WO2008044399A1 - Solution de traitement retardateur de flamme, matériau fibreux retardateur de flamme et matériau d'intérieur utilisant le matériau fibreux - Google Patents

Solution de traitement retardateur de flamme, matériau fibreux retardateur de flamme et matériau d'intérieur utilisant le matériau fibreux Download PDF

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Publication number
WO2008044399A1
WO2008044399A1 PCT/JP2007/066984 JP2007066984W WO2008044399A1 WO 2008044399 A1 WO2008044399 A1 WO 2008044399A1 JP 2007066984 W JP2007066984 W JP 2007066984W WO 2008044399 A1 WO2008044399 A1 WO 2008044399A1
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Prior art keywords
phenol
fiber
initial condensate
flame retardant
resin
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PCT/JP2007/066984
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English (en)
Japanese (ja)
Inventor
Masanori Ogawa
Makoto Fujii
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Nagoya Oilchemical Co., Ltd.
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Priority to TW096134387A priority Critical patent/TW200829616A/zh
Publication of WO2008044399A1 publication Critical patent/WO2008044399A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • C09K21/04—Inorganic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus

Definitions

  • the present invention relates to a flame-retardant treatment liquid mainly used for fiber materials.
  • ammonium polyphosphate having low toxicity has been widely used as a flame retardant.
  • ammonium polyphosphate has the property of being soluble in water, and if mixed or impregnated in a fiber material, it may leach out of the fiber material when exposed to humidity or moisture, which may reduce the flame retardancy. .
  • resin-coated ammonium polyphosphate particles are provided which are coated with melamine, urea, or the like on the surface of ammonium polyphosphate particles and made into resin by contacting with formalin.
  • the surface of the ammonium phosphate particles is covered with resinized melamine, urea, and the like, so that dissolution into water is suppressed.
  • Patent Document 1 Japanese Patent Laid-Open No. 7-277713
  • the conventional resin-coated ammonium polyphosphate particles have a complicated manufacturing process and are expensive.
  • the resin-coated ammonium polyphosphate particles are usually adhered to the fiber sheet by being dispersed in a resin solution applied or impregnated on the fiber sheet.
  • the resin-coated ammonium phosphate polyphosphate particles have poor dispersibility in the resin solution. ! /, It is easy to separate, and if it is dispersed in a large amount, the resin liquid will thicken.
  • the resin-coated ammonium polyphosphate particles are inferior in adhesion to the fibers.
  • the fiber sheet containing the resin-coated ammonium phosphate particles when the fiber sheet containing the resin-coated ammonium phosphate particles is hot-pressed alone or in combination with another sheet, the fiber sheet or other sheet Volatile components such as moisture contained in the product evaporate from the heat at the time of hot pressing and volatilize from the upper side of the sheet, and accordingly, the resin-covered ammonium polyphosphate particles migrate to the surface of the sheet and are exposed to uneven color on the surface of the sheet. There is a problem of generating.
  • the present invention aims to solve the above-mentioned conventional problems and to provide an ammonium polyphosphate having excellent water resistance at a low price. Therefore, the present invention provides an aqueous solution of a phenol resin initial condensate.
  • a flame retardant treatment solution in which ammonium phosphate particles having a solubility in water of 5% by mass or less in the solution is dispersed is used as the basis.
  • the phenol resin initial condensate is preferably a polyhydric phenol initial condensate and / or an initial condensate containing a polyvalent phenol. Furthermore, the phenol resin initial condensate is sulfomethylated and / or sulfimethylated. Te! In addition, a water-soluble resin is added as a dispersant to the aqueous solution of the phenol resin initial condensate!
  • the flame retardant fiber material further comprising a fiber sheet mixed or coated with the above flame retardant treatment liquid, and further, when the flame retardant fiber material is adhered to the substrate surface as a skin material, the predetermined value is obtained.
  • An interior material molded into a shape is provided.
  • the initial phenol resin condensate has good affinity for the surface of ammonium polyphosphate particles. Accordingly, when the ammonium polyphosphate particles are dispersed in the aqueous solution of the initial condensate, the initial condensate adheres firmly to the surface of the ammonium polyphosphate particles, and the ammonium polyphosphate particles It becomes a protective colloid and is stably dispersed in the aqueous solution. However, in the case of ammonium polyphosphate particles having a solubility in water exceeding 5% by mass, when dispersed in the aqueous solution, the particles dissolve in water, making it difficult to maintain the particle state.
  • the reaction rate with formaldehyde is increased.
  • Fast cure speed For example, when the fiber sheet is impregnated with the treatment solution and cured, the initial condensate quickly becomes a cured resin to coat the particles and prevent elution from water, and at the same time, remove the particles from the fiber sheet. Tightly binds to.
  • the aqueous solution of the initial condensate is stable in a wide pH range. Therefore, regardless of whether it is an acidic curing agent or an alkaline curing agent, a wide pH range can be obtained.
  • a curing agent can be used.
  • the ammonium polyphosphate particles in the treatment agent adhere firmly to the fiber sheet via the initial condensate, and have a water resistant and durable flame retardant. Fiber material is obtained.
  • the initial condensate covering the surface of the ammonium polyphosphate particles adhering to the fiber material is converted into a cured resin.
  • a water-resistant coating is formed.
  • the ammonium polyphosphate particles are strongly bound to the fiber sheet by the phenol resin, which is a resin product of the initial condensate. Even if it is applied, it does not accompany the evaporation of moisture and other volatile components contained in the skin material, and therefore, the ammonium polyphosphate is not transferred and exposed on the sheet surface.
  • the present invention provides a flame retardant treatment solution that imparts flame resistance with water resistance and durability and is inexpensive.
  • ammonium polyphosphate used in the present invention is particulate and has a solubility in water of 5% by mass or less.
  • ammonium polyphosphate there is an ammonium polyphosphate having a degree of polymerization of 10 to 40.
  • Ammonium polyphosphate having the above-mentioned degree of polymerization is hardly soluble or insoluble in water and decomposes at high temperature to generate a flame-retardant gas, but the flame-retardant gas has low toxicity to human livestock.
  • the degree of polymerization n of ammonium polyphosphate is calculated from the following equation.
  • N is the mole of nitrogen mol mol
  • N content for example, CH This is done by the N method.
  • the degree of polymerization is 10 or more, the ammonium polyphosphate is almost insoluble in water.
  • the degree of polymerization exceeds 40, the viscosity of the dispersion increases abnormally when the ammonium polyphosphate is dispersed in water or an aqueous dispersion medium.
  • the coating amount or impregnation amount becomes uneven, and as a result, sufficient flame retardancy cannot be obtained.
  • expanded graphite may be used in combination with the flame retardant.
  • natural black lead is immersed in an inorganic acid such as concentrated sulfuric acid, nitric acid, and selenic acid to oxidize perchloric acid, perchlorate, permanganate, dichromate, hydrogen peroxide, etc. It is obtained by adding an agent and processing, and the expansion start temperature is about 250 ° C to 300 ° C.
  • the expanded graphite has an expansion volume of about 30 to 300 ml / g and a particle size of about 300 to 30 mesh.
  • thermally expandable granules When the flame retardant treatment of the present invention is applied to or impregnated into a fiber sheet or mat, thermally expandable granules may be added.
  • thermally expandable particles include a thermoplastic resin having a low softening point and a low boiling point solvent.
  • thermoplastic resins having a low softening point examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropylene acrylate, n butyl acrylate, iso butyl acrylate, t butyl acrylate, 2— Ethylhexyl acrylate, Cyclohexyl acrylate, Tetrahydrofurnoreata acrylate, Methyl methacrylate, Ethyl methacrylate, n-Propyl methacrylate, Iso Propyl methacrylate, n Butyl methacrylate Aliphatic or cyclic and / or metatalylates such as butyl metatalylate, 2-ethylhexyl metatalylate, cyclohexyl metatalylate, tetrahydrofurfurinole metatalylate, stearyl metatalylate, lauryl metatalylate, Butyl ethers such
  • Nitrile monomers fatty acid such as butyl acetate, and propionate, butyl chloride, vinylidene chloride, butyl fluoride, vinylidene fluoride, etc.
  • Monogen containing monomers such as ethylene and propylene, gens such as isoprene, chloroprene and butadiene, ⁇ such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, atropic acid and citraconic acid , ⁇ Unsaturated carboxylic acid, 2-hydroxyethyl
  • 2-hydroxypropyl acrylate hydroxyl group-containing monomers such as aryl alcohol, amides such as acrylate, methacrylolamide, diacetone acrylamide, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl methacrylate
  • Amino group-containing monomers such as dimethylaminopropyl acrylate, epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, glycidyl allyl, other pyrrolidone, burpyridine, bur force
  • Water-soluble monomers such as rubazole, methoxy silyl styrene, ⁇ triethoxy silyl styrene, ⁇ ⁇ trimethoxy silyl mono- ⁇ -methyl styrene, ⁇ -triethoxy silylenol ⁇ -methyl styrene, ⁇ -
  • a crosslinking agent such as dibutylbenzene, diethylene glycol ditalylate or other polyvalent acrylate or metatalylate, diallyl phthalate, or allyl glycidyl ether
  • low softening point A thermoplastic resin having a softening point of 180 ° C or lower, such as polyamide and low softening point polyester, and examples of the low boiling point solvent include n hexane, cyclohexane, n-pentane, isopentane, n butane and isobutane.
  • the thermally expandable granules are composed of expandable beads obtained by impregnating the thermoplastic resin granules with the low-boiling solvent, microcapsules in which the low-softening point thermoplastic resin shell is filled with the low-boiling solvent.
  • the diameter of the granule is usually 0.5 to! OOO ⁇ m.
  • the thermally expandable particles used in the present invention include thermally expandable inorganic particles such as vermiculite, perlite, and shirasu balloon.
  • Phenolic resins are flame retardant and also have an affinity for the surface of ammonium polyphosphate particles and adhere firmly to the surface of the particles.
  • the phenol resin is obtained by condensing a phenol compound with formaldehyde and / or a formaldehyde donor.
  • the phenolic compound used in the above phenolic resin may be monovalent phenol alone, polyhydric phenol alone, or a mixture of monohydric phenol and polyhydric phenol.
  • polyhydric phenol alone or a mixture of monohydric phenol and polyhydric phenol is preferably used.
  • Examples of monohydric phenols include: phenolic alcohol, o crezomonole, m-cresomonole, p-cresol, ethylphenol, isopropylphenol, xylenol, 3,5-xylenomonole, butylphenol, t-butylphenol, nourphenol Etc.
  • polyhydric phenol examples include resorcin, alkyl resorcin, pyrogallol, catecholore, alkyl strength teconole, hydroquinone, alkylhydroquinone, phloroglucin, bisphenol, dihydroxynaphthalene, and the like. These polyvalent phenols may be used alone or in combination of two or more. Can be used. Of polyhydric phenols, preferred! / Are resorcinol or alkylresorcin, especially preferred! /, Are preferred to resorcin Alkylresorcin is a fast reaction rate with aldehydes.
  • alkyl resorcin examples include, for example, 5 methyl resorcin, 5 ethyl resorcin, dimethyl resorcin, 4, 5 jetyl resorcin, 2, 5 dityl resorcin, 4, 5 dipropyl resorcin, 2, 5 dipropyl resorcin, 4 -Methyl-5-ethylresorcin, 2-methyl-5-ethylresorcin, 2-methyl-5-propylresorcin, 2,4,5 trimethinoresorresin, 2,4,5 trietinoresorresin, etc.
  • the polyhydric phenol mixture obtained by dry distillation of Estonian oil shale is inexpensive and contains a large amount of highly reactive various alkylresorcins in addition to 5-methylresorcin. This is a polyphenolic raw material.
  • the force S that allows the phenolic compound and formaldehyde and / or formaldehyde donor to condense and the formaldehyde donor means a compound that forms formaldehyde when decomposed or a mixture of two or more thereof.
  • aldehyde donors include paraformaldehyde, trioxane, hexamethylenetetramine, tetraoxymethylene and the like.
  • the formaldehyde and the formaldehyde donor are collectively referred to as formaldehyde hereinafter.
  • resole obtained by reacting with an alkaline catalyst in excess of formaldehyde with respect to the phenolic compound
  • acid catalyst with excess of phenol with respect to formaldehyde.
  • the resol consists of a mixture of various phenol alcohols with phenol and formaldehyde added, usually provided as an aqueous solution of the initial condensate, and the nopolac is further condensed with phenol. It consists of various derivatives of dihydroxydiphenyl methane and is usually provided in the form of precondensate powder.
  • monovalent phenol and formaldehyde can be condensed to form a monovalent phenol alone initial condensate! /, Or a mixture of monovalent phenol and polyvalent phenol.
  • Monovalent phenol-polyvalent phenol by condensing formaldehyde with An initial co-condensate may be used.
  • one or both of monovalent phenol and polyvalent phenol may be preliminarily used as the initial condensate.
  • a desirable phenolic resin is a phenol-alkylresorcin cocondensate.
  • the above-mentioned phenol-alkylresorcin cocondensate has good stability of the aqueous solution of the cocondensate (initial cocondensate), compared with a condensate consisting of only phenol (initial condensate) at room temperature.
  • a condensate consisting of only phenol (initial condensate) at room temperature.
  • the fiber sheet obtained by impregnating or applying the aqueous solution to a sheet base material and precured has good stability. Even if the fiber sheet is stored for a long period of time, the moldability is not lost.
  • alkyl resorcin has high reactivity with formaldehydes, and has the advantage of reducing the amount of free aldehyde in the resin because it captures and reacts with free aldehyde.
  • a desirable method for producing the above-mentioned phenolic alkyl resorcinol condensate is to first react phenol and formaldehyde to produce a phenolic resin initial condensate, and then to! /, To the phenolic resin initial condensate. In this method, resorcin is added and, if desired, formaldehydes are added to react.
  • An initial condensate composed of an amino resin monomer and / or an amino resin monomer may be added for co-condensation with a phenol compound and / or an initial condensate.
  • phenol resin for example, before, during or after the reaction, for example, hydrochloric acid, sulfuric acid, orthophosphoric acid, boric acid, oxalic acid, formic acid, acetic acid, butyric acid, benzine Sulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, naphthalene mono ⁇ -sulfonic acid, inorganic or organic acid such as naphthalene / 3-sulfonic acid, organic acid esters such as dimethyl oxalate, maleic anhydride, phthalate Acid anhydrides such as acid anhydrides, ammonium chloride, ammonium chloride, ammonium nitrate, ammonium nitrate, ammonium acetate, ammonium phosphate, ammonium cyanide, ammonium imidonorephonate, monochloroacetic acid or its sodium salt , ⁇ , ⁇ , organic halides
  • Alkaline substances such as alkali earth metal oxides such as lime, weak carbonates of alkali metals such as sodium carbonate, sodium sulfite, sodium acetate, and sodium phosphate may be mixed as a catalyst or rhodium regulator.
  • the initial condensation product (including the initial co-condensation product) of the phenolic resin of the present invention may be further mixed with a curing agent such as the above-mentioned formaldehydes or alkylolated triazone derivatives.
  • the alkylolated triazone derivative is obtained by a reaction of a urea compound, an amine, and a formaldehyde.
  • urea compounds used in the production of alkylolated triazone derivatives include alkyl ureas such as urea, thiourea and methylurea, alkylthioureas such as methylthiourea, phenylurea, naphthylurea, halogenated phenylurea, and nitration. Examples thereof include single or a mixture of two or more of alkyl urea and the like. Particularly preferred, the urea compound is urea or thiourea.
  • amines such as aliphatic amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine and amylamine
  • amines such as benzylamine, furfurylamine, ethanolamine, ethylenediamine, hexamethylenediamine and hexamethylenetetramine.
  • ammonia is exemplified, and these are used alone or as a mixture of two or more.
  • the formaldehydes used in the production of the above-mentioned alkylolated triazone derivatives are phenolic It is the same as the formaldehydes used in the production of the initial condensate of the resin.
  • amines and / or ammonia are usually 0 ⁇ ;! ⁇ 1 ⁇ 2 mol and formaldehydes are 1.5 ⁇ 4.0 to 4.0 mol with respect to 1 mol of urea compound. React at a rate of In the above reaction, the order of addition is arbitrary.
  • the required amount of formaldehydes is charged into the reactor, and the amines and / or ammonia are usually kept at a temperature of 60 ° C or lower.
  • the addition amount of the curing agent is 10 to 100 parts by mass with respect to 100 parts by mass of the initial condensate (initial cocondensate) of the phenolic resin of the present invention in the case of formaldehyde, and in the case of an alkylolated triazone derivative.
  • the amount is 10 to 500 parts by mass with respect to 100 parts by mass of the initial condensate (initial cocondensate) of the phenol resin.
  • Water-soluble sulfites obtained by reacting quaternary amines or quaternary ammonia, and these water-soluble sulfites and aldehydes
  • aldehyde adducts obtained by reaction with aldehydes.
  • aldehyde adduct examples include formaldehyde, acetoaldehyde, propionaldehyde, chloral, furfural, glyoxal, n-butanolenoaldehyde, force proaldehyde, arinolealdehyde, benzaldehyde, crotonanoaldehyde, acrolein, phenylacetate.
  • This is an addition reaction of an aldehyde such as ⁇ anoldehydride, o- ⁇ nooleanolide, salicinoleanolide, etc. and the above-mentioned Sugisui Tosei Sulfate, for example, aldehyde addition consisting of formaldehyde and sulfite
  • the product is hydroxymethanesulfonate.
  • a sulfomethylating agent and / or a sulfmethylating agent is added to the initial condensate at an optional stage, and the phenolic compound and / or Alternatively, the precondensate is sulfomethylated and / or sulfimethylated.
  • the sulfomethylating agent and / or the sulfimelating agent may be added at any stage before, during or after the condensation reaction.
  • the total amount of the sulfomethylating agent and / or the sulfimelating agent is usually 0.001 to 1.5 mol per mol of the phenol compound.
  • the amount is less than 001 mol, the hydrophilicity of the phenolic resin is insufficient.
  • the amount is more than 5 mol, the water resistance of the phenolic resin deteriorates.
  • the content is preferably about 0.01 to 0.8 mol.
  • the sulfomethylating agent and / or the sulfimating agent added to sulfomethylate and / or sulfmethylate the initial condensate is a methylol group of the initial condensate and / or an aromatic ring of the initial condensate. Reacting the precondensate with sulfomethyl And / or sulfimethyl groups are introduced.
  • the aqueous solution of the initial condensate of the phenol-based resin thus sulfomethylated and / or sulfimethylated is stable in a wide range from acidic (pH 1.0) to alkaline, and is acidic, neutral and alkaline. It can be cured in any region. In particular, when it is cured on the acid side, the remaining methylol groups are reduced and the cured product is not decomposed to form formaldehyde.
  • the aqueous solution of the initial condensation product of the phenol resin may include methanol, ethanol, isopropanol, n propanol, isopropanol, n butanol, isobutanol, sec butanol, tert-butanol, n-amyl alcohol, if desired.
  • the aqueous solution of the initial condensate of the present invention produced as described above usually contains the initial condensate in the range of 5 to 80% by mass.
  • ammonium polyphosphate particles are dispersed in an aqueous solution of the initial condensation product of the phenol resin.
  • the ammonium polyphosphate since the ammonium polyphosphate has a solubility power in water of less than or equal to mass%, almost the entire amount maintains the particle state, and the initial condensate adheres to the particle surface efficiently.
  • the amount of the ammonium polyphosphate particles added to the aqueous solution of the initial condensate is usually 5 to 200% by mass, preferably 10 to 150% by mass.
  • the expanded graphite and thermally expandable particles may be further added and dispersed in the treatment liquid.
  • the expanded graphite is usually in the treatment liquid;! To 50% by mass, preferably 2 to 30% by mass, and the thermally expandable granule is usually in the treatment liquid 0.;! To 20% by mass, preferably; Add 10% by mass Disperse.
  • the initial condensate adhering to the surface of the ammonium polyphosphate particles acts as a protective colloid to stably disperse the ammonium phosphate particles in an aqueous solution.
  • the dispersion stability can be further improved.
  • water-soluble resin examples include polyacrylic acid soda, polyacrylic acid ester fractionated product, polybutyl alcohole, carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxychetylcellulose, and the like.
  • An alkali-soluble resin such as a copolymer of an acid ester and / or methacrylic acid ester and acrylic acid and / or methacrylic acid or a micro-crosslinked product of the copolymer may be used! /.
  • the above-mentioned copolymer or micro-crosslinked copolymer is usually provided as emulsion.
  • the water-soluble resin If the water-soluble resin is added and dissolved in the flame retardant treatment solution, it has a thickening effect! /, And the dispersion effect causes ammonium polyphosphate particles and expanded graphite to settle. ⁇ , and a uniform impregnation liquid is obtained. Further, the water-soluble resin enhances the adhesion of the ammonium polyphosphate particles and expanded graphite to the fiber sheet or mat, and effectively prevents the ammonium phosphate particles and expanded graphite from detaching from the fiber sheet or mat. .
  • the target of the flame retardant treatment liquid of the present invention is mainly a fiber material such as a fiber sheet or a mat.
  • foam sheets or mats of synthetic resins such as polystyrene, polypropylene, polyurethane, polychlorinated butyl, melamine resin, phenol resin, urea resin.
  • fibers used in the fiber sheet or mat include polyester fibers, polyamide fibers, acrylic fibers, urethane fibers, polychlorinated bur fibers, polyvinylidene chloride fibers, acetate fibers and other synthetic fibers, wool, Mohair, cashmere, camel hair, alpaca, vicuna, angora, silk thread, ivy, gama fiber, pulp, cotton, palm fiber, hemp fiber, bamboo fiber, kenaf fiber and other natural fibers, starch-based, polylactic acid-based biodegradable Fiber, rayon (human silk, sufu), polynosic, cupra, acetate, triacetate and other cellulosic artificial fibers, glass fiber, carbon fiber, ceramic fiber, asbestos fiber and other inorganic fibers, and fiber products using these fibers Recycled fiber obtained by defibrating the scrap. These fibers are used alone or in combination of two or more.
  • a low melting fiber having a melting point of 180 ° C or lower may be used as the fiber.
  • the low melting point fiber include polyolefin fibers such as polyethylene, polypropylene, ethylene acetate butyl copolymer, ethylene ethyl acrylate copolymer, polychlorinated bur fiber, polyurethane fiber, polyester fiber, and polyester copolymer. Fiber, polyamide fiber, polyamide copolymer fiber and the like. These low melting point fibers can be used alone or in combination of two or more.
  • the fineness of the low-melting fiber is in the range of 0.1 to 60 dtex.
  • the low melting point fiber is usually mixed in the fiber in an amount of 1 to 50% by mass.
  • the fiber sheet or mat is a method in which the fiber web sheet or mat is entangled by needle punching, or there is a fiber web sheet! /, Or the mat is made of the low-melting fiber.
  • the web of the mixed fiber is heated as it is or entangled by needle punching to soften the low-melting fiber.
  • the flame retardant solution is usually mixed with the fiber before the fiber is formed into a sheet or mat, or the sheet or mat is impregnated with or coated with the flame retardant solution.
  • the mixing ratio of the ammonium polyphosphate and the fiber may be arbitrary, but the ammonium polyphosphate is usually 0.5 to 100% by mass based on the fiber, and 0.5 to 50 when the expanded graphite is used.
  • the heat-expandable granule by mass% add 0.5 to 50 mass% of the granule.
  • the expanded graphite or thermally expandable particles may be added to the fiber as a separate body without being added to the treatment liquid.
  • the fiber sheet or mat is usually a force for immersing the sheet or mat in the treatment liquid, or The treatment liquid is applied by the spraying force on the sheet or mat, or by a knife coater, roll coater, flow coater or the like.
  • the sheet or mat is squeezed using a squeeze roll or a press machine after the treatment liquid is impregnated or mixed.
  • the sheet or mat After impregnating or applying the flame retardant treatment liquid to the sheet or mat, the sheet or mat is dried by heating.
  • the heat drying step when the phenolic resin in the flame retardant treatment solution is set to the B state, the sheet or mat can be stored for a long period of time, and can be molded at a low temperature for a short time.
  • the thickness is generally set to 0.1 lm m to 5 mm, and when used as a substrate, the thickness is generally set to 3 mm to 60 mm. Is done.
  • a press molding apparatus 1 composed of an upper mold 2 and a lower mold 3 as shown in FIG. 1 is usually stacked with the skin material 4 on the upper side and the base material 5 on the lower side. Set and hot-press fi.
  • the flame retardant treatment liquid applied or impregnated on the skin material 4 and / or the base material 5 The phenolic resin in the inside exudes to the adhesive surface between the skin material 4 and the base material 5 and functions as an adhesive, but separately, the adhesive is applied to the adhesive surface of the skin material 4 and / or the base material 5. It may be applied.
  • the powder When hot melt adhesive powder is used, the powder may be applied to the adhesive surface of the skin material 4 and / or the base material 5, and the flame retardant treatment liquid may be applied to the skin material 4 or When applied to the adhesive surface of the substrate 5, the hot melt adhesive powder may be dispersed in the flame retardant treatment liquid.
  • the hot melt adhesive powder is, for example, a polyolefin resin (including a modified polyolefin resin) such as polyethylene, polypropylene, ethylene-butyl acetate copolymer, ethylene ethyl acrylate copolymer, etc.
  • the material is a low-melting point resin such as polyurethane, polyester, polyester copolymer, polyamide, polyamide copolymer, or a mixture of two or more.
  • a hot-melt adhesive finolene may be used for bonding the skin material 4 and the base material 5.
  • the film is usually attached in advance to the adhesive surface of the skin material 4 or the base material 5 described above.
  • the interior material 7 of the present invention is formed into a flat plate shape or a predetermined shape as shown in Fig. 1.
  • hot press molding is applied to the molding, and the skin material 4 and / or the base material 5 is used.
  • the hot press temperature is set to be equal to or lower than the expansion start temperature of the expanded graphite, and the thermally expandable particles are attached to the fiber sheet or mat! /, In this case, the thermal expansion of the thermally expandable granules is performed while regulating the thickness of the fiber sheet or mat during the press molding.
  • the thermally expandable granules When the fiber sheet or mat is heated to a temperature equal to or higher than the expansion temperature of the thermally expandable granules containing the thickness thereof, the thermally expandable granules are expanded. Since the thickness of the fiber sheet or mat is regulated as described above, the surrounding fibers are compressed by the expansion of the granules, and the density of the fiber portion is increased and the rigidity is improved. However, the porosity of the fiber sheet or mat as a whole does not change, and therefore the weight does not change.
  • the flame retardant treatment liquid impregnated in the skin material 4 and / or the base material 5 during the hot pressing causes the phenolic resin initial condensate in the liquid to be resin-cured to stably maintain the molded shape, and On the surface of the ammonium polyphosphate particles, the resinated initial condensate, that is, phenolic A resin coating is formed to prevent the ammonium polyphosphate particles from eluting into water, and to firmly bind the ammonium phosphate particles to the skin material and / or the substrate.
  • the interior material 7 of the present invention includes, for example, an automobile ceiling material, a door trim, an instrument panel panel, a dash silencer, a hood silencer, an engine under cover silencer, a cylinder head cover silencer, a dash outer silencer, a floor mat, and a dashboard. It is useful as an interior material such as a card, or a sound absorbing material, a heat insulating material, a building material and the like.
  • a fiber sheet which is a non-woven fabric with a basis weight of 40 g / m 2 made of polyester fiber, is composed of 40 parts by mass of a resol-type phenol-formaldehyde initial condensate (solid content: 45 mass% aqueous solution), carbon black (solid content) : 30% by weight aqueous dispersion) 2 parts by weight, fluorine-based water and oil repellent (solid content: 25% by weight aqueous solution) 3 parts by weight, wax-based internal mold release agent (solid content: 40% by weight aqueous dispersion) 1 part by weight Part of the fiber sheet is impregnated with a roll so that the coating amount is 30% by mass of the fiber sheet, and the resol type phenol-formaldehyde is further applied to the back surface of the fiber sheet.
  • precondensate composed: (1 wt% or less particle size: 30 to 40 111, solubility in water), 30 parts of water 30 parts by mass (solid content 45 mass 0/0 aqueous solution) 40 parts by mass, polyphosphate Anmoniumu powder Flame retardant as a mixed dispersion
  • the treatment liquid was applied by spraying so that the amount of application was 25% by mass of the fiber sheet, and then dried and cured at 130 ° C. for 3 minutes to obtain a flame-retardant fiber sheet.
  • this flame-retardant fiber sheet as a skin material, and using a glass wool raw cotton (weight per unit area: 1000 g / m 2 ) coated with 15% by mass of uncured resol-type phenol resin as a base material, the flame-retardant With the back of the fiber sheet
  • the glass wool raw material was polymerized and subjected to hot press molding at 180 ° C., 200 ° C., and 220 ° C. for 60 seconds to obtain a molded product having a thickness of 1 Omm.
  • Example 1 In Example 1,! /, And in the flame retardant treatment solution! /, The resol-type phenol-formaldehyde initial condensate used was an acrylic copolymer emulsion (solid content: 45 mass% aqueous solution). Otherwise, a molded product having a thickness of 10 mm was obtained.
  • Example 1 the resole-type phenol-formaldehyde initial condensate was changed to a sulfomethylated phenol-alkylresorcin formaldehyde initial condensate.
  • a fiber sheet which is a nonwoven fabric made of polyester fiber with a weight per unit area of 90 g / m 2 by needle punching method, is added to 40 parts by mass of a sulfimethylated phenol-alkylresorcin formaldehyde initial condensate (solid content: 45% by mass aqueous solution), carbon black ( Solid content: 30% by mass aqueous dispersion) 2 parts by mass, fluorinated water and oil repellent (solid content: 25% by mass aqueous solution) 3 parts by mass, wax internal release agent (solid content: 40% by mass aqueous dispersion) ) Impregnated and applied to a mixed solution consisting of 1 part by weight and 54 parts by weight of water with a roll so that the amount applied is 40% by weight of the fiber sheet, and the sulfimethylated phenol on the back surface of the fiber sheet.
  • a sulfimethylated phenol-alkylresorcin formaldehyde initial condensate solid
  • Rualkyl resorcin formaldehyde initial condensate (solid content: 45% by weight aqueous solution) 30 parts by weight, ammonium polyphosphate powder (particle size: 30-40 m, solubility in water: 2% by weight or less) ) 30 parts by weight, copolymerized polyamide powder (particle size: 20-30 111, softening temperature: 130 ° C)
  • a flame retardant treatment liquid which is a mixed dispersion consisting of 10 parts by weight and 40 parts by weight of water. After coating so that the coating amount was 30% by mass of the sheet, it was dried and cured at 130 ° C for 3 minutes to obtain a flame-retardant fiber sheet.
  • the flame retardant fiber sheet is used as a skin material, and a melamine resin foam (thickness: 20 mm, density: 8.5 kg / m 3 ) is used as a flame retardant base material.
  • the back surface and the melamine resin foam were polymerized and subjected to hot press molding at 200 ° C. for 60 seconds to obtain a molded product having a thickness of 1 Omm.
  • Example 3 a sulfimethylated phenol-alkylresorcin formaldehyde initial condensate used as a flame retardant treatment liquid was changed to a polyester copolymer emulsion (solid content: 45% by mass aqueous solution). A molded product was obtained.
  • a fiber sheet which is a non-woven fabric with a basis weight of 80 g / m 2 made of polyester fiber, is converted into 40 parts by mass of a sulfomethylated phenol-alkylresorcin formaldehyde initial condensate (solid content: 45% by weight aqueous solution), carbon black ( Solid content: 30% by weight aqueous dispersion) 2 parts by weight, fluorinated water / oil repellent (solid content: 25% by weight aqueous solution) 3 parts by weight, wax-based internal release agent (solid content: 40% by weight aqueous dispersion) ) 1 part by weight, ayu-surfactant 0.1 part by weight, water 53.9 parts by weight impregnated with a roll so as to be 45% by weight of the fiber sheet, On the back surface of the fiber sheet, 30 parts by mass of the sulfomethylated phenol-alkylresorcin formaldehyde initial condensate (solid content: 45 mass% aque
  • the flame retardant fiber sheet is used as a skin material, and urethane foam containing expanded graphite (thickness: 30 mm, density: 15 kg / m 3 ) is used as a flame retardant base material.
  • the urethane foam containing expanded graphite was polymerized and subjected to hot press molding at 180 ° C. for 40 seconds to obtain a molded product having a thickness of 10 mm.
  • Example 4 the sulfomethylated phenol-alkyl resorcinol formaldehyde initial condensate used in the flame retardant treatment liquid was changed to an ethylene acetate butyl copolymer copolymer (solid content: 45% by mass aqueous solution), and the thickness was 10 mm. A molded product was obtained.
  • Example 1 the solubility of ammonium polyphosphate powder in water was 7%. In the same manner, a molded product having a thickness of 10 mm was obtained.
  • Table 1 shows the results of observation of the whitening state of the skin material surface over time.
  • ⁇ Whitening is observed in about 0.5 to 1% of the surface area of the skin material.
  • the low-melting polyester fiber is melted at 135 ° C. for 20 seconds while sucking the web-shaped sheet in a hot air furnace, and the fibers are bonded to each other to have a thickness of 35 mm and an apparent density of 20 kg / m. Three fiber sheets were obtained.
  • the fiber sheet was subjected to sulfomethylated phenol-alkylresorcin formaldehyde initial condensate (solid content: 40 mass% aqueous solution) 40 parts by mass, ammonium polyphosphate powder (particle size: 30 to 40 111, solubility in water: 1 mass)
  • the flame retardant treatment liquid which is a mixed dispersion consisting of 25 parts by weight and 35 parts by weight of water, is impregnated and applied with a roll so that the coating amount is 35% by weight of the fiber sheet. Dried while wicking I, a 20mm thick precured flame retardant fiber substrate was obtained.
  • the back side of the flame retardant fiber sheet and the obtained flame retardant fiber base material were polymerized and heated at 200 ° C for 90 seconds. Press molding was performed to obtain a molded product having a predetermined shape.
  • the flame retardancy of this molded product is UL94 V-0, excellent sound absorption, water resistance, weather resistance, and no whitening phenomenon on the surface of the skin material. is there.
  • acrylic copolymer emulsion is used to apply 50 g / m 2 on the calendered surface. It was applied and dried to form a uniform film.
  • the base material 70% by weight of kenaf fiber, 10% by weight of aramid fiber, and A low-melting polyester fiber having a core-sheath structure (softening point: 130 ° C) 20% by mass is formed into a web-like sheet having a thickness of 40 mm and a basis weight of 500 g / m 2 using a defibrating machine. While sucking in a hot air oven, the low-melting polyester fibers were melted at 135 ° C. for 20 seconds to bind the fibers together to obtain a fiber sheet having a thickness of 35 mm and an apparent density of 25 kg / m 3 .
  • the fiber sheet was mixed with 40 parts by mass of a sulfomethylated phenol-alkylresorcin formaldehyde initial condensate (solid content: 40% by mass aqueous solution), ammonium polyphosphate powder (particle size: 30 to 40 111, solubility in water: 1
  • the flame retardant treatment liquid which is a mixed dispersion consisting of 25 parts by mass and 35 parts by mass of water, is impregnated and applied with a roll so that the application amount is 35% by mass of the fiber sheet at 110 ° C. Drying while sucking for 10 minutes, a 20 mm thick pre-cured flame retardant fiber sheet substrate was obtained.
  • the obtained flame-retardant fiber base material and the flame-retardant fiber sheet skin material were polymerized and hot-pressed at 200 ° C. for 90 seconds to obtain a molded product having a predetermined shape.
  • the flame retardancy of this molded product is UL94 standard V-0, excellent in sound absorption, water resistance and weather resistance, and no whitening phenomenon occurs on the surface of the skin material. It is. Industrial applicability
  • the flame retardant treatment liquid of the present invention can be provided at low cost, and the skin material and base material treated with the flame retardant treatment liquid are imparted with water resistance and flame retardancy, it is particularly suitable as an interior material for automobiles and the like. Useful.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Manufacturing Of Multi-Layer Textile Fabrics (AREA)

Abstract

Le but est de conférer un caractère retardateur de flamme ainsi qu'une résistance à l'eau et une durabilité à un matériau d'intérieur pour une automobile ou similaire. L'invention concerne une solution de traitement retardateur de flamme comprenant : une solution aqueuse d'un précondensat de résine phénolique ; et des particules de polyphosphate d'ammonium ayant une vitesse de dissolution dans l'eau de 5 % en masse ou moins et dispersées dans la solution aqueuse. Dans la solution de traitement, le revêtement de résine phénolique est formé sur la surface des particules de polyphosphate d'ammonium. La résistance à l'eau peut être conférée en raison du revêtement.
PCT/JP2007/066984 2006-10-11 2007-08-31 Solution de traitement retardateur de flamme, matériau fibreux retardateur de flamme et matériau d'intérieur utilisant le matériau fibreux WO2008044399A1 (fr)

Priority Applications (1)

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TW096134387A TW200829616A (en) 2006-10-11 2007-09-14 Fire-retardant processing liquid, fire-retardant fiber material and interior material obtained by using the fiber material

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JP2006-277187 2006-10-11
JP2006277187A JP2008094925A (ja) 2006-10-11 2006-10-11 難燃処理液、難燃性繊維材料及びそれを用いた内装材

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