WO2019189410A1 - Binder for inorganic fiber products, method for manufacturing said binder, and method for manufacturing inorganic fiber product - Google Patents
Binder for inorganic fiber products, method for manufacturing said binder, and method for manufacturing inorganic fiber productDownload PDFInfo
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- WO2019189410A1 WO2019189410A1PCT/JP2019/013274JP2019013274WWO2019189410A1WO 2019189410 A1WO2019189410 A1WO 2019189410A1JP 2019013274 WJP2019013274 WJP 2019013274WWO 2019189410 A1WO2019189410 A1WO 2019189410A1
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- inorganic fiber
- binder
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- fiber products
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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 inventionrelates 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 binderare used as heat insulating materials, sound absorbing materials, or other various molded products (automobile roofs, bonnet liners, etc.). It is used.
- inorganic fiber productsare 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 bindera 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.
- Formaldehydeis a substance that adversely affects the human body.
- aldehyde released from building materialsis considered to be one of the causative substances of sick house syndrome.
- the revised Building Standard Lawwhich regulates the amount of formaldehyde emitted, was enforced in 2003.
- the amount of formaldehyde emittedis 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 resinis modified with urea.
- free formaldehyde in the phenol resinis 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 scavengersuch as ethylene urea or adipic acid dihydrazide (see, for example, Patent Document 1).
- the formaldehyde scavengerreacts with the generated formaldehyde and immobilizes it to reduce formaldehyde emission.
- Patent Documents 2 to 4when 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 4improve 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 6is 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 productmay 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 inventionprovides 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 objectis to provide a method for producing an inorganic fiber product using the inorganic fiber product binder.
- a binder for inorganic fiber productscomprising a resol type phenolic resin and a monoamine.
- a method for producing an inorganic fiber productcomprising 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 productswherein 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 appearancecan be produced with a binder for inorganic fiber products having excellent water reducibility.
- FIG. 5is 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. 5is 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 axisrepresents 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 bindercontains a resol type phenol resin and a monoamine.
- This bindermay 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 resinis a reaction product of a phenol and an aldehyde in the presence of an alkali catalyst.
- an addition reactionin which aldehydes are added to the aromatic ring of phenols occurs, and then polymerizes through a condensation reaction.
- Phenolsare compounds having an aromatic ring and a hydroxyl group bonded to the aromatic ring.
- phenolsinclude 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.
- Aldehydesare at least one compound selected from the group consisting of compounds having a formyl group and multimers thereof.
- aldehydesinclude 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 resinis 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 resinis 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 resinis a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
- the resol type phenol resinis preferably liquid.
- the resin solid content of the resol type phenol resinis 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 resinrefers to the non-volatile content of the resol type phenol resin.
- the nonvolatile contentindicates a value measured according to JIS K6910 5.6.
- the monoaminemay be linear or cyclic.
- the monoamineis 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 aminemay be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
- the molecular weight of the monoamineis 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 monoaminesinclude aliphatic monoamines, alicyclic monoamines, and aromatic monoamines.
- aliphatic monoamineexamples include monoalkanolamine (monoethanolamine, monoisopropanolamine, diethanolamine, etc.), alkylamine (monomethylamine, monoethylamine, dimethylamine, diethylamine, etc.) and the like.
- alkylaminemonomethylamine, monoethylamine, dimethylamine, diethylamine, etc.
- Examples of the alicyclic monoamineinclude piperidine, pyrrolidine, morpholine, pyrrole, and pyridine.
- aromatic monoamineexamples include aniline, aminophenol, toluidine and the like.
- the monoamineis 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 monoaminemay be used individually by 1 type and may use 2 or more types together.
- the content of monoamine in the binderis 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 contentis 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 strengthrefers 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 bindercontains 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 productis further increased. Can be reduced.
- the bindercontains urea
- the urea contentis 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 DCDAis the same as the preferable range of the urea content.
- this binderWhen 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 ammoniais preferably 0 to 20% by mass based on the resin solid content of the phenol resin.
- the bindermay further contain a curing accelerator.
- the curing acceleratorinclude ammonium salts such as ammonium sulfate, ammonium chloride, and ammonium phosphate.
- the content of the curing accelerator in the binderis 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 bindercontains a silane coupling agent, the water resistance and mechanical strength of the inorganic fiber product are improved.
- the silane coupling agentis 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 binderis 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 scavengersinclude formaldehyde scavengers described in JP-A No. 2001-178805.
- water repellentinclude a silicone water repellent and a fluorine water repellent.
- dust-preventing oilinclude mineral oil-based oil emulsions.
- the pH of the binderis 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 pHis a value at 25 ° C.
- This binderis obtained by adding a monoamine to a resol type phenol resin at less than 50 ° C.
- a monoaminefor 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 aldehydescan 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 temperaturecan be mentioned.
- an additional alkali catalyst and optional additivesmay be added as necessary.
- the molar ratio of aldehydes to phenolsis 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 catalystis 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 amineinclude 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 usedis 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 aldehydesis 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 timecan be, for example, 2 to 8 hours.
- the temperature of the resol type phenol resinis lowered to less than 50 ° C., and then the monoamine is added.
- a monoamineat 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 phenolsare unreacted phenols measured according to JIS K6910 5.16.
- Free aldehydesare unreacted aldehydes measured according to 5.17 of JIS K6910.
- the temperature of the resol type phenol resin when adding the monoamineis 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 addedis 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 monoamineis 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 neutralizationinclude 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 acidmay 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 componentsis preferably less than 50 ° C, preferably 10 to 40 ° C, more preferably 20 to 35 ° C.
- this binderis not limited to an above described method.
- the temperature of the binder before useis 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 monoamineis used.
- This binderis excellent in water dilutability because the monoamine is contained without reacting with free phenols or aldehydes to form a condensate.
- this binderis excellent in water reducibility even if it does not make it acidic, it can also prevent that an equipment load increases.
- this binderwhen 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 inventionis 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 inventioninclude a heat insulating material, a sound absorbing material, an automobile roof, a liner such as a bonnet, and the like.
- the present inventionis particularly useful for the production of thermal insulation.
- the inorganic fiber product manufactured by the manufacturing method of the present inventionmay 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 fiberis not particularly limited, and examples thereof include glass wool, rock wool, and ceramic fiber.
- An inorganic fibermay 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 fiberinclude 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 fiberis 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 attachedcan be performed by a known method.
- the inorganic fibers to which the binder is attachedare 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)
- curedA method of curing the binder by sending it to a furnace and baking it.
- the firing temperaturemay 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 timecan be appropriately set depending on the size of the aggregate, the firing temperature, and the like.
- Example 1After 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 wateris added so that the resin solid part becomes 50% by mass.
- a binder A-1 for inorganic fiber productswas obtained.
- Binder B-1 for inorganic fiber productswas obtained.
- Binders A-2 to A-6 for inorganic fiber productswere 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 7In 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 1A 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 2A 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 3A 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 sugaris added, and adjusted water is added so that the resin solid content becomes 50% by mass
- binder A-10for inorganic fiber products.
- other componentswere added to the inorganic fiber product binder A-10 in the same manner as in Example 1 to obtain an inorgan
- Example 4Inorganic 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.
- FPfree phenol content
- FFfree 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 strengthwas 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 emissionMeasurement of formaldehyde emission (amount of emission F) was performed according to 7 of JIS A 1902-4: 2015.
- the binder for inorganic fiber productswas 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 binderwas about 40% by mass.
- the glass filter paper to which the binder for inorganic fiber products was made to adherewas baked at 200 degreeC for 10 minute (s).
- An inner lid with a holewas 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.
- Formaldehydewas 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 collectionwas extracted with acetonitrile so that the extract became 5 mL.
- the formaldehyde concentration in the extractwas 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 4show 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 lessare 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 7have reduced formaldehyde emission, and test pieces was yellow and the appearance was good.
- Table 2Table 2, FIG. 1, FIG. 2 and FIG. 4
- the normal strength and the moisture resistanceincreased as the amount of monoethanolamine added increased.
- Comparative Examples 1 and 2where 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 productswas obtained.
- Example 6In 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 3shows the conditions of various examples of binders for inorganic fiber products and various evaluation results.
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Abstract
Description
Translated fromJapanese 本発明は、無機繊維製品用バインダー及びその製造方法、無機繊維製品の製造方法に関する。
本願は、２０１８年３月２９日に、日本に出願された特願２０１８－０６５１４６号に基づき優先権を主張し、その内容をここに援用する。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.
This application claims priority on March 29, 2018 based on Japanese Patent Application No. 2018-065146 filed in Japan, the contents of which are incorporated herein by reference.
従来、グラスウール、ロックウール、又はセラミック繊維等の無機繊維をバインダーで結合することにより成形した無機繊維製品が、断熱材、吸音材、又はその他各種成形品（自動車の屋根、ボンネットのライナー等）に用いられている。
無機繊維製品は、一般的に、無機繊維にバインダーを付着させ、集積して目的の無機繊維製品の形状の集積体とした後、加熱し、バインダーを硬化することにより製造されている。バインダーとしては、フェノール類とホルムアルデヒド類との反応により得られるフェノール樹脂を主成分としたもの（以下、フェノール樹脂系バインダーということがある。）が、比較的安価で、機械的強度等の性能に優れた製品が得られることから汎用されている。Conventionally, 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.
In general, 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. As 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.
しかし、フェノール樹脂系バインダーを用いた場合、製造工程でホルムアルデヒドが揮散する問題や、得られる無機繊維製品からホルムアルデヒドが放散する問題がある。ホルムアルデヒドは人体に悪影響を及ぼす物質で、例えば建材から放散するアルデヒドはシックハウス症候群の原因物質の一つとされている。そのため、日本国では２００３年にホルムアルデヒドの放散量を規制する改正建築基準法が施行されている。改正建築基準法においては、ホルムアルデヒド放散量が、ＪＩＳ Ａ１９０１により測定されるホルムアルデヒド放散速度として５μｇ／ｍ２・ｈｒ以下のものは規制対象となっていない。そのため、無機繊維製品としてもホルムアルデヒド放散速度が５μｇ／ｍ２・ｈｒ以下のものが要望される。However, when a phenol resin binder is used, there are problems that formaldehyde is volatilized in the manufacturing process and formaldehyde is diffused from the resulting inorganic fiber product. Formaldehyde is a substance that adversely affects the human body. For example, aldehyde released from building materials is considered to be one of the causative substances of sick house syndrome. For this reason, in 2003, the revised Building Standard Law, which regulates the amount of formaldehyde emitted, was enforced in 2003. Under the revised Building Standard Law, the amount of formaldehyde emitted is 5 μg / m2 · 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 μg / m2 · hr or less is desired.
無機繊維製品の製造工程（バインダーの吹きつけ時等）でホルムアルデヒドが揮散する問題の対応策の一つとして、フェノール樹脂を尿素で変性させることが行われている。この場合、フェノール樹脂に導入された尿素によってフェノール樹脂中の遊離ホルムアルデヒドが捕捉され、製造工程中のホルムアルデヒド揮散量が低減し、作業環境が改善する。
無機繊維製品からホルムアルデヒドが放散する問題の対応策としては、現在、エチレン尿素、又はアジピン酸ジヒドラジド等のホルムアルデヒド捕捉剤を併用することが一般的になっている（例えば特許文献１参照）。ホルムアルデヒド捕捉剤は、発生したホルムアルデヒドと反応し、固定化することでホルムアルデヒド放散量を低減する。
しかし、従来の方法では、ホルムアルデヒド放散量が少なく、性能も良好な無機繊維製品を低コストで製造することは難しい。As one of countermeasures for the problem of formaldehyde volatilization in the manufacturing process of inorganic fiber products (when the binder is sprayed, etc.), phenol resin is modified with urea. In this case, 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.
As a countermeasure against the problem of formaldehyde being diffused from inorganic fiber products, it is now common to use 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.
However, in the conventional method, it is difficult to produce an inorganic fiber product with low formaldehyde emission and good performance at low cost.
例えばフェノール樹脂を尿素変性させる方法は、製造工程でのホルムアルデヒド揮散量の低減には有効であるものの、得られた無機繊維製品からのホルムアルデヒド放散量は逆に多くなる傾向がある。これは、ホルムアルデヒド源が無機繊維製品中に固定されて潜在ホルムアルデヒドとして滞在し、加水分解等により再放出されるためと考えられる。また、バインダーとして尿素で変性させたフェノール樹脂を用いた場合、尿素変性していないフェノール樹脂を用いた場合に比べて、得られた無機繊維製品の耐水強度等の性能が低くなる等の問題もある。For example, although a method of modifying a phenol resin with urea is effective in reducing the amount of formaldehyde volatilized in the manufacturing process, the amount of formaldehyde emitted from the obtained inorganic fiber product tends to increase. This is presumably because the formaldehyde source is fixed in the inorganic fiber product, stays as latent formaldehyde, and is re-released by hydrolysis or the like. In addition, when a phenol resin modified with urea is used as a binder, there is a problem that the performance of the obtained inorganic fiber product, such as water resistance, is lower than when a phenol resin not modified with urea is used. is there.
また、ホルムアルデヒド捕捉剤の使用は、ホルムアルデヒド放散量の低減には有効であるものの、従来のホルムアルデヒド捕捉剤がフェノール樹脂に比べて高価である。しかもホルムアルデヒド放散速度が５μｇ／ｍ２・ｈｒ以下の無機繊維製品を得ようとすると、ホルムアルデヒド捕捉剤の使用量も多くなることからコストアップにつながり、フェノール樹脂系バインダーのコストメリットが損なわれる。また、ホルムアルデヒド捕捉剤は、通常、特許文献１に記載されているように、硬化後に添加されるため、工程の煩雑化にもつながる。そのため、前記ホルムアルデヒド捕捉剤を併用しなくても、ホルムアルデヒド放散速度が５μｇ／ｍ２・ｈｒ以下の無機繊維製品を得ることが可能なフェノール樹脂系バインダーが求められる。Moreover, although the use of formaldehyde scavengers is effective in reducing the amount of formaldehyde emitted, conventional formaldehyde scavengers are more expensive than phenolic resins. Moreover, when an inorganic fiber product having a formaldehyde emission rate of 5 μg / m2 · hr or less is obtained, the amount of formaldehyde scavenger used is increased, leading to an increase in cost, and the cost merit of the phenol resin binder is impaired. Moreover, since the formaldehyde scavenger is usually added after curing as described in Patent Document 1, it leads to complication of the process. Therefore, there is a need for a phenolic resin binder that can obtain an inorganic fiber product having a formaldehyde emission rate of 5 μg / m2 · hr or less without using the formaldehyde scavenger in combination.
このような状況のなか、近年、無機繊維製品の製造工程でホルムアルデヒドが揮散する問題の対応策の一つとして、ホルムアルデヒドとフェノールを反応させてレゾール型フェノール樹脂を得た後に５０～６５℃でアミンを添加し、未反応のホルムアルデヒド及びフェノールをアミンと反応させて縮合物を形成させる方法が提案されている（特許文献２～４）。また、ホルムアルデヒドの放散量を低減する方法としては、レゾール型フェノール樹脂に糖を添加した無機繊維製品用バインダーも知られている（特許文献５、６）。Under these circumstances, as a countermeasure for the problem of formaldehyde volatilization in the manufacturing process of inorganic fiber products in recent years, a resol-type phenol resin is obtained by reacting formaldehyde with phenol, and then an amine at 50 to 65 ° C. Has been proposed in which unreacted formaldehyde and phenol are reacted with an amine to form a condensate (
特許文献２～４のように、未反応のホルムアルデヒド及びフェノールにアミンを反応させて縮合物を形成させると、無機繊維製品用バインダーの水希釈性が悪くなる。そのため、無機繊維製品用バインダーを無機繊維に付着させることが困難になる。特許文献２～４の無機繊維製品用バインダーは、ｐＨを酸性に調整することで水希釈性がある程度改善するが、無機繊維製品用バインダーを酸性にすると、設備が腐食する等、設備負荷が増大する。
また、特許文献５、６のような無機繊維製品用バインダーは、水希釈性は優れるが、製造される無機繊維製品の色味が茶系色となり、従来の色味と異なるため、一部の顧客からは外観上好ましくないと指摘される場合がある。また、高密度のボード製品では、既存のフェノール樹脂を使用した製品に比べ、タワミ量が大きくなる等の強度低下を招く場合がある。As in
Moreover, although the binder for inorganic fiber products like
本発明は、水希釈性に優れ、かつホルムアルデヒド放散量が低減され、強度を充分に有し、外観に優れた無機繊維製品を製造できる無機繊維製品用バインダー、前記無機繊維製品用バインダーの製造方法、及び前記無機繊維製品用バインダーを用いた無機繊維製品の製造方法を提供することを目的とする。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.
本発明は、以下の態様を有する。
［１］レゾール型フェノール樹脂と、モノアミンとを含む無機繊維製品用バインダー。
［２］前記モノアミンの含有量が、前記レゾール型フェノール樹脂の樹脂固形分１００質量部に対して、０．５～４０質量部である、［１］に記載の無機繊維製品用バインダー。
［３］ｐＨが７．０～１３．０である、［１］又は［２］に記載の無機繊維製品用バインダー。
［４］［１］～［３］のいずれかに記載の無機繊維製品用バインダーを無機繊維に付着させ、前記無機繊維を成形して無機繊維製品を得る、無機繊維製品の製造方法。
［５］５０℃未満でレゾール型フェノール樹脂にモノアミンを添加する、無機繊維製品用バインダーの製造方法。
［６］前記モノアミンの添加量が、前記レゾール型フェノール樹脂の樹脂固形分１００質量部に対して、０．５～４０質量部である、［５］に記載の無機繊維製品用バインダーの製造方法。The present invention has the following aspects.
[1] A binder for inorganic fiber products comprising a resol type phenolic resin and a monoamine.
[2] The binder for inorganic fiber products according to [1], wherein the content of the monoamine is 0.5 to 40 parts by mass with respect to 100 parts by mass of the resin solid content of the resol type phenol resin.
[3] The binder for inorganic fiber products according to [1] or [2], wherein the pH is 7.0 to 13.0.
[4] 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.
[5] 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.
[6] The method for producing a binder for an inorganic fiber product according to [5], wherein the addition amount of the monoamine is 0.5 to 40 parts by mass with respect to 100 parts by mass of the resin solid content of the resol type phenol resin. .
本発明によれば、水希釈性に優れた無機繊維製品用バインダーにより、ホルムアルデヒド放散量が低減され、強度を充分に有し、外観に優れた無機繊維製品を製造できる。According to the present invention, 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.
［無機繊維製品用バインダー］
本発明の無機繊維製品用バインダー（以下、「本バインダー」とも記す。）は、無機繊維製品において、グラスウール、ロックウール、セラミック繊維等の無機繊維を結合するためのバインダーである。本バインダーは、レゾール型フェノール樹脂と、モノアミンとを含む。
本バインダーは、必要に応じて、本発明の効果を損なわない範囲で、レゾール型フェノール樹脂及びモノアミン以外の他の成分をさらに含んでもよい。[Binder for inorganic fiber products]
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.
（レゾール型フェノール樹脂）
レゾール型フェノール樹脂は、フェノール類とアルデヒド類とのアルカリ触媒存在下での反応生成物である。
フェノール類とアルデヒド類とをアルカリ触媒存在下で反応させると、フェノール類の芳香環にアルデヒド類が付加する付加反応が起き、その後縮合反応を経て高分子化する。(Resol type phenol resin)
The resol type phenol resin is a reaction product of a phenol and an aldehyde in the presence of an alkali catalyst.
When phenols and aldehydes are reacted 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.
フェノール類は、芳香環及び芳香環に結合した水酸基を有する化合物である。フェノール類としては、例えば、フェノール、アルキルフェノール類（ｏ，ｍ，ｐの各クレゾール、ｏ，ｍ，ｐの各エチルフェノール、キシレノールの各異性体等）、多芳香環フェノール類（α，βの各ナフトール等）、多価フェノール類（ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ピロガロール、レゾルシン、カテコール、ハイドロキノン等）等が挙げられる。これらのフェノール類は、１種を単独で用いてもよく、２種以上を併用してもよい。これらのうち、実用的な物質は、フェノール、ｏ，ｍ，ｐの各クレゾール、キシレノールの各異性体、レゾルシン、カテコールである。Phenols are compounds having an aromatic ring and a hydroxyl group bonded to the aromatic ring. Examples of phenols include phenol, alkylphenols (o, m, p cresol, o, m, p ethylphenol, xylenol isomers, etc.), polyaromatic phenols (α, β 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.
アルデヒド類は、ホルミル基を有する化合物及びその多量体からなる群から選ばれる少なくとも１種の化合物である。アルデヒド類としては、例えば、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、プロピルアルデヒド、ベンズアルデヒド、サリチルアルデヒド、グリオキザール等が挙げられる。これらのアルデヒド類は、１種を単独で用いてもよく、２種以上を併用してもよい。これらのうち、実用的な物質は、ホルムアルデヒド、パラホルムアルデヒドである。Aldehydes are at least one compound selected from the group consisting of compounds having a formyl group and multimers thereof. Examples of 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.
レゾール型フェノール樹脂の重量平均分子量は、水希釈性、経時安定性の点から、８００以下が好ましく、６００以下がより好ましく、４００以下がさらに好ましい。レゾール型フェノール樹脂の重量平均分子量は、１５０未満の場合は、無機繊維製品におけるバインダーの歩留まり低下や、強度低下等の恐れがあり好ましくない。
なお、レゾール型フェノール樹脂の重量平均分子量は、ポリスチレンを標準物質として用いたゲル浸透クロマトグラフィー（ＧＰＣ）により測定した値である。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. When 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.
レゾール型フェノール樹脂は、液状が好ましい。
レゾール型フェノール樹脂の樹脂固形分は、輸送コストの点から、３０質量％以上が好ましく、４０質量％以上がより好ましい。
なお、レゾール型フェノール樹脂の「樹脂固形分」とは、レゾール型フェノール樹脂の不揮発分を示す。不揮発分は、ＪＩＳ Ｋ６９１０の５．６の規定に準じて測定される値を示す。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.
（モノアミン）
モノアミンは、鎖状であってもよく、環状であってもよい。
モノアミンとしては、ホルムアルデヒド放散量を低減する効果が得られやすい点から、１級アミン又は２級アミンが好ましく、１級アミンがより好ましい。(Monoamine)
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.
アミンが有する炭化水素基は、飽和炭化水素基であってもよく、不飽和炭化水素基であってもよい。The hydrocarbon group possessed by the amine may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
モノアミンの分子量は、放散ホルムアルデヒドの低減効果と水希釈性の低下抑制の点から、３００以下が好ましく、２００以下がより好ましく、１５０以下がさらに好ましい。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.
モノアミンとしては、脂肪族モノアミン、脂環式モノアミン、芳香族モノアミン等が挙げられる。
脂肪族モノアミンとしては、例えば、モノアルカノールアミン（モノエタノールアミン、モノイソプロパノールアミン、ジエタノールアミン等）、アルキルアミン（モノメチルアミン、モノエチルアミン、ジメチルアミン、ジエチルアミン等）等が挙げられる。
脂環式モノアミンとしては、例えば、ピペリジン、ピロリジン、モルホリン、ピロール、ピリジン等が挙げられる。
芳香族モノアミンとしては、例えば、アニリン、アミノフェノール、トルイジン等が挙げられる。Examples of monoamines include aliphatic monoamines, alicyclic monoamines, and aromatic monoamines.
Examples of the aliphatic monoamine include monoalkanolamine (monoethanolamine, monoisopropanolamine, diethanolamine, etc.), alkylamine (monomethylamine, monoethylamine, dimethylamine, diethylamine, etc.) and the like.
Examples of the alicyclic monoamine include piperidine, pyrrolidine, morpholine, pyrrole, and pyridine.
Examples of the aromatic monoamine include aniline, aminophenol, toluidine and the like.
モノアミンとしては、ホルムアルデヒド放散量を低減する効果が得られやすい点から、脂肪族モノアミンが好ましく、１級又は２級のアミンがさらに好ましく、モノエタノールアミン、モノエチルアミンが特に好ましい。
モノアミンは、１種を単独で用いてもよく、２種以上を併用してもよい。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.
本バインダー中のモノアミンの含有量は、レゾール型フェノール樹脂の樹脂固形分１００質量部に対して、０．５～４０質量部が好ましく、５～２５質量部がより好ましい。モノアミンの含有量が前記範囲の下限値以上であれば、ホルムアルデヒド放散量が充分に低減され、常態強度及び耐湿強度が高い無機繊維製品が得られやすい。モノアミンの含有量が前記範囲の上限値以下であれば、経済性に優れる。
なお、本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。常態強度とは、乾燥状態での機械的強度（引っ張り強度、曲げ強度等）を示す。耐湿強度とは、湿潤状態での機械的強度を示す。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. When 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.
In the present specification, 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.
（他の成分）
他の成分としては、本バインダーに配合し得る成分として公知のもののなかから適宜選択して使用できる。例えば、尿素、エチレン尿素、レゾルシン、メラミン、ジシアンジアミド、アンモニア、硬化促進剤、シランカップリング剤、公知のホルムアルデヒド捕捉剤、撥水剤、発塵防止オイル、水等が挙げられる。他の成分は、１種を単独で用いてもよく、２種以上を併用してもよい。(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.
本バインダーが尿素、メラミン、エチレン尿素、レゾルシン、ジシアンジアミド（ＤＣＤＡ）から選ばれる少なくとも１種を含むことで、無機繊維製品の製造工程時に揮散の原因となる、本バインダー中の遊離ホルムアルデヒドの量をさらに低減できる。
本バインダーが尿素を含む場合、尿素の含有量は、レゾール型フェノール樹脂の樹脂固形分１００質量部に対して、５～１００質量部が好ましく、１０～７０質量部がより好ましい。メラミン、エチレン尿素、レゾルシン、ＤＣＤＡの含有量の好ましい範囲は、尿素の含有量の好ましい範囲と同じである。When 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.
When 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.
本バインダーがアンモニアを含むことで、本バインダー中の遊離ホルムアルデヒドと反応し、ヘキサミンに転換することにより、作業環境を改善する。また、アンモニアを配合することで、本バインダーのｐＨが高まり、水希釈性が向上する。水希釈性の向上は、配管への本バインダーの付着やスプレーノズルの詰まりを防止する点から好ましい。
アンモニアの配合量は、フェノール樹脂の樹脂固形分に対し、０～２０質量％が好ましい。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 | blending ammonia, pH of this binder increases and water dilutability improves. The improvement of water dilutability is preferable from the viewpoint of preventing adhesion of the binder to the piping and clogging of the spray nozzle.
The amount of ammonia is preferably 0 to 20% by mass based on the resin solid content of the phenol resin.
本バインダーには、さらに、硬化促進剤を用いてもよい。
硬化促進剤としては、例えば、硫酸アンモニウム、塩化アンモニウム、リン酸アンモニウム等のアンモニウム塩が挙げられる。
本バインダー中の硬化促進剤の含有量は、レゾール型フェノール樹脂の樹脂固形分１００質量部に対して、０～１０質量部が好ましく、３～５質量部がより好ましい。The binder may further contain a curing accelerator.
Examples of 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.
本バインダーがシランカップリング剤を含むことで、無機繊維製品の耐水性、機械的強度が向上する。
シランカップリング剤としては、特に限定されず、例えば、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、３－アミノプロピルトリエトキシシラン等のアミノシラン化合物が挙げられる。
本バインダー中のシランカップリング剤の含有量は、レゾール型フェノール樹脂の樹脂固形分１００質量部に対して、０～１質量部が好ましい。When 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.
ホルムアルデヒド捕捉剤としては、例えば、特開２００１－１７８８０５号公報に記載のホルムアルデヒド捕捉剤等が挙げられる。
撥水剤としては、シリコーン系撥水剤、フッ素系撥水剤等が挙げられる。
発塵防止オイルとしては、鉱物油ベースのオイルエマルジョン等が挙げられる。Examples of formaldehyde scavengers include formaldehyde scavengers described in JP-A No. 2001-178805.
Examples of the water repellent include a silicone water repellent and a fluorine water repellent.
Examples of the dust-preventing oil include mineral oil-based oil emulsions.
本バインダーのｐＨは、７．０～１３．０が好ましく、７．５～１２．０がより好ましく、８．０～１１．０がさらに好ましく、８．０～１０．０が特に好ましい。ｐＨが前記範囲の下限以上であれば、設備を傷めない。また、水への溶解性がより良好になる。
ｐＨが前記範囲の上限以下であれば、触媒及び添加剤等の使用量の点から経済的である。ｐＨは、２５℃における値である。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.
［無機繊維製品用バインダーの製造方法］
本バインダーは、５０℃未満でレゾール型フェノール樹脂にモノアミンを添加することで得られる。例えば、フェノール類とアルデヒド類とをアルカリ触媒の存在下に反応させてレゾール型フェノール樹脂を得た後、５０℃未満でモノアミンを添加する方法が挙げられる。[Method for producing binder for inorganic fiber product]
This binder is obtained by adding a monoamine to a resol type phenol resin at less than 50 ° C. 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.
フェノール類とアルデヒド類との反応は、公知の方法で行える。例えば、撹拌機、還流器及び温度制御機構を有する反応容器にフェノール類、アルデヒド類、アルカリ触媒、水等を仕込み、任意の反応温度で任意の反応時間保持する方法が挙げられる。反応の開始後、必要に応じて、追加のアルカリ触媒及び任意の添加剤等を添加してもよい。The reaction between phenols and aldehydes can be performed by a known method. For example, 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. After the start of the reaction, an additional alkali catalyst and optional additives may be added as necessary.
フェノール類に対するアルデヒド類のモル比（アルデヒド類／フェノール類）は、１．０～４．０が好ましく、１．５～２．５がより好ましい。フェノール類に対するアルデヒド類のモル比が前記範囲の下限値以上であれば、未反応のフェノール類の揮散による臭気発生、又は歩留低下を抑制しやすい。フェノール類に対するアルデヒド類のモル比が前記範囲の上限値以下であれば、未反応のアルデヒド類が多量に残留することなく、製造工程中の作業環境雰囲気下にホルムアルデヒドが揮発せず、作業員の健康を害さない。また、本バインダーを用いて得られる無機繊維製品からのアルデヒド類の放散量がより少なくなる。The molar ratio of aldehydes to phenols (aldehydes / 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.
アルカリ触媒としては、フェノール類とアルデヒド類との反応を進行させ得るものであれば特に制限はなく、種々のアルカリ性物質を用いることができる。具体例としては、ナトリウム、カリウム等のアルカリ金属の水酸化物（水酸化ナトリウム、水酸化カリウム等）、カルシウム、マグネシウム、バリウム等のアルカリ土類金属の水酸化物（水酸化カルシウム、水酸化マグネシウム、水酸化バリウム等）、無機アルカリ性物質（炭酸ナトリウム、アンモニア等）、有機アルカリ性物質（第３級アミン、環式アミン等）等が挙げられる。第３級アミンとしては、トリエチルアミン、トリメチルアミン、トリエタノールアミン等が挙げられる。環式アミンとしては、ＤＢＵ（１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン）、ＤＢＮ（１，５－ジアザビシクロ［４．３．０］ノナ－５－エン）等が挙げられる。通常、アルカリ土類金属を使用した場合、アルカリ金属を使用した場合よりも、樹脂の水希釈性や経時安定性は低下するが、耐水特性は向上する。これはアルカリ金属に比べアルカリ土類金属やその塩が、水に対して溶解性が低いためである。これらのアルカリ触媒は、１種を単独で用いてもよく、２種以上を併用してもよい。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.
アルカリ触媒の使用量は、フェノール類１００質量部に対して、１～３０質量部が好ましい。アルカリ触媒の使用量が前記範囲の下限値以上であれば、反応が充分に進行する。アルカリ触媒の使用量が前記範囲の上限値以下であれば、反応の制御が容易である。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.
フェノール類とアルデヒド類の反応の反応温度は、５０～９０℃が好ましく、６０～８０℃がより好ましい。反応温度が前記範囲の下限値以上であれば、充分な反応速度が得られる。反応温度が前記範囲の上限値以下であれば、反応の制御が容易である。
反応時間は、例えば２～８時間とすることができる。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.
フェノール類とアルデヒド類を前記範囲のような５０℃以上の反応温度で反応させた後、レゾール型フェノール樹脂の温度を５０℃未満まで降温させてからモノアミンを添加する。５０℃未満でモノアミンを添加することで、レゾール型フェノール樹脂中に含まれる遊離のフェノール及び遊離のホルムアルデヒドとモノアミンが反応して縮合物が形成されることを抑制できる。これにより、得られる本バインダーの水希釈性が低下することが抑制される。
なお、遊離のフェノール類とは、ＪＩＳ Ｋ６９１０の５．１６の規定に準じて測定される未反応のフェノール類である。遊離のアルデヒド類とは、ＪＩＳ Ｋ６９１０の５．１７の規定に準じて測定される未反応のアルデヒド類である。After the phenols and aldehydes are reacted at a reaction temperature of 50 ° C. or higher as in the above range, the temperature of the resol type phenol resin is lowered to less than 50 ° C., and then the monoamine is added. By adding 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.
モノアミンを添加する際のレゾール型フェノール樹脂の温度は、５０℃未満であり、１０～４０℃が好ましく、２０～３５℃がより好ましい。モノアミン添加時のレゾール型フェノール樹脂の温度が前記範囲の上限値以下であれば、水希釈性に優れた本バインダーが得られやすい。モノアミン添加時のレゾール型フェノール樹脂の温度が前記範囲の下限値以上であれば、アミンが樹脂に溶解しやすく、アミン添加時の溶解熱を緩和し、温度管理が容易にできる。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.
モノアミンの添加量は、レゾール型フェノール樹脂の樹脂固形分１００質量部に対して、０．５～４０質量部が好ましく、５～２５質量部がより好ましい。モノアミンの添加量が前記範囲内であれば、無機繊維製品のホルムアルデヒド放散量を充分に低減でき、かつ水希釈性に優れた本バインダーが得られやすい。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. When 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.
本発明では、フェノール類とアルデヒド類とをアルカリ触媒存在下で反応させた後、又はモノアミンを添加した後に、必要に応じて酸による中和や、水による希釈等の処理を行ってもよい。
中和に用いる酸としては、ホウ酸、硫酸、塩酸、硝酸、リン酸、スルファミン酸等の無機酸、ギ酸、シュウ酸、酢酸、クエン酸、乳酸、スルファニル酸、安息香酸、フェノールスルホン酸、パラトルエンスルホン酸、メタンスルホン酸、ラウリン酸等の有機酸が挙げられる。酸は、１種を単独で用いてもよく、２種以上を併用してもよい。In the present invention, after reacting phenols and aldehydes in the presence of an alkali catalyst, or after adding a monoamine, treatments such as neutralization with an acid or dilution with water may be performed as necessary.
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.
また、本発明では、フェノール類とアルデヒド類とをアルカリ触媒存在下で反応させた後、又はモノアミンを添加した後に、必要に応じて他の成分を添加する。
他の成分を添加する際のレゾール型フェノール樹脂の温度は、５０℃未満が好ましく、１０～４０℃が好ましく、２０～３５℃がより好ましい。Moreover, in this invention, after making phenols and aldehydes react in presence of an alkali catalyst, or after adding a monoamine, another component is added as needed.
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.
なお、本バインダーの製造方法は、前記した方法には限定されない。例えば、５０℃未満で市販のレゾール型フェノール樹脂にモノアミンを添加してもよい。
使用前の本バインダーの温度は、５０℃未満が好ましく、１０～４０℃が好ましく、２０～３５℃がより好ましい。In addition, the manufacturing method of this binder is not limited to an above described method. For example, you may add a monoamine to a commercially available resol type phenol resin at less than 50 degreeC.
The temperature of the binder before use is preferably less than 50 ° C, preferably 10 to 40 ° C, more preferably 20 to 35 ° C.
以上説明したように、本発明では、レゾール型フェノール樹脂と、モノアミンとを含む無機繊維製品用バインダーとする。本バインダーは、モノアミンを、遊離のフェノール類やアルデヒド類と反応させて縮合物とせずに含ませるため、水希釈性に優れている。また、本バインダーは、酸性にしなくても水希釈性に優れているため、設備負荷が増大することも防げる。As described above, in the present invention, 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. Moreover, since this binder is excellent in water reducibility even if it does not make it acidic, it can also prevent that an equipment load increases.
また、本バインダーは、無機繊維に付着させ、焼成して硬化する際に、バインダー中の遊離のフェノール類やアルデヒド類とモノアミンとがマンニッヒ反応により縮合物を形成する。このマンニッヒ縮合物が放散ホルムアルデヒドを捕捉すると考えられるため、本バインダーを用いて製造した無機繊維製品においては、ホルムアルデヒド放散量は充分に低減される。
また、モノアミンを含む本バインダーを用いて製造した無機繊維製品は、従来品と同様に黄色い発色になり、また常態強度及び耐湿強度も向上する。
本バインダーは、断熱材の製造に特に有用である。Moreover, 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.
［無機繊維製品の製造方法］
本発明の無機繊維製品の製造方法は、本バインダーを無機繊維に付着させ、前記無機繊維を成形することで、無機繊維製品を得る方法である。必要に応じて、本バインダーを無機繊維に付着させた後に焼成することで本バインダーを硬化させてもよい。
本発明の製造方法で製造する無機繊維製品としては、断熱材、吸音材や、自動車の屋根、ボンネット等のライナー等が挙げられる。本発明は、断熱材の製造に特に有用である。
本発明の製造方法で製造する無機繊維製品は、成形体のみからなるものでもよく、梱包のための表皮材等の成形体以外の他の部材をさらに備えるものであってもよい。[Production method of inorganic fiber products]
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.
無機繊維としては、特に限定されず、グラスウール、ロックウール、セラミック繊維等が挙げられる。無機繊維は、１種を単独で用いてもよく、２種以上を併用してもよい。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.
本バインダーを無機繊維に付着させる方法としては、例えば、無機繊維に対し、スプレー装置等を用いて本バインダーを吹き付ける方法、無機繊維を本バインダーに浸漬して含浸させる方法等が挙げられる。
本バインダーは、水希釈性に優れるため、必要に応じて水により適度な濃度まで希釈することで、容易に無機繊維に均一に付着させることができる。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.
無機繊維への本バインダーの付着量は、特に限定されず、例えば、無機繊維（１００質量％）に対し、本バインダーの樹脂固形分として０．５～２０質量％とすることができる。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).
本バインダーを付着させた無機繊維の成形は、公知の方法で行える。例えば、板状の断熱材の場合、本バインダーを付着させた無機繊維をコンベア上に堆積し、この堆積物をコンベアの上下方向から押圧して圧縮して集積体とし、これを加熱炉（硬化炉）に送って焼成して本バインダーを硬化させる方法が挙げられる。The formation of the inorganic fiber to which the binder is attached can be performed by a known method. For example, in the case of a plate-like heat insulating material, 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) A method of curing the binder by sending it to a furnace and baking it.
焼成温度は、本バインダーが硬化する温度範囲であればよく、１８０～２７０℃が好ましい。焼成温度が前記範囲の下限値以上であれば、バインダーの硬化が充分に進行しやすく、またホルムアルデヒド放散量が充分に低減されやすい。焼成温度が前記範囲の上限値以下であれば、本バインダーが分解しにくく、歩留りの低下及び機械的強度の低下が抑制されやすい。
焼成時間は、集積体の大きさ、焼成温度等によって適宜設定できる。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.
以下、実施例によって本発明を具体的に説明するが、本発明は以下の記載によっては限定されない。以下の説明において、「部」は、特に言及がない場合は「質量部」を示す。
［実施例１］
コンデンサー、温度計、撹拌装置を備えた反応装置にフェノール１３５０部、５０質量％ホルムアルデヒド水溶液１８９３．７部、水酸化バリウム８水和物１３５部をそれぞれ仕込み、６０℃にて３６０分間反応させた後、３５℃に冷却し、レゾール型フェノール樹脂を合成した。ホルムアルデヒド／フェノール［Ｆ／Ｐ］のモル比は２．２であり、得られた樹脂の特性は、重量平均分子量＝３４０、遊離フェノール＝５．０質量％、遊離ホルムアルデヒド＝３．８質量％であった。
上記レゾール型フェノール樹脂固形分１００部に対して０．７部の割合でモノエタノールアミンを３５℃以下に溶解熱を抑えて添加した後、樹脂固形分が５０質量％となるように調整水を加えて無機繊維製品用バインダーＡ－１を得た。
さらに、３５℃の無機繊維製品用バインダーＡ－１の固形分１００部に対して、他の成分として、尿素４３部、硫酸アンモニウム３部、アミノシラン１部、２５質量％アンモニア水１０部を混合して無機繊維製品用バインダーＢ－１を得た。EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by the following description. In the following description, “part” means “part by mass” unless otherwise specified.
[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. The molar ratio of formaldehyde / phenol [F / P] is 2.2, and the properties of the obtained resin are as follows: weight average molecular weight = 340, free phenol = 5.0 mass%, free formaldehyde = 3.8 mass%. there were.
After adding monoethanolamine at a ratio of 0.7 part to 100 parts by weight of the above-mentioned resol type phenolic resin while suppressing the heat of dissolution to 35 ° C. or less, adjusting water is added so that the resin solid part becomes 50% by mass. In addition, a binder A-1 for inorganic fiber products was obtained.
Furthermore, with respect to 100 parts of solid content of binder A-1 for inorganic fiber products at 35 ° C., 43 parts of urea, 3 parts of ammonium sulfate, 1 part of aminosilane, and 10 parts of 25 mass% ammonia water were mixed as other components. Binder B-1 for inorganic fiber products was obtained.
［実施例２～６］
モノエタノールアミンの添加量を表１に示すように変更した以外は、実施例１と同様にして無機繊維製品用バインダーＡ－２～Ａ－６を調製した。さらに、無機繊維製品用バインダーＡ－２～Ａ－６に、実施例１と同様に他の成分を添加して無機繊維製品用バインダーＢ－２～Ｂ－６を得た。[Examples 2 to 6]
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.
［実施例７］
実施例１と同様にしてレゾール型フェノール樹脂を合成し、樹脂固形分１００部に対して６部の割合でモノエチルアミンを３５℃以下に溶解熱を抑えて添加した後、樹脂固形分が５０質量％となるように調整水を加えて無機繊維製品用バインダーＡ－７を得た。さらに、無機繊維製品用バインダーＡ－７に、実施例１と同様に他の成分を添加して無機繊維製品用バインダーＢ－７を得た。[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.
［比較例１］
実施例１と同様にしてレゾール型フェノール樹脂を合成し、樹脂固形分が５０質量％となるように調整水を加えたものを無機繊維製品用バインダーＡ－８とした。さらに、無機繊維製品用バインダーＡ－８に、実施例１と同様に他の成分を添加して無機繊維製品用バインダーＢ－８を得た。[Comparative 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.
［比較例２］
実施例１と同様にしてレゾール型フェノール樹脂を合成し、３５℃まで冷却後にｐＨ７．３になるように３０質量％硫酸を加えて中和した後、樹脂固形分が５０質量％となるように調整水を加えたものを無機繊維製品用バインダーＡ－９とした。さらに、無機繊維製品用バインダーＡ－９に、実施例１と同様に他の成分を添加して無機繊維製品用バインダーＢ－９を得た。[Comparative 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.
［比較例３］
実施例１と同様にしてレゾール型フェノール樹脂を合成し、３５℃まで冷却後にｐＨ７．３になるように３０質量％硫酸を加えて中和し、樹脂固形分１００部に対して３０部の割合でぶどう糖果糖液糖（異性化糖、製品名：スリーシュガー７５ＦＧ、固形分濃度７５質量％、群栄化学工業社製）を添加し、樹脂固形分が５０質量％となるように調整水を加えたものを無機繊維製品用バインダーＡ－１０とした。さらに、無機繊維製品用バインダーＡ－１０に、実施例１と同様に他の成分を添加して無機繊維製品用バインダーＢ－１０を得た。[Comparative 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.
［比較例４］
モノエタノールアミンを添加する際のレゾール型フェノール樹脂の温度を７０℃に変更し、遊離のフェノール及びホルムアルデヒドとモノエタノールアミンを反応させて縮合物とした以外は、実施例１と同様にして無機繊維製品用バインダーＡ－１１を得た。さらに、無機繊維製品用バインダーＡ－１１に、実施例１と同様に他の成分を添加して無機繊維製品用バインダーＢ－１１を得た。[Comparative 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.
［水希釈性（混和性）］
ＪＩＳ Ｋ６９１０：２００７の５．５の規定に準じて、水に対する混和性（質量分率％）を測定し、水希釈性を評価した。なお、混和性の算出における試料の質量には、樹脂固形分を用いた。混和性の測定において、混和性４０００％に相当する量の水を添加しても濁りが見られない場合は、その時点で測定を終了し、混和性は４０００％超である、と判定した。
なお、試料の樹脂固形分の質量を用いて算出した混和性が４０００％以上であれば、無機繊維製品用バインダーとして問題なく使用できる。[Water reducibility (miscibility)]
According to the provisions of JIS K6910: 2007, 5.5, water miscibility (mass fraction%) was measured to evaluate water dilutability. In addition, resin solid content was used for the mass of the sample in calculation of miscibility. In the measurement of the miscibility, when no turbidity was observed even when an amount of water corresponding to the miscibility of 4000% was added, the measurement was terminated at that point, and the miscibility was determined to be over 4000%.
In addition, if the miscibility computed using the mass of the resin solid content of a sample is 4000% or more, it can be used without a problem as a binder for inorganic fiber products.
［ｐＨ］
無機繊維製品用バインダーのｐＨは、ＪＩＳ Ｋ６９１０：２００７の５．４の規定に準じて測定した。[PH]
The pH of the binder for inorganic fiber products was measured according to JIS K6910: 2007 5.4.
［ＦＰ（遊離フェノール量）］
無機繊維製品用バインダーのＦＰ（遊離フェノール量）は、ＪＩＳ Ｋ６９１０：２００７の５．１６の規定に準じて測定した。[FP (free phenol content)]
The FP (free phenol amount) of the binder for inorganic fiber products was measured in accordance with 5.16 of JIS K6910: 2007.
［ＦＦ（遊離ホルムアルデヒド量）］
無機繊維製品用バインダーのＦＦ（遊離ホルムアルデヒド量）は、ＪＩＳ Ｋ６９１０：２００７の５．１７の規定に準じて測定した。[FF (free formaldehyde amount)]
The FF (free formaldehyde amount) of the binder for inorganic fiber products was measured in accordance with 5.17 of JIS K6910: 2007.
［引っ張り強度］
各例における無機繊維製品用バインダーを、樹脂固形分の濃度が３５質量％となるように水で希釈した後に、ガラスビーズ（平均粒径１００μｍ）２５ｇに、樹脂固形分が３質量％になるように添加混合した。得られた混合物をドッグボーン型の金型（長さ７５ｍｍ、最小幅（長さ方向の中央部）２５ｍｍ、最大幅４２ｍｍ、厚さ７ｍｍ）に均一充填し、１９０℃で３０分間焼成してテストピースを作製した。テストピースは同じ条件で合計６個作製した。
３つのテストピースを用いて引っ張り強度（常態強度）を測定し、残り３つのテストピースは温度６５℃、湿度９５％の恒温恒湿機中で２４時間放置後に引っ張り強度（耐湿強度）を測定した。
引っ張り強度は、ＪＩＳ Ｋ６９１１：２００６の５．１８の規定に準拠して、荷重速度５ｍｍ／分の条件で実施した。引っ張り強度（Ｎ／ｍｍ２）は、測定値（Ｎ）／破断面積（２５×７＝１７５ｍｍ２）で計算されるが、破断面積は１７５（ｍｍ２）で一定としたため、測定値（Ｎ）のみで比較した。[Tensile strength]
After diluting the binder for inorganic fiber products in each example with water so that the concentration of the resin solid content is 35% by mass, the resin solid content is 3% by mass in 25 g of glass beads (average particle size 100 μm). And mixed. The obtained mixture was uniformly filled into a dogbone mold (length 75 mm, minimum width (center in the length direction) 25 mm, maximum width 42 mm, thickness 7 mm), and fired at 190 ° C. for 30 minutes for testing. Pieces were made. A total of 6 test pieces were produced under the same conditions.
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. The tensile strength (N / mm2 ) is calculated by the measurement value (N) / breakage area (25 × 7 = 175 mm2 ), but the break area was constant at 175 (mm2 ), so the measurement value (N) Only compared.
［ホルムアルデヒド放散量］
ホルムアルデヒド放散量（放散Ｆ量）の測定は、ＪＩＳ Ａ １９０２－４：２０１５の７に準拠して行った。
無機繊維製品用バインダーを樹脂固形分の濃度が１０質量％となるように水で希釈し、１５ｃｍ角に裁断したガラスろ紙（ＡＤＶＡＮＴＥＣ製ＧＡ－１００）に含浸させた。バインダーの付着量は、約４０質量％であった。次いで、無機繊維製品用バインダーを付着させたガラスろ紙を２００℃で１０分間焼成した。焼成後、ろ紙の中心部を５ｃｍ角に切り出し（表面の面積２５ｃｍ２）、１Ｌ容量のポリ容器に入れた（ろ紙表面の面積／ポリ容器体積＝２．２ｍ２／ｍ３。）。穴の開いた内蓋をポリ容器の開口部に嵌め、アルデヒド／ケトン補修用パッシブサンプラーＤＳＤ－ＤＮＰＨ（Ｓｕｐｅｌｃｏ製）を差し込み、シールテープを巻いて密閉した。温度２８℃、湿度５０％で２４時間放置し、ホルムアルデヒドを捕集した。捕集後のサンプラーで補修したホルムアルデヒドは、アセトニトリルにて抽出液が５ｍＬになるよう抽出した。抽出液中のホルムアルデヒド濃度を、高速液体クロマトグラフ（ＨＰＬＣ）にて以下の条件で分析した。放散Ｆ量が５μｇ／Ｌ以下のものは、放散等級Ｆ☆☆☆☆を達成するものであることを示している。
（ＨＰＬＣ測定条件）
使用機器及び型式：東ソー社製ＰＤ８０２０、
カラム：ＩｎｅｒｔＳｕｓｔａｉｎＣ１８ ３．０×１５０、
溶離液：アセトニトリルと水の混合液（アセトニトリル：水（体積比）＝５５：４５）、
流速：０．４５ｍＬ／分、
注入量：２０μＬ、
検出器条件：ＵＶ３６０ｎｍ。[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. Subsequently, 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). After firing, the center of the filter paper was cut into 5 cm square (
(HPLC measurement conditions)
Equipment and model used: PD8020 manufactured by Tosoh Corporation
Column: Inert Sustain C18 3.0 × 150,
Eluent: A mixture of acetonitrile and water (acetonitrile: water (volume ratio) = 55: 45),
Flow rate: 0.45 mL / min,
Injection volume: 20 μL,
Detector conditions: UV 360 nm.
各例の無機繊維製品用バインダーの条件、各種の評価結果を表１、表２、及び図１～４に示す。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.
表１に示すように、レゾール型フェノール樹脂に３５℃以下でモノエタノールアミン、モノエチルアミンを添加した実施例１～７の無機繊維製品用バインダーＡ－１～Ａ－７は、水希釈性に優れていた。また、表２及び図３に示すように、実施例１～７においてさらに他の成分を添加した無機繊維製品用バインダーＢ－１～Ｂ－７は、ホルムアルデヒド放散量が低減されており、テストピースが黄色で外観が良好であった。
また、表１、表２、図１、図２及び図４に示すように、モノエタノールアミンの添加量が多くなるにつれて、常態強度及び耐湿強度が高くなった。As shown in Table 1, 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. In addition, as shown in Table 2 and FIG. 3, 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.
Moreover, as shown in Table 1, Table 2, FIG. 1, FIG. 2 and FIG. 4, the normal strength and the moisture resistance increased as the amount of monoethanolamine added increased.
一方、モノエタノールアミンを添加していない比較例１、２では、ホルムアルデヒド放散量が充分に低減されなかった。また、異性化糖を添加した比較例３では、放散ホルムアルデヒド量は低減されるものの、常態強度及び耐湿強度は低くなり、テストピースが茶系の発色となった。また、７０℃でモノエタノールアミンを添加し、フェノール、ホルムアルデヒド及びモノエタノールアミンの縮合物を形成させた比較例４の無機繊維製品用バインダーＡ－１１は、水希釈性が著しく劣っていた。On the other hand, in 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.
［実施例８］
コンデンサー、温度計、撹拌装置を備えた反応装置にフェノール１３５０部、５０質量％ホルムアルデヒド水溶液２０６５．９部、５０質量％水酸化ナトリウム１０８部をそれぞれ仕込み、６５℃にて３００分間反応させた後、３５℃に冷却し、レゾール型フェノール樹脂を合成した。ホルムアルデヒド／フェノール［Ｆ／Ｐ］のモル比は２．４であり、得られた樹脂の特性は、重量平均分子量＝３８０、遊離フェノール＝１．５質量％、遊離ホルムアルデヒド＝３．０質量％であった。
上記レゾール型フェノール樹脂固形分１００部に対して６部の割合でモノエタノールアミンを３５℃以下に溶解熱を抑えて添加した後、樹脂固形分が５０質量％となるように調整水を加えて無機繊維製品用バインダーＣ－１を得た。[Example 8]
A reactor equipped with a condenser, a thermometer, and a stirring device was charged with 1350 parts of phenol, 2065.9 parts of 50% by weight aqueous formaldehyde solution and 108 parts of 50% by weight sodium hydroxide, and reacted at 65 ° C. for 300 minutes. After cooling to 35 ° C., a resol type phenol resin was synthesized. The molar ratio of formaldehyde / phenol [F / P] is 2.4, and the properties of the obtained resin are as follows: weight average molecular weight = 380, free phenol = 1.5 mass%, free formaldehyde = 3.0 mass%. there were.
After adding monoethanolamine at a ratio of 6 parts or less to 35 ° C. or less with respect to 100 parts of the resol type phenol resin solids, adjusting water was added so that the resin solids would be 50% by mass. Binder C-1 for inorganic fiber products was obtained.
［比較例５］
実施例８と同様にしてレゾール型フェノール樹脂を合成し、樹脂固形分が５０質量％となるように調整水を加えたものを無機繊維製品用バインダーＣ－２とした。[Comparative Example 5]
In the same manner as in Example 8, a resol type phenol resin was synthesized, and adjusted water was added so that the resin solid content was 50% by mass, which was designated as binder C-2 for inorganic fiber products.
［比較例６］
実施例８と同様にしてレゾール型フェノール樹脂を合成し、５０℃まで冷却後にｐＨ７．３になるようにホウ酸を加えて中和した後、樹脂固形分が５０質量％となるように調整水を加えたものを無機繊維製品用バインダーＣ－３とした。[Comparative 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.
［比較例７］
モノエタノールアミンを添加する際のレゾール型フェノール樹脂の温度を７０℃に変更し、遊離のフェノール及びホルムアルデヒドとモノエタノールアミンを反応させて縮合物とした以外は、実施例８と同様にして無機繊維製品用バインダーＣ－４を得た。[Comparative Example 7]
Inorganic fiber in the same manner as in Example 8, 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 C-4 was obtained.
［比較例８］
比較例７と同様にしてレゾール型フェノール樹脂にモノエタノールアミンを反応させ、５０℃まで冷却後にｐＨ７．３になるようにホウ酸を加えて中和した後、樹脂固形分が５０質量％となるように調整水を加えたものを無機繊維製品用バインダーＣ－５とした。[Comparative Example 8]
In the same manner as in Comparative Example 7, the resol type phenol resin was reacted with monoethanolamine, and after cooling to 50 ° C. and neutralizing with boric acid so that the pH became 7.3, the resin solid content became 50% by mass. In this manner, a binder C-5 for inorganic fiber products was added with adjusted water.
［比較例９］
比較例７と同様にしてレゾール型フェノール樹脂にモノエタノールアミンを反応させ、５０℃まで冷却後にｐＨ５．０になるようにホウ酸を加えて中和した後、樹脂固形分が５０質量％となるように調整水を加えたものを無機繊維製品用バインダーＣ－６とした。[Comparative Example 9]
In the same manner as in Comparative Example 7, the resol type phenol resin was reacted with monoethanolamine, and after cooling to 50 ° C. and neutralizing with boric acid so that the pH became 5.0, the resin solid content became 50% by mass. In this manner, a binder C-6 for inorganic fiber products was added with adjusted water.
各例の無機繊維製品用バインダーの条件、各種の評価結果を表３に示す。Table 3 shows the conditions of various examples of binders for inorganic fiber products and various evaluation results.
表３に示すように、触媒に水酸化ナトリウムを使用したレゾール型フェノール樹脂に３５℃以下でモノエタノールアミンを添加した実施例８の無機繊維製品用バインダーＣ－１や、モノエタノールアミンを添加していない比較例５、６のＣ－２、Ｃ－３は、水希釈性に優れていた。As shown in Table 3, the inorganic fiber product binder C-1 of Example 8 in which monoethanolamine was added at 35 ° C. or lower to a resol type phenol resin using sodium hydroxide as a catalyst, and monoethanolamine were added. In Comparative Examples 5 and 6, C-2 and C-3, which were not, were excellent in water dilutability.
一方、７０℃でモノエタノールアミンを添加し、フェノール、ホルムアルデヒド及びモノエタノールアミンの縮合物を形成させた比較例７～９の無機繊維製品用バインダーＣ－４、Ｃ－５、Ｃ－６は、水希釈性が著しく劣っていた。またｐＨを酸性にしても水希釈性は改善しなかった。On the other hand, binders C-4, C-5, and C-6 for inorganic fiber products of Comparative Examples 7 to 9, in which monoethanolamine was added at 70 ° C. to form a condensate of phenol, formaldehyde, and monoethanolamine, Water dilutability was extremely inferior. Moreover, even when the pH was acidified, the water dilutability did not improve.
Claims (6)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022210093A1 (en)* | 2021-03-29 | 2022-10-06 | 群栄化学工業株式会社 | Thermally curable composition for cellulosic product and cellulosic product |
| JP2022153295A (en)* | 2021-03-29 | 2022-10-12 | 群栄化学工業株式会社 | Thermosetting composition for cellulose products and cellulose products |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0453024U (en)* | 1990-09-03 | 1992-05-06 | ||
| JP2005194634A (en)* | 2003-12-26 | 2005-07-21 | Asahi Fiber Glass Co Ltd | Inorganic fiber mat |
| JP2005264387A (en)* | 2004-03-19 | 2005-09-29 | Dainippon Ink & Chem Inc | Resin composition for mineral fiber binder |
| JP2006028649A (en)* | 2004-07-12 | 2006-02-02 | Asahi Fiber Glass Co Ltd | Manufacturing method of inorganic fiber mat for vacuum heat insulating material |
| JP2007291332A (en)* | 2006-01-26 | 2007-11-08 | Central Glass Co Ltd | Method for producing adhesive composition |
| JP2009517514A (en)* | 2005-11-28 | 2009-04-30 | サン−ゴバン・イソベール | Formaldehyde-free phenolic resin binder |
- 2018
- 2018-03-29JPJP2018065146Apatent/JP7082893B2/enactiveActive
- 2019
- 2019-03-27WOPCT/JP2019/013274patent/WO2019189410A1/ennot_activeCeased
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0453024U (en)* | 1990-09-03 | 1992-05-06 | ||
| JP2005194634A (en)* | 2003-12-26 | 2005-07-21 | Asahi Fiber Glass Co Ltd | Inorganic fiber mat |
| JP2005264387A (en)* | 2004-03-19 | 2005-09-29 | Dainippon Ink & Chem Inc | Resin composition for mineral fiber binder |
| JP2006028649A (en)* | 2004-07-12 | 2006-02-02 | Asahi Fiber Glass Co Ltd | Manufacturing method of inorganic fiber mat for vacuum heat insulating material |
| JP2009517514A (en)* | 2005-11-28 | 2009-04-30 | サン−ゴバン・イソベール | Formaldehyde-free phenolic resin binder |
| JP2007291332A (en)* | 2006-01-26 | 2007-11-08 | Central Glass Co Ltd | Method for producing adhesive composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022210093A1 (en)* | 2021-03-29 | 2022-10-06 | 群栄化学工業株式会社 | Thermally curable composition for cellulosic product and cellulosic product |
| JP2022153295A (en)* | 2021-03-29 | 2022-10-12 | 群栄化学工業株式会社 | Thermosetting composition for cellulose products and cellulose products |
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