WO2019111449A1 - Binder composition for mineral wool, mineral wool, and production method for mineral wool - Google Patents
Binder composition for mineral wool, mineral wool, and production method for mineral wool Download PDFInfo
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- WO2019111449A1 WO2019111449A1 PCT/JP2018/031034 JP2018031034W WO2019111449A1 WO 2019111449 A1 WO2019111449 A1 WO 2019111449A1 JP 2018031034 W JP2018031034 W JP 2018031034W WO 2019111449 A1 WO2019111449 A1 WO 2019111449A1
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- mineral wool
- binder composition
- isocyanate compound
- binder
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/25—Non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4218—Glass fibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
- D04H1/645—Impregnation followed by a solidification process
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/395—Isocyanates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
Definitions
- the present invention relates to a binder composition for mineral wool, mineral wool and a method for producing mineral wool.
- a binder In mineral wool such as glass wool or rock wool, a binder (a binder for mineral wool) is used to bond the fibers.
- Patent Document 1 discloses an inorganic material obtained by mixing a water-soluble polymer containing a polyvinyl alcohol resin as a main component, a crosslinking agent, an adhesion inhibitor, a silane coupling agent, and a releasing agent.
- a water-soluble binder for inorganic fibers which is a water-soluble binder for fibers, and its cured product has excellent elasticity and water resistance.
- the present inventors have found that mineral wool using a binder containing polyvinyl alcohol as a main component sometimes lacks hardness when heated as compared to mineral wool using a binder containing a phenol resin as a main component. It was found that there is room for improvement in the handleability in a heated state, such as when taking out mineral wool after press molding.
- the main object of the present invention is mineral wool which improves hardness at the time of heating of mineral wool, and makes it possible to control generation of an odor about mineral wool using a binder containing polyvinyl alcohol resin. It is providing a binder composition.
- One aspect of the present invention relates to a binder composition for mineral wool comprising a polyvinyl alcohol resin, an isocyanate compound having two or more reactive groups selected from an isocyanate group and a blocked isocyanate group, and an aqueous solvent.
- the content of the isocyanate compound may be 12 to 90 parts by mass with respect to 100 parts by mass of the content of the polyvinyl alcohol resin.
- the binder composition may further contain a surfactant.
- the surfactant may be a nonionic surfactant.
- the isocyanate compound may be a hexamethylene diisocyanate-based isocyanate compound, a diphenylmethane diisocyanate-based isocyanate compound, a blocked hexamethylene diisocyanate-based isocyanate compound, or a blocked diphenylmethane diisocyanate-based isocyanate compound.
- One aspect of the present invention relates to an intermediate fiber substrate containing an inorganic fiber and the binder composition attached to the inorganic fiber.
- Another aspect of the present invention relates to mineral wool comprising inorganic fibers and a binder attached to the inorganic fibers.
- the binder contains a polyvinyl alcohol resin and an isocyanate compound having two or more reactive groups selected from an isocyanate group and a blocked isocyanate group, and the polyvinyl alcohol resin is crosslinked by the 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 content of the polyvinyl alcohol resin.
- Another aspect of the present invention is a process of attaching the above-mentioned binder composition to inorganic fibers, a process of forming a wool-like intermediate fiber base material comprising inorganic fibers and the above-mentioned binder composition attached thereto, and an intermediate process Heating the fibrous substrate to obtain mineral wool having inorganic fibers and a binder formed from the above binder composition, and a method of producing mineral wool.
- another aspect of the present invention comprises the steps of heating the intermediate fiber substrate to obtain mineral wool having inorganic fibers and a binder formed from the binder composition for mineral wool. It relates to a method of producing wool.
- the hardness at the time of heating of the mineral wool is improved, and it is possible to suppress generation of odor.
- a binder composition is provided.
- a mineral wool using a binder composition containing a polyvinyl alcohol resin is improved in hardness upon heating and generation of odor is suppressed, and a method for producing the same Can be provided.
- glass wool 1 is a sectional view showing glass wool 1 as one embodiment of mineral wool.
- the binder composition for mineral wool (hereinafter, also simply referred to as "binder composition") according to the present embodiment is a polyvinyl alcohol resin, and an isocyanate compound having two or more reactive groups selected from an isocyanate group and a blocked isocyanate group. And an aqueous solvent.
- the binder composition for mineral wool may be crosslinked. That is, the binder composition may contain a crosslinked polyvinyl alcohol resin which is a crosslinked product of polyvinyl alcohol resin.
- the crosslinked polyvinyl alcohol resin may be a polyvinyl alcohol resin chemically crosslinked by a crosslinking agent.
- the crosslinked polyvinyl alcohol resin means a polyvinyl alcohol resin which is at least partially chemically crosslinked.
- the polymerization degree of the polyvinyl alcohol resin may be, for example, in the range of 300 to 3000, in the range of 350 to 1000, and in the range of 400 to 800.
- the degree of polymerization of the polyvinyl alcohol resin is, for example, a value of the average degree of polymerization determined by the method defined in JIS K 6726: 1994.
- the degree of saponification of the polyvinyl alcohol resin may be, for example, in the range of 60 to 100 (mol%), and may be in the range of 75 to 99 (mol%).
- the degree of saponification of the polyvinyl alcohol resin can be determined, for example, by the method defined in JIS K 6726: 1994. Examples of commercially available products of polyvinyl alcohol resins include “JL-05E” (degree of polymerization: 500, degree of saponification: 80 to 84 (mol%)) manufactured by Nippon Shokuhin Biba-Poval.
- the binder composition for mineral wool according to the present embodiment contains, as a crosslinking agent, an isocyanate compound having two or more reactive groups selected from an isocyanate group and a blocked isocyanate group (hereinafter, also simply referred to as "isocyanate compound").
- isocyanate compound an isocyanate compound having two or more reactive groups selected from an isocyanate group and a blocked isocyanate group
- blocked isocyanate groups are obtained by blocking isocyanate groups with a blocking agent. Examples of blocking agents include methyl ketoxime and caprolactam.
- the isocyanate compound may be an isocyanate compound having two or more blocked isocyanate groups.
- isocyanate compound 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 And blocked TDI-based isocyanate compounds, which may be HDI-based isocyanate compounds, MDI-based isocyanate compounds, blocked HDI-based isocyanate compounds, or blocked MDI-based isocyanate compounds, HDI-based isocyanate compounds, Alternatively, it may be a blocked HDI based isocyanate compound.
- HDI hexamethylene diisocyanate
- MDI diphenylmethane diisocyanate
- TDI toluene diisocyanate
- blocked HDI based isocyanate compound blocked MDI based isocyanate compound
- the HDI-based isocyanate compound means hexamethylene diisocyanate or an oligomer (for example, a 2- to 10-mer) of hexamethylene diisocyanate, which may be hexamethylene diisocyanate.
- the MDI-based isocyanate compound means diphenylmethane diisocyanate or an oligomer (for example, a 2- to 10-mer) of diphenylmethane diisocyanate, and may be diphenylmethane diisocyanate.
- TDI-based isocyanate compound means toluene diisocyanate or an oligomer (for example, 2- to 10-mer) of toluene diisocyanate, and may be toluene diisocyanate.
- the isocyanate compound may be a commercially available product.
- Examples of commercially available isocyanate compounds include "Elastron BN 11", “Elastron BN 77” and “F 2462 D 1" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. .
- 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.
- 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.
- the total content of the polyvinyl alcohol resin and the isocyanate compound is more excellent in economy for industrial production with respect to the total amount of components other than the aqueous solvent of the binder composition (hereinafter, also simply referred to as “solid content”). It may be 70 to 92% by mass, 80 to 91% by mass, or 85 to 90% by mass.
- the binder composition for mineral wool of the present embodiment may contain a crosslinking agent other than the isocyanate compound.
- the crosslinking agent other than the isocyanate compound may have two or more reactive groups that react with the hydroxyl group of the polyvinyl alcohol resin to form a covalent bond or a noncovalent bond, and examples thereof include aliphatic carboxylic acids, The homopolymer or copolymer which contains aliphatic carboxylic acid as a monomer unit, a boron compound, or these combination is mentioned.
- the proportion of the isocyanate compound based on the total mass of the crosslinking agent may be more than 50 mass%, 70 mass% or more, 80 mass% or more, 90 mass% or more, or 95 mass% or more.
- the crosslinking agents In the binder composition or the binder formed therefrom, it is not necessary for all of the crosslinking agents to form a covalent or non-covalent bond with the hydroxyl group of the polyvinyl alcohol resin.
- the binder composition according to the present embodiment contains an aqueous solvent.
- the aqueous solvent means water or a hydrophilic solvent compatible with water in any proportion.
- the aqueous solvent can be used as a solvent or dispersion medium for the components contained in the binder composition.
- Examples of the aqueous solvent include water, methanol, ethanol, ethylene glycol, glycerin and the like, which may be water from the viewpoint of economy and handleability.
- the aqueous solvent may be used alone or in combination of two or more.
- the pH of the binder composition according to this embodiment may be 7.0 to 10.0, 7.5 to 9.5, 8.1 to 9.5, or 8.8 to 9.2.
- Adjustment of pH can be performed, for example, by addition of a pH adjuster (eg, ammonia, various carboxylic acids).
- the pH can be measured by pH test paper.
- the binder composition according to the present embodiment may further contain a surfactant.
- a surfactant As surfactant, nonionic surfactant and anionic surfactant are mentioned, for example.
- the surfactant may be a nonionic surfactant from the viewpoint of further improving the hardness of the mineral wool at the time of heating.
- the binder composition according to the present embodiment may further contain a dustproof agent.
- a dustproof agent An oil emulsion etc. are mentioned as a dustproof agent.
- heavy oil emulsion "Daphny prosolvable PF" by Idemitsu Kosan Co., Ltd. is mentioned.
- the content of the dustproof agent may be 1 to 30 parts by mass with respect to 100 parts by mass of the crosslinked polyvinyl alcohol resin.
- the binder composition according to the present embodiment may further contain a water repellent.
- a water repellent silicone type additives, such as a silicone oil emulsion, and a fluorine type additive are mentioned, for example.
- silicone oil emulsion "Polon MR" by Shin-Etsu Chemical Co., Ltd. is mentioned.
- the content of the water repellent may be 0.05 to 20 parts by mass with respect to 100 parts by mass of the crosslinked polyvinyl alcohol resin.
- the binder composition according to the present embodiment may further contain a silane coupling agent.
- the silane coupling agent contributes to the interfacial adhesion between the crosslinked polyvinyl alcohol resin and the inorganic fiber.
- a silane coupling agent aminosilane coupling agents such as 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3-glycidoxypropyl
- epoxy silane coupling agents such as trimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane.
- silane coupling agent Shin-Etsu Chemical Co., Ltd. aminopropyl trimethoxysilane "KBE903" is mentioned.
- 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 may be 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the cross-linked polyvinyl alcohol resin from the viewpoint of water solubility and reactivity of the polyvinyl alcohol resin, and the production cost. When the content of the silane coupling agent is 0.1 parts by mass or more, sufficient interfacial adhesion between the crosslinked polyvinyl alcohol resin and the inorganic fiber is easily obtained.
- the silane coupling agent also contributes to the fixing of the silicone additive to the inorganic fiber surface. Therefore, the water resistance of mineral wool can be further improved by using it in combination with a water-repellent agent such as a silane coupling agent and a silicone-based additive.
- the binder composition according to the present embodiment may further contain other components as necessary in addition to the components exemplified above.
- Other components include adhesion inhibitors, mold release agents, colorants, and dihydrazides that contribute to shape retention of mineral wool.
- 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 with respect to the total amount of the binder composition.
- content of components other than an aqueous solvent is 2.0 mass% or more, the time which the heat processing for drying mineral wool requires becomes short, and there exists a tendency for productivity to improve.
- the viscosity of a solution (binder composition) fully falls that content of components other than an aqueous solvent is 20.0 mass% or less, and the permeability with respect to a wool-like inorganic fiber becomes favorable.
- the content of components other than the aqueous solvent may be 2.0 to 10.0% by mass.
- the binder composition according to the present embodiment includes, for example, an aqueous solution containing a polyvinyl alcohol resin, and an isocyanate compound, and, if necessary, a dustproof agent, a water repellant, a silane coupling agent and other components together with water. It mixes and stirs, and if necessary, water is added and it is obtained by adjusting content of the said component.
- reaction of polyvinyl alcohol resin and an isocyanate compound advances by heating the binder composition for mineral wool during preparation of the binder composition for mineral wool, and / or.
- the intermediate fiber base according to the present embodiment contains inorganic fibers and the above-described binder composition for mineral wool attached to the inorganic fibers. Since the intermediate fiber base according to the present embodiment is wet and flexible since it contains an aqueous solvent, it can be molded into any three-dimensional shape.
- the mineral wool which concerns on this embodiment contains an inorganic fiber and the binder adhering to the inorganic fiber.
- the binder contains a polyvinyl alcohol resin and an isocyanate compound having two or more reactive groups selected from an isocyanate group and a blocked isocyanate group, and the polyvinyl alcohol resin is crosslinked by the above-mentioned 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 content of the polyvinyl alcohol resin.
- the mineral wool according to the present embodiment is substantially free of an aqueous solvent and has an appropriate hardness, so it is used as a sound absorbing material for automobiles and other complicated objects without further processing. Can be used as heat insulation, sound absorption material, etc.
- Mineral wool is a wool-like fiber assembly containing inorganic fibers, and inorganic fibers are bound to each other via a binder or a binder composition.
- the inorganic fibers may be glass fibers, or blast furnace slag mainly composed of silicon and lime components, or fibers made from rocks or the like.
- Mineral wool containing glass fibers as inorganic fibers is generally referred to as glass wool.
- blast furnace slag mainly composed of silicic acid and lime, or mineral wool containing fibers derived from rocks and the like is generally called rock wool.
- Mineral wool may be glass wool containing glass fibers from the viewpoint of better heat insulation and sound absorption.
- FIG. 1 is a cross-sectional view showing glass wool 1 as one embodiment of mineral wool.
- the density of mineral wool may be 10 to 250 kg / m 3 .
- the density and thickness of mineral wool can be measured in accordance with JIS A 9521: 2014.
- the density here is an apparent density based on the volume including the void volume.
- the mineral wool may be mat-like, and the thickness of the mat-like mineral wool may be, for example, 10 to 300 mm.
- the fiber diameter (including the thickness of the binder) of the inorganic fibers constituting the mineral wool may be 3.0 to 10.0 ⁇ m, 3.5 to 8.0 ⁇ m, or 4.0 to 7.0 ⁇ m.
- 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.
- a binder is formed by heating the binder composition which concerns on the above-mentioned embodiment. That is, the binder can also be referred to as a cured product or a heat-treated product of the binder composition.
- the adhesion amount of the binder may be 0.5 to 15.0 parts by mass, or 1.0 to 6.0 parts by mass with respect to 100 parts by mass of the mineral wool.
- the adhesion amount of a binder can be measured by the method as described in the Example mentioned later.
- the mineral wool according to the present embodiment includes, for example, the step of attaching the above-mentioned binder composition to inorganic fibers, the step of forming a wool-like intermediate fiber base material comprising inorganic fibers and the binder composition attached thereto, And heating the fibrous substrate. Further, the intermediate fiber base before heating may be used as mineral wool as it is.
- a binder composition is formed on the inorganic fiber formed while fiberizing an inorganic raw material such as thermally melted glass or a mineral such as rock to form an inorganic fiber. May be attached.
- a method of forming inorganic fibers for example, a usual method such as a flame method, a blowing method, a centrifugal method (also referred to as a rotary method) can be used. In the case of producing glass wool, centrifugation may be used as a fiberization method.
- a method of adhering the binder composition to the inorganic fiber for example, a method of spraying a misty binder composition to the inorganic fiber by a spray device or the like can be used.
- a wool-like intermediate fiber base can be formed by depositing the inorganic fiber to which the binder composition has been attached while attaching the binder composition to the inorganic fibers.
- the deposited inorganic fibers are gradually intertwined to form a wool-like form.
- the binder composition may be attached to the inorganic fiber at any time after the inorganic fiber is formed, but since the adhesion of the binder composition to the inside of the intermediate fiber substrate is easy, the binder composition may be attached immediately after the formation.
- the binder composition may be attached to the inorganic fibers and then a wooly intermediate fiber substrate may be formed.
- the binder composition attached to the inorganic fibers is heated and cured to form a binder, whereby mineral wool containing the inorganic fibers and the binder attached to the inorganic fibers is obtained.
- the method of heating the intermediate fiber base is not particularly limited.
- the intermediate fiber substrate can be heated by passing through one or more heating zones set at a predetermined heating temperature.
- the plurality of heating zones may be installed in series along the transport direction of the intermediate fiber substrate.
- the heating temperature may be set to remove the aqueous solvent from the binder composition, and for example, the average heating temperature may be 200 ° C. or more, and is 200 ° C. or more and 250 ° C. or less, or 210 ° C. or more and 240 ° C. or less You may When the average heating temperature is in these ranges, the generation of the undried portion (remaining of water) in the mineral wool can be prevented or suppressed, and as a result, the recoverability of the mineral wool is secured.
- the average heating temperature Tave is a value calculated by the following formula (1).
- L i represents a distance intermediate fiber substrate is carried in each heating zone
- T i denotes the set temperature of each heating zone.
- i represents the number of heating zones, which is an integer of 1 or more.
- the heating time of the intermediate fiber base 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 after the heating step that is, the mineral wool may be formed into, for example, a mat, if necessary, and may be further cut into a desired width and length.
- Mineral wool may be used as it is, or the surface of mineral wool may be coated with a skin material to make a member such as a panel having mineral wool and a skin material.
- the surface material is not particularly limited, but, for example, paper (especially 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 combinations thereof may be used.
- the mineral wool according to the present embodiment can be suitably used, for example, as a material having a heat insulation / sound absorption function.
- the mineral wool according to the present embodiment can be particularly suitably used as a sound absorbing material for automobiles (in particular, a sound absorbing material disposed on the back of a bonnet).
- Example 1 100 parts by mass (solid content conversion) of polyvinyl alcohol resin (NPLA-made "JL-05E”; aqueous solution) having a degree of polymerization of 300 and a degree of saponification of 88% (heavy oil emulsion as a dustproof agent) (Daphne Prosolvable PF manufactured by Idemitsu Kosan Co., Ltd.) 15.0 parts by mass (in terms of solid content), and 0.5 part by mass of ⁇ -aminopropyltriethoxysilane as a silane coupling agent (in terms of solid content) The solution was mixed and stirred, and adjusted with water so that the solid content concentration of the obtained mixture became 4.0% by mass.
- polyvinyl alcohol resin NPLA-made "JL-05E”
- aqueous solution having a degree of polymerization of 300 and a degree of saponification of 88% (heavy oil emulsion as a dustproof agent)
- a solution of blocked HDI-based isocyanate compound (made by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Elastron BN11) containing a nonionic surfactant as a crosslinking agent in the obtained mixed solution, the content of polyvinyl alcohol resin being 100 It added so that content of a crosslinking agent (isocyanate compound) might be 25 mass parts (solid content conversion) with respect to mass, and the binder composition of Example 1 was obtained.
- the pH of the obtained binder composition was 9.0.
- the "solid content” here is the amount of the solid component (content of components other than the aqueous solvent) remaining after the aqueous solvent is evaporated and dried.
- addition of the solution of the said isocyanate compound was implemented just before making a binder composition adhere to glass fiber.
- Example 2 in the same manner as Example 1 except that a solution of blocked MDI isocyanate compound containing a nonionic surfactant (trade name: F2462D1 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a crosslinking agent.
- a solution of blocked MDI isocyanate compound containing a nonionic surfactant (trade name: F2462D1 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a crosslinking agent.
- Example 3 of Example 3 in the same manner as Example 1 except that a solution of blocked TDI-based isocyanate compound containing a nonionic surfactant (manufactured by Meisei Chemical Co., Ltd., trade name: Maycanate TP10) was used as a crosslinking agent. A binder composition was obtained.
- a solution of blocked TDI-based isocyanate compound containing a nonionic surfactant manufactured by Meisei Chemical Co., Ltd., trade name: Maycanate TP10
- a binder composition was obtained.
- Example 4 The binder of Example 4 in the same manner as Example 1 except that a solution of blocked HDI-based isocyanate compound containing an anionic surfactant (made by Meisei Chemical Co., Ltd., trade name: SU268A) was used as a crosslinking agent. The composition was obtained.
- a solution of blocked HDI-based isocyanate compound containing an anionic surfactant made by Meisei Chemical Co., Ltd., trade name: SU268A
- Example 5 in the same manner as Example 1 except that a solution of a blocked MDI-based isocyanate compound containing an anionic surfactant (product of Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Elastron BN77) was used as a crosslinking agent.
- a solution of a blocked MDI-based isocyanate compound containing an anionic surfactant product of Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Elastron BN77
- Comparative Example 1 A binder composition of Comparative Example 1 was obtained in the same manner as Example 1, except that the amount of the crosslinking agent was changed to 100 parts by mass.
- Comparative example 2 A binder composition of Comparative Example 2 was obtained in the same manner as Example 1, except that the amount of the crosslinking agent was changed to 10 parts by mass.
- the heat-melted raw material glass was introduced into a fiberizing apparatus, and the heat-melted raw material glass was jetted into a fibrous form by a centrifugal method to form glass fibers.
- the binder compositions were adhered to the glass fibers by spraying each binder composition of the example or the comparative example in a mist form.
- the glass fibers with the binder composition attached were deposited to form a wooly intermediate fiber substrate. At this time, the moisture content of the obtained intermediate fiber base was 5% or less.
- the obtained intermediate fiber base material was prepared at a basis weight of 1000 g / m 2 , heated under conditions of an average heating temperature of 200 ° C., a heating time of 5 minutes, and press-formed into a shape of 300 mm ⁇ 300 mm ⁇ 15 mm.
- a binder containing a polyvinyl alcohol resin crosslinked by an isocyanate compound was formed.
- Example and Comparative Example 1 water was added to the binder compositions of Example and Comparative Example 1 to adjust the solid content concentration to 2%.
- a binder composition adjusted in solid content is impregnated with glass paper (manufactured by Whatman, trade name: GF / A 70 mm in diameter), and then dried at 180 ° C. for 10 minutes, and the width is 30 mm and the length is 50 mm. It cut out to size and produced the sample for measurement.
- the measurement sample was held with a jig so that the length of the portion not fixed to the jig was 30 mm from the short side of the manufactured measurement sample, and the measurement sample was held horizontally.
- a 1 g double clip (13 mm in width) was attached as a weight to the tip of the measurement sample not fixed to the jig.
- the measurement sample was inserted into the double clip so that the tip of the measurement sample reached the back of the double clip's clip.
- the measurement sample was placed in a constant temperature bath at 220 ° C. (manufactured by Yamato Scientific Co., Ltd., trade name: DN43N) and heated, and after 10 minutes, the measurement sample was taken out.
- the double clip is removed, and the amount of sag of the tip not fixed to the jig of the measurement sample based on the position of the tip not fixed to the jig of the measurement sample before attaching the double clip (heating load fluctuation) was measured.
- the results are shown in Table 1.
- the load fluctuation amount at the time of heating is smaller, it means that the degree of improvement of the hardness of the glass wool by the binder composition is larger.
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Abstract
Description
本発明は、ミネラルウール用バインダー組成物、ミネラルウール及びミネラルウールの製造方法に関する。 The present invention relates to a binder composition for mineral wool, mineral wool and a method for producing mineral wool.
グラスウール、又は、ロックウール等のミネラルウールにおいて、繊維間を接着させるためにバインダー(ミネラルウール用バインダー)が使用されている。 In mineral wool such as glass wool or rock wool, a binder (a binder for mineral wool) is used to bond the fibers.
従来、ミネラルウールには、フェノール樹脂を主成分とするバインダーが用いられてきた。近年、フェノール樹脂から放散されるホルムアルデヒドへの健康上の懸念から、バインダーにはフェノール樹脂に代えて、ポリビニルアルコール樹脂が用いられることがある。例えば、特許文献1には、ポリビニルアルコール系樹脂を主成分とする水溶性高分子と、架橋剤と、粘着抑制剤と、シランカップリング剤と、離型剤とを混合して得られた無機繊維用水溶性バインダーであって、その硬化物に優れた弾力性と耐水性とがある事を特徴とする、無機繊維用水溶性バインダーが開示されている。
Conventionally, a binder mainly composed of a phenol resin has been used for mineral wool. In recent years, polyvinyl alcohol resin may be used as a binder in place of phenol resin because of health concerns to formaldehyde emitted from phenol resin. For example,
本発明者らは、ポリビニルアルコールを主成分とするバインダーを用いたミネラルウールは、フェノール樹脂を主成分とするバインダーを用いたミネラルウールと比較して、加熱時の硬さが不足することがあり、プレス成形後のミネラルウールを取り出す際等、加熱された状態での取扱性に改善の余地があることを見出した。 The present inventors have found that mineral wool using a binder containing polyvinyl alcohol as a main component sometimes lacks hardness when heated as compared to mineral wool using a binder containing a phenol resin as a main component. It was found that there is room for improvement in the handleability in a heated state, such as when taking out mineral wool after press molding.
また、発明者らは、加熱時の硬さの向上を目的として、バインダーの組成を検討したところ、バインダーの組成によっては、加熱時の硬さが向上する一方で、加熱時に臭気が発生することがあり、これにより作業性が損なわれるという新たな課題を見出した。 Moreover, when the inventors examined the composition of the binder for the purpose of improving the hardness at the time of heating, depending on the composition of the binder, while the hardness at the time of heating is improved, an odor is generated at the time of heating Found a new problem that this would impair the workability.
そこで、本発明の主な目的は、ポリビニルアルコール樹脂を含むバインダーを用いたミネラルウールに関して、ミネラルウールの加熱時の硬さが向上し、かつ、臭気の発生を抑制することを可能とするミネラルウール用バインダー組成物を提供することにある。 Then, the main object of the present invention is mineral wool which improves hardness at the time of heating of mineral wool, and makes it possible to control generation of an odor about mineral wool using a binder containing polyvinyl alcohol resin. It is providing a binder composition.
本発明の一側面は、ポリビニルアルコール樹脂と、イソシアネート基及びブロックイソシアネート基から選ばれる反応性基を2個以上有するイソシアネート化合物と、水性溶媒と、を含有する、ミネラルウール用バインダー組成物に関する。ミネラルウール用バインダー組成物において、イソシアネート化合物の含有量は、ポリビニルアルコール樹脂の含有量100質量部に対して、12~90質量部であってよい。 One aspect of the present invention relates to a binder composition for mineral wool comprising a polyvinyl alcohol resin, an isocyanate compound having two or more reactive groups selected from an isocyanate group and a blocked isocyanate group, and an aqueous solvent. In the binder composition for mineral wool, the content of the isocyanate compound may be 12 to 90 parts by mass with respect to 100 parts by mass of the content of the polyvinyl alcohol resin.
上記バインダー組成物は、界面活性剤を更に含有していてもよい。上記バインダー組成物において、界面活性剤はノニオン性界面活性剤であってよい。 The binder composition may further contain a surfactant. In the binder composition, the surfactant may be a nonionic surfactant.
上記バインダー組成物において、イソシアネート化合物は、ヘキサメチレンジイソシアネート系イソシアネート化合物、ジフェニルメタンジイソシアネート系イソシアネート化合物、ブロックされたヘキサメチレンジイソシアネート系イソシアネート化合物、又は、ブロックされたジフェニルメタンジイソシアネート系イソシアネート化合物であってよい。 In the binder composition, the isocyanate compound may be a hexamethylene diisocyanate-based isocyanate compound, a diphenylmethane diisocyanate-based isocyanate compound, a blocked hexamethylene diisocyanate-based isocyanate compound, or a blocked diphenylmethane diisocyanate-based isocyanate compound.
本発明の一側面は、無機繊維と、無機繊維に付着した上記バインダー組成物と、を含有する、中間繊維基材に関する。 One aspect of the present invention relates to an intermediate fiber substrate containing an inorganic fiber and the binder composition attached to the inorganic fiber.
本発明の別の一側面は、無機繊維と、無機繊維に付着したバインダーと、を含有するミネラルウールに関する。ミネラルウールにおいて、バインダーはポリビニルアルコール樹脂及びイソシアネート基及びブロックイソシアネート基から選ばれる反応性基を2個以上有するイソシアネート化合物を含み、ポリビニルアルコール樹脂はイソシアネート化合物により架橋されている。ミネラルウール用バインダー組成物において、イソシアネート化合物の含有量は、ポリビニルアルコール樹脂の含有量100質量部に対して、12~90質量部であってよい。 Another aspect of the present invention relates to mineral wool comprising inorganic fibers and a binder attached to the inorganic fibers. In mineral wool, the binder contains a polyvinyl alcohol resin and an isocyanate compound having two or more reactive groups selected from an isocyanate group and a blocked isocyanate group, and the polyvinyl alcohol resin is crosslinked by the isocyanate compound. In the binder composition for mineral wool, the content of the isocyanate compound may be 12 to 90 parts by mass with respect to 100 parts by mass of the content of the polyvinyl alcohol resin.
本発明の別の一側面は、上記バインダー組成物を無機繊維に付着させる工程と、無機繊維とこれに付着した上記バインダー組成物とを含むウール状の中間繊維基材を形成させる工程と、中間繊維基材を加熱して、無機繊維と上記バインダー組成物から形成されたバインダーとを有するミネラルウールを得る工程と、を備える、ミネラルウールを製造する方法に関する。 Another aspect of the present invention is a process of attaching the above-mentioned binder composition to inorganic fibers, a process of forming a wool-like intermediate fiber base material comprising inorganic fibers and the above-mentioned binder composition attached thereto, and an intermediate process Heating the fibrous substrate to obtain mineral wool having inorganic fibers and a binder formed from the above binder composition, and a method of producing mineral wool.
また、本発明の別の一側面は、上記中間繊維基材を加熱して、無機繊維と上記ミネラルウール用バインダー組成物から形成されたバインダーとを有するミネラルウールを得る工程と、を備える、ミネラルウールを製造する方法に関する。 In addition, another aspect of the present invention comprises the steps of heating the intermediate fiber substrate to obtain mineral wool having inorganic fibers and a binder formed from the binder composition for mineral wool. It relates to a method of producing wool.
本発明の一側面によれば、ポリビニルアルコール樹脂を含むバインダーを用いたミネラルウールに関して、ミネラルウールの加熱時の硬さが向上し、かつ、臭気の発生を抑制することを可能とするミネラルウール用バインダー組成物が提供される。また、本発明の一側面によれば、加熱時の硬さが向上しており、かつ、臭気の発生が抑制されている、ポリビニルアルコール樹脂を含むバインダー組成物を用いたミネラルウール及びその製造方法を提供することができる。 According to one aspect of the present invention, with respect to mineral wool using a binder containing a polyvinyl alcohol resin, the hardness at the time of heating of the mineral wool is improved, and it is possible to suppress generation of odor. A binder composition is provided. Moreover, according to one aspect of the present invention, a mineral wool using a binder composition containing a polyvinyl alcohol resin is improved in hardness upon heating and generation of odor is suppressed, and a method for producing the same Can be provided.
以下、本発明のいくつかの実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
本実施形態に係るミネラルウール用バインダー組成物(以下、単に「バインダー組成物」ともいう。)は、ポリビニルアルコール樹脂と、イソシアネート基及びブロックイソシアネート基から選ばれる反応性基を2個以上有するイソシアネート化合物と、水性溶媒と、を含有する。 The binder composition for mineral wool (hereinafter, also simply referred to as "binder composition") according to the present embodiment is a polyvinyl alcohol resin, and an isocyanate compound having two or more reactive groups selected from an isocyanate group and a blocked isocyanate group. And an aqueous solvent.
本実施形態に係るミネラルウール用バインダー組成物において、ポリビニルアルコール樹脂の少なくとも一部が架橋されていてもよい。つまり、バインダー組成物は、ポリビニルアルコール樹脂の架橋体である、架橋ポリビニルアルコール樹脂を含有していてもよい。架橋ポリビニルアルコール樹脂は、架橋剤により化学的に架橋されたポリビニルアルコール樹脂であってよい。ここで、架橋ポリビニルアルコール樹脂は、少なくとも一部が化学的に架橋されたポリビニルアルコール樹脂を意味する。 In the binder composition for mineral wool according to the present embodiment, at least a part of the polyvinyl alcohol resin may be crosslinked. That is, the binder composition may contain a crosslinked polyvinyl alcohol resin which is a crosslinked product of polyvinyl alcohol resin. The crosslinked polyvinyl alcohol resin may be a polyvinyl alcohol resin chemically crosslinked by a crosslinking agent. Here, the crosslinked polyvinyl alcohol resin means a polyvinyl alcohol resin which is at least partially chemically crosslinked.
ポリビニルアルコール樹脂の重合度は、例えば、300~3000の範囲であってよく、350~1000の範囲であってよく、400~800の範囲であってよい。ポリビニルアルコール樹脂の重合度は、例えば、JIS K 6726:1994に規定されている方法で求められる平均重合度の値である。ポリビニルアルコール樹脂のケン化度は、例えば、60~100(モル%)の範囲であってよく、75~99(モル%)の範囲であってよい。ポリビニルアルコール樹脂のケン化度は、例えば、JIS K 6726:1994で規定されている方法で求めることができる。ポリビニルアルコール樹脂の市販品としては、例えば、日本酢ビ・ポバール社製の「JL-05E」(重合度:500、けん化度:80~84(モル%))が挙げられる。 The polymerization degree of the polyvinyl alcohol resin may be, for example, in the range of 300 to 3000, in the range of 350 to 1000, and in the range of 400 to 800. The degree of polymerization of the polyvinyl alcohol resin is, for example, a value of the average degree of polymerization determined by the method defined in JIS K 6726: 1994. The degree of saponification of the polyvinyl alcohol resin may be, for example, in the range of 60 to 100 (mol%), and may be in the range of 75 to 99 (mol%). The degree of saponification of the polyvinyl alcohol resin can be determined, for example, by the method defined in JIS K 6726: 1994. Examples of commercially available products of polyvinyl alcohol resins include “JL-05E” (degree of polymerization: 500, degree of saponification: 80 to 84 (mol%)) manufactured by Nippon Shokuhin Biba-Poval.
本実施形態に係るミネラルウール用バインダー組成物は、イソシアネート基及びブロックイソシアネート基から選ばれる反応性基を2個以上有するイソシアネート化合物(以下、単に「イソシアネート化合物」ともいう。)を架橋剤として含有する。ブロックイソシアネート基は、イソシアネート基をブロック剤によりブロック化して得られる。ブロック剤としては、例えば、メチルケトオキシム、カプロラクタムが挙げられる。イソシアネート化合物は、ブロックイソシアネート基を2個以上有するイソシアネート化合物であってよい。 The binder composition for mineral wool according to the present embodiment contains, as a crosslinking agent, an isocyanate compound having two or more reactive groups selected from an isocyanate group and a blocked isocyanate group (hereinafter, also simply referred to as "isocyanate compound"). . Blocked isocyanate groups are obtained by blocking isocyanate groups with a blocking agent. Examples of blocking agents include methyl ketoxime and caprolactam. The isocyanate compound may be an isocyanate compound having two or more blocked isocyanate groups.
イソシアネート化合物としては、ヘキサメチレンジイソシアネート(HDI)系イソシアネート化合物、ジフェニルメタンジイソシアネート(MDI)系イソシアネート化合物、トルエンジイソシアネート(TDI)系イソシアネート化合物、ブロックされたHDI系イソシアネート化合物、ブロックされたMDI系イソシアネート化合物、又は、ブロックされたTDI系イソシアネート化合物を挙げられるが、HDI系イソシアネート化合物、MDI系イソシアネート化合物、ブロックされたHDI系イソシアネート化合物、又は、ブロックされたMDI系イソシアネート化合物であってよく、HDI系イソシアネート化合物、又は、ブロックされたHDI系イソシアネート化合物であってよい。ここで、HDI系イソシアネート化合物とは、ヘキサメチレンジイソシアネート、又は、ヘキサメチレンジイソシアネートのオリゴマー(例えば、2~10量体)を意味し、ヘキサメチレンジイソシアートであってよい。また、MDI系イソシアネート化合物とは、ジフェニルメタンジイソシアネート、又は、ジフェニルメタンジイソシアネートのオリゴマー(例えば、2~10量体)を意味し、ジフェニルメタンジイソシアネートであってよい。また、TDI系イソシアネート化合物とは、トルエンジイソシアネート、又は、トルエンジイソシアネートのオリゴマー(例えば、2~10量体)を意味し、トルエンジイソシアネートであってよい。 As the isocyanate compound, 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 And blocked TDI-based isocyanate compounds, which may be HDI-based isocyanate compounds, MDI-based isocyanate compounds, blocked HDI-based isocyanate compounds, or blocked MDI-based isocyanate compounds, HDI-based isocyanate compounds, Alternatively, it may be a blocked HDI based isocyanate compound. Here, the HDI-based isocyanate compound means hexamethylene diisocyanate or an oligomer (for example, a 2- to 10-mer) of hexamethylene diisocyanate, which may be hexamethylene diisocyanate. Further, the MDI-based isocyanate compound means diphenylmethane diisocyanate or an oligomer (for example, a 2- to 10-mer) of diphenylmethane diisocyanate, and may be diphenylmethane diisocyanate. Further, TDI-based isocyanate compound means toluene diisocyanate or an oligomer (for example, 2- to 10-mer) of toluene diisocyanate, and may be toluene diisocyanate.
イソシアネート化合物は市販品であってもよい。市販のイソシアネート化合物の例としては、第一工業製薬株式会社製の「エラストロンBN11」、「エラストロンBN77」、及び「F2462D1」、明成化学工業株式会社の「メイカネートTP10」及び「SU268A」等が挙げられる。
The isocyanate compound may be a commercially available product. Examples of commercially available isocyanate compounds include "Elastron BN 11", "Elastron BN 77" and "F 2462
イソシアネート化合物の含有量は、ポリビニルアルコール樹脂100質量部に対して、12~90質量部であってよい。イソシアネート化合物の含有量が、12質量部以上であると、臭気の発生がより一層抑制されることとなる。また、イソシアネート化合物の含有量が90質量部以下であると、加熱時の硬さがより一層向上する。イソシアネート化合物の含有量は、ポリビニルアルコール樹脂100質量部に対して、14~70質量部、16~50質量部、18~40質量部、又は20~30質量部であってもよい。 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 an odor is further suppressed. Moreover, the hardness at the time of a heating improves further that content of an isocyanate compound is 90 mass parts or less. 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.
ポリビニルアルコール樹脂及びイソシアネート化合物の合計含有量は、バインダー組成物の水性溶媒以外の成分全量(以下、単に「固形分」ともいう。)に対して、工業的生産のための経済性により優れるという観点から、70~92質量%、80~91質量%、又は85~90質量%であってよい。 The total content of the polyvinyl alcohol resin and the isocyanate compound is more excellent in economy for industrial production with respect to the total amount of components other than the aqueous solvent of the binder composition (hereinafter, also simply referred to as “solid content”). It may be 70 to 92% by mass, 80 to 91% by mass, or 85 to 90% by mass.
本実施形態のミネラルウール用バインダー組成物は、イソシアネート化合物以外の架橋剤を含んでいてもよい。イソシアネート化合物以外の架橋剤は、ポリビニルアルコール樹脂の水酸基と反応して共有結合又は非共有結合を形成する反応性基を2個以上有していればよく、その例としては、脂肪族カルボン酸、脂肪族カルボン酸を単量体単位として含む単独重合体若しくは共重合体、ホウ素化合物、又はこれらの組合せが挙げられる。架橋剤の全体質量を基準とするイソシアネート化合物の割合は、50質量%超、70質量%以上、80質量%以上、90質量%以上、又は95質量%以上であってもよい。 The binder composition for mineral wool of the present embodiment may contain a crosslinking agent other than the isocyanate compound. The crosslinking agent other than the isocyanate compound may have two or more reactive groups that react with the hydroxyl group of the polyvinyl alcohol resin to form a covalent bond or a noncovalent bond, and examples thereof include aliphatic carboxylic acids, The homopolymer or copolymer which contains aliphatic carboxylic acid as a monomer unit, a boron compound, or these combination is mentioned. The proportion of the isocyanate compound based on the total mass of the crosslinking agent may be more than 50 mass%, 70 mass% or more, 80 mass% or more, 90 mass% or more, or 95 mass% or more.
バインダー組成物又はこれから形成されるバインダーにおいて、必ずしも架橋剤の全てが、ポリビニルアルコール樹脂の水酸基と共有結合又は非共有結合を形成していなくてもよい。 In the binder composition or the binder formed therefrom, it is not necessary for all of the crosslinking agents to form a covalent or non-covalent bond with the hydroxyl group of the polyvinyl alcohol resin.
本実施形態に係るバインダー組成物は、水性溶媒を含有する。水性溶媒とは、水、又は水と任意の割合で相溶し得る親水性溶媒を意味する。水性溶媒は、バインダー組成物に含まれる成分の溶媒又は分散媒として用いることができる。水性溶媒としては、水、メタノール、エタノール、エチレングリコール、グリセリン等が挙げられ、経済性及び取扱性の観点から水であってよい。水性溶媒は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。 The binder composition according to the present embodiment contains an aqueous solvent. The aqueous solvent means water or a hydrophilic solvent compatible with water in any proportion. The aqueous solvent can be used as a solvent or dispersion medium for the components contained in the binder composition. Examples of the aqueous solvent include water, methanol, ethanol, ethylene glycol, glycerin and the like, which may be water from the viewpoint of economy and handleability. The aqueous solvent may be used alone or in combination of two or more.
本実施形態に係るバインダー組成物のpHは、7.0~10.0、7.5~9.5、8.1~9.5、又は8.8~9.2であってよい。バインダー組成物のpHがこの範囲内であることで、ミネラルウールの製造設備の腐食を防止又は抑制することができる。pHの調整は、例えば、pH調整剤(例えば、アンモニア、各種カルボン酸)の添加により行うことができる。pHはpH試験紙により測定することができる。 The pH of the binder composition according to this embodiment may be 7.0 to 10.0, 7.5 to 9.5, 8.1 to 9.5, or 8.8 to 9.2. When the pH of the binder composition is in this range, the corrosion of mineral wool production equipment can be prevented or suppressed. Adjustment of pH can be performed, for example, by addition of a pH adjuster (eg, ammonia, various carboxylic acids). The pH can be measured by pH test paper.
本実施形態に係るバインダー組成物は、界面活性剤を更に含有していてよい。界面活性剤としては、例えば、ノニオン性界面活性剤、アニオン性界面活性剤が挙げられる。界面活性剤は、ミネラルウールの加熱時の硬さがより一層向上するという観点から、ノニオン性界面活性剤であってよい。 The binder composition according to the present embodiment may further contain a surfactant. As surfactant, nonionic surfactant and anionic surfactant are mentioned, for example. The surfactant may be a nonionic surfactant from the viewpoint of further improving the hardness of the mineral wool at the time of heating.
本実施形態に係るバインダー組成物は、防塵剤を更に含有していてよい。防塵剤としては、オイルエマルション等が挙げられる。防塵剤の市販品の例としては、出光興産株式会社製の重質オイルエマルション「ダフニープロソルブルPF」が挙げられる。防塵剤の含有量は、架橋ポリビニルアルコール樹脂100質量部に対して、1~30質量部であってよい。 The binder composition according to the present embodiment may further contain a dustproof agent. An oil emulsion etc. are mentioned as a dustproof agent. As an example of a commercial item of a dustproof agent, heavy oil emulsion "Daphny prosolvable PF" by Idemitsu Kosan Co., Ltd. is mentioned. The content of the dustproof agent may be 1 to 30 parts by mass with respect to 100 parts by mass of the crosslinked polyvinyl alcohol resin.
本実施形態に係るバインダー組成物は、撥水剤を更に含有していてよい。撥水剤としては、例えば、シリコーンオイルエマルション等のシリコーン系添加剤、及び、フッ素系添加剤が挙げられる。撥水剤の市販品の例としては、信越化学工業株式会社製のシリコーンオイルエマルション「Polon MR」が挙げられる。撥水剤の含有量は、架橋ポリビニルアルコール樹脂100質量部に対して、0.05~20質量部であってよい。 The binder composition according to the present embodiment may further contain a water repellent. As a water repellent, silicone type additives, such as a silicone oil emulsion, and a fluorine type additive are mentioned, for example. As an example of a commercial item of a water repellent, silicone oil emulsion "Polon MR" by Shin-Etsu Chemical Co., Ltd. is mentioned. The content of the water repellent may be 0.05 to 20 parts by mass with respect to 100 parts by mass of the crosslinked polyvinyl alcohol resin.
本実施形態に係るバインダー組成物は、シランカップリング剤を更に含有していてよい。シランカップリング剤は、架橋ポリビニルアルコール樹脂と無機繊維との界面接着に寄与する。シランカップリング剤としては、3-アミノプロピルトリエトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、アミノプロピルトリエトキシシラン等のアミノシランカップリング剤、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン等のエポキシシランカップリング剤等が挙げられる。シランカップリング剤の市販品の例としては、信越化学工業株式会社製のアミノプロピルトリメトキシシラン「KBE903」が挙げられる。シランカップリング剤は、1種類単独で用いてもよく、又は、2種類以上を併用して用いてもよい。シランカップリング剤の含有量は、ポリビニルアルコール樹脂の水溶性及び反応性並びに製造コストの観点から、架橋ポリビニルアルコール樹脂100質量部に対して、0.1~3.0質量部であってよい。シランカップリング剤の含有量が0.1質量部以上であると、架橋ポリビニルアルコール樹脂と無機繊維との十分な界面接着が得られ易い。シランカップリング剤は、シリコーン系添加剤の無機繊維表面への定着にも寄与する。そのため、シランカップリング剤とシリコーン系添加剤等の撥水剤と組み合わせて用いることにより、ミネラルウールの耐水性をより向上させることができる。 The binder composition according to the present embodiment may further contain a silane coupling agent. The silane coupling agent contributes to the interfacial adhesion between the crosslinked polyvinyl alcohol resin and the inorganic fiber. As a silane coupling agent, aminosilane coupling agents such as 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3-glycidoxypropyl Examples thereof include epoxy silane coupling agents such as trimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane. As an example of the commercial item of a silane coupling agent, Shin-Etsu Chemical Co., Ltd. aminopropyl trimethoxysilane "KBE903" is mentioned. 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 may be 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the cross-linked polyvinyl alcohol resin from the viewpoint of water solubility and reactivity of the polyvinyl alcohol resin, and the production cost. When the content of the silane coupling agent is 0.1 parts by mass or more, sufficient interfacial adhesion between the crosslinked polyvinyl alcohol resin and the inorganic fiber is easily obtained. The silane coupling agent also contributes to the fixing of the silicone additive to the inorganic fiber surface. Therefore, the water resistance of mineral wool can be further improved by using it in combination with a water-repellent agent such as a silane coupling agent and a silicone-based additive.
本実施形態に係るバインダー組成物は、以上例示した成分に加えて、必要に応じてその他の成分を更に含有していてよい。その他の成分としては、粘着抑制剤、離型剤、着色剤、ミネラルウールの形状保持に寄与するジヒドラジド類等が挙げられる。 The binder composition according to the present embodiment may further contain other components as necessary in addition to the components exemplified above. Other components include adhesion inhibitors, mold release agents, colorants, and dihydrazides that contribute to shape retention of mineral wool.
バインダー組成物における、固形分濃度、すなわち水性溶媒以外の成分の含有量が、バインダー組成物全量に対して、2.0~20質量%であってよい。水性溶媒以外の成分の含有量が、2.0質量%以上である場合、ミネラルウールを乾燥させるための加熱処理に要する時間が短くなり、生産性が向上する傾向がある。水性溶媒以外の成分の含有量が、20.0質量%以下であると、溶液(バインダー組成物)の粘度が充分に低下し、ウール状の無機繊維に対する浸透性が良好になる。同様の観点から、水性溶媒以外の成分の含有量が2.0~10.0質量%であってよい。 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 with respect to the total amount of the binder composition. When content of components other than an aqueous solvent is 2.0 mass% or more, the time which the heat processing for drying mineral wool requires becomes short, and there exists a tendency for productivity to improve. The viscosity of a solution (binder composition) fully falls that content of components other than an aqueous solvent is 20.0 mass% or less, and the permeability with respect to a wool-like inorganic fiber becomes favorable. From the same viewpoint, the content of components other than the aqueous solvent may be 2.0 to 10.0% by mass.
本実施形態に係るバインダー組成物は、例えば、ポリビニルアルコール樹脂を含有する水溶液、及びイソシアネート化合物、並びに、必要に応じて、防塵剤、撥水剤、シランカップリング剤及びその他の成分を、水とともに混合及び攪拌し、必要に応じて、水を添加して、上記成分の含有量を調整して得られる。なお、ポリビニルアルコール樹脂と、イソシアネート化合物との反応は、ミネラルウール用バインダー組成物の調製中、及び/又は、ミネラルウール用バインダー組成物を加熱することにより進行する。 The binder composition according to the present embodiment includes, for example, an aqueous solution containing a polyvinyl alcohol resin, and an isocyanate compound, and, if necessary, a dustproof agent, a water repellant, a silane coupling agent and other components together with water. It mixes and stirs, and if necessary, water is added and it is obtained by adjusting content of the said component. In addition, reaction of polyvinyl alcohol resin and an isocyanate compound advances by heating the binder composition for mineral wool during preparation of the binder composition for mineral wool, and / or.
本実施形態に係る中間繊維基材は、無機繊維と、無機繊維に付着した上述のミネラルウール用バインダー組成物と、を含有する。本実施形態に係る中間繊維基材は、水性溶媒を含むことから、湿潤であり柔軟であるので、任意の立体形状に成形加工することが可能である。 The intermediate fiber base according to the present embodiment contains inorganic fibers and the above-described binder composition for mineral wool attached to the inorganic fibers. Since the intermediate fiber base according to the present embodiment is wet and flexible since it contains an aqueous solvent, it can be molded into any three-dimensional shape.
本実施形態に係るミネラルウールは、無機繊維と、無機繊維に付着したバインダーと、を含有する。ミネラルウールにおいて、バインダーはポリビニルアルコール樹脂と、イソシアネート基及びブロックイソシアネート基から選ばれる反応性基を2個以上有するイソシアネート化合物と、を含み、ポリビニルアルコール樹脂は上記イソシアネート化合物により架橋されている。上記イソシアネート化合物の含有量は、ポリビニルアルコール樹脂の含有量100質量部に対して、12~90質量部であってよい。本実施形態に係るミネラルウールは、水性溶媒を実質的に含まず、適度な硬さを有することから、その後の加工がなくとも、自動車用吸音材、その他の複雑な形状をとる対象物に用いられる断熱・吸音材等として利用することが可能である。 The mineral wool which concerns on this embodiment contains an inorganic fiber and the binder adhering to the inorganic fiber. In mineral wool, the binder contains a polyvinyl alcohol resin and an isocyanate compound having two or more reactive groups selected from an isocyanate group and a blocked isocyanate group, and the polyvinyl alcohol resin is crosslinked by the above-mentioned 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 content of the polyvinyl alcohol resin. The mineral wool according to the present embodiment is substantially free of an aqueous solvent and has an appropriate hardness, so it is used as a sound absorbing material for automobiles and other complicated objects without further processing. Can be used as heat insulation, sound absorption material, etc.
ミネラルウールは、無機繊維を含むウール状の繊維集合体であり、バインダー又はバインダー組成物を介して無機繊維同士が結着している。無機繊維は、ガラス繊維、又は、けい酸分と石灰分を主成分とする高炉スラグ、又は岩石等を原料とした繊維であってよい。無機繊維としてガラス繊維を含むミネラルウールは、一般にグラスウールと称される。無機繊維として、けい酸分と石灰分を主成分とする高炉スラグ、又は岩石等を原料とした繊維を含むミネラルウールは、一般にロックウールと称される。ミネラルウールは、断熱性及び吸音性がより優れたものとなる観点から、ガラス繊維を含むグラスウールであってよい。図1は、ミネラルウールの一実施形態としてのグラスウール1を示す断面図である。
Mineral wool is a wool-like fiber assembly containing inorganic fibers, and inorganic fibers are bound to each other via a binder or a binder composition. The inorganic fibers may be glass fibers, or blast furnace slag mainly composed of silicon and lime 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 mineral fibers, blast furnace slag mainly composed of silicic acid and lime, or mineral wool containing fibers derived from rocks and the like is generally called rock wool. Mineral wool may be glass wool containing glass fibers from the viewpoint of better heat insulation and sound absorption. FIG. 1 is a cross-sectional view showing
ミネラルウールの密度は10~250kg/m3であってよい。ミネラルウールの密度及び厚さは、JIS A 9521:2014に準拠して測定することができる。ここでの密度は、空隙体積を含む体積を基準とする見かけ密度である。ミネラルウールはマット状であってもよく、マット状のミネラルウールの厚さは、例えば、10~300mmであってよい。 The density of mineral wool may be 10 to 250 kg / m 3 . The density and thickness of mineral wool can be measured in accordance with JIS A 9521: 2014. The density here is an apparent density based on the volume including the void volume. The mineral wool may be mat-like, and the thickness of the mat-like mineral wool may be, for example, 10 to 300 mm.
ミネラルウールを構成する無機繊維の繊維径(バインダーの厚さを含む。)は、3.0~10.0μm、3.5~8.0μm、又は4.0~7.0μmであってよい。ここでの繊維径は、マイクロネア法で測定される値である。ミネラルウールを構成する無機繊維の繊維長は、2.0~500.0mmであってよい。 The fiber diameter (including the thickness of the binder) of the inorganic fibers constituting the mineral wool 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.
バインダーは、上述の実施形態に係るバインダー組成物を加熱することにより形成される。つまり、バインダーは、バインダー組成物の硬化物又は加熱処理物ということもできる。 A binder is formed by heating the binder composition which concerns on the above-mentioned embodiment. That is, the binder can also be referred to as a cured product or a heat-treated product of the binder composition.
バインダーの付着量が、ミネラルウール100質量部に対して、0.5~15.0質量部、又は1.0~6.0質量部であってもよい。バインダーの付着量は、後述する実施例に記載の方法で測定することができる。 The adhesion amount of the binder may be 0.5 to 15.0 parts by mass, or 1.0 to 6.0 parts by mass with respect to 100 parts by mass of the mineral wool. The adhesion amount of a binder can be measured by the method as described in the Example mentioned later.
本実施形態に係るミネラルウールは、例えば、上記バインダー組成物を無機繊維に付着させる工程と、無機繊維及びこれに付着したバインダー組成物を含むウール状の中間繊維基材を形成させる工程と、中間繊維基材を加熱する工程とを含む方法によって製造することができる。また、加熱前の中間繊維基材をそのままミネラルウールとして用いてもよい。 The mineral wool according to the present embodiment includes, for example, the step of attaching the above-mentioned binder composition to inorganic fibers, the step of forming a wool-like intermediate fiber base material comprising inorganic fibers and the binder composition attached thereto, And heating the fibrous substrate. Further, the intermediate fiber base before heating may be used as mineral wool as it is.
バインダー組成物を無機繊維に付着させる工程では、例えば、熱溶融されたガラス、又は岩石等の鉱物のような無機質原料を繊維化して無機繊維を形成させながら、形成された無機繊維にバインダー組成物を付着させてもよい。無機繊維を繊維化する方法としては、例えば、火焔法、吹き飛ばし法、遠心法(ロータリー法とも言う)等の通常の方法を用いることができる。グラスウールを製造する場合、繊維化する方法として、遠心法を用いてよい。無機繊維にバインダー組成物を付着させる方法としては、例えば、無機繊維に対し、スプレー装置等により、霧状のバインダー組成物を吹き付ける方法を用いることができる。 In the step of adhering the binder composition to the inorganic fiber, for example, a binder composition is formed on the inorganic fiber formed while fiberizing an inorganic raw material such as thermally melted glass or a mineral such as rock to form an inorganic fiber. May be attached. As a method of forming inorganic fibers, for example, a usual method such as a flame method, a blowing method, a centrifugal method (also referred to as a rotary method) can be used. In the case of producing glass wool, centrifugation may be used as a fiberization method. As a method of adhering the binder composition to the inorganic fiber, for example, a method of spraying a misty binder composition to the inorganic fiber by a spray device or the like can be used.
バインダー組成物を無機繊維に付着させながら、バインダー組成物が付着した無機繊維を堆積させることによって、ウール状の中間繊維基材を形成させることができる。堆積した無機繊維同士が徐々に絡み合い、ウール状の形態をとる。無機繊維にバインダー組成物を付着させる時期は、無機繊維が形成された後であればいつでもよいが、中間繊維基材の内部におけるバインダー組成物の付着が容易であることから、形成された直後の無機繊維にバインダー組成物を付着させ、その後、ウール状の中間繊維基材を形成させてよい。 A wool-like intermediate fiber base can be formed by depositing the inorganic fiber to which the binder composition has been attached while attaching the binder composition to the inorganic fibers. The deposited inorganic fibers are gradually intertwined to form a wool-like form. The binder composition may be attached to the inorganic fiber at any time after the inorganic fiber is formed, but since the adhesion of the binder composition to the inside of the intermediate fiber substrate is easy, the binder composition may be attached immediately after the formation. The binder composition may be attached to the inorganic fibers and then a wooly intermediate fiber substrate may be formed.
中間繊維基材を加熱することにより、無機繊維に付着したバインダー組成物が加熱硬化することでバインダーが形成されて、無機繊維と無機繊維に付着したバインダーとを含むミネラルウールが得られる。中間繊維基材を加熱する方法は、特に制限されない。例えば、所定の加熱温度に設定された1つ又は複数の加熱ゾーンを通過させることにより、中間繊維基材を加熱することができる。複数の加熱ゾーンは中間繊維基材の搬送方向に沿って直列的に設置されていてもよい。加熱温度は、バインダー組成物から水性溶媒を除去するように設定すればよく、例えば平均加熱温度が200℃以上であってもよく、200℃以上250℃以下、又は210℃以上240℃以下であってよい。平均加熱温度が、これら範囲内であることで、ミネラルウールにおける未乾燥部分の発生(水の残留)を防止又は抑制することができ、結果としてミネラルウールの復元性が確保される。 By heating the intermediate fiber base, the binder composition attached to the inorganic fibers is heated and cured to form a binder, whereby mineral wool containing the inorganic fibers and the binder attached to the inorganic fibers is obtained. The method of heating the intermediate fiber base is not particularly limited. For example, the intermediate fiber substrate can be heated by passing through one or more heating zones set at a predetermined heating temperature. The plurality of heating zones may be installed in series along the transport direction of the intermediate fiber substrate. The heating temperature may be set to remove the aqueous solvent from the binder composition, and for example, the average heating temperature may be 200 ° C. or more, and is 200 ° C. or more and 250 ° C. or less, or 210 ° C. or more and 240 ° C. or less You may When the average heating temperature is in these ranges, the generation of the undried portion (remaining of water) in the mineral wool can be prevented or suppressed, and as a result, the recoverability of the mineral wool is secured.
それぞれ所定の加熱温度に設定可能なn個の加熱ゾーンを通過させることによって中間繊維基材を加熱する場合、平均加熱温度Taveは、下記式(1)によって算出される値である。式(1)において、Liは各加熱ゾーン内で中間繊維基材が搬送される距離を示し、Tiは各加熱ゾーンの設定温度を示す。iは加熱ゾーンの数を示し、これは1以上の整数である。
中間繊維基材の加熱時間は、バインダー組成物が付着した無機繊維の密度、厚さにより、適宜調整される。加熱時間は、例えば、30秒~10分、又は、2分~10分であってよい。 The heating time of the intermediate fiber base 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.
加熱工程後の中間繊維基材、すなわちミネラルウールは、必要により例えばマット状に成形され、さらに所望の幅、長さに切断してもよい。 The intermediate fiber base after the heating step, that is, the mineral wool may be formed into, for example, a mat, if necessary, and may be further cut into a desired width and length.
ミネラルウールは、そのままの形態で用いてもよく、また、ミネラルウールの表面を表皮材で被覆して、ミネラルウール及び表皮材を有するパネル等の部材を作製してもよい。表皮材としては、特に制限されないが、例えば、紙(特に耐熱紙、例えば、ガラスペーパー)、合成樹脂フィルム、金属箔フィルム、不織布(例えば、ガラスチョップドストランドマット)、織布(例えば、ガラス繊維織物)又はこれらを組み合わせたものを用いることができる。 Mineral wool may be used as it is, or the surface of mineral wool may be coated with a skin material to make a member such as a panel having mineral wool and a skin material. The surface material is not particularly limited, but, for example, paper (especially 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 combinations thereof may be used.
本実施形態に係るミネラルウールは、例えば、断熱・吸音機能を持つ素材として好適に用いることができる。とりわけ、本実施形態に係るミネラルウールは、自動車用吸音材(特に、ボンネット裏に配置される吸音材)として特に好適に用いることができる。 The mineral wool according to the present embodiment can be suitably used, for example, as a material having a heat insulation / sound absorption function. In particular, the mineral wool according to the present embodiment can be particularly suitably used as a sound absorbing material for automobiles (in particular, a sound absorbing material disposed on the back of a bonnet).
以下、実施例を挙げて本発明についてさらに具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to these examples.
<バインダー組成物の調製>
実施例1
重合度が300で、ケン化度が88%であるポリビニルアルコール樹脂(日本酢ビ・ポバール社製「JL-05E」;水溶液)100質量部(固形分換算)、防塵剤である重質オイルエマルション(出光興産社製の「ダフニープロソルブルPF」)15.0質量部(固形分換算)、及び、シランカップリング剤であるγ-アミノプロピルトリエトキシシラン0.5質量部(固形分換算)を混合及び撹拌し、得られた混合液の固形分濃度が4.0質量%になるように水で調整した。得られた混合液に、架橋剤として、ノニオン性界面活性剤を含む、ブロックされたHDI系イソシアネート化合物の溶液(第一工業製薬製、商品名:エラストロンBN11)を、ポリビニルアルコール樹脂の含有量100質量に対して、架橋剤(イソシアネート化合物)の含有量が25質量部(固形分換算)となるように添加し、実施例1のバインダー組成物を得た。得られたバインダー組成物のpHは9.0であった。ここで、pHは、pH試験紙により測定した。ここでの「固形分」は、水性溶媒を揮発させて乾燥した後に残存する固体成分の量(水性溶媒以外の成分の含有量)である。なお、上記イソシアネート化合物の溶液の添加は、バインダー組成物をガラス繊維に付着させる直前に実施した。
<Preparation of Binder Composition>
Example 1
100 parts by mass (solid content conversion) of polyvinyl alcohol resin (NPLA-made "JL-05E"; aqueous solution) having a degree of polymerization of 300 and a degree of saponification of 88% (heavy oil emulsion as a dustproof agent) (Daphne Prosolvable PF manufactured by Idemitsu Kosan Co., Ltd.) 15.0 parts by mass (in terms of solid content), and 0.5 part by mass of γ-aminopropyltriethoxysilane as a silane coupling agent (in terms of solid content) The solution was mixed and stirred, and adjusted with water so that the solid content concentration of the obtained mixture became 4.0% by mass. A solution of blocked HDI-based isocyanate compound (made by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Elastron BN11) containing a nonionic surfactant as a crosslinking agent in the obtained mixed solution, the content of polyvinyl alcohol resin being 100 It added so that content of a crosslinking agent (isocyanate compound) might be 25 mass parts (solid content conversion) with respect to mass, and the binder composition of Example 1 was obtained. The pH of the obtained binder composition was 9.0. Here, the pH was measured by pH test paper. The "solid content" here is the amount of the solid component (content of components other than the aqueous solvent) remaining after the aqueous solvent is evaporated and dried. In addition, addition of the solution of the said isocyanate compound was implemented just before making a binder composition adhere to glass fiber.
実施例2
架橋剤として、ノニオン性界面活性剤を含む、ブロックされたMDI系イソシアネート化合物の溶液(第一工業製薬製、商品名:F2462D1)を用いたこと以外は、実施例1と同様にして実施例2のバインダー組成物を得た。
Example 2
Example 2 in the same manner as Example 1 except that a solution of blocked MDI isocyanate compound containing a nonionic surfactant (trade name: F2462D1 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a crosslinking agent. The binder composition of
実施例3
架橋剤として、ノニオン性界面活性剤を含む、ブロックされたTDI系イソシアネート化合物の溶液(明成化学製、商品名:メイカネートTP10)を用いたこと以外は、実施例1と同様にして実施例3のバインダー組成物を得た。
Example 3
Example 3 of Example 3 in the same manner as Example 1 except that a solution of blocked TDI-based isocyanate compound containing a nonionic surfactant (manufactured by Meisei Chemical Co., Ltd., trade name: Maycanate TP10) was used as a crosslinking agent. A binder composition was obtained.
実施例4
架橋剤として、アニオン性界面活性剤を含む、ブロックされたHDI系イソシアネート化合物の溶液(明成化学製、商品名:SU268A)を用いたこと以外は、実施例1と同様にして実施例4のバインダー組成物を得た。
Example 4
The binder of Example 4 in the same manner as Example 1 except that a solution of blocked HDI-based isocyanate compound containing an anionic surfactant (made by Meisei Chemical Co., Ltd., trade name: SU268A) was used as a crosslinking agent. The composition was obtained.
実施例5
架橋剤として、アニオン性界面活性剤を含む、ブロックされたMDI系イソシアネート化合物の溶液(第一工業製薬製、商品名:エラストロンBN77)を用いた以外は、実施例1と同様にして実施例5のバインダー組成物を得た。
Example 5
Example 5 in the same manner as Example 1 except that a solution of a blocked MDI-based isocyanate compound containing an anionic surfactant (product of Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Elastron BN77) was used as a crosslinking agent. The binder composition of
比較例1
架橋剤の量を100質量部に変更したこと以外は、実施例1と同様にして比較例1のバインダー組成物を得た。
Comparative Example 1
A binder composition of Comparative Example 1 was obtained in the same manner as Example 1, except that the amount of the crosslinking agent was changed to 100 parts by mass.
比較例2
架橋剤の量を10質量部に変更したこと以外は、実施例1と同様にして比較例2のバインダー組成物を得た。
Comparative example 2
A binder composition of Comparative Example 2 was obtained in the same manner as Example 1, except that the amount of the crosslinking agent was changed to 10 parts by mass.
(グラスウールの製造)
熱溶融した原料ガラスを繊維化装置に導入し、遠心法により、熱溶融した原料ガラスを繊維状に噴出させることで、ガラス繊維を形成した。形成されたガラス繊維が空冷される際に、実施例又は比較例の各バインダー組成物を霧状にして吹きつけることで、バインダー組成物をガラス繊維に付着させた。バインダー組成物が付着したガラス繊維を堆積させて、ウール状の中間繊維基材を形成させた。このとき、得られた中間繊維基材の含水率は5%以下とした。
(Manufacture of glass wool)
The heat-melted raw material glass was introduced into a fiberizing apparatus, and the heat-melted raw material glass was jetted into a fibrous form by a centrifugal method to form glass fibers. When the formed glass fibers were air-cooled, the binder compositions were adhered to the glass fibers by spraying each binder composition of the example or the comparative example in a mist form. The glass fibers with the binder composition attached were deposited to form a wooly intermediate fiber substrate. At this time, the moisture content of the obtained intermediate fiber base was 5% or less.
得られた中間繊維基材を1000g/m2の目付量で準備し、平均加熱温度200℃、加熱時間5分間の条件で加熱すると共に、300mm×300mm×15mmの形状にプレス成形した。これにより、バインダーが付着したガラス繊維を含むマット状のグラスウールを得た。加熱することによって、イソシアネート化合物によって架橋されたポリビニルアルコール樹脂を含むバインダーが形成された。 The obtained intermediate fiber base material was prepared at a basis weight of 1000 g / m 2 , heated under conditions of an average heating temperature of 200 ° C., a heating time of 5 minutes, and press-formed into a shape of 300 mm × 300 mm × 15 mm. As a result, mat-like glass wool containing glass fiber to which a binder was attached was obtained. By heating, a binder containing a polyvinyl alcohol resin crosslinked by an isocyanate compound was formed.
(バインダーの付着量)
まず、グラスウールの質量(焼却前質量)を測定し、次いで、空気雰囲気下、500℃の条件で30分間加熱して、バインダーを焼却した。残ったガラス繊維の質量(焼却後質量)を測定し、下記式によりバインダーの付着量を算出した。実施例及び比較例のいずれのグラスウールについても、バインダーの付着量は、グラスウール100質量部に対して、3.1質量部であった。
バインダーの付着量=(焼却前質量-焼却後質量)/焼却前質量×100
(Attachment amount of binder)
First, the mass (mass before incineration) of glass wool was measured, and then the binder was incinerated by heating for 30 minutes under the condition of 500 ° C. in an air atmosphere. The mass (mass after incineration) of the glass fiber which remained was measured, and the adhesion amount of the binder was computed by the following formula. The amount of the binder attached was 3.1 parts by mass with respect to 100 parts by mass of the glass wool in any of the glass wools of the examples and the comparative examples.
Binder adhesion amount = (mass before incineration-mass after incineration) / mass before incineration x 100
(臭気(プレス作業性)の評価)
グラスウールをプレス成形により得た後、プレス成形機を冷却せずにグラスウールを取り出した。このとき、10人の作業者が同じ作業を行い、臭気に違和感を感じた作業者が2人以下の場合を「A」、3人以上の場合を「C」とした。結果を表1に示す。
(Evaluation of odor (press workability))
After glass wool was obtained by press molding, the glass wool was taken out without cooling the press molding machine. At this time, ten workers performed the same work, and the case where two or less workers felt uncomfortable with the odor was "A", and the case where three or more workers were "C". The results are shown in Table 1.
(加熱時の硬さの評価)
グラスウールをプレス成形により得た後、プレス成形機を冷却せずにグラスウールを取り出すことにより、加熱時の硬さを評価した。このとき、グラスウールの一辺の中心を手袋で持って取り出す際に自重で折れ曲がってしまったものを「C」、そうでないものを「A」とした。結果を表1に示す。
(Evaluation of hardness during heating)
After the glass wool was obtained by press molding, the hardness at the time of heating was evaluated by taking out the glass wool without cooling the press molding machine. At this time, when holding the center of one side of glass wool with a glove and taking it out, the thing which was bent by dead weight was made into "C", and the thing which is not so was made into "A". The results are shown in Table 1.
(加熱時の荷重変動量の測定)
加熱時の硬さの評価が「A」となるバインダー組成物について、バインダー組成物による、加熱時におけるグラスウールの硬さ向上の程度を定量的に対比するため、以下の手順で加熱時の荷重変動量を測定した。結果を表1に示す。
(Measurement of load fluctuation during heating)
In order to quantitatively compare the degree of improvement in hardness of glass wool at the time of heating by the binder composition, the load fluctuation at the time of heating is as follows for the binder composition in which the hardness evaluation at the time of heating is “A”. The amount was measured. The results are shown in Table 1.
まず、実施例及び比較例1のバインダー組成物に、水を加えて、固形分濃度2%に調整した。固形分濃度が調整されたバインダー組成物に、ガラスペーパー(Whatman製、商品名:GF/A 直径70mm)を含浸し、次いで、180℃10分間の条件で乾燥させ、幅30mm、長さ50mmのサイズに切り出して、測定用サンプルを作製した。 First, water was added to the binder compositions of Example and Comparative Example 1 to adjust the solid content concentration to 2%. A binder composition adjusted in solid content is impregnated with glass paper (manufactured by Whatman, trade name: GF / A 70 mm in diameter), and then dried at 180 ° C. for 10 minutes, and the width is 30 mm and the length is 50 mm. It cut out to size and produced the sample for measurement.
次いで、作製した測定用サンプルの短辺側から、治具に固定されていない部分の長さが30mmとなるように、測定用サンプルを治具で挟み、水平方向に測定用サンプルを保持した。次いで、治具に固定されていない測定用サンプルの先端に1gのダブルクリップ(幅13mm)を重りとして取り付けた。なお、ダブルクリップを取り付ける際には、ダブルクリップのクリップの奥に測定用サンプル先端位置が達するように、測定用サンプルをダブルクリップに差し込んだ Next, the measurement sample was held with a jig so that the length of the portion not fixed to the jig was 30 mm from the short side of the manufactured measurement sample, and the measurement sample was held horizontally. Next, a 1 g double clip (13 mm in width) was attached as a weight to the tip of the measurement sample not fixed to the jig. When attaching the double clip, the measurement sample was inserted into the double clip so that the tip of the measurement sample reached the back of the double clip's clip.
次いで、治具に取り付けられた状態で、測定用サンプルを220℃の恒温槽(ヤマト科学製、商品名:DN43N)に入れて加熱し、10分後に測定用サンプルを取り出した。 Next, in a state of being attached to a jig, the measurement sample was placed in a constant temperature bath at 220 ° C. (manufactured by Yamato Scientific Co., Ltd., trade name: DN43N) and heated, and after 10 minutes, the measurement sample was taken out.
次いで、ダブルクリップを取り除き、ダブルクリップを取り付ける前の測定用サンプルの治具に固定されない先端の位置を基準とした、測定用サンプルの治具に固定されない先端の垂れ下がり量(加熱時荷重変動量)を測定した。結果を表1に示す。ここで、加熱時の荷重変動量が少ない程、バインダー組成物によるグラスウールの硬さ向上の程度が大きいことを意味する。 Next, the double clip is removed, and the amount of sag of the tip not fixed to the jig of the measurement sample based on the position of the tip not fixed to the jig of the measurement sample before attaching the double clip (heating load fluctuation) Was measured. The results are shown in Table 1. Here, as the load fluctuation amount at the time of heating is smaller, it means that the degree of improvement of the hardness of the glass wool by the binder composition is larger.
1…グラスウール 1 ... Glass wool
Claims (8)
イソシアネート基及びブロックイソシアネート基から選ばれる反応性基を2個以上有するイソシアネート化合物と、
水性溶媒と、を含有する、ミネラルウール用バインダー組成物であって、
前記イソシアネート化合物の含有量が、前記ポリビニルアルコール樹脂の含有量100質量部に対して、12~90質量部である、ミネラルウール用バインダー組成物。 Polyvinyl alcohol resin,
An isocyanate compound having two or more reactive groups selected from an isocyanate group and a blocked isocyanate group,
A binder composition for mineral wool, comprising: an aqueous solvent;
A binder composition for mineral wool, wherein the content of the isocyanate compound is 12 to 90 parts by mass with respect to 100 parts by mass of the content of the polyvinyl alcohol resin.
前記バインダーが、ポリビニルアルコール樹脂と、イソシアネート基及びブロックイソシアネート基から選ばれる反応性基を2個以上有するイソシアネート化合物と、を含み、
前記ポリビニルアルコール樹脂が前記イソシアネート化合物により架橋されており、
前記イソシアネート化合物の含有量が、前記ポリビニルアルコール樹脂の含有量100質量部に対して、12~90質量部である、ミネラルウール。 Containing inorganic fibers and a binder attached to the inorganic fibers,
The binder comprises a polyvinyl alcohol resin, and an isocyanate compound having two or more reactive groups selected from an isocyanate group and a blocked isocyanate group,
The polyvinyl alcohol resin is crosslinked by the isocyanate compound,
Mineral wool wherein the content of the isocyanate compound is 12 to 90 parts by mass with respect to 100 parts by mass of the content of the polyvinyl alcohol resin.
前記無機繊維とこれに付着した前記ミネラルウール用バインダー組成物とを含むウール状の中間繊維基材を形成させる工程と、
前記中間繊維基材を加熱して、前記無機繊維と前記ミネラルウール用バインダー組成物から形成されたバインダーとを有するミネラルウールを得る工程と、を備える、ミネラルウールを製造する方法。 Attaching the mineral wool binder composition according to any one of claims 1 to 4 to inorganic fibers;
Forming a wooly intermediate fiber substrate comprising the inorganic fibers and the mineral wool binder composition attached thereto;
Heating the intermediate fiber substrate to obtain mineral wool having the inorganic fibers and the binder formed from the binder composition for mineral wool, and producing mineral wool.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2017-235391 | 2017-12-07 | ||
| JP2017235391A JP6769426B2 (en) | 2017-12-07 | 2017-12-07 | Binder composition for mineral wool, manufacturing method of mineral wool and mineral wool |
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| WO2019111449A1 true WO2019111449A1 (en) | 2019-06-13 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021086803A1 (en) * | 2019-10-28 | 2021-05-06 | Ocv Intellectual Capital, Llc | Cross-linked non-woven mat |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5069139A (en) * | 1973-10-08 | 1975-06-09 | ||
| JPS534047A (en) * | 1976-07-02 | 1978-01-14 | Koyo Sangyo Co | Adhesive composion |
| JP2011153395A (en) * | 2010-01-28 | 2011-08-11 | Nisshin Chem Ind Co Ltd | Binder for inorganic fiber, and inorganic fiber mat processed with the binder |
| JP2016108707A (en) * | 2014-12-10 | 2016-06-20 | パラマウント硝子工業株式会社 | Water-soluble binder for inorganic fiber containing no formaldehyde and method for producing inorganic fiber heat-insulating and acoustic material |
| JP2016155370A (en) * | 2015-02-19 | 2016-09-01 | 名古屋油化株式会社 | Air permeability adjusting sheet, moldable air permeability adjusting sheet and sound absorber |
-
2017
- 2017-12-07 JP JP2017235391A patent/JP6769426B2/en not_active Expired - Fee Related
-
2018
- 2018-08-22 WO PCT/JP2018/031034 patent/WO2019111449A1/en not_active Ceased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5069139A (en) * | 1973-10-08 | 1975-06-09 | ||
| JPS534047A (en) * | 1976-07-02 | 1978-01-14 | Koyo Sangyo Co | Adhesive composion |
| JP2011153395A (en) * | 2010-01-28 | 2011-08-11 | Nisshin Chem Ind Co Ltd | Binder for inorganic fiber, and inorganic fiber mat processed with the binder |
| JP2016108707A (en) * | 2014-12-10 | 2016-06-20 | パラマウント硝子工業株式会社 | Water-soluble binder for inorganic fiber containing no formaldehyde and method for producing inorganic fiber heat-insulating and acoustic material |
| JP2016155370A (en) * | 2015-02-19 | 2016-09-01 | 名古屋油化株式会社 | Air permeability adjusting sheet, moldable air permeability adjusting sheet and sound absorber |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021086803A1 (en) * | 2019-10-28 | 2021-05-06 | Ocv Intellectual Capital, Llc | Cross-linked non-woven mat |
| US12152324B2 (en) | 2019-10-28 | 2024-11-26 | Owens Corning Intellectual Capital, Llc | Cross-linked non-woven mat |
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| JP2019099971A (en) | 2019-06-24 |
| JP6769426B2 (en) | 2020-10-14 |
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