pieces when cut, leaving room for improvement in workability.

Therefore, the main object of the present invention is to provide a mineral wool which is excellent in workability 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 comprising inorganic fibers and a binder attached to the inorganic fibers. The binder comprises a water-soluble resin and the following formula (1):

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

ADVANTAGE OF THE INVENTION According to one aspect of the present invention, it is possible to provide a mineral wool excellent in workability while containing a resin other than a polycondensate of formaldehyde and other monomers.

1 is a cross-sectional view showing one embodiment of mineral wool; FIG.

Several embodiments of the invention are described in detail below. However, the present invention is not limited to the following embodiments.

FIG. 1 is a cross-sectional view showing one 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 the mineral wool is not limited to this. The binder contains a water-soluble resin and a diol compound having hydroxyl groups at the 1- and 2-positions. Since the mineral wool 1 according to the present embodiment is excellent in workability, it can be used as a heat insulating material for building materials (especially a heat insulating material arranged inside a building material such as inside a wall or inside a ceiling). .

The mineral wool 1 includes a wool-like fiber assembly containing inorganic fibers. The inorganic fibers forming the fiber assembly are bound together via a binder. The inorganic fibers may be glass fibers, blast furnace slag containing silicic acid and lime as main components, or fibers made from rocks or the like. Mineral wool containing glass fibers as inorganic fibers is generally referred to as glass wool. As inorganic fibers, blast furnace slag containing silicic acid and lime as main components, or mineral wool containing fibers made from rock or the like is generally called rock wool. The mineral wool may be glass wool containing glass fiber from the viewpoint of better heat insulation and sound absorption.

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

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

The binder for 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.

A water-soluble resin is a resin that dissolves in water. A water-soluble resin is usually a resin that dissolves in 100 g of water at 25° C. in an amount of 0.1 g or more. Since the water-soluble resin is a resin other than a polycondensate of formaldehyde and other monomers, it does not substantially contain structural units derived from formaldehyde. Examples of "other monomers" herein include phenol compounds and amine compounds such as urea, melamine and dicyandiamide. Examples of polycondensates of formaldehyde and other monomers include phenolic resins, urea resins, and melamine resins (melamine-formaldehyde resins), and water-soluble resins other than these may be used.

The water-soluble resin may be, for example, at least one selected from the group consisting of polyvinyl alcohol resins, (meth)acrylic resins, and polysaccharides. As used herein, "(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 of further excellent workability. The water-soluble resin may be a polyvinyl alcohol resin, from the viewpoints of better workability, further suppression of odor generation in the drying process, and better drying workability.

At least part of the water-soluble resin may be crosslinked. In this specification, a polyvinyl alcohol resin forming a crosslinked body is sometimes referred to as a crosslinked polyvinyl alcohol resin. The cross-linked polyvinyl alcohol resin may be a polyvinyl alcohol resin chemically cross-linked with a cross-linking agent, or a polyvinyl alcohol resin physically cross-linked due to the crystal structure or the like in the resin without depending on the cross-linking agent. . When the binder does not contain a cross-linking agent, the binder usually contains a component for promoting physical cross-linking of the polyvinyl alcohol resin, such as a crystallization accelerator described below. The crosslinked polyvinyl alcohol resin means a polyvinyl alcohol resin that is at least partially chemically or physically crosslinked. It may be a partially chemically crosslinked polyvinyl alcohol resin.

Polyvinyl alcohol resin is a saponified product of polyvinyl acetate. The polyvinyl alcohol resin may contain a structural unit having an ester group derived from vinyl acetate. The degree of polymerization of the polyvinyl alcohol resin may be, for example, 150-3000, 200-1500, 220-1000, 250-800, or 280-500. The degree of polymerization of the polyvinyl alcohol resin is, for example, the value of the average degree of polymerization determined by the method specified in JIS K 6726:1994. The degree of saponification of the polyvinyl alcohol resin may be, for example, 60-100 mol %, or 75-99 mol %. The degree of saponification of the polyvinyl alcohol resin can be determined, for example, by the method specified in JIS K 6726:1994. Commercially available polyvinyl alcohol resins include, for example, “JL-05E” (degree of polymerization: 500, degree of saponification: 80 to 84 mol %) manufactured by Nippon Vinyl Poval.

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 the hydroxyl groups of the polyvinyl alcohol resin to bond the molecular chains of the polyvinyl alcohol resin together. composed of one or more compounds that crosslink the The cross-linking agent may contain a compound having two or more functional groups capable of reacting with hydroxyl groups to form covalent bonds. Examples of functional groups that can react with hydroxyl groups to form covalent bonds include carboxyl groups.

The cross-linking agent for the polyvinyl alcohol resin includes a reactive group selected from, for example, an aliphatic carboxylic acid, a homopolymer or copolymer containing an aliphatic carboxylic acid as a monomer unit, a boron compound, 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 polymers or copolymers 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. Coalesces or copolymers may be mentioned. 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" (a maleic acid-based copolymer) manufactured by Gokyo Sangyo Co., Ltd.

Examples of boron compounds include borax, boric acid, and boric acid complexes. A boron compound can advance a cross-linking reaction of a polyvinyl alcohol resin at the stage of preparing a binder composition containing the boron compound. Therefore, from the viewpoint of suppressing excessive viscosity increase of the binder composition, the boron compound may be used in the preparation of the binder composition in the form of a low-concentration aqueous solution. For example, a 4.0% concentration aqueous solution prepared by dissolving commercially available borax in water is used.

The isocyanate compound has two or more reactive groups selected from isocyanate groups and blocked isocyanate groups. A blocked isocyanate group is a group formed by blocking an isocyanate group with a blocking agent. Blocking agents include, for example, methyl ketoxime and caprolactam. The isocyanate compound may be an isocyanate compound having two or more blocked isocyanate groups.

Examples of isocyanate compounds include hexamethylene diisocyanate (HDI)-based isocyanate compounds, diphenylmethane diisocyanate (MDI)-based isocyanate compounds, toluene diisocyanate (TDI)-based isocyanate compounds, blocked HDI-based isocyanate compounds, and blocked MDI-based isocyanate compounds. Examples include isocyanate compounds and blocked TDI-based isocyanate compounds. The isocyanate compound may be an HDI isocyanate compound, an MDI isocyanate compound, a blocked HDI isocyanate compound, or a blocked MDI isocyanate compound, an HDI isocyanate compound, or a blocked An HDI-based isocyanate compound may be used. Here, the HDI-based isocyanate compound means hexamethylene diisocyanate or an oligomer of hexamethylene diisocyanate (eg, 2- to 10-mers). The MDI-based isocyanate compound means diphenylmethane diisocyanate or an oligomer of diphenylmethane diisocyanate (eg, 2- to 10-mers). The TDI-based isocyanate compound means toluene diisocyanate or an oligomer of toluene diisocyanate (eg, 2- to 10-mer).

Examples of commercially available isocyanate compounds include "Elastron BN11", "Elastron BN77", and "F2462D1" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and "Meikanate TP10" and "SU268A" manufactured by Meisei Chemical Industry Co., Ltd. be done.

The content of the cross-linking agent may be 1.0 parts by mass or more with respect to 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 cross-linking 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. Alternatively, it may be 10 parts by mass or less.

When the cross-linking 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, the generation of odor is 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 the polyvinyl alcohol resin contains a cross-linking agent, the content of the cross-linked polyvinyl alcohol resin means the sum of the mass of the polyvinyl alcohol resin and the mass of the cross-linking agent. The binder may contain a cross-linking agent that does not form covalent or non-covalent bonds with the hydroxyl groups of the polyvinyl alcohol resin.

The binder containing polyvinyl alcohol resin may further contain a crystallization accelerator. A 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 size of 1 μm or less (eg, talc, etc.), crystalline organic substances (eg, carboxylic acid amide, etc.), 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).

A (meth)acrylic resin is a polymer containing as a main monomer unit a (meth)acrylic monomer selected from (meth)acrylic acid and (meth)acrylic acid esters. The (meth)acrylic resin may contain structural units derived from monomers other than the (meth)acrylic monomer, but usually the ratio of the (meth)acrylic monomer is 50% of the total mass of the polymer. ~100% by mass.

The (meth)acrylic resin may have a carboxyl group. A (meth)acrylic resin having a carboxyl group usually contains monomer units derived from a monomer having a carboxyl group. Examples of monomers having a carboxyl group include (meth)acrylic acid (acrylic acid or methacrylic acid).

The (meth)acrylic resin having a carboxyl group may contain structural units derived from monomers other than the monomer having a carboxyl group. In the (meth)acrylic resin having a carboxyl group, the ratio of the number of structural units derived from monomers other than the monomer having a carboxyl group is 50 with respect to the total number of structural 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 consist only of structural units derived from a monomer having a carboxyl group, and poly(meth)acrylic acid consisting 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 ions (Zn ²⁺ ) and zirconium ions (Zr ⁴⁺ ), and may be zinc ions (Zn ²⁺ ) or zirconium ions (Zr ⁴⁺ ), It may be a zinc ion (Zn ²⁺ ).

In a binder containing a (meth)acrylic resin having carboxyl groups and metal ions, at least some of the carboxyl groups form ionic bonds with the metal ions, thereby cross-linking the (meth)acrylic resin. A (meth)acrylic resin that 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 ions to carboxyl groups/valence of metal ions) with respect to the total amount of carboxyl groups in the (meth)acrylic resin. From the viewpoint of further improving the hardness of the wool, it may be 0.07 chemical equivalents or more, 0.20 chemical equivalents or more, or 0.30 chemical equivalents or more, and 1.00 chemical equivalents or less and 0.90 chemical equivalents 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 the mineral wool, the content of the metal ions is 0.03 to 0.80 chemical equivalents, 0.07 to 0.80 chemical equivalents, relative to the total amount of carboxyl groups possessed by the (meth)acrylic resin. It may be 70 chemical equivalents, 0.20-0.60 chemical equivalents, or 0.30-0.50 chemical equivalents. When the content of metal ions is 0.80 chemical equivalents or less with respect to the total amount of carboxyl groups possessed by the (meth)acrylic resin, the amount of dispersing aid (e.g. aqueous ammonia solution) used during mineral wool production is As it is reduced, the production of mineral wool becomes easier.

Polysaccharides as water-soluble resins include, for example, dextrin, chemically modified starch (e.g., hydroxypropylated starch, carboxymethylated starch, phosphate esterified starch), or celluloses (e.g., carboxymethylcellulose, carboxyethylcellulose, methylcellulose, hydroxypropyl cellulose, methyl propyl cellulose, etc.).

The number average molecular weight of the water-soluble resin may be greater than 1000, 1100 or greater, 3000 or greater, 5000 or greater, 7000 or greater, or 9000 or greater, and may be 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. As used herein, the number average molecular weight (Mn) means a value measured by gel permeation chromatography (GPC) and converted to standard polyethylene glycol.

An aqueous solution with a concentration of 20% by mass containing a water-soluble resin (concentration is a value when the total amount of the aqueous solution is 100% by mass.) s or less.

The content of the water-soluble resin is 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 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 40-100% by weight, 60-100% by weight, 70-100% by weight, 80-100% by weight, or 100% by weight relative to the weight of the binder.

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

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

The content of the diol compound of formula (1) may be 45.0% by mass or less relative to the mass of the binder, which tends to further improve the processability of mineral wool. From the same viewpoint, the content of the diol compound of formula (1) may be 20.0% by mass or less, or 15.0% by mass or less, based on the mass of the binder, 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 dustproof agent. Dustproof agents include oil emulsions and the like. Examples of commercially available dustproof 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 water repellents include silicone additives such as silicone oil emulsions, and fluorine additives. Examples of commercially available water repellent agents include Shin-Etsu Chemical Co., Ltd.'s silicone oil emulsion "Polon MR". The content of the water repellent agent 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. Silane coupling agents contribute to interfacial adhesion between water-soluble resins and inorganic fibers. Examples of silane coupling agents include aminosilane coupling agents such as 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3-glycides, Epoxysilane coupling agents such as xypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane are included. Examples of commercially available silane coupling agents include aminopropyltrimethoxysilane “KBE903” manufactured by Shin-Etsu Chemical Co., Ltd. The silane coupling agents may be used singly or in combination of two or more.

The content of the silane coupling agent may be 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the water-soluble resin, from the viewpoint of the water solubility and reactivity of the water-soluble resin and production costs. When the content of the silane coupling agent is 0.1 parts by mass or more, sufficient interfacial adhesion between the water-soluble resin and the inorganic fibers is likely to be obtained. The silane coupling agent also contributes to fixation of the silicone-based additive to the inorganic fiber surface. Therefore, a combination of a silane coupling agent and a water repellent such as a silicone additive can further improve the water resistance of mineral wool.

In addition to the components exemplified above, the binder composition according to one embodiment may further contain other components as necessary. Examples of other components include adhesion inhibitors, release agents, colorants, and dihydrazides that contribute to the shape retention of mineral wool.

The amount of binder may be 0.5 to 15.0 parts by weight, 1.0 to 15.0 parts by weight, or 1.0 to 6.0 parts by weight with respect to 100 parts by weight of mineral wool. The amount of the binder attached to 100 parts by mass of mineral wool may be 1.0 parts 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. It may be 10.0 parts by mass or less, 6.0 parts by mass or less, or 5.0 parts by mass or less. The adhesion amount of the binder 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 optionally other components with an aqueous medium. The cross-linking reaction of the water-soluble resin proceeds during preparation of the binder composition and/or by heating the binder composition. Aqueous solvents include, for example, at least one selected from the group consisting of water, methanol, ethanol, ethylene glycol, and glycerin. The aqueous solvent may contain water from the viewpoint of economy and handling. Even if the proportion of water in the aqueous solvent is 50 to 100% by weight, 60 to 100% by weight, 70 to 100% by weight, 80 to 100% by weight, or 90 to 100% by weight based on the weight 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% by mass relative to the total amount of the binder composition. When the content of 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 shortened. When the content of components other than the aqueous solvent is 20.0% by mass or less, the binder composition tends to easily permeate the wool-like inorganic fibers. From the same point of view, 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 inorganic fibers, a step of forming a wool-like intermediate fiber base material containing the inorganic fibers and the binder composition attached thereto, and an intermediate and heating the fiber base material.

In the step of attaching the binder composition to the inorganic fibers, for example, inorganic raw materials such as heat-melted glass or minerals such as rocks are fiberized to form inorganic fibers, and the binder composition is applied to the formed inorganic fibers. may be attached. Examples of methods for fiberizing inorganic fibers include a flame method, a blowing method, and a centrifugal method (also referred to as a rotary method). Examples of the method of adhering the binder composition to the inorganic fibers include a method of spraying a misty binder composition onto the inorganic fibers using a spray device or the like.

A wool-like intermediate fibrous base material can be formed by depositing the inorganic fibers with the binder composition while adhering the binder composition to the inorganic fibers. The deposited inorganic fibers are gradually entangled with each other to form a wool-like form. The timing of attaching the binder composition to the inorganic fibers may be any time after the inorganic fibers are formed. The binder composition may be applied to the inorganic fibers and then formed into a woolly intermediate fibrous substrate.

By heating the intermediate fiber base material, the binder composition adhering to the inorganic fibers is heat-cured to form a binder, thereby obtaining a mineral wool containing the inorganic fibers and the binder adhering to the inorganic fibers. A method for heating the intermediate fiber base material is not particularly limited. For example, the intermediate fibrous substrate can be heated by passing it through one or more heating zones set at predetermined heating temperatures. A plurality of heating zones may be installed in series along the conveying direction of the intermediate fibrous base material. The heating temperature may be set so as to remove the aqueous solvent from the binder composition. may When the average heating temperature is within these ranges, it is possible to prevent or suppress the occurrence of undried portions (remaining water) in the mineral wool, and as a result, the resilience of the mineral wool is ensured.

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 equation (1), L _i represents the distance over which the intermediate fibrous base material is conveyed within each heating zone, and T _i represents the set temperature of each heating zone. i indicates the number of heating zones and is an integer of 1 or greater.

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

After the heating step, the intermediate fibrous base material, that is, the mineral wool, may be formed into, for example, a mat shape if necessary, and further cut into desired widths and lengths.

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 examples thereof include paper (particularly heat-resistant paper, such as glass paper), synthetic resin film, metal foil film, nonwoven fabric (eg, glass chopped strand mat), woven fabric (eg, glass fiber fabric). ) or a combination thereof can be used.

Mineral wool according to the present embodiment can be used, for example, as a material having heat insulating and sound absorbing functions. The mineral wool according to this embodiment may be used as a heat insulating material for building materials (in particular, a heat insulating material placed inside building materials such as inside walls and ceilings).

EXAMPLES 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 of aqueous solution of polyvinyl alcohol resin ("JL-05E" manufactured by Nippon Vinyl Poval Co., Ltd., degree of polymerization: 300, number average molecular weight: 13200, degree of saponification: 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), ethylene glycol 10.0 parts by mass , 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 mixture 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 glass was introduced into a fiberization apparatus, and the hot-melted raw glass was spouted in a fibrous state by a centrifugal method to form glass fibers. While the formed glass fibers were air-cooled, the binder composition was adhered to the glass fibers by spraying a mist of the binder composition onto the glass fibers. The glass fibers with the binder composition were deposited thereby forming a woolly intermediate fiber substrate.

The resulting 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, a mat-like glass wool of Example 1 containing glass fibers to which a binder was attached was obtained. The binder after heat treatment contains a polyvinyl alcohol resin crosslinked by a maleic acid-based copolymer as a crosslinking agent. Also, part of the ethylene glycol in the binder composition was volatilized by the heat treatment.

In the resulting glass wool, the amount of binder adhered was 3.1 parts by mass with respect to 100 parts by mass of 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, the "alcohol compound content (mass%) in the binder" is a value measured by the measuring method described below.
Percentage of residual alcohol compound = (content of alcohol compound in binder (% by mass))/(content of alcohol compound relative to mass of all components other than water in binder composition (% by mass))

Example 2
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 amount of binder adhered was 2.8 parts by mass with respect to 100 parts by mass of 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 resulting glass wool, the amount of binder adhered was 2.6 parts by mass with respect to 100 parts by mass of 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 resulting glass wool, the amount of binder adhered was 2.8 parts by mass with respect to 100 parts by mass of 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 amount of binder adhered was 3.3 parts by mass with respect to 100 parts by mass of glass wool, and the content of ethylene glycol was 30.6% by mass with respect to the mass of the binder.

Example 6
Glass wool of Example 6 was obtained in the same manner as in Example 1, except that ethylene glycol was changed to 1,2-butanediol. In the obtained glass wool, the amount of binder adhered was 2.7 parts by mass with respect to 100 parts by mass of glass wool, and the content of 1,2-butanediol was 5.7% by mass with respect to the mass of the binder. rice field. The residual proportion of the alcohol compound (here, 1,2-butanediol) was 0.72.

Example 7
A polymethacrylic acid aqueous solution was prepared by radically polymerizing methacrylic acid in deionized water using potassium persulfate as a polymerization initiator. 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 is added to the polymethacrylic acid aqueous solution so that the content of metal ions (Zn ²⁺ ) is 0.4 chemical equivalents with respect to the total amount of carboxyl groups possessed by polymethacrylic acid, and zinc A polymethacrylic acid-containing aqueous solution was obtained. The viscosity of this zinc-containing polymethacrylic aqueous solution was 24 mPa·s at 25°C. The viscosity of the zinc-containing polymethacrylic aqueous solution was measured using a Brookfield viscometer in accordance with JIS K6833-1:2008.

Then, 100 parts by weight of zinc-containing polymethacrylic acid (converted to solid content), 40.0 parts by weight of ethylene glycol, heavy oil emulsion (manufactured by Idemitsu Kosan "Daphne Prosolvable PF") 15.0 parts by weight (converted to solid content) ) and 0.5 parts by mass of γ-aminopropyltriethoxysilane were mixed and stirred, and water was added to the resulting mixture to obtain a binder composition having a solid content concentration of 4.0% by mass.

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 amount of binder adhered was 3.5 parts by mass with respect to 100 parts by mass of glass wool, and the content of ethylene glycol was 18.7% by mass with respect to the mass of the binder. The binder after heat treatment comprises polymethacrylic resin crosslinked by 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 parts by mass. In the resulting glass wool, the amount of binder adhered was 2.7 parts by mass with respect to 100 parts by mass of glass wool, and the content of ethylene glycol was undetectable by HPLC, that is, 0.0 mass with respect to the mass of the binder. %Met.

Comparative example 2
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 resulting glass wool, the amount of binder adhered was 3.1 parts by mass with respect to 100 parts by mass of glass wool, and the content of 1,4-butanediol was 4.9% by mass with respect to the mass of the binder. rice field. The residual proportion of the alcohol compound (here, 1,4-butanediol) was 0.61.

Comparative example 3
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 amount of binder adhered was 3.0 parts by mass with respect to 100 parts by mass of glass wool, and the content of diethylene glycol was 4.4% by mass with respect to the mass of the binder. The residual proportion of the alcohol compound (here diethylene glycol) was 0.55.

Comparative example 4
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 resulting glass wool, the amount of binder attached was 2.9 parts by weight per 100 parts by weight of glass wool, and the content of 2-propanol was 3.9% by weight with respect to the weight of the binder. The residual proportion of the alcohol compound (here, 2-propanol) was 0.49.

Comparative example 5
Glass wool of Comparative Example 5 was obtained in the same manner as in Example 1 except that ethylene glycol was changed to glycerol. In the resulting glass wool, the amount of binder adhered was 2.7 parts by mass with respect to 100 parts by mass of glass wool, and the content of glycerol was 6.5% by mass with respect to the mass of the binder. The residual proportion of alcohol compounds (here glycerol) was 0.82.

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

2. Evaluation (fiber diameter, density, width, length, thickness and thermal performance λ)
The density, width, length, thickness and thermal performance λ of the glass wool were measured according to JIS A 9521:2014. The example and comparative example glass wool 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 the apparent density based on the volume including void volume.

(Binder adhesion amount)
The weight of the glass wool to which the binder adhered (mass before incineration) 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} x 100

(Content of alcohol compound)
0.2144 g of standards of alcohol compounds (herein meaning ethylene glycol, 1,2-butanediol, 1,4-butanediol, diethylene glycol, 2-propanol and glycerol) were weighed. A weighed alcohol compound was dissolved in 100 mL of ultrapure water in a volumetric flask and then diluted 10-fold with ultrapure water to prepare standard solution 1. Then, standard solution 1 was diluted 2-fold, 10-fold, 20-fold, 50-fold or 100-fold with ultrapure water to prepare standard solutions 2-6. The obtained standard solutions 1 to 6 were analyzed by HPLC (UltiMate 3000 type manufactured by ThermoFisher SCIENTIFIC) to measure the peak area of the alcohol compound. From the measurement results, a calibration curve was prepared for the concentration of the alcohol compound.

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

(Processability of glass wool)
The continuously produced glass wool was cut continuously for 10 hours using a slitter (equipment for cutting glass wool with a blade (chip saw) attached to the edge of a disk with 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 workability of the glass wool was evaluated according to the following criteria.
A: Continuous cutting of the glass wool could be performed for 10 hours without intermittently causing an uncut portion on the lower surface of the glass wool.
B: Continuous cutting of glass wool could be carried out for 10 hours, although uncut parts (portions exceeding the prescribed cutting width of 430 mm of the glass wool product) were intermittently generated on the lower surface of the glass wool.
C: Continuous cutting of glass wool is impossible.

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 formula (1), compared with the case where the binder contains other alcohol compounds It was confirmed that a glass wool having excellent workability was obtained.

1... Mineral wool.

Claims (6)

Including an inorganic fiber and a binder attached to the inorganic fiber,
The binder is
a water-soluble resin;
Formula (1) below:

and a diol compound represented by R is a hydrogen atom or an alkyl group,
The water-soluble resin is a polyvinyl alcohol resin ,
mineral wool. The mineral wool according to claim 1, wherein the content of said diol compound is 45.0% by mass or less with respect to the mass of said binder. 2. The mineral wool according to claim 1, wherein the content of said diol compound is 1.5 to 20.0% by mass with respect to the mass of said binder. The mineral wool according to any one of claims 1 to 3, wherein the diol compound contains at least one selected from the group consisting of ethylene glycol, 1,2-propanediol and 1,2-butanediol. 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 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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