JP2020196969A - Mineral wool - Google Patents

Abstract

To provide mineral wool which has sufficient hardness, is excellent in workability and has high compressive stress.SOLUTION: Mineral wool 1 contains an inorganic fiber, and a binder attached to the inorganic fiber. The binder contains a polyvinyl alcohol resin, a (meth)acrylic resin having a carboxyl group, and a carboxylic acid dihydrazide compound. At least a part of the (meth)acrylic resin forms a crosslinking structure by reaction with the carboxylic acid dihydrazide compound, and a ratio of the total mass of the (meth)acrylic resin and the carboxylic acid dihydrazide compound to the mass of the polyvinyl alcohol resin is 0.03-20.00.SELECTED DRAWING: Figure 1

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).

JP-A-2007-169545

Various resins have been used as the main component of the binder for mineral wool. However, it has been difficult for conventional binders to satisfy all the required properties such as hardness, workability, and compressive stress of mineral wool. Therefore, an object of the present invention is to provide mineral wool having sufficient hardness, excellent workability, and high compressive stress.

One aspect of the present invention relates to mineral wool containing inorganic fibers and a binder attached to the inorganic fibers. The binder contains a polyvinyl alcohol resin, a (meth) acrylic resin having a carboxyl group, and a carboxylic acid dihydrazide compound. At least a part of the (meth) acrylic resin forms a crosslinked structure by reaction with the carboxylic acid dihydrazide compound, and the ratio of the total mass of the (meth) acrylic resin and the carboxylic acid dihydrazide compound to the mass of the polyvinyl alcohol resin is , 0.03 to 20.00.

According to the present invention, mineral wool having sufficient hardness, excellent workability, and high compressive stress is provided.

It is sectional drawing which shows 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 cross-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.

Mineral wool 1 contains a wool-like fiber aggregate containing inorganic fibers. Inorganic fibers constituting the fiber aggregate are bound to each other via a binder. The inorganic fiber may be a glass fiber, a blast furnace slag containing silicate and lime as main components, or a fiber made from rock or the like. Mineral wool containing glass fiber as an inorganic fiber is generally called glass wool. As inorganic fibers, blast furnace slag containing silicic acid and lime as main components, or mineral wool containing fibers made from rocks and the like is generally referred to as rock wool. The mineral wool may be glass wool containing glass fibers from the viewpoint of improving heat insulation and sound absorption.

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 micronea method. The fiber length of the inorganic fibers constituting the mineral wool may be 2.0 to 500.0 mm.

The binder attached to the inorganic fiber contains a polyvinyl alcohol resin, a (meth) acrylic resin having a carboxyl group, and a carboxylic acid dihydrazide compound. As used herein, the term "(meth) acrylic" means "acrylic" or the corresponding "methacrylic".

The 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, 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 even more preferably in the range of 250 to 800. The range is, particularly preferably the range of 280 to 500. The degree of polymerization of the polyvinyl alcohol resin is, for example, a 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%), preferably in the range of 75 to 99 (mol%). The degree of saponification of the polyvinyl alcohol resin can be determined by, for example, the method specified in JIS K 6726: 1994. Commercially available products of polyvinyl alcohol resin include, for example, "JL-05E" manufactured by Japan Vam & Poval Co., Ltd. (degree of polymerization: 500, saponification degree: 80 to 84 (mol%)), manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Examples thereof include "Gosenol GL-03" (degree of polymerization: 400, degree of saponification: 86.5-89.0).

At least a part of the polyvinyl alcohol resin may be crosslinked. That is, the binder may contain a crosslinked polyvinyl alcohol resin, which is a crosslinked product of the polyvinyl alcohol resin. The crosslinked polyvinyl alcohol resin may be a polyvinyl alcohol resin chemically crosslinked with a crosslinking agent, or may be a polyvinyl alcohol resin physically crosslinked by a crystal structure or the like in the resin regardless of the crosslinking agent. .. When the binder does not contain a cross-linking agent, the binder may contain a component for promoting physical cross-linking of the polyvinyl alcohol resin, such as a crystallization accelerator described later. The crosslinked polyvinyl alcohol resin means a polyvinyl alcohol resin which is at least partially chemically or physically crosslinked, and may be a polyvinyl alcohol resin which is at least partially chemically crosslinked.

When the crosslinked polyvinyl alcohol resin is a polyvinyl alcohol resin chemically crosslinked with a crosslinking agent, the crosslinking agent forms a covalent bond or a non-covalent bond with the hydroxyl group of the polyvinyl alcohol resin, thereby forming molecular chains of the polyvinyl alcohol resin with each other. Consists of one or more compounds that crosslink. The cross-linking 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 that can react 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 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. It may contain an isocyanate compound (hereinafter, also simply referred to as “isocyanate compound”) or a combination thereof.

Examples of the polymer or copolymer containing an aliphatic carboxylic acid as a monomer unit include maleic acid homopolymer or copolymer, (meth) acrylic acid homopolymer or copolymer, and fumaric acid monopoly weight. Examples include coalescing or copolymers. The cross-linking agent may be, in particular, a copolymer having two carboxyl groups and containing a monomer unit derived from maleic acid. The cross-linking agent may be a commercially available product. Examples of the commercially available cross-linking agent include "Gantrentz AN-119" (maleic acid-based copolymer) manufactured by Gokyo Sangyo Co., Ltd.

Examples of the boron compound include borax, boric acid, and a boric acid complex. The boron compound can allow the cross-linking reaction of the polyvinyl alcohol resin to proceed at the stage of preparing the binder composition containing the boron compound. 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 ketooxime and caprolactam. The isocyanate compound is preferably an isocyanate compound having two or more blocked isocyanate groups.

Examples of the isocyanate compound include hexamethylene diisocyanate (HDI) -based isocyanate compound, diphenylmethane diisocyanate (MDI) -based isocyanate compound, toluene diisocyanate (TDI) -based isocyanate compound, blocked HDI-based isocyanate compound, blocked MDI-based isocyanate compound, or , Blocked TDI-based isocyanate compounds, preferably HDI-based isocyanate compounds, MDI-based isocyanate compounds, blocked HDI-based isocyanate compounds, or blocked MDI-based isocyanate compounds, and more preferably HDI-based isocyanate compounds. Isocyanate compound or blocked HDI-based isocyanate compound. Here, the HDI-based isocyanate compound means hexamethylene diisocyanate or an oligomer of hexamethylene diisocyanate (for example, a 2 to 10 dimer), and is preferably hexamethylene diisocyanate. The MDI-based isocyanate compound means diphenylmethane diisocyanate or an oligomer of diphenylmethane diisocyanate (for example, a 2 to 10 dimer), and is preferably diphenylmethane diisocyanate. The TDI-based isocyanate compound means toluene diisocyanate or an oligomer of toluene diisocyanate (for example, 2 to 10 mer), and is 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., and "Meisei Chemical Works, Ltd." "Meikanate TP10" and "SU268A". ..

The content of the cross-linking agent may be 1.0 part by mass or more, 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 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 cross-linking agent contains an isocyanate compound, the content of the isocyanate compound is 12 to 90 parts by mass, 14 to 70 parts by mass, 16 to 50 parts by mass, 18 to 40 parts by mass with respect to 100 parts by mass of the polyvinyl alcohol resin. Alternatively, it may be 20 to 30 parts by mass.

When the binder containing the polyvinyl alcohol resin contains a cross-linking agent, the mass 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. In the binder, not all of the cross-linking agents need to form covalent or non-covalent bonds with the hydroxyl groups 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 size of 1 μm or less (for example, talc), crystalline organic substances (for example, 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).

The content of the polyvinyl alcohol resin in the binder attached to the inorganic fiber is 10% by mass or more, 30% by mass or more, 50% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass based on the total mass of the binder. % Or more, or 75% by mass or more, and may be 95% by mass or less, 90% by mass or less, or 85% by mass or less. The content here also includes the amount of the polyvinyl alcohol resin forming the crosslinked structure. This also applies to the following description herein.

The (meth) acrylic resin is a polymer containing a (meth) acrylic monomer selected from (meth) acrylic acid and (meth) acrylic acid ester as a main monomer unit. The (meth) acrylic resin may contain monomer units derived from a monomer other than the (meth) acrylic monomer, but usually, the proportion of the monomer units derived from the (meth) acrylic monomer is It is 50 to 100% by mass with respect to the total mass of the polymer.

A (meth) acrylic resin having a carboxyl group usually contains a monomer unit derived from a monomer having a carboxyl group. The monomer having a carboxyl group is, for example, (meth) acrylic acid.

The (meth) acrylic resin having a carboxyl group may contain a monomer unit derived from a monomer other than the monomer having a carboxyl group. The proportion of monomer units derived from monomers other than the monomer having a carboxyl group is less than 50 mol% and less than 30 mol% with respect to the total number of monomer units constituting the (meth) acrylic resin. It may be less than 10 mol% or less than 1 mol%. The (meth) acrylic resin having a carboxyl group may consist only of monomer units derived from a monomer having a carboxyl group, and may consist only of monomer units derived from (meth) acrylic acid. ) It may be acrylic acid.

The carboxylic acid dihydrazide compound is a compound derived from a compound having two carboxyl groups and has two hydrazino groups (-NHNH ₂ ). The carboxylic acid dihydrazide compound may be, for example, adipic acid dihydrazide, succinic acid dihydrazide or a mixture thereof, or may be adipic acid dihydrazide.

At least a part of the (meth) acrylic resin contained in the binder is crosslinked by the reaction with the carboxylic acid dihydrazide compound. Usually, the (meth) acrylic resin is crosslinked by the reaction of the carboxyl group of the (meth) acrylic resin with the hydradino group of the carboxylic acid dihydrazide compound.

The total content of the (meth) acrylic resin and the carboxylic acid dihydrazide compound in the binder attached to the inorganic fiber is 3% by mass or more, 5% by mass or more, or 8% by mass or more based on the total mass of the binder. It may be 95% by mass or less, 75% by mass or less, 60% by mass or less, 45% by mass or less, 30% by mass or less, or 20% by mass or less. The content here also includes the amount of the (meth) acrylic resin and the carboxylic acid dihydrazide compound forming the crosslinked structure. This also applies to the following description herein.

The molar ratio of the total amount of hydrazino groups contained in the carboxylic acid dihydrazide compound to the total amount of carboxyl groups contained in the (meth) acrylic resin may be 0.1 to 1.0. When the molar ratio of hydrazino groups is within this range, a particularly remarkable effect is obtained in improving the hardness of mineral wool. From the same viewpoint, the molar ratio of hydrazino groups may be 0.5 to 1.0 or 0.7 to 1.0. By analyzing the binder attached to the inorganic fiber by time-of-flight secondary ion mass spectrometry (TOF-SIMS), the molar ratio of hydrazino groups to the total amount of carboxyl groups can be quantified. When the obtained molar ratio is within the above range, it can be considered that all of the carboxylic acid dihydrazide compounds form a crosslinked structure.

The binder may contain a relatively large amount of a carboxylic acid dihydrazide compound that does not form a crosslinked structure (hereinafter, may be referred to as “uncrosslinked carboxylic acid dihydrazide compound”). For example, the content of the uncrosslinked carboxylic acid dihydrazide compound is 0.5 to 30 parts by mass with respect to 100 parts by mass of the total amount of the (meth) acrylic resin and the carboxylic acid dihydrazide compound forming the crosslinked structure. You may. When the molar ratio of hydrazino groups to the total amount of carboxyl groups obtained by analyzing the binder attached to the inorganic fibers by TOF-SIMS exceeds 1.0, the carboxylic acid corresponding to the hydradino groups in the portion exceeding 1.0 The dihydrazide compound can be considered not to form a crosslinked structure. In the following, the term "carboxylic acid dihydrazide compound" does not include "uncrosslinked carboxylic acid dihydrazide compound".

In the binder, the ratio of the total mass of the (meth) acrylic resin and the carboxylic acid dihydrazide compound to the mass of the polyvinyl alcohol resin (hereinafter, also referred to as “PMMA / PVA”) is 0.03 to 20.00. PMMA / PVA is 15.00 or less, 10.00 or less, 5.00 or less, 1.00 or less, 0.50 or less, 0.30 from the viewpoint of obtaining a particularly remarkable effect on improving the hardness of mineral wool. Hereinafter, it may be 0.28 or less, or 0.25 or less, for example, 0.03 to 15.00, 0.05 to 10.00, 0.05 to 5.00, 0.05 to 1.00. , 0.05 to 0.30, 0.08 to 0.28, or 0.10 to 0.25. PMMA / PVA may be 1.00 or more, 5.00 or more, or 8.00 or more, for example, 1.00 to 20.00, from the viewpoint of obtaining a particularly remarkable effect on the improvement of compressive stress. It may be 5.00 to 15.00, or 8.0 to 12.00.

The binder may further contain urea. In the mineral wool according to the present embodiment, the urea content may be 0.3 to 50.0% by mass with respect to the mass of the binder. The urea content is 0.3 to 40.0% by mass and 0.5 to 35.% With respect to the mass of the binder from the viewpoint of further improving workability and improving drying workability. It may be 0% by mass or 3.0 to 15.0% by mass. From the same viewpoint, the urea content is 0.3% by mass or more, 0.5% by mass or more, 1.0% by mass or more, 1.5% by mass or more, and 2.0% by 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% by mass or less, 25.0% by mass or less, 20.0% by mass or less, 18.0% by mass or less, 15.0% by mass or less, or 14.0% by mass or less. The urea content remains in the binder in a state where a part of urea contained in the binder composition is volatilized by heating and then is not covalently bonded to the cured polyvinyl alcohol resin and / or (meth) acrylic resin. The amount of urea to be used.

Specifically, the urea content with respect to the mass of the binder can be measured by the following method. First, 0.2144 g of a urea standard product is weighed, dissolved in 100 ml of ultrapure water in a volumetric flask, and then diluted 10-fold with ultrapure water to prepare standard solution 1. Next, the standard solution 1 is diluted 2-fold, 10-fold, 20-fold, 50-fold or 100-fold with ultrapure water to prepare standard solutions 2-6. HPLC (Thermo Fisher SCIENTIFIC UltratiMate 3000 type) measurement is carried out on the obtained standard solutions 1 to 6 to prepare a calibration curve for urea concentration. Next, 7 g of a mineral wool sample and 500 ml of ultrapure water are added to the beaker, and ultrasonic waves (40 kHz) are dispersed for 30 minutes. The beaker is then well stirred with a spatula. The solution in the beaker is then filtered through a 0.45 μm filter to obtain a sample solution. Next, the obtained sample solution was subjected to HPLC (UltraMate 3000 type) measurement 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. Calculation, formula: Urea content = ((Urea content obtained by calibration curve / 100 x sample solution amount (unit: g)) / (weight of mineral wool sample (7 g) x binder adhesion amount / 100)) Calculate from × 100. If the urea content in the sample solution is extremely low and it is difficult to quantify by the calibration curve, the sample solution is distilled with a rotary evaporator, concentrated up to 10 times, the sample solution is reprepared, and urea is again prepared. The content of is measured.

The binder may further contain a silane coupling agent. The silane coupling agent is, for example, a compound having an alkoxysilyl group and a reactive functional group, and can contribute to further improvement in hardness of mineral wool. Examples of silane coupling agents include aminosilane coupling agents such as 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and aminopropyltriethoxysilane, and 3-glycid. Examples thereof include epoxysilane coupling agents such as xypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane. Examples of commercially available silane coupling agents include aminopropyltrimethoxysilane "KBE903" manufactured by Shin-Etsu Chemical Co., Ltd. One type of silane coupling agent may be used alone, or two or more types may be used in combination.

The content of the silane coupling agent in the binder may be 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the total amount of the polyvinyl alcohol resin, the (meth) acrylic resin and the carboxylic acid dihydrazide compound. It may be 0.2 to 2.0 parts by mass, and may be 0.3 to 1.0 parts by mass.

The binder may further contain a dustproofing agent. Examples of the dustproof agent include oil emulsions and the like. Examples of commercially available dustproof agents include the heavy oil emulsion "Daphne Prosolve PF" manufactured by Idemitsu Kosan Co., Ltd. The content of the dustproof agent may be 1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the polyvinyl alcohol resin, the (meth) acrylic resin and the carboxylic acid dihydrazide compound.

The binder may further contain a water repellent. Examples of the water repellent include silicone-based additives such as silicone oil emulsions and fluorine-based additives. An example of a commercially available water repellent is a silicone oil emulsion "Polon MR" manufactured by Shin-Etsu Chemical Co., Ltd. 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 total amount of the polyvinyl alcohol resin, the (meth) acrylic resin and the carboxylic acid dihydrazide compound.

The amount of the binder attached to the inorganic fibers was 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. Good. 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 10 parts by mass or less, 10.0 parts by mass or less, 6.0 parts by mass or less, or 5.0 parts by mass or less. To determine the amount of binder attached, first measure the weight of the mineral wool to which the binder is attached (mass before incineration), and then heat the mineral wool in an air atmosphere at 500 ° C. for 60 minutes to incinerate the binder. Then, it can be obtained by a method including measuring the mass of the remaining mineral wool (mass after incineration) and calculating the amount of the binder adhered by the following formula.
Binder adhesion amount (mass%) = {(mass before incineration-mass after incineration) / mass before incineration} x 100

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

Mineral wool 1 includes, for example, a step of adhering a binder composition to an inorganic fiber, a step of forming a wool-like intermediate fiber base material containing the inorganic fiber and the binder composition attached to the inorganic fiber, and a step of forming the intermediate fiber base material. It can be produced by a method including a step of heating to obtain mineral wool.

The binder composition contains a polyvinyl alcohol resin, a (meth) acrylic resin having a carboxyl group, a carboxylic acid dihydrazide compound, other components added as needed, and an aqueous medium. A part of the (meth) acrylic resin contained in the binder composition may form a crosslinked structure by reacting with the carboxylic acid dihydrazide compound.

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 ratio 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 the components other than the aqueous solvent may be 2.0 to 20% by mass or 2.0 to 10.0% by mass with respect to the total amount of the binder composition. ..

In the step of adhering the binder composition to the inorganic fiber, for example, the binder composition is attached to the formed inorganic fiber while fiberizing an inorganic raw material such as heat-melted glass or a mineral such as rock to form the inorganic fiber. May be attached. Examples of the method for converting the inorganic fiber into a fiber include a flame method, a blow-off method, and a centrifugation method (also referred to as a rotary method). Examples of the method of adhering the binder composition to the inorganic fiber include a method of spraying the inorganic fiber with a mist-like binder composition by a spray device or the like.

A wool-like intermediate fiber base material can be formed by depositing the inorganic fibers to which the binder composition is attached while adhering the binder composition to the inorganic fibers. The deposited inorganic fibers gradually become entangled with each other, forming a wool-like morphology. The binder composition may be attached to the inorganic fiber immediately after the formation, 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 fiber is heat-cured to form a binder, and mineral wool containing the inorganic fiber and the binder attached to the inorganic fiber can be obtained. The method for heating the intermediate fiber base material is not particularly limited. For example, the intermediate fiber substrate can be heated by passing through one or more heating zones set to a predetermined heating temperature. 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 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, if necessary, and further cut to a desired width and length.

The mineral wool may be used as it is, or the surface of the mineral wool may be coated with a skin material to prepare a member such as a panel having the mineral wool and the skin material. The skin material is not particularly limited, but is, 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 of these can be used.

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

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

1-1. Preparation of binder composition A binder composition was prepared by the following procedure.

Example 1
A precursor solution containing methacrylic acid, adipic acid dihydrazide (a cross-linking substance having a hydradino group as a cross-linking group, hereinafter sometimes referred to as "ADH"), and ammonium persulfate (polymerization initiator) (solid content concentration 20.0 mass). %) Was prepared. The amount of ADH contained in the precursor solution was adjusted so that the molar ratio of the total amount of hydrazino groups to the total amount of carboxyl groups of methacrylic acid was 1.0.

A polyvinyl alcohol resin (PVA, product name: Gosenol GL-03, degree of polymerization: 400, degree of saponification: 86.5-89.0) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. is diluted with water to contain a PVA-containing solution (solid). (Dilution concentration 20.0% by mass) was obtained. The PVA-containing solution, the precursor solution, and urea were mixed and stirred to obtain a binder composition of Example 1 having the composition shown in Table 1. The binder composition of Example 1 was adjusted so that the ratio of the total mass of the methacrylic resin and the adipic acid dihydrazide (hereinafter, also referred to as “PMMA / PVA”) to the mass of the polyvinyl alcohol resin was 0.10.

Examples 2-5
The ratio of the total mass of the polyvinyl alcohol resin, the total mass of the methacrylic resin and the adipate dihydrazide (ADH), the urea content, and the mass of the polyvinyl alcohol resin to the mass of the polyvinyl alcohol resin in the binder ( The binder compositions of Examples 2 to 5 were obtained in the same manner as in Example 1 except that PMMA / PVA) was adjusted to the amount shown in Table 1.

Comparative Example 1
The PVA-containing liquid prepared in Example 1 was used as the binder composition of Comparative Example 1.

Comparative Example 2
The precursor solution and urea were mixed and stirred to obtain a binder composition of Comparative Example 2 having the composition shown in Table 1.

1-2. Production of glass wool to which a binder is attached Glass fibers are formed by introducing a heat-melted raw material glass into a fiberizing apparatus and ejecting the heat-melted raw material glass into a fibrous form by a centrifugal method. While the formed glass fibers were air-cooled, the binder composition was adhered to the glass fibers by spraying the binder composition of the atomized example or comparative example onto the glass fibers. The glass fibers to which the binder composition was attached were deposited, thereby forming a wool-like intermediate fiber base material.

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, a mat-like glass wool containing glass fibers to which a binder was attached was obtained.

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.

2. 2. Evaluation 2-1. Hardness Water was added to each of the binder compositions of Examples and Comparative Examples to adjust the solid content concentration to 2% by mass. Next, the binder composition was impregnated with glass paper (manufactured by Whatman, trade name: GF / A, diameter 70 mm). The glass paper removed from the binder composition was dried by heating at 180 ° C. for 10 minutes. After drying, a measurement sample having a width of 30 mm and a length of 50 mm was cut out from the glass paper to which the binder was attached.

The end on one short side of the prepared measurement sample was sandwiched between jigs. The length of the measurement sample in the portion protruding from the jig was 30 mm. The measurement sample sandwiched between the jigs was held so that its main surface was horizontal. A 1 g double clip (width 13 mm) was attached as a weight to the tip of the portion protruding from the jig of the measurement sample. The double clip was attached to the measurement sample so that the tip of the measurement sample reached the depth of the double clip.

The measurement sample to which the double clip was attached was heated in a constant temperature bath at 220 ° C. for 10 minutes. By this heating, in the case of the binder compositions of Examples 1 to 5 and Comparative Example 2, cross-linking of polymethacrylic acid by ADH proceeded.

The double clip is removed from the measurement sample taken out from the constant temperature bath, and the difference in height between the position of the tip of the measurement sample at this point and the position of the tip of the measurement sample before the double clip is attached is the load fluctuation amount. Recorded as (unit: mm). A small amount of load fluctuation means that the degree of hardness improvement by the binder is large. It can be said that a binder that improves the hardness of glass paper also improves the hardness of mineral wool.

2-2. Workability The continuously produced glass wool was cut continuously for 10 hours using a slitter (a facility for cutting glass wool with a blade (tipped saw) attached to the edge of a disk having a diameter of 405 mm). The slitter was placed 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 leaving a cut residue on the lower surface of the glass wool.
B: Although intermittent uncut parts (a portion exceeding the specified cutting width of 430 mm of the glass wool product) are generated on the lower surface of the glass wool, continuous cutting of the glass wool could be carried out for 10 hours.
C: Continuous cutting of glass wool is not possible.

2-3. Compressive stress First, a measurement sample of 50 mm × 100 mm × 100 mm was cut out from glass wool (density: 32 kg / m ³ ). Next, using a universal testing machine (manufactured by Shimadzu Corporation, AG-IS 10 kN, load cell: 5 kN), stress was applied to the 100 mm × 100 mm surface of the measurement sample at 50 mm / min to make the thickness 90% (45 mm). The stress when compressed to the extent was measured.

The evaluation results are shown in Table 1. It was shown that the mineral wool of the example had sufficient hardness, excellent workability, and high compressive stress.

1 ... Mineral wool.

Claims (3)

Including an inorganic fiber and a binder attached to the inorganic fiber,
The binder contains a polyvinyl alcohol resin, a (meth) acrylic resin having a carboxyl group, and a carboxylic acid dihydrazide compound.
At least a part of the (meth) acrylic resin forms a crosslinked structure by reaction with the carboxylic acid dihydrazide compound.
A mineral wool in which the ratio of the total mass of the (meth) acrylic resin and the carboxylic acid dihydrazide compound to the mass of the polyvinyl alcohol resin is 0.03 to 20.00. The mineral wool according to claim 1, wherein the ratio of the total mass of the (meth) acrylic resin and the carboxylic acid dihydrazide compound to the mass of the polyvinyl alcohol resin is 0.05 to 0.30. The mineral wool according to claim 1 or 2, wherein the carboxylic acid dihydrazide compound is adipic acid dihydrazide.

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