WO2011111182A1 - Matière fibreuse ignifugeante et son procédé de production - Google Patents

Matière fibreuse ignifugeante et son procédé de production Download PDF

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Publication number
WO2011111182A1
WO2011111182A1 PCT/JP2010/053975 JP2010053975W WO2011111182A1 WO 2011111182 A1 WO2011111182 A1 WO 2011111182A1 JP 2010053975 W JP2010053975 W JP 2010053975W WO 2011111182 A1 WO2011111182 A1 WO 2011111182A1
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WIPO (PCT)
Prior art keywords
fiber material
melamine
resin
flame
phenolic resin
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PCT/JP2010/053975
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English (en)
Japanese (ja)
Inventor
正則 小川
慎 藤井
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Nagoya Oil Chemical Co Ltd
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Nagoya Oil Chemical Co Ltd
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Priority to PCT/JP2010/053975 priority Critical patent/WO2011111182A1/fr
Priority to JP2012504203A priority patent/JP5577401B2/ja
Priority to CN201080055643.6A priority patent/CN102822412A/zh
Publication of WO2011111182A1 publication Critical patent/WO2011111182A1/fr
Anticipated expiration legal-status Critical
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/44—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 containing nitrogen and phosphorus
    • D06M13/453—Phosphates or phosphites containing nitrogen atoms
    • 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
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • D06M13/358—Triazines
    • 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
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

Definitions

  • the present invention relates to a flame retardant fiber material used for interior materials of automobiles and buildings.
  • ammonium polyphosphate is used for this kind of flame-retardant fiber material, but since the above-mentioned ammonium polyphosphate is easily soluble in water, the product consisting of the above-mentioned flame-retardant fiber material has poor water resistance, The problem is that the above-mentioned ammonium polyphosphate dissolves into water when it is affected by moisture or the like, and the effect of flame retardancy is lost. Therefore, a melamine resin-coated ammonium polyphosphate in which the surface of the ammonium polyphosphate is coated with a melamine resin or the like is provided.
  • the above-mentioned melamine resin-coated ammonium polyphosphate prevents the ammonium polyphosphate from coming into direct contact with water by the melamine resin coating, it is difficult to completely coat the ammonium polyphosphate surface with the melamine resin, and the above-mentioned melamine resin coated
  • the molding pressure may break the melamine coating, and thus when using a melamine resin-coated ammonium polyphosphate in which a defect portion exists in the melamine coating, product preservation There is a problem that the ammonium polyphosphate which has come out of the defect part of the melamine coating precipitates on the surface of the product to be whitened to deteriorate the appearance.
  • the present invention is characterized in that a melamine derivative is used as a flame retardant for making a fiber material flame-retardant as a means for solving the above-mentioned conventional problems. Since the above-mentioned melamine derivative is almost insoluble in water, it is not necessary to apply a resin coating, and the use of a molding resin as a flame retardant is mainly disclosed in the past, but an example added to a fiber material is disclosed Not. Commonly used as the above-mentioned melamine derivatives are melamine pyrophosphate, melamine orthophosphate, melamine polyphosphate and melamine borate.
  • the above-mentioned fiber material is usually impregnated with a synthetic resin in order to impart formability, but when a phenolic resin is used as the above-mentioned synthetic resin, good flame retardancy is exhibited in coordination with the above-mentioned melamine derivative.
  • the phenolic resin is desirably sulfomethylated and / or sulfimethylated.
  • a process 1 of impregnating the fiber material with a synthetic resin, and a melamine derivative powder in which a phenolic resin initial condensate is added to the surface of the fiber material impregnated with the synthetic resin It is desirable that the method comprising the steps 1 and 2 of the step 2 of applying and drying the aqueous dispersion be applied.
  • the method comprising the steps 1 and 2 of the step 2 of applying and drying the aqueous dispersion be applied.
  • the above-mentioned melamine derivative powder flows out of the fiber material and separates.
  • the melamine derivative powder is dispersed in a synthetic resin solution to be impregnated into an untreated fiber material and then the synthetic resin solution is impregnated, the melamine is impregnated with the synthetic resin solution.
  • Derivative powder may be separated from the synthetic resin solution, or the above-mentioned melamine derivative powder may be dispelled to the back side of the fiber material together with the synthetic resin solution, so that the flame retardancy tends to be uneven depending on the place.
  • a phenolic resin precondensate is added to the aqueous dispersion of the above-mentioned melamine derivative powder to increase the viscosity a little to achieve uniform dispersion of the above-mentioned melamine derivative powder, and the melamine derivative powder in the above-mentioned aqueous dispersion is a fiber It is desirable to reliably prevent the back side of the material from coming off.
  • the desirable viscosity of the aqueous dispersion of the above-mentioned melamine derivative is in the range of 50 to 1000 cps at 23 ° C. It is desirable that the above-mentioned phenolic resin precondensation product is a precondensation product of a phenolic resin which is sulfomethylated and / or sulfimethylated.
  • the flame-retardant fiber material of the present invention exhibits high water resistance and high flame resistance which is durable, and is particularly useful as an automotive material and a building material.
  • the fibrous material used in the present invention is provided mainly in the form of a sheet.
  • fibers used for the above fiber material include polyester fibers, polyamide fibers, acrylic fibers, urethane fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, acetate fibers, polyolefin fibers such as polyethylene fibers and polypropylene fibers, aramid fibers, etc.
  • the hollow fibers may be polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, poly-1,4-dimethylcyclohexane terephthalate, polyamides such as nylon 6, nylon 66, nylon 46, nylon 10, polyethylene, polypropylene, etc. It is made of a thermoplastic resin such as polyolefin, acrylic, urethane, polyvinyl chloride, polyvinylidene chloride and acetate. These hollow fibers are used singly or in combination of two or more.
  • the hollow fiber is produced by a known method such as melt spinning, or by preferentially eluting and removing one component of the fiber obtained by composite spinning of two polymers.
  • the hollow fiber has one or two or more hollow tube portions having a circular, elliptical, etc. cross section, and the hollow rate is 5% to 70%, preferably 10% to 50%.
  • the hollow ratio is the ratio of the hollow tube cross-sectional area to the fiber cross-sectional area.
  • the fineness of the hollow fiber is in the range of 1 dtex to 50 dtex, preferably in the range of 2 dtex to 20 dtex.
  • the tube effect improves the rigidity of the fiber sheet.
  • a low melting point fiber having a melting point of 180 ° C. or less may be used.
  • the low melting point fiber include polyolefin fibers such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyvinyl chloride fiber, polyurethane fiber, polyester fiber, polyester copolymer fiber Or polyamide fiber, polyamide copolymer fiber, core-sheath type composite fiber, etc. in which the low melting point fiber is sheathed around a normal fiber having a melting point of 180 ° C. or more as a core.
  • These low melting point fibers are used alone or in combination of two or more.
  • the fineness of the low melting fiber is in the range of 0.1 dtex to 60 dtex.
  • the low melting point fiber is usually mixed with the above fiber in an amount of 1 to 50% by mass.
  • the above-mentioned fiber material is usually provided as a non-woven fabric or a woven fabric as a sheet.
  • a non-woven fabric a needle-punched non-woven fabric, a resin non-woven fabric using a synthetic resin binder described later, a web of mixed fibers obtained by mixing the low melting point fiber alone or the low melting point fiber into ordinary fibers or a needle punched non-woven fabric
  • a fusion-bonded non-woven fabric or the like is fusion-bonded non-woven fabric or the like.
  • the melamine derivative used in the present invention is not particularly limited, and examples thereof include nitrogen-containing cyclic compounds having an amino group other than melamine, such as melam, melem and melon, and amino groups such as melam, melem, melon and melamine.
  • melamine pyrophosphate, melamine orthophosphate, melamine polyphosphate and melamine borate are useful melamine derivatives and are commercially available.
  • the fiber material of the present invention is impregnated with a synthetic resin, if desired, to impart formability and stiffness.
  • a synthetic resin acrylic ester resin, methacrylic ester resin, ionomer resin, ethylene-ethyl acrylate (EEA) resin, acrylonitrile-styrene-acrylic rubber copolymer (ASA) resin, acrylonitrile-styrene copolymer (AS) Resin, acrylonitrile, chlorinated polyethylene, styrene copolymer (ACS) resin, ethylene vinyl acetate copolymer (EVA) resin, ethylene vinyl alcohol copolymer (EVOH) resin, methacrylic resin (PMMA), polybutadiene (BDR), polystyrene (PS) ), Polyethylene (PE), acrylonitrile butadiene styrene copolymer (ABS) resin, chlorinated polyethylene (CPE), polyvinyl chloride
  • a desirable synthetic resin is the above-mentioned phenolic resin.
  • the phenolic resin has an affinity to the melamine derivative and cooperates to impart excellent flame retardancy to the fiber material.
  • a phenolic resin is obtained by condensing a phenolic compound and an aldehyde and / or an aldehyde donor.
  • the phenolic resin is desirably sulfomethylated and / or sulfimethylated to impart water solubility.
  • the phenolic resin is impregnated into the fiber material as an aqueous solution of an initial condensate (initial condensate liquid).
  • the precondensate liquid is optionally methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, n-amyl alcohol, isoamyl alcohol, n-hexanol, methylamyl alcohol 2-ethylbutanol, n-heptanol, n-octanol, trimethylnonyl alcohol, cyclohexanol, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, abiethyl alcohol, alcohols such as diacetone alcohol, acetone, methylacetone, Methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, diethyl ketone, di-n-propyl ketone
  • the phenolic compound used for the phenolic resin may be a monohydric phenol, a polyhydric phenol, or a mixture of a monohydric phenol and a polyhydric phenol.
  • polyhydric phenol or a mixture of monohydric phenol and polyhydric phenol is preferably used because formaldehyde is easily released during and after curing.
  • Examples of the monohydric phenol include phenol, alkylphenols such as o-cresol, m-cresol, p-cresol, ethylphenol, isopropylphenol, xylenol, 3,5-xylenol, butylphenol, t-butylphenol and nonylphenol, o-fluoro Phenol, m-fluorophenol, p-fluorophenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, o-iodophenol, m-iodo Phenol, p-iodophenol, o-aminophenol, m-aminophenol, p-aminophenol, o-nitrophenol, m-nitrophenol, p-nitrophenol, 2,4-dinitro And monohydric phenol substitutes
  • alkylphenols
  • polyhydric phenol examples include resorcin, alkyl resorcin, pyrogallol, catechol, alkyl catechol, hydroquinone, alkyl hydroquinone, phloroglucin, bisphenol, dihydroxynaphthalene and the like, and these polyhydric phenols may be used alone or in combination of two or more kinds can do.
  • polyhydric phenols preferred are resorcin and alkyl resorcins, and particularly preferred are alkyl resorcins, which have a faster reaction rate with aldehyde than resorcin.
  • alkylresorcin examples include 5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol, 5-n-butylresorcinol, 4,5-dimethylresorcinol, 2,5-dimethylresorcinol, 4,5-diethylresorcinol, 2 , 5-diethylresorcinol, 4,5-dipropylresorcinol, 2,5-dipropylresorcinol, 4-methyl-5-ethylresorcinol, 2-methyl-5-ethylresorcinol, 2-methyl-5-propylresorcinol, 2 , 4,5-trimethyl resorcinol, 2,4,5- triethyl resorcinol and the like.
  • the polyhydric phenol mixture obtained by dry distillation of Estonian oil shale is a particularly preferable polyhydric phenol raw material in the present invention because it is inexpensive and contains a large amount of various highly reactive alkylresorcins in addition to 5-methylresorcinol.
  • the above-mentioned phenolic compound and an aldehyde and / or an aldehyde donor are condensed, but the above-mentioned aldehyde donor means a compound or a mixture thereof which produces an aldehyde upon decomposition.
  • aldehydes include formaldehyde, acetaldehyde, propionaldehyde, chloral, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, etc.
  • aldehyde donor include paraformaldehyde, trioxane, hexamethylenetetramine, tetraoxymethylene and the like.
  • sulfomethylating agent examples include, for example, sulfite, bisulfite or metabisulfite, alkali metals or quaternary amines such as trimethylamine or benzyltrimethylammonium. Examples thereof include water-soluble sulfites obtained by reacting with a class ammonium and aldehyde adducts obtained by reacting these water-soluble sulfites with aldehydes.
  • aldehyde adduct examples include formaldehyde, acetaldehyde, propionaldehyde, chloral, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde and the like
  • the aldehyde of the present invention is an addition reaction of the above-mentioned water-soluble sulfite, and an aldehyde adduct consisting of, for example, formaldehyde and sulfite is hydroxymethane sulfonate.
  • Sulfymethylating agents that can be used to improve the stability of water-soluble phenolic resins include alkali metal sulfoxylates of aliphatic and aromatic aldehydes such as formaldehyde sodium sulfoxylate (longgarite) and benzaldehyde sodium sulfoxylate Examples thereof include alkali metal such as sodium hydrosulfite and magnesium hydrosulfite, hydrosulfite (dithionite) of alkaline earth metal, and hydroxyalkanesulfinate such as hydroxymethanesulfinate.
  • alkali metal such as sodium hydrosulfite and magnesium hydrosulfite, hydrosulfite (dithionite) of alkaline earth metal, and hydroxyalkanesulfinate such as hydroxymethanesulfinate.
  • phenolic resin if necessary, for example, hydrochloric acid, sulfuric acid, orthophosphoric acid, boric acid, boric acid, formic acid, formic acid, acetic acid, butyric acid, benzenesulfonic acid, phenolsulfonic acid, paratoluenesulfonic acid, naphthalene- ⁇ - Inorganic or organic acids such as sulfonic acid and naphthalene- ⁇ -sulfonic acid, esters of organic acids such as oxalic acid dimethyl ester, acid anhydrides such as maleic anhydride and phthalic anhydride, ammonium chloride, ammonium sulfate, ammonium nitrate, oxalic acid Ammonium salts such as ammonium, ammonium acetate, ammonium phosphate, ammonium thiocyanate, ammonium imidosulfonate, monochloroacetic acid or its sodium salt,
  • the above-mentioned phenolic resin (precondensed product) can be produced by a conventional method, and specifically, (a) a method of condensing monohydric phenol and / or polyhydric phenol with aldehydes, (b) monovalent A method of condensing a precondensate obtained by condensing phenol and an aldehyde and / or an initial condensate obtained by condensing a polyhydric phenol with an aldehyde with a monohydric phenol and / or a polyhydric phenol, (c) A method of condensing an initial condensation product of a polyhydric phenol, a polyhydric phenol and an aldehyde with a monohydric phenol and / or a polyhydric phenol, (d) an initial condensation with a monohydric phenol and an aldehyde condensed Of condensation products and precondensed products obtained by condensation of polyhydric phenol
  • the desirable phenolic resin is a phenol-alkyl resorcinol cocondensate.
  • the above-mentioned phenol-alkyl resorcin co-condensates have good stability of the aqueous solution of the co-condensates (initial co-condensates) and can be stored for a long time at ordinary temperature as compared with condensates consisting only of phenols (pre-condensates) It has the advantage of being able to Further, the aqueous solution is impregnated into the above-mentioned fiber material, and the stability of the resin-impregnated fiber material obtained by pre-curing is good, and the formability is not lost even if the fiber material is stored for a long time.
  • alkylresorcin is highly reactive with an aldehyde and captures and reacts with free aldehyde, it also has an advantage of reducing the amount of free aldehyde in the resin.
  • the desirable method for producing the above-mentioned phenol-alkyl resorcin co-condensate is to first react phenol and aldehyde to produce a phenolic resin precondensate, and then add an alkyl resorcin to the phenolic resin precondensate to make it desired. For example, it is the method of adding an aldehyde and making it react.
  • aldehyde is usually used per 0.2 mol of aldehyde per 1 mol of monohydric phenol and 1 mol of polyphenol. 0.1 to 0.8 mol of the reaction mixture, if necessary, a solvent and a third component are added, and the mixture is heated and reacted at a liquid temperature of 55 to 100 ° C. for 8 to 20 hours. At this time, the aldehydes may be added all at the start of the reaction, or may be added in portions or continuously.
  • a sulfomethylating agent and / or a sulfimethylating agent is added to the precondensate at any stage to obtain a phenolic compound and / or precondensate Is sulfomethylated and / or sulfimethylated.
  • the addition of the sulfomethylating agent and / or the sulfimethylating agent may be performed at any stage before, during or after the condensation reaction.
  • the total amount of the sulfomethylating agent and / or sulfimethylating agent added is usually 0.001 to 1.5 moles relative to 1 mole of the phenolic compound. If it is less than 0.001 mol, the hydrophilicity of the phenolic resin is not sufficient, and if it is more than 1.5 mol, the water resistance of the phenolic resin is deteriorated. In order to maintain good properties such as the curability of the precondensed product to be produced and the physical properties of the resin after curing, it is preferable to use about 0.01 to 0.8 mol.
  • the sulfomethylating agent and / or sulfimethylating agent added to sulfomethylate and / or sulfimethylate the precondensate is reacted with the methylol group of the precondensate and / or the aromatic ring of the precondensate.
  • a sulfomethyl group and / or a sulfimethyl group is introduced into the initial condensation product.
  • the aqueous solution of the pre-condensate of sulfomethylated and / or sulfimethylated phenolic resin is stable in a wide range of acidity (pH 1.0) to alkalinity, whether in the acid, neutral or alkaline region. It can be cured. In particular, when curing is carried out on the acid side, the residual methylol group is reduced, and there is no possibility that the cured product is decomposed to generate formaldehyde. Also, the use of sulfomethylated and / or sulfimethylated phenolic resins results in fiber materials that are more flame retardant than the use of non-sulfomethylated and / or sulfimethylated phenolic resins.
  • an amino resin monomer of urea, thiourea, melamine, thiomelamine, dicyandiamine, guanidine, guanamine, acetoguanamine, benzoguanamine, 2,6 diamino-1,3-diamine And / or a precondensate consisting of the amino resin monomer may be added and cocondensed with the phenolic compound and / or the precondensate.
  • a curing agent such as an aldehyde and / or an aldehyde donor or an alkylolated triazone derivative may be further added to and mixed with the above-mentioned initial condensation product of the phenol resin (including the initial cocondensation product).
  • an aldehyde and / or an aldehyde donor similar to the aldehyde and / or aldehyde donor used for producing an initial condensate (initial cocondensate) of a phenolic resin is used, and an alkylolated triazone derivative is used are obtained by the reaction of a urea compound, an amine and an aldehyde and / or an aldehyde donor.
  • urea compounds used for producing alkylolated triazone derivatives include urea, alkylureas such as thiourea and methylurea, alkylthioureas such as methylthiourea, phenylurea, naphthylurea, halogenated phenylurea, nitrated alkyl
  • alkylureas such as thiourea and methylurea
  • alkylthioureas such as methylthiourea
  • phenylurea, naphthylurea halogenated phenylurea
  • nitrated alkyl A single or a mixture of two or more such as urea is exemplified.
  • Particularly desirable urea compounds are urea or thiourea.
  • aliphatic amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine and amylamine, benzylamine, furfurylamine, ethanolamine, ethylenediamine, hexamethylenediamine, hexamethylenetetramine and the like, and further ammonia are used alone or as a mixture of two or more.
  • the aldehyde and / or aldehyde donor used in the preparation of the alkylolated triazone derivative is similar to the aldehyde and / or aldehyde donor used in the preparation of the precondensate of phenolic resin.
  • alkylolated triazone derivatives usually 0.1 to 1.2 moles of amines and / or ammonia, and 1.5 to 4 aldehydes and / or aldehyde donors, relative to 1 mole of the urea compound.
  • the reaction is carried out at a rate of 0 mol.
  • the order of addition is arbitrary, but as a preferable reaction method, amines are first charged while the required amount of aldehyde and / or aldehyde donor is charged into the reactor and kept at a temperature of usually 60 ° C. or lower.
  • the required amount of ammonia and / or ammonia is gradually added, and further the required amount of urea compound is added, and the reaction is carried out with stirring and heating at 80 to 90 ° C. for 2 to 3 hours.
  • 37% formalin is usually used as the aldehyde and / or aldehyde donor, part of it may be replaced with paraformaldehyde to increase the concentration of the reaction product.
  • using hexamethylenetetramine higher solids reaction products are obtained.
  • reaction of a urea compound, an amine and / or ammonia, and an aldehyde and / or an aldehyde donor is usually carried out in an aqueous solution, but methanol, ethanol, isopropanol, n-butanol, replacing part or all of the water
  • methanol, ethanol, isopropanol, n-butanol replacing part or all of the water
  • a mixture of one or more alcohols such as ethylene glycol and diethylene glycol may be used, or a mixture of one or more water-soluble organic solvents such as ketones such as acetone and methyl ethyl ketone may be used. .
  • the addition amount of the curing agent is 10 to 100 parts by mass with respect to 100 parts by mass of the initial condensation product (initial cocondensation product) of the phenol resin in the case of aldehyde and aldehyde donor, and in the case of alkylolated triazone derivative
  • the amount is 10 to 500 parts by mass with respect to 100 parts by mass of the initial condensation product of the phenol resin (initial cocondensation product).
  • flame retardants other than the above-mentioned melamine derivatives such as phosphorus compounds, nitrogen compounds, sulfur compounds, aluminum hydroxide, boron compounds, bromine compounds, guanidine compounds, phosphate compounds, phosphate esters Flame retardants such as base compounds, amino resins and cyclic phosphonic acid esters may be used in combination.
  • calcium carbonate, talc, gypsum, carbon Fillers such as black flour, walnut flour, coconut husk flour, wheat flour and rice flour; surfactants; higher fatty acids such as stearic acid and palmitic acid; higher alcohols such as palmityl alcohol and stearyl alcohol; butyryl stearate, glycerin Fatty acid esters such as monostearate; fatty acid amides; natural waxes such as carnauba wax, synthetic waxes; paraffins, paraffin oil, silicone oil, silicone resin, silicone resin, fluorine resin, polyvinyl alcohol, grease, etc.
  • Organic blowing agents such as azodicarbonamide, dinitrosopentamethylenetetramine, p, p'-oxybis (benzenesulfonylhydrazide), azobis-2,2 '-(2-methylgropiononitrile), etc .
  • bicarbonate Inorganic foaming agents such as sodium, potassium bicarbonate and ammonium bicarbonate
  • hollow particles such as shirasu balloon, pearlite, glass balloon, foam glass and hollow ceramics
  • plastic foams and foam particles such as foam polyethylene, foam polystyrene and foam polypropylene Pigments, dyes, antioxidants, antistatic agents, crystallization accelerators, expanded graphite, flameproofing agents, water repellents, oil repellents, insect repellents, preservatives, waxes, lubricants, antiaging agents, UV absorbers Phthalate plasticizers such as DBP, DOP, dicyclohexyl phthalate and other tricresyls Adding a plasticizer
  • the synthetic resin-impregnated fiber material after squeezing reduces the thickness, but when the synthetic resin-impregnated fibrous material contains hollow fibers, the rigidity is high, and after squeezing, the thickness elastically recovers, A certain degree of thickness is secured.
  • the fiber material contains a low melting point fiber
  • the fiber material is further improved in strength and rigidity, workability in impregnation with a synthetic resin is improved, and recovery of thickness after drawing becomes remarkable.
  • the sheet becomes highly rigid when made into a sheet, and the content of the synthetic resin in the synthetic resin-impregnated fiber material can be impregnated with the synthetic resin not containing hollow fibers. It can be less than the content of the synthetic resin of the fiber material.
  • the synthetic resin-impregnated fiber material is dried at room temperature or by heating.
  • the synthetic resin is a thermosetting resin
  • the resin when the resin is kept in the B state during heat drying, the moldability is maintained for a long period of time, and low temperature short time molding becomes possible.
  • the synthetic resin-impregnated fiber material is imparted with rigidity, moldability and the like by the synthetic resin, but for the purpose, the synthetic resin is 5 to 200% by mass, preferably 10 to 100% by mass with respect to the fiber material. It is desirable to impregnate in a proportion of mass%, more preferably 20 to 70 mass%. When the impregnation amount of the synthetic resin is less than 5% by mass, the rigidity and the formability of the synthetic resin-impregnated fiber material are not improved, and when it exceeds 200% by mass, the rigidity is too high and the formability is deteriorated.
  • the above-mentioned phenolic resin precondensate exhibits good compatibility with the above-mentioned melamine derivative, and the viscosity of the above-mentioned aqueous dispersion moderately increases, so that the above-mentioned aqueous dispersion can be used as the surface of the above-mentioned fiber material or synthetic resin impregnated fiber material When applied to the above, it is prevented that the melamine derivative powder in the aqueous dispersion exudes to the back surface of the fiber material or the synthetic resin impregnated fiber material.
  • the melamine derivative powder in the aqueous dispersion soaks out on the back surface of the fiber material or the synthetic resin impregnated fiber material, spots due to the melamine derivative powder are generated on the back surface of the fiber material or the synthetic resin impregnated fiber material, and appearance Is worse.
  • the above-mentioned phenolic resin precondensate for thickening the same one as the phenolic resin precondensate to be impregnated into the above-mentioned fiber material is used, and in order to obtain a stable uniform aqueous solution, sulfomethylation and / or Alternatively, it is desirable to use sulfimethylated phenolic resin precondensates.
  • the ratio of the above-mentioned phenol resin initial condensation product: melamine derivative is smaller than 5:95 mass ratio (solid content) (when the phenol resin initial condensation product is less than 5 mass ratio), The viscosity is less than 50 cps at 23 ° C., and the aqueous dispersion applied to the surface of the fiber material or the synthetic resin-impregnated fiber material easily exudes to the back surface of the fiber material or the synthetic resin-impregnated fiber material, and the phenol resin
  • the ratio of initial condensation product: melamine derivative exceeds 50:50 mass ratio (solid content) (when the phenolic resin initial condensation product is more than 50 mass ratio)
  • the viscosity increases largely to 1000 cps or more, It becomes difficult to coat and impregnate the aqueous dispersion uniformly on the surface of the above-mentioned fiber material or synthetic resin impregnated fiber material.
  • the above-mentioned melamine derivative powder is usually adhered in an amount of 5 to
  • the method of producing the flame-retardant fiber material described above first draws the sheet-like fiber material 2 from the raw fabric roll 7 of the manufacturing apparatus 1, passes the induction roller 8, and is impregnated by the impregnating roller 9.
  • the synthetic resin 5 is impregnated, and the squeeze roller 10 adjusts the amount of impregnation of the synthetic resin 5 in the fiber material 2 and then the heater 11 heats and dries the synthetic resin to produce the synthetic resin-impregnated fiber material 3 .
  • a melamine derivative powder aqueous dispersion 6 containing a phenolic resin initial condensate prepared in the aqueous dispersion mixing tank 13 is applied from the spray port 12 onto the synthetic resin-impregnated fiber material 3 and dried by the heater 14. Flame retardant fiber material 4 is produced.
  • the process of the heater 11 may be omitted, and after impregnating the synthetic resin 5, the process may be advanced to the process of applying the phenolic resin initial condensate-containing melamine derivative powder aqueous dispersion 6.
  • the flame retardant fiber material 4 is thereafter cut into a predetermined length or formed into a predetermined shape to be a product.
  • Example 1 The following three types of precondensates were used as phenolic resins.
  • Conventional aqueous solution of alkaline resol type phenolic resin initial condensation product using sodium hydroxide as a condensation reaction catalyst (1) Sulfomethylated phenol-alkyl resorcin cocondensation resin initial condensation product aqueous solution (2) Sulfymethylated phenol-alkylresorcinol cocondensed resin initial condensation product aqueous solution (3)
  • the properties of the above three types are shown in Table 1.
  • the measurement method is as follows. Nonvolatile content: It conforms to 5.2 of JIS K 6802. pH: in accordance with JIS K 6802 5.6. Viscosity: According to 5.7 of JIS K 6802. Water miscibility: According to JIS K 6802 5.4.
  • Example 1 a processing liquid in which only a melamine derivative powder is mixed and dispersed in water without adding a processing liquid in which the compounding ratio of the phenolic resin initial condensate and the melamine derivative powder is changed and the phenolic resin initial condensate is further dispersed
  • Table 3 shows the viscosities of working fluids in which the melamine derivative powder is replaced with melamine resin-coated ammonium polyphosphate (melamine-coated APP) as a flame retardant.
  • spray coating is applied on one side at a coating amount of 80 g / m 2 (32 g / m 2 as solid content) by spray method, and heated at 140 ° C. in a dryer for 2 minutes while suctioning to make a phenol system
  • the working fluid of each composition shown in Table 4 is used by fixing the resin precondensed product to the B state and simultaneously fixing the flame retardant (MPP-A) to the non-woven fabric using the phenolic resin precondensed product contained in the working fluid as a binder.
  • MPP-A flame retardant
  • the obtained flame retardant fiber sheet is used as a skin material, and it is polymerized to a glass wool base cotton having a weight per unit area of 800 g / m 2 and a thickness of 30 mm mixed with 10% by mass of uncured phenol resin.
  • Molded sheet No. 1 shown in Table 4 which is hot pressed for 2 seconds and the middle thickness of the product is 10 mm and the peripheral thickness is 2 mm. 1 to No. 6 was produced.
  • the whitening test of the surface of the skin material which is the flame retardant fiber sheet of the obtained molded article sheet and the test result of the spray workability of each working fluid at the time of preparation of the flame retardant fiber sheet are shown in Table 4.
  • Example 2 Comparative Example 2 In Example 2, the working fluid No. 1 described in Table 3 was used. 7 to No. No. 16 was used in the same manner as in the case of the molded sheet No. 1 shown in Table 4. 7 to No. 16 was produced. The test results of each molded sheet are shown in Table 4.
  • ⁇ The viscosity is high, and the discharge amount per time is small, but there is no exudation of the resin to the back surface of the non-woven fabric.
  • ⁇ The viscosity is high and uniform coating can not be performed. There is no exudation of the resin to the back of the non-woven fabric.
  • X The viscosity is low and the spray work is good, but the resin exudes to the back of the non-woven fabric.
  • Whitening test No. of laminated molded article sheets of each flame retardant fiber sheet and glass wool. 1 to No. 16 was subjected to a moisture resistance test at 40 ° C. ⁇ 95% RH for 48 hours, and then left at room temperature for 30 days to observe the surface of the surface of the molded sheet.
  • processing solution No. 1 in the range of the ratio of the mass ratio of phenolic resin initial condensate / melamine derivative powder 5: 95 to 50: 50 by weight. 1 to No.
  • the processing viscosity of 6 is 50 to 1000 cps / 23 ° C., and it can be seen that the sprayability is good.
  • No. 16 is a molded sheet No. 16 when it is used as a molded sheet. 9, No. 13, No. In No. 16, the melamine coating is broken at high density points (thickness 2 mm) by heat and pressure during molding, and whitening caused by ammonium polyphosphate which has gone out is produced. Mold sheet No. 7, No. 8, No. 10, no. 11, No. 12, no. 14, no. No. 15 has a viscosity of less than 50 cps / 23 ° C. or more than 1000 cps / 23 ° C., and whitening is not observed, but coating unevenness on the surface or appearance defects due to back surface bleeding of the melamine derivative powder in the sprayed resin Be
  • Example 3 A non-woven fabric having a basis weight of 80 g / m 2 by a needle punching method consisting of polyester fibers was used as a fiber sheet.
  • synthetic resin 30 parts by mass of phenol-formaldehyde initial condensate (50% by mass nonvolatile solution), 2 parts by mass of fluorine-based water and oil repellent (20% by mass aqueous solution), carbon black (30% by mass aqueous dispersion) 2
  • a mixture consisting of parts by mass and 66 parts by mass of water was impregnated with a roll so as to have a coated amount of 50% by mass of the fiber sheet.
  • a viscosity of 380 cps / 23 comprising 30 parts by mass of melamine polyphosphate (MPP-B, trade name, manufactured by Sanwa Chemical Co., Ltd., particle size: 12 ⁇ 2 ⁇ m), 20 parts by mass of the phenol-formaldehyde initial condensate, and 50 parts by mass of water.
  • the flame retardant mixed liquid of 60 ° C is applied to one side of the synthetic resin impregnated fiber sheet at a coating amount of 60 g / m 2 by a spray method and dried at 140 ° C to make the phenolic resin initial condensation product B state A fiber sheet was made.
  • the above-mentioned flame retardant fiber sheet is used as a surface material, and a glass wool raw cotton coated with 800 g / m 2 of uncured phenolic resin as a base material is polymerized on the flame retardant coated side and heat pressed at 200 ° C for 70 seconds.
  • a molding having a predetermined shape was produced.
  • the molded product obtained is V-0 having a flame retardancy of UL-94 standard, and no abnormality such as whitening is observed even in long-term storage, and the hood silencer of an automobile, engine undercover silencer, cylinder head cover silencer, It is a molding useful for dash silencers and the like.
  • Example 4 A fiber sheet was prepared by bonding a crepe paper consisting of pulp fibers having a basis weight of 20 g / m 2 to a single side of a nonwoven fabric having a basis weight of 50 g / m 2 made of polyester fibers using a granular hot melt adhesive. .
  • melamine sulfate (Apinon-901, trade name, Sanwa Chemical Co., Ltd., particle size: 17 ⁇ 2 ⁇ m)
  • polyester-based hot melt adhesive powder (particle size: 40-80 ⁇ m, softening temperature: 145 ° C.)
  • the fiber sheet comprising a flame retardant mixed liquid having a viscosity of 450 cps / 23 ° C.
  • the above-mentioned flame retardant fiber sheet is used as a surface material, and a felt raw cotton to which a curing agent-containing novolak type phenolic resin powder with a basis weight of 600 g / m 2 is applied and mixed as a base material is polymerized on the flame retardant coated side.
  • a molded product pressed and molded into a predetermined shape for a second has excellent sound absorption by laminating crepe paper and adjusting air permeability, and is excellent in flame retardancy, and does not cause abnormality such as whitening in appearance even in long-term storage. It is useful as a sound absorbing flame-retardant molded article for automobiles, etc.
  • the flame retardant fiber material of the present invention is highly resistant to water, exhibits high flame retardancy, is excellent in appearance, and is useful as an automotive material or a building material, so that it can be used industrially.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une matière ignifugeante présentant une résistance élevée à l'eau et une durabilité élevée. La présente invention concerne spécifiquement une matière fibreuse ignifugeante comprenant une matière fibreuse à laquelle est arrimé un dérivé de mélamine. Il est recherché que le dérivé de mélamine soit un composé choisi dans le groupe constitué par le pyrophosphate de mélamine, l'orthophosphate de mélamine, le polyphosphate de mélamine et le borate de mélamine, ou un mélange de deux composés ou plus choisis dans le groupe susmentionné, et il est également recherché que la matière fibreuse soit imprégnée d'une résine de synthèse.
PCT/JP2010/053975 2010-03-10 2010-03-10 Matière fibreuse ignifugeante et son procédé de production Ceased WO2011111182A1 (fr)

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JP2012504203A JP5577401B2 (ja) 2010-03-10 2010-03-10 難燃性繊維材料の製造方法
CN201080055643.6A CN102822412A (zh) 2010-03-10 2010-03-10 阻燃性纤维材料以及其制造方法

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Cited By (3)

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CN102562123A (zh) * 2011-12-31 2012-07-11 枣庄矿业集团新安煤业有限公司 矿井高爆煤尘抑爆剂及其制作方法
CN103209552A (zh) * 2012-01-13 2013-07-17 宏碁股份有限公司 电子装置壳体及其处理方法
CN103526445A (zh) * 2013-09-30 2014-01-22 苏州潮盛印花制版实业有限公司 一种防酸针织面料

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CN106285345A (zh) * 2016-08-19 2017-01-04 安徽省双鹏实业有限公司 一种环保安全门
CN112847689A (zh) * 2021-01-06 2021-05-28 广东中晨电子科技有限公司 一种高端垫板及其制备方法

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JP2000355672A (ja) * 1999-04-30 2000-12-26 Clariant Gmbh 繊維材料用の難燃性被覆剤
WO2008044399A1 (fr) * 2006-10-11 2008-04-17 Nagoya Oilchemical Co., Ltd. Solution de traitement retardateur de flamme, matériau fibreux retardateur de flamme et matériau d'intérieur utilisant le matériau fibreux

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CN1849422A (zh) * 2003-09-02 2006-10-18 名古屋油化株式会社 阻燃性纤维片材及其成型物
CN101094952A (zh) * 2005-01-07 2007-12-26 名古屋油化株式会社 阻燃性纤维片材及其成型物
CN101165265A (zh) * 2006-10-17 2008-04-23 山东海龙博莱特化纤有限责任公司 输送带用阻燃浸胶帆布的生产方法

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JP2000355672A (ja) * 1999-04-30 2000-12-26 Clariant Gmbh 繊維材料用の難燃性被覆剤
WO2008044399A1 (fr) * 2006-10-11 2008-04-17 Nagoya Oilchemical Co., Ltd. Solution de traitement retardateur de flamme, matériau fibreux retardateur de flamme et matériau d'intérieur utilisant le matériau fibreux

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102562123A (zh) * 2011-12-31 2012-07-11 枣庄矿业集团新安煤业有限公司 矿井高爆煤尘抑爆剂及其制作方法
CN103209552A (zh) * 2012-01-13 2013-07-17 宏碁股份有限公司 电子装置壳体及其处理方法
CN103526445A (zh) * 2013-09-30 2014-01-22 苏州潮盛印花制版实业有限公司 一种防酸针织面料

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