WO2019189410A1 - Liant pour produits à base de fibres inorganiques, procédé de fabrication dudit liant et procédé de fabrication d'un produit à base de fibres inorganiques - Google Patents

Liant pour produits à base de fibres inorganiques, procédé de fabrication dudit liant et procédé de fabrication d'un produit à base de fibres inorganiques Download PDF

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WO2019189410A1
WO2019189410A1 PCT/JP2019/013274 JP2019013274W WO2019189410A1 WO 2019189410 A1 WO2019189410 A1 WO 2019189410A1 JP 2019013274 W JP2019013274 W JP 2019013274W WO 2019189410 A1 WO2019189410 A1 WO 2019189410A1
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inorganic fiber
binder
formaldehyde
mass
fiber products
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PCT/JP2019/013274
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English (en)
Japanese (ja)
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慧 石井
勘二 長壁
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群栄化学工業株式会社
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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
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/34—Condensation polymers of aldehydes, e.g. with phenols, ureas, melamines, amides or amines
    • 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
    • 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
    • D06M13/325—Amines
    • D06M13/328—Amines the amino group being bound to an acyclic or cycloaliphatic carbon atom
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/41—Phenol-aldehyde or phenol-ketone resins

Definitions

  • the present invention relates to a binder for inorganic fiber products, a method for producing the same, and a method for producing an inorganic fiber product.
  • inorganic fiber products formed by bonding inorganic fibers such as glass wool, rock wool, or ceramic fibers with a binder are used as heat insulating materials, sound absorbing materials, or other various molded products (automobile roofs, bonnet liners, etc.). It is used.
  • inorganic fiber products are produced by attaching a binder to inorganic fibers and accumulating them to obtain an aggregate in the shape of the desired inorganic fiber product, followed by heating and curing the binder.
  • a binder a resin mainly composed of a phenol resin obtained by a reaction between phenols and formaldehyde (hereinafter, sometimes referred to as a phenol resin binder) is relatively inexpensive and has performance such as mechanical strength. Widely used because excellent products can be obtained.
  • Formaldehyde is a substance that adversely affects the human body.
  • aldehyde released from building materials is considered to be one of the causative substances of sick house syndrome.
  • the revised Building Standard Law which regulates the amount of formaldehyde emitted, was enforced in 2003.
  • the amount of formaldehyde emitted is 5 ⁇ g / m 2 ⁇ hr or less as the formaldehyde emission rate measured according to JIS A1901 is not regulated. Therefore, an inorganic fiber product having a formaldehyde emission rate of 5 ⁇ g / m 2 ⁇ hr or less is desired.
  • phenol resin is modified with urea.
  • free formaldehyde in the phenol resin is captured by the urea introduced into the phenol resin, the amount of formaldehyde volatilization during the manufacturing process is reduced, and the working environment is improved.
  • a formaldehyde scavenger such as ethylene urea or adipic acid dihydrazide (see, for example, Patent Document 1).
  • the formaldehyde scavenger reacts with the generated formaldehyde and immobilizes it to reduce formaldehyde emission.
  • Patent Documents 2 to 4 when an unreacted formaldehyde and phenol are reacted with an amine to form a condensate, the water-dilutability of the binder for inorganic fiber products becomes poor. Therefore, it becomes difficult to adhere the binder for inorganic fiber products to inorganic fiber.
  • the binders for inorganic fiber products in Patent Documents 2 to 4 improve water dilution to some extent by adjusting the pH to acid. However, if the binder for inorganic fiber products is acidified, the equipment load increases, for example, the equipment corrodes. To do.
  • the binder for inorganic fiber products like patent documents 5 and 6 is excellent in water reducibility, since the color of the manufactured inorganic fiber product turns into a tea system color and differs from the conventional color, some There are cases in which it is pointed out by the customer that the appearance is not preferable.
  • a high-density board product may cause a decrease in strength such as an increase in the amount of warping as compared with a product using an existing phenol resin.
  • the present invention provides an inorganic fiber product binder that is excellent in water dilutability, has reduced formaldehyde emission, has sufficient strength, and has an excellent appearance, and a method for producing the inorganic fiber product binder
  • Another object is to provide a method for producing an inorganic fiber product using the inorganic fiber product binder.
  • a binder for inorganic fiber products comprising a resol type phenolic resin and a monoamine.
  • a method for producing an inorganic fiber product comprising attaching the inorganic fiber product binder according to any one of [1] to [3] to the inorganic fiber, and molding the inorganic fiber to obtain an inorganic fiber product.
  • a method for producing a binder for inorganic fiber products wherein a monoamine is added to a resol-type phenolic resin at less than 50 ° C.
  • an inorganic fiber product with reduced formaldehyde emission, sufficient strength, and excellent appearance can be produced with a binder for inorganic fiber products having excellent water reducibility.
  • FIG. 5 is a graph with the amount of monoethanolamine added on the horizontal axis and the normal strength on the vertical axis for binders A-1 to A-6 and A-8 for inorganic fiber products of Examples 1 to 6 and Comparative Example 1. .
  • FIG. 5 is a graph with the amount of monoethanolamine added on the horizontal axis and the moisture resistance strength on the vertical axis for binders A-1 to A-6 and A-8 for inorganic fiber products of Examples 1 to 6 and Comparative Example 1.
  • the horizontal axis represents the amount of monoethanolamine added and the vertical axis represents the amount of diffused F is there.
  • the tensile strength (normal strength, moisture resistance) is longitudinal with the addition amount of monoethanolamine as the horizontal axis. It is a graph taken on the axis.
  • the binder for inorganic fiber products of the present invention (hereinafter also referred to as “the present binder”) is a binder for binding inorganic fibers such as glass wool, rock wool, and ceramic fibers in inorganic fiber products.
  • This binder contains a resol type phenol resin and a monoamine.
  • This binder may further contain other components other than the resol type phenol resin and monoamine, as long as the effects of the present invention are not impaired, if necessary.
  • the resol type phenol resin is a reaction product of a phenol and an aldehyde in the presence of an alkali catalyst.
  • an addition reaction in which aldehydes are added to the aromatic ring of phenols occurs, and then polymerizes through a condensation reaction.
  • Phenols are compounds having an aromatic ring and a hydroxyl group bonded to the aromatic ring.
  • phenols include phenol, alkylphenols (o, m, p cresol, o, m, p ethylphenol, xylenol isomers, etc.), polyaromatic phenols ( ⁇ , ⁇ Naphthol, etc.), polyhydric phenols (bisphenol A, bisphenol F, bisphenol S, pyrogallol, resorcin, catechol, hydroquinone, etc.). These phenols may be used individually by 1 type, and may use 2 or more types together. Among these, practical substances are phenol, cresols of o, m, and p, isomers of xylenol, resorcin, and catechol.
  • Aldehydes are at least one compound selected from the group consisting of compounds having a formyl group and multimers thereof.
  • aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propyl aldehyde, benzaldehyde, salicylaldehyde, glyoxal, and the like. These aldehydes may be used individually by 1 type, and may use 2 or more types together. Among these, practical substances are formaldehyde and paraformaldehyde.
  • the weight average molecular weight of the resol type phenol resin is preferably 800 or less, more preferably 600 or less, and still more preferably 400 or less, from the viewpoint of water dilution and stability over time.
  • the weight average molecular weight of the resol type phenol resin is less than 150, there is a possibility that the yield of the binder in the inorganic fiber product may be reduced or the strength may be reduced.
  • the weight average molecular weight of the resol type phenol resin is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
  • the resol type phenol resin is preferably liquid.
  • the resin solid content of the resol type phenol resin is preferably 30% by mass or more, and more preferably 40% by mass or more from the viewpoint of transportation cost.
  • the “resin solid content” of the resol type phenol resin refers to the non-volatile content of the resol type phenol resin.
  • the nonvolatile content indicates a value measured according to JIS K6910 5.6.
  • the monoamine may be linear or cyclic.
  • the monoamine is preferably a primary amine or a secondary amine, and more preferably a primary amine, from the viewpoint that an effect of reducing formaldehyde emission is easily obtained.
  • the hydrocarbon group possessed by the amine may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • the molecular weight of the monoamine is preferably 300 or less, more preferably 200 or less, and even more preferably 150 or less, from the viewpoint of the effect of reducing the diffused formaldehyde and the suppression of the decrease in water dilution.
  • Examples of monoamines include aliphatic monoamines, alicyclic monoamines, and aromatic monoamines.
  • aliphatic monoamine examples include monoalkanolamine (monoethanolamine, monoisopropanolamine, diethanolamine, etc.), alkylamine (monomethylamine, monoethylamine, dimethylamine, diethylamine, etc.) and the like.
  • alkylamine monomethylamine, monoethylamine, dimethylamine, diethylamine, etc.
  • Examples of the alicyclic monoamine include piperidine, pyrrolidine, morpholine, pyrrole, and pyridine.
  • aromatic monoamine examples include aniline, aminophenol, toluidine and the like.
  • the monoamine is preferably an aliphatic monoamine, more preferably a primary or secondary amine, and particularly preferably monoethanolamine or monoethylamine, from the viewpoint that an effect of reducing formaldehyde emission is easily obtained.
  • a monoamine may be used individually by 1 type and may use 2 or more types together.
  • the content of monoamine in the binder is preferably 0.5 to 40 parts by mass, and more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the resin solid content of the resol type phenol resin.
  • the monoamine content is at least the lower limit of the above range, the amount of formaldehyde emitted is sufficiently reduced, and an inorganic fiber product having high normal strength and high humidity resistance is easily obtained. If the monoamine content is not more than the upper limit of the above range, the economy is excellent.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • Normal strength refers to mechanical strength (tensile strength, bending strength, etc.) in a dry state. The moisture resistance indicates the mechanical strength in a wet state.
  • (Other ingredients) As other components, it can be used by appropriately selecting from known components that can be blended in the binder. Examples thereof include urea, ethylene urea, resorcin, melamine, dicyandiamide, ammonia, a curing accelerator, a silane coupling agent, a known formaldehyde scavenger, a water repellent, a dust prevention oil, and water. Other components may be used alone or in combination of two or more.
  • the binder contains at least one selected from urea, melamine, ethylene urea, resorcin, and dicyandiamide (DCDA)
  • the amount of free formaldehyde in the binder further causing volatilization during the manufacturing process of the inorganic fiber product is further increased. Can be reduced.
  • the binder contains urea
  • the urea content is preferably 5 to 100 parts by mass and more preferably 10 to 70 parts by mass with respect to 100 parts by mass of the resin solid content of the resol type phenol resin.
  • the preferable range of the content of melamine, ethylene urea, resorcin, and DCDA is the same as the preferable range of the urea content.
  • this binder When this binder contains ammonia, it reacts with the free formaldehyde in this binder and converts to hexamine, thereby improving the working environment. Moreover, by mix
  • the amount of ammonia is preferably 0 to 20% by mass based on the resin solid content of the phenol resin.
  • the binder may further contain a curing accelerator.
  • the curing accelerator include ammonium salts such as ammonium sulfate, ammonium chloride, and ammonium phosphate.
  • the content of the curing accelerator in the binder is preferably 0 to 10 parts by mass and more preferably 3 to 5 parts by mass with respect to 100 parts by mass of the resin solid content of the resol type phenol resin.
  • this binder contains a silane coupling agent, the water resistance and mechanical strength of the inorganic fiber product are improved.
  • the silane coupling agent is not particularly limited, and examples thereof include aminosilane compounds such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane and 3-aminopropyltriethoxysilane.
  • the content of the silane coupling agent in the binder is preferably 0 to 1 part by mass with respect to 100 parts by mass of the resin solid content of the resol type phenol resin.
  • formaldehyde scavengers include formaldehyde scavengers described in JP-A No. 2001-178805.
  • water repellent include a silicone water repellent and a fluorine water repellent.
  • dust-preventing oil include mineral oil-based oil emulsions.
  • the pH of the binder is preferably 7.0 to 13.0, more preferably 7.5 to 12.0, still more preferably 8.0 to 11.0, and particularly preferably 8.0 to 10.0. If pH is more than the lower limit of the said range, an installation will not be damaged. Moreover, the solubility in water becomes better. If pH is below the upper limit of the said range, it is economical from the point of usage-amounts, such as a catalyst and an additive.
  • the pH is a value at 25 ° C.
  • This binder is obtained by adding a monoamine to a resol type phenol resin at less than 50 ° C.
  • a monoamine for example, there may be mentioned a method in which phenols and aldehydes are reacted in the presence of an alkali catalyst to obtain a resol type phenol resin, and then a monoamine is added at less than 50 ° C.
  • the reaction between phenols and aldehydes can be performed by a known method.
  • a method of charging a reaction vessel having a stirrer, a reflux device and a temperature control mechanism with phenols, aldehydes, an alkali catalyst, water and the like and maintaining an arbitrary reaction time at an arbitrary reaction temperature can be mentioned.
  • an additional alkali catalyst and optional additives may be added as necessary.
  • the molar ratio of aldehydes to phenols is preferably 1.0 to 4.0, more preferably 1.5 to 2.5. If the molar ratio of aldehydes to phenols is not less than the lower limit of the above range, it is easy to suppress odor generation or yield reduction due to volatilization of unreacted phenols. If the molar ratio of aldehydes to phenols is below the upper limit of the above range, a large amount of unreacted aldehydes will not remain, formaldehyde will not volatilize in the working environment atmosphere during the manufacturing process, and Does not harm health. Moreover, the amount of aldehydes emitted from the inorganic fiber product obtained using the binder is reduced.
  • the alkali catalyst is not particularly limited as long as the reaction of phenols and aldehydes can proceed, and various alkaline substances can be used. Specific examples include hydroxides of alkali metals such as sodium and potassium (sodium hydroxide and potassium hydroxide), and alkaline earth metal hydroxides such as calcium, magnesium and barium (calcium hydroxide and magnesium hydroxide). , Barium hydroxide, etc.), inorganic alkaline substances (sodium carbonate, ammonia, etc.), organic alkaline substances (tertiary amine, cyclic amine, etc.) and the like. Examples of the tertiary amine include triethylamine, trimethylamine, and triethanolamine.
  • Examples of the cyclic amine include DBU (1,8-diazabicyclo [5.4.0] undec-7-ene), DBN (1,5-diazabicyclo [4.3.0] non-5-ene) and the like. It is done. Usually, when an alkaline earth metal is used, the water dilutability and stability over time of the resin are lower than when an alkali metal is used, but the water resistance is improved. This is because alkaline earth metals and their salts are less soluble in water than alkali metals. These alkali catalysts may be used individually by 1 type, and may use 2 or more types together.
  • the amount of alkali catalyst used is preferably 1 to 30 parts by mass with respect to 100 parts by mass of phenols. If the usage-amount of an alkali catalyst is more than the lower limit of the said range, reaction will fully advance. If the usage-amount of an alkali catalyst is below the upper limit of the said range, control of reaction will be easy.
  • the reaction temperature for the reaction of phenols and aldehydes is preferably 50 to 90 ° C, more preferably 60 to 80 ° C. If the reaction temperature is at least the lower limit of the above range, a sufficient reaction rate can be obtained. If reaction temperature is below the upper limit of the said range, control of reaction will be easy.
  • the reaction time can be, for example, 2 to 8 hours.
  • the temperature of the resol type phenol resin is lowered to less than 50 ° C., and then the monoamine is added.
  • a monoamine at less than 50 ° C., it is possible to suppress the formation of a condensate by reacting the free phenol and free formaldehyde contained in the resol type phenol resin with the monoamine. Thereby, it is suppressed that the water dilution property of this binder obtained falls.
  • the free phenols are unreacted phenols measured according to JIS K6910 5.16.
  • Free aldehydes are unreacted aldehydes measured according to 5.17 of JIS K6910.
  • the temperature of the resol type phenol resin when adding the monoamine is less than 50 ° C., preferably 10 to 40 ° C., more preferably 20 to 35 ° C. If the temperature of the resol type phenol resin at the time of monoamine addition is below the upper limit of the said range, this binder excellent in water reducibility will be easy to be obtained. If the temperature of the resol-type phenol resin at the time of monoamine addition is equal to or higher than the lower limit of the above range, the amine is easily dissolved in the resin, the heat of solution at the time of amine addition is relaxed, and temperature control can be facilitated.
  • the amount of monoamine added is preferably 0.5 to 40 parts by mass, and more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the resin solid content of the resol type phenol resin.
  • the added amount of monoamine is within the above range, the present form binder which can sufficiently reduce the formaldehyde emission amount of the inorganic fiber product and is excellent in water dilutability is easily obtained.
  • Acids used for neutralization include inorganic acids such as boric acid, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and sulfamic acid, formic acid, oxalic acid, acetic acid, citric acid, lactic acid, sulfanilic acid, benzoic acid, phenolsulfonic acid, para Organic acids such as toluenesulfonic acid, methanesulfonic acid, lauric acid and the like can be mentioned.
  • An acid may be used individually by 1 type and may use 2 or more types together.
  • the temperature of the resol type phenolic resin when adding other components is preferably less than 50 ° C, preferably 10 to 40 ° C, more preferably 20 to 35 ° C.
  • this binder is not limited to an above described method.
  • the temperature of the binder before use is preferably less than 50 ° C, preferably 10 to 40 ° C, more preferably 20 to 35 ° C.
  • a binder for an inorganic fiber product including a resol type phenol resin and a monoamine is used.
  • This binder is excellent in water dilutability because the monoamine is contained without reacting with free phenols or aldehydes to form a condensate.
  • this binder is excellent in water reducibility even if it does not make it acidic, it can also prevent that an equipment load increases.
  • this binder when this binder is made to adhere to an inorganic fiber and baked and hardened, free phenols and aldehydes in the binder and a monoamine form a condensate by a Mannich reaction. Since it is thought that this Mannich condensation product captures diffused formaldehyde, the amount of formaldehyde emitted is sufficiently reduced in inorganic fiber products produced using this binder. Moreover, the inorganic fiber product manufactured using this binder containing a monoamine becomes yellow color development like a conventional product, and normal-state strength and moisture-proof strength are also improved. The binder is particularly useful for the production of insulation.
  • the method for producing an inorganic fiber product of the present invention is a method for obtaining an inorganic fiber product by attaching the binder to the inorganic fiber and molding the inorganic fiber. As needed, you may harden this binder by baking after making this binder adhere to an inorganic fiber.
  • Examples of the inorganic fiber product manufactured by the manufacturing method of the present invention include a heat insulating material, a sound absorbing material, an automobile roof, a liner such as a bonnet, and the like.
  • the present invention is particularly useful for the production of thermal insulation.
  • the inorganic fiber product manufactured by the manufacturing method of the present invention may be composed of only a molded body, or may further include other members other than the molded body such as a skin material for packaging.
  • the inorganic fiber is not particularly limited, and examples thereof include glass wool, rock wool, and ceramic fiber.
  • An inorganic fiber may be used individually by 1 type, and may use 2 or more types together.
  • Examples of the method of attaching the binder to the inorganic fiber include a method of spraying the binder on the inorganic fiber using a spray device and the like, a method of impregnating the inorganic fiber by immersing the binder in the binder, and the like. Since this binder is excellent in water dilutability, it can be easily and uniformly adhered to inorganic fibers by diluting to an appropriate concentration with water as necessary.
  • the amount of the binder attached to the inorganic fiber is not particularly limited, and can be, for example, 0.5 to 20% by mass as the resin solid content of the binder with respect to the inorganic fiber (100% by mass).
  • the formation of the inorganic fiber to which the binder is attached can be performed by a known method.
  • the inorganic fibers to which the binder is attached are deposited on a conveyor, and the deposit is pressed from the up and down direction of the conveyor to be compressed into an aggregate, which is heated in a heating furnace (cured)
  • cured A method of curing the binder by sending it to a furnace and baking it.
  • the firing temperature may be in the temperature range where the binder is cured, and is preferably 180 to 270 ° C. If the firing temperature is equal to or higher than the lower limit of the above range, curing of the binder is likely to proceed sufficiently, and the formaldehyde emission amount is likely to be sufficiently reduced. When the firing temperature is equal to or lower than the upper limit of the above range, the present binder is difficult to be decomposed, and a decrease in yield and a decrease in mechanical strength are easily suppressed.
  • the firing time can be appropriately set depending on the size of the aggregate, the firing temperature, and the like.
  • Example 1 After charging 1350 parts of phenol, 1893.7 parts of a 50% by weight aqueous formaldehyde solution and 135 parts of barium hydroxide octahydrate in a reactor equipped with a condenser, thermometer, and stirrer and reacting at 60 ° C. for 360 minutes. The mixture was cooled to 35 ° C. to synthesize a resol type phenol resin.
  • adjusting water is added so that the resin solid part becomes 50% by mass.
  • a binder A-1 for inorganic fiber products was obtained.
  • Binder B-1 for inorganic fiber products was obtained.
  • Binders A-2 to A-6 for inorganic fiber products were prepared in the same manner as in Example 1 except that the amount of monoethanolamine added was changed as shown in Table 1. Further, other components were added to the inorganic fiber product binders A-2 to A-6 in the same manner as in Example 1 to obtain inorganic fiber product binders B-2 to B-6.
  • Example 7 In the same manner as in Example 1, a resol type phenol resin was synthesized, and after adding monoethylamine to 35 ° C. or less with a heat of dissolution at a ratio of 6 parts to 100 parts of resin solids, the resin solids was 50 mass. % Water was added to obtain a binder A-7 for inorganic fiber products. Further, other components were added to the inorganic fiber product binder A-7 in the same manner as in Example 1 to obtain an inorganic fiber product binder B-7.
  • Example 1 A resol type phenol resin was synthesized in the same manner as in Example 1, and adjusted water was added so that the resin solid content was 50% by mass, and this was designated as binder A-8 for inorganic fiber products. Further, other components were added to the inorganic fiber product binder A-8 in the same manner as in Example 1 to obtain an inorganic fiber product binder B-8.
  • Example 2 A resol type phenol resin was synthesized in the same manner as in Example 1, neutralized by adding 30% by mass sulfuric acid so that the pH was 7.3 after cooling to 35 ° C., and the resin solid content was 50% by mass. What added adjustment water was made into the binder A-9 for inorganic fiber products. Further, other components were added to the inorganic fiber product binder A-9 in the same manner as in Example 1 to obtain an inorganic fiber product binder B-9.
  • Example 3 A resol type phenol resin was synthesized in the same manner as in Example 1, neutralized by adding 30% by mass sulfuric acid so that the pH was 7.3 after cooling to 35 ° C., and a ratio of 30 parts to 100 parts of resin solid content Glucose fructose liquid sugar (isomerized sugar, product name: Three Sugar 75FG, solid content concentration 75% by mass, manufactured by Gunei Chemical Industry Co., Ltd.) is added, and adjusted water is added so that the resin solid content becomes 50% by mass This was designated as binder A-10 for inorganic fiber products. Further, other components were added to the inorganic fiber product binder A-10 in the same manner as in Example 1 to obtain an inorganic fiber product binder B-10.
  • Glucose fructose liquid sugar is added, and adjusted water is added so that the resin solid content becomes 50% by mass
  • binder A-10 for inorganic fiber products.
  • other components were added to the inorganic fiber product binder A-10 in the same manner as in Example 1 to obtain an inorgan
  • Example 4 Inorganic fiber in the same manner as in Example 1 except that the temperature of the resol-type phenolic resin when adding monoethanolamine was changed to 70 ° C. and free phenol, formaldehyde and monoethanolamine were reacted to form a condensate. A product binder A-11 was obtained. Further, other components were added to the inorganic fiber product binder A-11 in the same manner as in Example 1 to obtain an inorganic fiber product binder B-11.
  • FP free phenol content
  • FF free formaldehyde amount
  • Tensile strength (normal strength) was measured using three test pieces, and the remaining three test pieces were measured for tensile strength (humidity resistance) after being left for 24 hours in a thermo-hygrostat at a temperature of 65 ° C. and a humidity of 95%. .
  • the tensile strength was carried out under the condition of a load speed of 5 mm / min in accordance with 5.18 of JIS K6911: 2006.
  • Form of formaldehyde emission Measurement of formaldehyde emission (amount of emission F) was performed according to 7 of JIS A 1902-4: 2015.
  • the binder for inorganic fiber products was diluted with water so that the concentration of the resin solid content was 10% by mass, and impregnated into glass filter paper (AD-100, manufactured by ADVANTEC) cut into 15 cm square.
  • the adhesion amount of the binder was about 40% by mass.
  • the glass filter paper to which the binder for inorganic fiber products was made to adhere was baked at 200 degreeC for 10 minute (s).
  • An inner lid with a hole was fitted into the opening of the plastic container, a passive sampler DSD-DNPH (supplied by Supelco) for aldehyde / ketone repair was inserted, and sealed with a sealing tape.
  • Formaldehyde was collected by allowing to stand at a temperature of 28 ° C. and a humidity of 50% for 24 hours.
  • the formaldehyde repaired with the sampler after collection was extracted with acetonitrile so that the extract became 5 mL.
  • the formaldehyde concentration in the extract was analyzed by high performance liquid chromatograph (HPLC) under the following conditions. Those having an emission F amount of 5 ⁇ g / L or less indicate that the emission grade F ⁇ is achieved.
  • Tables 1 and 2 and FIGS. 1 to 4 show the conditions of the binder for inorganic fiber products in each example and various evaluation results.
  • the binders A-1 to A-7 for inorganic fiber products of Examples 1 to 7 in which monoethanolamine and monoethylamine were added to a resol type phenolic resin at 35 ° C. or less are excellent in water dilutability. It was.
  • the binders B-1 to B-7 for inorganic fiber products to which other components were further added in Examples 1 to 7 have reduced formaldehyde emission, and test pieces was yellow and the appearance was good.
  • Table 2 Table 2, FIG. 1, FIG. 2 and FIG. 4
  • the normal strength and the moisture resistance increased as the amount of monoethanolamine added increased.
  • Comparative Examples 1 and 2 where no monoethanolamine was added, the amount of formaldehyde emitted was not sufficiently reduced. Further, in Comparative Example 3 in which isomerized sugar was added, although the amount of diffuse formaldehyde was reduced, the normal strength and the moisture resistance were low, and the test piece was colored brown. In addition, the binder A-11 for inorganic fiber products of Comparative Example 4 in which monoethanolamine was added at 70 ° C. to form a condensate of phenol, formaldehyde and monoethanolamine was extremely inferior in water dilutability.
  • Binder C-1 for inorganic fiber products was obtained.
  • Example 6 In the same manner as in Example 8, a resol type phenol resin was synthesized, neutralized by adding boric acid so as to have a pH of 7.3 after cooling to 50 ° C., and adjusted water so that the resin solid content was 50% by mass. To which inorganic fiber product binder C-3 was added.
  • Table 3 shows the conditions of various examples of binders for inorganic fiber products and various evaluation results.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)

Abstract

Le but de la présente invention est de fournir : un liant pour des produits à base de fibres inorganiques qui est facilement dilué dans l'eau, présente un taux d'émission de formaldéhyde réduit, et présente une résistance suffisante, avec lequel il est possible de fabriquer un produit de fibre inorganique ayant un aspect externe exceptionnel ; un procédé de fabrication du liant pour des produits de fibre inorganique ; et un procédé de fabrication d'un produit de fibre inorganique dans lequel le liant pour des produits de fibre inorganique est utilisé. Un liant pour des produits à base de fibres inorganiques comprend une résine phénolique de type résol et une monoamine, la teneur en monoamine étant de 0,5 à 40 parties en masse par rapport à 100 parties en masse de la teneur en résine solide de la résine phénolique de type résol. L'invention concerne également un procédé de fabrication du liant pour des produits fibreux inorganiques, le procédé comprenant l'ajout de La monoamine à la résine phénolique de type résol à une température inférieure à 50 °C. L'invention concerne en outre un procédé de fabrication d'un produit fibreux inorganique, le procédé comprenant l'étape consistant à amener le liant pour des produits fibreux inorganiques à adhérer à des fibres inorganiques, à mouler les fibres inorganiques, et à obtenir un produit fibreux inorganique.
PCT/JP2019/013274 2018-03-29 2019-03-27 Liant pour produits à base de fibres inorganiques, procédé de fabrication dudit liant et procédé de fabrication d'un produit à base de fibres inorganiques WO2019189410A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022210093A1 (fr) * 2021-03-29 2022-10-06 群栄化学工業株式会社 Composition thermodurcissable pour produit cellulosique et produit cellulosique

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0453024U (fr) * 1990-09-03 1992-05-06
JP2005194634A (ja) * 2003-12-26 2005-07-21 Asahi Fiber Glass Co Ltd 無機質繊維マット
JP2005264387A (ja) * 2004-03-19 2005-09-29 Dainippon Ink & Chem Inc 鉱物繊維バインダー用樹脂組成物
JP2006028649A (ja) * 2004-07-12 2006-02-02 Asahi Fiber Glass Co Ltd 真空断熱材用無機繊維マットの製造方法
JP2007291332A (ja) * 2006-01-26 2007-11-08 Central Glass Co Ltd 接着性組成物の製造方法
JP2009517514A (ja) * 2005-11-28 2009-04-30 サン−ゴバン・イソベール ホルムアルデヒドフリーのフェノール樹脂バインダ

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0453024U (fr) * 1990-09-03 1992-05-06
JP2005194634A (ja) * 2003-12-26 2005-07-21 Asahi Fiber Glass Co Ltd 無機質繊維マット
JP2005264387A (ja) * 2004-03-19 2005-09-29 Dainippon Ink & Chem Inc 鉱物繊維バインダー用樹脂組成物
JP2006028649A (ja) * 2004-07-12 2006-02-02 Asahi Fiber Glass Co Ltd 真空断熱材用無機繊維マットの製造方法
JP2009517514A (ja) * 2005-11-28 2009-04-30 サン−ゴバン・イソベール ホルムアルデヒドフリーのフェノール樹脂バインダ
JP2007291332A (ja) * 2006-01-26 2007-11-08 Central Glass Co Ltd 接着性組成物の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022210093A1 (fr) * 2021-03-29 2022-10-06 群栄化学工業株式会社 Composition thermodurcissable pour produit cellulosique et produit cellulosique

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