CN101094952A - Flame-retardant fiber sheet and formed article thereof - Google Patents

Abstract

The object of the present invention is to provide a fiber sheet or a molded fiber sheet having excellent flame retardancy A flame retardant fiber sheet containing a polyammonium phosphate with average degree of polymerization in the range of between 10 and 40 is provided in the present invention. The polyammonium phosphate is insoluble or sparingly soluble in water so that said polyammonium phosphate gives the fiber sheet excellent flame retardancy with water resistance and durability, and is also inexpensive. The molded fiber sheet is highly flame retardant and harmless, so that the molded fiber sheet is useful for automobile and building interiors.

Description

Flame-retardant fiber sheet and article shaped thereof

Technical field

The present invention relates to a kind of flame-retardant fiber sheet and article shaped thereof that is used for automobile or building built-in material etc.

Background technology

In the past,, provided a kind of needle punched non-woven fabrics or Nomex that forms by needle point method complexing fibrous web sheet, reached the resin nonwoven fabric or the resin felt that form by synthetic resin viscose fibre net sheet, fibrous braid etc. as this fibre sheet material.For this fibre sheet material, when requiring to have soundproof property and thermal insulation, also require to have anti-flammability.In order to give this fibre sheet material anti-flammability, be that the phosphoric acid based flame retardant that toxicity is less contains in this fibre sheet material (for example, with reference to patent documentation 1,2,3) in the past.

Patent documentation: the spy opens the 2002-348766 communique

Patent documentation: the spy opens flat 10-226952 communique

Patent documentation: the spy opens flat 10-168756 communique

But above-mentioned phosphoric acid based flame retardant is water-soluble, as contacting just stripping from this fibre sheet material with moisture, and can't obtain having persistent anti-flammability.In order to give phosphoric acid based flame retardant resistance to water, coated the fire retardant of synthetic resin epithelium and provide a kind of at the fire retardant powder surface, but become very high because of coating the processing price.

Summary of the invention

As solution to the problems described above, the invention provides and a kind ofly in fiber, contain the flame retardant fiber sheet that average degree of polymerization is 10～40 APP, and to contain average degree of polymerization in fiber be 10～40 the polyphosphoric acid and the flame-retardant fiber sheet of expanded graphite.

In this fiber, preferably be mixed with fusing point and be the low-melting fiber below 180 ℃.

With the fibre sheet material moulding time, this fiber preferably bonds and/or complexing by synthetic resin cement and/or acupuncture.At this moment, this synthetic resin adhesive is the aqueous solution or powder, when being the aqueous solution, preferably is that 10～40 APP or this ammonium phosphate and this expanded graphite are dispersed in this aqueous solution and impregnation or coat in this fibre sheet material with average degree of polymerization.And, preferably in this aqueous solution, be dissolved with water-soluble resin.And this synthetic resin cement is a phenolic resinoid, wherein, and processing that this phenolic resinoid preferably methylates through sulfo group and/or sulfino methylates.

The present invention provides a kind of article shaped again, and this article shaped is to make by above-mentioned flame-retardant fiber sheet is shaped to the regulation shape.Wherein, the aeration resistance of this shaping thing is preferably 0.01～100kPas/m.

Average degree of polymerization is that 10～40 APP is because of water-soluble hardly, so even the moisture contact contains the fibre sheet material of this APP, this APP that is contained in this fibre sheet material also hardly can stripping.

When also containing expanded graphite except this APP in this fibre sheet material, this fibre sheet material is when being exposed under the high temperature, and then the expanded graphite that is contained expands, and further gives this fibre sheet self-extinguishment except this APP.This fibre sheet material generally bonds and/or complexing fiber by synthetic resin cement and/or acupuncture mutually.And in this fibre sheet material as to be mixed with fusing point be low-melting fiber below 180 ℃, or fiber bonds by synthetic resin cement, and then this fibre sheet material can obtain mouldability.Usually synthetic resin cement is the powder or the aqueous solution, when this synthetic resin cement is the aqueous solution, with this APP or this APP with expanded graphite is dispersed in this aqueous solution and impregnation or coat this fibre sheet material, in this aqueous solution as be dissolved with water-soluble resin, then this aqueous solution then can prevent the precipitation of this APP or this expanded graphite through tackify, and improves this APP or the expanded graphite adhesive force to fiber.And this water-soluble resin also becomes releasing agent, when flame-retardant fiber sheet is carried out extrusion forming, can improve the release property of article shaped.

Fibre sheet material of the present invention has enhanced water resistance, lasting anti-flammability, and to the person poultry harmless, and can provide at an easy rate.

Description of drawings

Fig. 1 represents the key diagram of the measuring principle of aeration resistance.

The specific embodiment

Below describe the present invention in detail

[fiber]

As employed fiber among the present invention, for example; Polyethylene fiber, polyacrylonitrile fibre, vinal, polypropylene fibre, polyester fiber, polyamide fiber, acrylic fiber, polyurethane fiber, polyvinyl chloride fibre, Saran, synthetic fiber such as typel; Wool, mohair, cashmere, camel hair, alpaca fibre, vicugna, mohair, silk, red silk cotton, common cattail fiber, paper pulp, kapok, cocoanut fiber, flax fibre, bamboo fibre, natural fabrics such as kenaf; What obtain from starch such as maize is the biodegradable fiber of raw material with lactic acid; Artificial silk (artificial schappe silk, staple fiber), viscose silk fiber, copper ammonia fibre, acetic acid esters, cellulose family artificial fibres such as tricel; Glass fibre, carbon fiber, ceramic fibre, inorfils such as asbestos fibre; And the chip (cloth) that will use the fibre of these fibers divides comb and the regenerated fiber that obtains etc.These fibers can use separately, also can two kinds or more kinds of being used in combination.

Preferred fiber is a doughnut.

This doughnut is by polyethylene terephthalate, polybutylene terephthalate (PBT), poly terephthalic acid hexylene glycol ester, gather-1, polyester such as 4-dimethyl cyclohexane terephthalic acid (TPA), nylon 6, nylon 66, nylon 46, nylon 10 polyamide such as grade, polyethylene, polyolefin such as polypropylene, acrylic acid, polyurethane, polyvinyl chloride, Vingon, thermoplastic resins such as acetic acid esters are formed.These doughnuts can use separately, also can two kinds or more kinds of being used in combination.

This doughnut, by melt spinning method, or a side who removes in 2 kinds of polymer gained of composite spinning fiber by preferential wash-out becomes the known method grade to make.

This doughnut, the hollow tube portion with shapes such as cross section circle more than 1 or 2, ellipticalnesses, hollow rate is 5%～70%, is preferably 10%～50%.This hollow rate is the hollow tube portion sectional area ratio long-pending with respect to the fibre section.

And the fiber number of this doughnut is the scope of 1dtex～50dtex, is preferably the scope of 2dtex～20dtex.

During with above-mentioned doughnut and the use of other mixed with fibers, above-mentioned doughnut preferably mixes more than the 30 quality %.

As use above-mentioned doughnut, then the rigidity of fibre sheet material strengthens by the hollow tube effect.

And also can use fusing point in the present invention is low-melting fiber below 180 ℃.As this low-melting fiber, for example; Polyethylene, polypropylene, vinyl-vinyl acetate copolymer, TPO fibers such as ethylene-ethyl acrylate copolymer, polyvinyl chloride fibre, polyurethane fiber, polyester fiber, polyethylene terephthalate copolymer fibres, polyamide fiber, polyamide copolymer fiber etc.These low-melting fibers can use separately, also can two kinds or more kinds of being used in combination.

And in the present invention, also can use with resin with high melting point to be core, low-melting-point resin is the core-sheath-type composite fibre of sheath, or resin with high melting point fiber and low-melting-point resin fiber is fitted and face-face type composite fibre of obtaining

The Denier range of this low-melting fiber is 0.1dtex～60dtex.

Above-mentioned low-melting fiber usually with the mixed of 1～50 quality % in above-mentioned fiber.

[APP]

APP used in the present invention is an indissoluble or water insoluble.As this APP, preferred degree of polymerization is more than 10 below 40.At this, the polymerization degree n of APP is calculated by following calculating formula.

Calculating formula 1

$n=\frac{2\×P_{\mathrm{mol}}}{N_{\mathrm{mol}}-P_{\mathrm{mol}}}$

At this, P _MolBe meant in the APP phosphorous molal quantity, N _MolBe meant the molal quantity of nitrogen, P _MolAnd N _MolCalculate from the calculating formula of next.

Calculating formula 2

Calculating formula 3

The P analysis on Content, for example by ICP ICP Atomic Emission Spectrophotometer method, the N analysis on Content is for example undertaken by CHN meter method.

The degree of polymerization is as being more than 10, and then APP is dissolved in water hardly.But the degree of polymerization is as surpassing 40, then be dispersed in APP in the water or the water-based dispersion solvent in the time, viscosity abnormality increase because of dispersion liquid, therefore be difficult to coating or impregnation equably during to coating such as fibre sheet material or impregnation, coating weight or impregnation amount are inhomogeneous even, consequently can't obtain sufficient anti-flammability.

[expanded graphite]

Employed expanded graphite among the present invention, be that native graphite is immersed in the concentrated sulfuric acid, nitric acid is in the inorganic acids such as selenic acid, and by adding perchloric acid, perchlorate, permanganate, bichromate, oxidants such as hydrogen peroxide handle and, the beginning temperature that expands is about 200 ℃～300 ℃, and the allowance for expansion of this expanded graphite is about about 30～300ml/g, and particle diameter is about 50～500 μ m.

[thermal expansivity granule]

In the present invention, also can in fibre sheet material, add the thermal expansivity granule during use,, for example be formed by thermoplastic resin with low softening point and low boiling point solvent as this thermal expansivity granule.As thermoplastic resin, for example with low softening point; Methyl acrylate, ethyl acrylate, the acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, the acrylic acid-2-ethyl hexyl ester, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, methacrylic acid-2-ethylhexyl, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, stearyl methacrylate, aliphatic or ring type acrylic acid and/or methacrylates such as lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, vinyl ethers such as IVE, styrene, phenylethylenes such as α-Jia Jibenyixi, acrylonitrile, nitrile monomers such as methacrylonitrile, vinyl acetate, fatty acid vinyl esters such as propionate, vinyl chloride, vinylidene chloride, PVF, halogen containing monomers such as vinylidene, ethene, olefines such as propylene, isoprene, chlorobutadiene, dienes such as butadiene, acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, atropine acid, α such as citraconic acid, beta-unsaturated carboxylic acid, 2-hydroxyethyl methacry-late, acrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxypropyl acrylate, acrylic acid 2-hydroxypropyl acrylate, hydroxyl monomers such as allyl alcohol, acrylamide, Methacrylamide, amide-types such as diacetone acrylamide, Dimethylaminoethyl Methacrylate, acrylic acid dimethylamino ethyl ester, dimethylaminoethyl acrylate methyl amido propyl ester, amino-contained monomers such as acrylic acid dimethylamino propyl ester, glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether etc. contains the epoxy radicals monomer, and other vinyl pyrrolidone, vinylpyridine, water-soluble monomers such as vinylcarbazole, and will be as above-mentioned γ-(methacryloxy) propyl trimethoxy silicane, vinyltriacetoxy silane, right-trimethoxy silane styrene, right-triethoxysilane styrene, right-trimethoxy silane-α-Jia Jibenyixi, right-triethoxysilane-α-Jia Jibenyixi, γ-(acryloxy) propyl trimethoxy silicane, vinyltrimethoxy silane, N-β (N-vinyl benzyl amido ethyl-γ-aminocarbonyl propyl) trimethoxy silane hydrochloride etc. contain vinyl monomer of water-disintegrable silylation etc. one or two or more kinds polymer or above-mentioned polymer with divinylbenzene, multicomponent methacrylate or methacrylates such as diacrylate binaryglycol ester, dially phthalate, crosslinking agents such as allyl glycidyl ether make its crosslinked polymer, low softening point polyamide, low-softening point polyester etc. preferably have the thermoplastic resin of softening point below 180 ℃; As low boiling point solvent, for example; N-hexane, cyclohexane, pentane, isopentane, normal butane, iso-butane, normal heptane, normal octane, isooctane, gasoline, ether, acetone, boiling points such as benzene are the organic solvent below 150 ℃.And the thermal expansivity granule is by above-mentioned low boiling point solvent being immersed in the above-mentioned thermoplastic resin particle body and the foaminess bead that obtains, and in above-mentioned low softening point thermoplastic resin shell filling above-mentioned low boiling point solvent and the microcapsules that obtain etc. are formed.The diameter of this granule is 0.5～1000 μ m normally.

As the thermal expansivity granule that is used among the present invention, also has vermiculite, perlite, thermal expansivity inorganic particulate plastochondrias such as silica-gel sphere.

[synthetic resin cement]

As the bonding agent of above-mentioned fiber and the synthetic resin that uses for example can use; Polyethylene, polypropylene, ethylene-propylene copolymer, the ethylene-propylene ter-polymers, vinyl-vinyl acetate copolymer, polyvinyl chloride, Vingon, polystyrene, polyvinyl acetate, fluorine resin, thermoplastic acrylic resin, thermoplastic polyester, polyamide thermoplastic, TPU(Thermoplastic polyurethanes), acrylonitrile-butadiene copolymer, Styrene-Butadiene, thermoplasticity synthetic resin such as acrylonitrile-butadiene-styrene, polyurethane resin, melamine resin, thermal-curable acrylic resin, urea resin, phenolic resins, epoxy resin, these thermoset synthetic resins such as heat curing-type polyester etc. also can use the polyurethane resin prepolymer that generates this synthetic resin, epoxy prepolymer, the melamine resin prepolymer, urea resin prepolymer (initial stage condensation product), phenolic resins prepolymer (initial stage condensation product), dially phthalate prepolymer, acrylic acid oligomer, multicomponent isocyanate, methacrylate monomers, the prepolymer of dially phthalate monomer etc., oligomer, the precursor of synthetic resin such as monomer.Above-mentioned synthetic resin also can use separately or more than two kinds and usefulness, usually as latex, and emulsion, the aqueous solution, organic solvent solution etc. and using.

When above-mentioned synthetic resin cement is the aqueous solution, preferably in advance water-soluble resin is dissolved in this aqueous solution.As above-mentioned water-soluble resin, for example; Sodium Polyacrylate, the partly-hydrolysed thing of polyacrylate, polyvinyl alcohol, carboxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyethylcellulose etc., and can use; The copolymer of polyacrylate and/or methacrylate and acrylic acid and/or methacrylic acid, or the alkali soluble resins such as little cross-linking agent of this copolymer.Above-mentioned copolymer or micro-crosslinked copolymer provide as latex usually.

As add the above-mentioned aqueous solution resin of dissolving in above-mentioned synthetic resin aqueous solution, then owing to its tackify effect or dispersion effect, the expanded graphite that is dispersed in this aqueous solution is difficult for Shen Dian, thereby obtains uniform maceration extract.And this aqueous solution resin can strengthen the adhesive force of expanded graphite to fiber, prevents that effectively expanded graphite breaks away from from fibre sheet material.

Above-mentioned water-soluble resin uses 0.01～20 quality % usually approximately with solid component meter in the above-mentioned aqueous solution.

As synthetic resin cement used in the present invention, be preferably phenolic resinoid.Below explanation is about phenolic resinoid used in the present invention.

Phenolic resinoid obtains by making phenolic compound and formaldehyde and/or the condensation of formaldehyde donor.

[phenolic compound]

As employed phenolic compound in the above-mentioned phenolic resinoid, can be monohydric phenol or polyhydric phenols, or the mixture of the pure and mild polyhydric phenols of monohydric phenol, but when only using monohydric phenol, owing to discharge formaldehyde easily when solidifying and after solidifying, so preferably use the mixture of polyhydric phenols or monohydric phenol and polyhydric phenols.

[monohydric phenol]

As above-mentioned monohydric phenol, can example illustrate: phenol, orthoresol, metacresol, paracresol, ethyl-phenol, isopropyl-phenol, xylenols, 3,5-xylenols, butylphenol, tert-butyl phenol, alkylphenols such as nonyl phenol, adjacent fluorophenol, m fluorophenol, p-fluorophenol, o-chlorphenol, m-Chlorophenol, parachlorophenol, adjacent bromophenol, between bromophenol, p bromophenol, phenol o-iodine, an iodophenol, to iodophenol, o-aminophenol, m-aminophenol, para-aminophenol, o-nitrophenol, metanitrophenol, p-nitrophenol, 2,2, 4-dinitrophenol, 2,4, monobasic phenol substituents such as 6-trinitrophenol; Polycycle monohydric phenols such as naphthols etc., these monohydric phenols can use separately, also can two kinds or more kinds of mixing use.

[polyhydric phenols]

As above-mentioned polyhydric phenols, can example illustrate: resorcinol, alkyl-resorcin, pyrogallol, catechol, alkyl catechol, quinhydrones, alkyl quinhydrones, 1,3,5-trihydroxybenzene, bis-phenol, dihydroxy naphthlene etc.These polyhydric phenols can use separately, also can 2 kinds or more polyhybird use.Preferred resorcinol or alkyl-resorcin are preferably the alkyl-resorcin faster than resorcinol with the reaction speed of aldehyde especially among these polyhydric phenols.

As alkyl-resorcin, the oreinol diphenol is for example arranged, the 5-ethyl resorcinol, 5-propyl group resorcinol, 5-n-butyl resorcinol, 4,5-dimethyl resorcinol, 2,5-dimethyl resorcinol, 4,5-diethyl resorcinol, 2,5-diethyl resorcinol, 4,5-dipropyl resorcinol, 2,5-dipropyl resorcinol, 4-methyl-5-ethyl resorcinol, 2-methyl-5-ethyl resorcinol, 2-methyl-5-propyl group resorcinol, 2,4,5-trimethyl resorcinol, 2,4,5-triethyl group resorcinol etc.

To carry out the polyhydric phenols mixture price that destructive distillation obtains cheap owing to the oil shale that Estonia is produced, and volume ground contains the reactive high various alkyl-resorcins except that the oreinol diphenol, so be particularly preferred polyhydric phenols raw material among the present invention.

[formaldehyde donor]

Among the present invention, above-mentioned phenolic compound and formaldehyde and/or formaldehyde donor are carried out condensation, above-mentioned formaldehyde donor is meant to generate when decomposing and provides the compound of formaldehyde or their mixture more than two kinds, as such formaldehyde donor, can for example paraformaldehyde be shown example; trioxane, hexa, tetramethyl aldehyde etc.Below formaldehyde of the present invention and formaldehyde donor are commonly referred to as " formaldehydes ".

[manufacturing of phenolic resinoid]

Above-mentioned phenolic resinoid has two types, and a kind of is that above-mentioned relatively phenolic compound makes formaldehydes resol excessive and that obtain by base catalyst reaction, and another kind is; Relatively formaldehydes makes phenol linear phenol-aldehyde resin excessive and that obtain by the acidic catalyst reaction, resol by phenol and formaldehyde addition and the mixture of the various phenolic alcohol that obtain formed, usually be provided as the aqueous solution, linear phenol-aldehyde resin contract with phenolic alcohol again by phenol and and the various derivative of the dioxydiphenyl methane class that obtains is formed, be provided as Powdered usually.

In phenolic resinoid used in the present invention, be the initial stage condensation product at first, and after making this initial stage condensation product attached to fibre sheet material, make its resinification by curing catalysts and/or heat treated with above-mentioned phenolic compound of resin and formaldehydes condensation.

In order to make above-mentioned condensation product, can be the independent initial stage condensation product of monohydric phenol with monohydric phenol and formaldehydes condensation, and the initial stage cocondensation compound that also mixture and the formaldehydes condensation of monohydric phenol and polyhydric phenols can be monohydric phenol one polyhydric phenols.In order to make above-mentioned initial stage condensation product, can be with any or two kinds in monohydric phenol and the polyhydric phenols in advance as the initial stage condensation product.

Preferred phenolic resinoid is phenol-alkyl-resorcin cocondensation compound among the present invention.Above-mentioned phenol-alkyl-resorcin cocondensation compound has following advantage: the aqueous stability of this cocondensation compound (initial stage condensation product) is good, and with only compare by the formed condensation product of phenol (initial stage condensation product), have advantage with long preservation period under normal temperature condition.And this aqueous solution impregnation or coat in the sheet substrate and the having good stability of precuring and the fibre sheet material that obtains is not even this sheet substrate long preservation is lost mouldability yet.Have again, alkyl-resorcin because of and formaldehyde reactive higher, catch free aldehyde and reaction, so also have advantages such as the quantitative change that makes free aldehyde in the resin is few.

The preferable production process of above-mentioned phenol-alkyl-resorcin cocondensation compound is, phenol and formaldehydes are reacted make phenolic resinoid initial stage condensation product, then, in this phenolic resinoid initial stage condensation product, add alkyl-resorcin, if necessary, add formaldehydes and make the method for its reaction again.

For example, in the condensation of above-mentioned (a) monohydric phenol and/or polyhydric phenols and formaldehydes, usually with respect to 1 mole of monohydric phenol, add 0.2～3 mole formaldehydes, with respect to 1 mole of polyhydric phenols, adding 0.1～0.8 moles of formaldehyde class, and according to required interpolation solvent and the 3rd composition, is to make it add thermal response 8～20 hours under 55～100 ℃ the condition in the liquid temperature.This moment, formaldehydes can all add when the reaction beginning, and also graded adds or drips continuously.

Have again, in the present invention, as above-mentioned phenolic resinoid, also can add urea, thiocarbamide, melamine if needed, the sulfo-melamine, dicyandiamide, guanidine, guanamines, acetylguanamine, benzoguanamine, 2, the 6-diaminostilbene, the amine resins monomer of 3 diamines and/or the initial stage condensation product that is formed by this amine resins monomer make itself and phenolic compound and/or initial stage condensation product carry out cocondensation.

When making above-mentioned phenolic resinoid, need, can react in preceding, the reaction or after the reaction following substances is adjusted agent as catalyst or pH and mix, for example: hydrochloric acid by it, sulfuric acid, orthophosphoric acid, boric acid, oxalic acid, formic acid, acetic acid, butyric acid, benzene sulfonic acid, phenol sulfonic acid, p-methyl benzenesulfonic acid, naphthalene-α-sulfonic acid, naphthalene-β-inorganic or organic acids such as sulfonic acid, organic acid ester classes such as dimethyl oxalate, maleic anhydride, acid anhydrides such as phthalic acid; Ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium oxalate, ammonium acetate, ammonium phosphate, ammonium thiocyanate, ammonium salts such as acid imide ichthyodin, monochloro acetate or sodium salt, α, α '-organohalogen compounds such as dichlorohydrin, triethanolamine hydrochloride, the hydrochloride of amines such as aniline hydrochloride, the salicylic acid urea adduct, the plain adduct of hard ester uraturia, urea adducts such as enanthic acid urea adduct, N-trimethyl taurine, zinc chloride, acidic materials such as iron chloride; Ammonia, amine, NaOH, potassium hydroxide, barium hydroxide, the hydroxide of alkali metal such as calcium hydroxide or alkaline-earth metal, the oxide of alkaline-earth metals such as lime, sodium carbonate, sodium sulfite, sodium acetate, alkaline matters such as alkali-metal weak acid salt such as sodium phosphate.

In the initial stage of phenolic resinoid of the present invention condensation product (comprising initial stage cocondensation compound), also can add again and mix above-mentioned formaldehydes, or curing agent such as hydroxyalkylation triazinone derivative.

Above-mentioned hydroxyalkylation triazinone derivative is by urea compound, amine, the reaction of formaldehydes and obtaining.Employed above-mentioned urea compound during as manufacturing hydroxyalkylation triazinone derivative can example illustrate: urea, thiocarbamide, alkyl urea such as methylurea; Alkyl thioureas such as methylthiourea, phenylurea, naphthyl urea, independent a kind such as halogenation phenylurea and nitration ureine, the mixture of two or more.Particularly preferred urea compound is urea or thiocarbamide.And as amine, except methylamine, ethamine, propylamine, isopropylamine, butylamine, aliphatic amines such as amylamine; Benzylamine, chaff amine, monoethanolamine, ethylenediamine, hexamethylene diamine outside the amines such as hexa, can also example illustrate ammonia, and these can use separately, also can use the mixture of two or more.Employed formaldehydes is and the initial stage of making phenolic resinoid same material of employed formaldehydes during condensation product when making above-mentioned hydroxyalkylation triazinone derivative.

When synthetic above-mentioned hydroxyalkylation triazinone derivative, usually according to respect to 1 mole of urea compounds, amine and/or ammonia are 0.1～1.2 mole, and formaldehydes is that 1.5～4.0 moles ratio makes its reaction.When carrying out above-mentioned reaction, the interpolation of these materials is arbitrarily in proper order, but be as preferred reaction method, at first in reactor, drop into the formaldehydes of aequum, normally while keeping 60 ℃ or following temperature gently to add the amine and/or the ammonia of aequum, then add the urea compound of aequum again, and under 80～90 ℃ condition, add thermal agitation 2～3 hours and make the method for its reaction.Usually use 37% formalin as formaldehydes, but in order to improve the concentration of reaction product, wherein the also replaceable one-tenth paraformaldehyde of a part.And,, then can obtain the higher reaction product of solid constituent as using hexa.Urea compound, the reaction between amine and/or ammonia and the formaldehydes is carried out in the aqueous solution usually, but also available methyl alcohol, ethanol, isopropyl alcohol, n-butanol, ethylene glycol, independent a kind of alcohols such as diethylene glycol (DEG), the mixture of two or more replaces part or all of water, and also can add use acetone, independent a kind of the water-miscible organic solvent of ketones such as methyl ethyl ketone, the mixture of two or more.The addition of above-mentioned curing agent, when being aldehyde and aldehyde donor, initial stage condensation product (initial stage cocondensation compound) with respect to the phenolic resinoid of the present invention of 100 parts by mass is 10～100 parts by mass, when being hydroxyalkylation triazinone derivative, the initial stage condensation product of the above-mentioned phenolic resinoid with respect to 100 parts (initial stage cocondensation compound) is 10～500 parts by mass.

[sulfo group of phenolic resinoid methylates and/or sulfino methylates]

In order to improve the resinoid stability of water soluble phenolic, preferably above-mentioned phenolic resinoid is carried out that sulfo group methylates and/or sulfino methylates.

[sulfo group methylating agent]

As the sulfo group methylating agent that can be used for improveing water-soluble phenolic air aldehyde resin stability, can example for example illustrate: with sulfurous acid, quaternary amines such as acidic sulfurous acid or meta-acid formula sulfurous acid and alkali metal or trimethylamine or benzyltrimethylammon.um or quaternary ammonium react and the water-soluble sulfite that obtains, or the aldehyde adducts that obtains by these water-soluble sulfites and aldehyde reaction.

This aldehyde adducts is meant formaldehyde, acetaldehyde, propionic aldehyde, chloral, furfural, glyoxal, hutanal, hexanal, allyl aldehyde, benzaldehyde, crotonaldehyde, acrolein, phenylacetaldehyde, tolualdehyde, aldehyde such as salicylide and above-mentioned water-soluble sulfurous acid carry out the material of addition reaction gained, and for example the formed aldehyde adducts of formaldehyde and sulphite is the hydroxyl methane sulfonates.

[sulfino methylating agent]

As the sulfino methylating agent that can be used for improveing water-soluble phenolic air aldehyde resin stability, can formaldehyde sodium sulfoxylate (rongalite) be shown example, the alkali metal sulphoxylic acid salt of aliphatic such as benzaldehyde sodium hydrosulfide and aromatic aldehyde, sodium hydrogensulfite, bisulfites (dithionite) class of alkali metal such as magnesium bisulfite and alkaline-earth metal; Hydroxyl alkane sulfinates such as hydroxyl methane inferior sulfonate etc.

The initial stage condensation product of above-mentioned phenolic resinoid carried out that sulfo group methylates and/or during the sulfinic acid ylmethyl, can in this initial stage condensation product, add sulfo group methylating agent and/or sulfino methylating agent in any stage, thereby phenolic compound and/or initial stage condensation product be carried out sulfo group methylates and/or sulfino methylates.

The interpolation of sulfo group methylating agent and/or sulfino methylating agent can be before condensation reaction, in the reaction or reacted arbitrary stage carry out.

The total addition level of sulfo group methylating agent and/or sulfino methylating agent is 0.001 mole～1.5 moles with respect to 1 moles of phenol compounds usually.At total addition level is below 0.001 mole the time, and the hydrophily of phenolic resinoid is insufficient, and more than 1.5 moles the time, the resistance to water variation of phenolic resinoid.For the curable of the initial stage condensation product that keeps manufacturing well with the performances such as rerum natura of the resin after solidifying, preferably be about 0.01～0.8 mole.

The sulfo group methylating agent that is used for the initial stage condensation product carried out that sulfo group methylates and/or sulfino methylates and adds and/or the methylol of sulfino methylating agent and this initial stage condensation product and/or aromatic rings that should the initial stage condensation product react, thereby sulfo group methyl and/or sulfino methyl are directed in this initial stage condensation product.

Like this, sulfo group methylates and/or the aqueous solution of the initial stage condensation product of the methylated phenolic resinoid of sulfino, stablizes in the broad range of acid (pH1.0)～alkalescence, even in acidity, each neutral and alkaline scope is all curable.If it is solidified, then remaining methylol reduces, and decomposes and the worry of generation formaldehyde with regard to not having solidfied material.

In the employed in the present invention synthetic resin cement, also can add and mixed calcium carbonate magnesium carbonate, barium sulfate, calcium sulfate, calcium sulfite again, calcium phosphate, calcium hydroxide, magnesium hydroxide, aluminium hydroxide, magnesia, titanium oxide, iron oxide, zinc oxide, aluminium oxide, silica, diatomite, dolomite, gypsum, talcum, clay, asbestos, mica, calcium silicates, bentonite, white carbon, carbon black, iron powder, aluminium powder, glass dust, stone flour, blast-furnace cinder, floating dust, cement, inorganic fillers such as zirconia; The natural rubber or derivatives thereof, SBR styrene butadiene rubbers, acrylonitrile-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, isoprene rubber, isoamyl-diene-synthetic rubber such as isobutene rubber; Polyvinyl alcohol, mosanom, starch, starch derivatives, gelatine, gel, blood meal, methylcellulose, carboxymethyl cellulose, hydroxyethylcellulose, polyacrylate, water soluble polymer or natural rubbers such as polyacrylamide; Wood powder, English walnut powder, coconut shell flour, wheat flour, organic fillers such as ground rice, stearic acid, senior aliphatic acid such as palmitic acid, palmityl alcohol, higher alcohols such as stearyl alcohol; Butyl stearate, fatty acid esters such as glycerin monostearate; The fatty acid acyl amine, natural waxes such as Brazil wax, synthetic wax class; Paraffin class, paraffin oil, silicone oil, silicone resin, fluororesin, polyvinyl alcohol, releasing agents such as lubricating ester, azodicarboamide, dinitropentamethylenetetramine, P, P '-OBSH, azo-2,2 '-organic foaming agents such as (2-methyl propionitrile); Sodium bicarbonate, saleratus, inorganic foaming agents such as carbonic hydroammonium, silica-gel sphere, perlite, glass marble, foamed glass, hollow particle bodies such as hollow ceramic; Polyethylene foamed, expanded polystyrene (EPS), plastic foam material or expanded beads such as expanded polypropylene, pigment, dyestuff, antioxidant, antistatic agent, crystallization promoter, Phosphorus compound, nitrogen compound, sulphur compounds, boron compound, the bromine compounds, guanidine compound, phosphoric acid salt compound, phosphate compounds, fire retardants such as amine resins, fireproof agent, waterproofing agent, oil-proofing agent, insect-proof agent, preservative agent, wax class, surfactant, lubricant, age resister, ultra-violet absorber, DOP, DBP, the phthalate plasticizer that dicyclohexyl phthalate is such or other are as plasticizer such as tricresyl phosphate etc.

[manufacturing of fibre sheet material]

Fibre sheet material of the present invention is by following method manufacturing: the method for utilizing needle point method complexing fibrous web sheet or fiber mat, or by dipping or mixing low-melting fiber or synthetic resin cement in fibrous web sheet or pad, or by the method that bonds of dipping synthetic resin cement behind needle point method complexing fiber mat or the fiber mat, and the method for braided fiber etc.

Above-mentioned APP, expanded graphite or thermal expansion granule were blended in the fiber before fiber is made into sheet material or pad usually, but in above-mentioned sheet material or pad dipping or during the painting synthetic resin bonding agent, also can be blended in this synthetic resin cement.Blending ratio can be any, but usually with respect to fiber, add this APP 0.5～50 quality %; When using this expanded graphite, add 0.5～50 quality %, when using this thermal expansion granule, add this granule 0.1～50 quality %.

Have again, fibre sheet material is added this APP or this expanded graphite or this thermal expansivity granule, can be behind fibre sheet material impregnation synthetic resin cement, at this synthetic resin cement, or Sodium Polyacrylate, the partly-hydrolysed thing of polyacrylate, polyvinyl alcohol, carboxymethyl cellulose, methylcellulose, ethyl cellulose, the aqueous solution of water-soluble resins such as hydroxyethylcellulose, or the copolymer of acrylate and/or methacrylate and acrylic acid and/or methacrylic acid, or the alkali soluble resin of little cross-linking agent of this copolymer etc. etc. latex in disperse this APP or this expanded graphite or this thermal expansivity granule to modulate dispersion liquid, these dispersion liquids can be coated with, and contain to be dipped in fibre sheet material.

This APP or this expanded graphite or this thermal expansivity granule are at the latex of synthetic resin cement, and homogenizer is preferably used in the dispersion in the aqueous solution, ultrasonic emulsifier unit etc.

When using the ultrasonic emulsifier unit, this APP or this expanded graphite or this thermal expansivity granule are scattered in the aqueous solution equably, in the latex.Especially this expanded graphite is by ultrasonic and by refinement, as make even disperseed by refinement the latex of synthetic resin cement of expanded graphite or the aqueous solution contain and be immersed in the fibre sheet material, then expanded graphite just is penetrated into fibre sheet material inside easily, thereby improves the anti-flammability of fibre sheet material.

After this fibre sheet material impregnation or having mixed synthetic resin solution, this fibre sheet material is carried out drying.When being contained in synthetic resin cement in this fibre sheet material and being heat-curing resin, just but as make this resin be B state long preservation, but and low temperature short time moulding.

When making in the above-mentioned fibre sheet material impregnation synthetic resin, this fibre sheet material of dipping in aqueous synthetic resin or synthetic resin solution normally, or by spraying, blade coating, roller coat, flow coats etc. are coated with aqueous synthetic resin or synthetic resin solution to this fibre sheet material.

In order to regulate impregnation or to have mixed synthetic resin amount in the fibre sheet material of synthetic resin, be after the synthetic resin impregnation or mixing, use compression roller or platen that fibre sheet material is pushed.At this moment, though fibre sheet material thickness reduces, in this fibre sheet material as when containing doughnut, rigidity is higher, after the extruding, and the thickness elastic recovery, thus keep to a certain degree thickness.When particularly containing low-melting fiber in this fibre sheet material, preferably in advance with this fibre sheet materialization, heating makes the low-melting fiber fusion, and by this fused mass viscose fibre.So, the intensity and the rigidity of this fibre sheet material further improve, and the operability when the synthetic resin impregnation also improves, and the recovery of the thickness after the extruding also becomes obvious.

As mentioned above, in the fiber of the present invention when containing doughnut, the fibre sheet material of sheet materialization becomes high rigidity, and can make the content of synthetic resin cement in this fibre sheet material be less than the content of the synthetic resin cement in the fibre sheet material that does not contain doughnut.

When synthetic resin cement is the aqueous synthetic-resin latex, preferably in this aqueous synthetic-resin latex, adds expanded graphite and disperse, or apply ultrasonic it is disperseed with agitating devices such as homogenizers.At this moment, supersonic wavelength is preferably 10～700kHz.As apply ultrasonic, but just refinement of expanded graphite is dipped into fibre sheet material inside thereby it can be contained.

When synthetic resin cement is phenolic resinoid, when being linear phenol-aldehyde resin, be blended in the fiber and by sheet materialization as pulverous initial stage condensation product, and, when being the aqueous solution (initial stage condensation product liquid) of initial stage condensation product, being impregnation or coating this fibre sheet material.As this initial stage condensation product liquid, also can use following water-miscible organic solvent as required: methyl alcohol, ethanol, isopropyl alcohol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, methyl anyl alcohol, 2-ethyl butanol, n-heptanol, n-octyl alcohol, Exxal 12, cyclohexanol, phenmethylol, furfuryl alcohol, tetrahydrofurfuryl alcohol, abienol, alcohols such as diacetone alcohol; Acetone, methyl acetone, methyl ethyl ketone, methyl n-pro-pyl ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), metacetone, di ketone, diisobutyl ketone, acetonyl acetone, methyl ether, cyclohexanone, methyl cyclohexanone, acetophenone, ketones such as camphor; Ethylene glycol, diethylene glycol (DEG), triethylene glycol, propylene glycol, 1, ammediol, glycolss such as polyethylene glycol; Glycol monoethyl ether, ethylene glycol monoethyl ether, glycol isopropyl ether, diethylene glycol monomethyl ether, glycol ethers such as triethylene glycol monomethyl ether; Ethylene acetate, the ester class or derivatives thereof of above-mentioned glycolss such as diethylene glycol monoethyl ether acetic acid esters; Ethers such as 1,4 dioxane, ethylene glycol diethyl ether, diethyl carbitol, ethyl lactate, isopropyl lactate, diethylene glycol diacetate, dimethyl formamide etc.

[moulding of fibre sheet material]

Fibre sheet material of the present invention is shaped to tabular or regulation shape, usually the shaping applied heat is molded, when on above-mentioned fibre sheet material, being attached with expanded graphite, the expansion that hot pressing temperature is set at this expanded graphite begins below the temperature, when in above-mentioned fibre sheet material, containing the thermal expansivity granule, while the thermal expansion that adds of this thermal expansivity granule is that the thickness that limits this fibre sheet material when above-mentioned extrusion forming carries out.If this fibre sheet material is heated to more than the expansion temperature of this thermal expansivity granule that is contained while the thickness that limits this fibre sheet material, then this thermal expansivity granule thermal expansion.As mentioned above, because of having limited the thickness of this fibre sheet material, so by the fiber around the inflate compression of this particle, the density of pars fibrosa then uprises, rigidity strengthens.But all as fibre sheet material, its voidage is constant, thereby weight is also constant.Fibre sheet material of the present invention by hot-forming be tabular after, also can be by hot-forming for stipulating shape, and when containing low-melting fiber or thermoplastic resin bonding agent, can heat also that to make the softening back of low-melting fiber or thermoplastic resin bonding agent be the regulation shape by cold moudling.The also denumerable ply of fibre sheet material of the present invention uses.Fibre sheet material of the present invention for example can be used as: the roof material of automobile, instrument board quieter material, hood quieter material, engine loam cake quieter material, engine lower cover quieter material, cylinder head cover quieter material, the damping and silencing material, carpet, instrument board, door trim bar etc. start the base material of the built-in material in indoor or the car, or be layered in reinforcing material on the base material, or sound absorber, heat-barrier material, construction material etc.

Aeration resistance by the prepared article shaped of fibre sheet material of the present invention is preferably 0.1～100kPas/m.

Wherein, aeration resistance R (Pas/m) is the ventilation degree of expression aeration material.The mensuration of this aeration resistance R is to measure mode by the current stabilization differential pressure to carry out.As shown in Figure 1, configuration test film T in vent passage W cylindraceous, state with certain throughput V (direction of arrow among the figure), measure the interior pressure P 1 of vent passage W of the starting point side of arrow among the figure, with the pressure differential of the terminal point P2 of arrow among the figure, just can calculate aeration resistance R according to following formula again.

(formula) R=Δ P/V

Wherein, Δ P (P1-P2): pressure differential (Pa), V: the throughput (m of unit are ³/ m ²S), be the relation of C=1/R between aeration resistance R (Pas/m) and the venting quality C (m/Pas).

Aeration resistance for example can pass through aeration testing machine (the goods name: KES-F8-AP1), Kato-tech limited company makes, and the current stabilization differential pressure is measured mode) and measure.

Aeration resistance is in the article shaped of 0.01～100kPas/m scope, and its sound absorption properties is good.

At fibre sheet material one or both sides of the present invention, also can stacked surface layer material, liner material, core, other materials such as other fibre sheet materials.Fibre sheet material of the present invention and other materials bonding is across the heat fusing sheet material, hot melt adhesives powder and carrying out, and when on this fibre sheet material, being coated with synthetic resin cement, also can be bonding by this synthetic resin cement.

This heat fusing sheet material or heat fusing powder, for example with polyethylene, polypropylene, vinyl-vinyl acetate copolymer, polyolefin resins such as ethylene-ethyl acrylate copolymer (modifier that comprises polyolefin resin), polyurethane, polyester, polyester copolymer, polyamide, the low-melting-point resins such as mixture more than a kind or 2 kinds of polyamide copolymer etc. are as material.

Use the heat fusing sheet material to be used for for example being pressed on the flame-retardant fiber sheet when bonding, more stacked other fibre sheet materials and be shaped on this fibre sheet material through hot pressing by the heat fusing sheet layer that will from mold T, be extruded.

And have again, when this fibre sheet material is installed, can use assembly parts on parts, or above-mentioned bonding agent, and when parts are plastics, can thermal welding or apply methods such as high frequency, ultrasonic be bonding and install.

In order to ensure aeration, this heat fusing sheet material is preferably porous.In order to make this heat fusing sheet material is porous, be that this heat fusing sheet material is set in advance porous, or after with this flame-retardant fiber sheet and this heat fusing sheet material lamination, offer porous by methods such as acupunctures, or the heat fusing sheet layer of the thermoplastic state that is in that for example will be extruded from mold T is pressed on the fibre sheet material, once extruding, just in this film, form fine porous.This porous is that the fine hair by the fibre sheet material surface forms.In the method, need not to make in advance the heat fusing sheet material to become the operation of porous, and fine porous sound absorption properties for goods have desirable influence.Use above-mentioned hot melt adhesives powder to be used for when bonding, also can guarantee the aeration of sandwich.

Above-mentioned sandwich is shaped to the regulation shape, and the aeration resistance of gained sandwich is preferably 0.01～100kPas/m.Aeration resistance is in the article shaped of 0.01～100kPas/m scope, and its sound absorption properties is good.

Below, describe the present invention in detail by embodiment.But the present invention has more than and is defined in embodiment shown below.

[embodiment 1]

By to polyester fiber (fiber number 12.5dtex by 80 quality %, fibre length: 55mm) and the low melting point polyester fiber of 20 quality % (softening point: 110 ℃, fiber number: 15dtex, fibre length: 50mm) to implement acupuncture and make weight per unit area be 120g/m to the net of the blended fiber of being formed ²Fibre sheet material.Then, relatively this fibre sheet material in the mode of the coating weight that reaches 30 quality % with after being coated with the P-F initial stage condensation product (aqueous solution of 45 quality % solid constituents) of roller coat cloth as synthetic resin cement, again at its back side relatively this fibre sheet material scatter the average degree of polymerization n=10 that respectively does for oneself in the mode that reaches 20 quality %, 30,40 APP (particle diameter: 50～75 μ m), and be dried 3 minutes with 130～140 ℃ temperature.By this fibre sheet material of precuring, and be fixedly attached to this APP on this fibre sheet material back side simultaneously, thereby make flame-retardant fiber sheet.Again with these 60 seconds of flame-retardant fiber sheet of 200 ℃ the hot-forming gained of temperature and make the thick article shaped of 3mm.

[comparative example 1]

Except the average degree of polymerization with the APP among the embodiment 1 is set at n=5,8, other and embodiment 1 similarly carry out, and make the thick article shaped of 3mm.

[embodiment 2]

To comb into cotton shape by polyester or the cotton regeneration chip branch of being formed by carding machine and make velvet apple.Then, relatively this plays velvet apple and adds the linear phenol-aldehyde resin powder that comprises hexa (particle diameter: 20～30 μ m by 50 parts by mass separately in the mode that reaches 30 quality %, fusing point: 78 to 85 ℃) and the average degree of polymerization of 50 parts by mass be n=10,30,40 APP (particle diameter: the mixture of being formed 50～75 μ m), and then divide comb, mix this and rise after velvet apple forms long wool, it is thick to make 15mm with the two sides of these long wools of hot blast precuring of 150 ℃, and weight per unit area is 800g/m ²Flame-retardant fiber sheet.At last with 200 ℃ temperature with this flame-retardant fiber sheet of gained hot-forming 60 seconds, thereby make the thick article shaped of 5mm.

[comparative example 2]

Except with the APP among the embodiment 2 (particle diameter: average degree of polymerization 50～75 μ m) is set at n=5,8, other and embodiment 2 similarly carry out, and make the thick article shaped of 5mm.。

[embodiment 3]

To comb into cotton shape by polyester or the cotton regeneration chip branch of being formed by carding machine and make velvet apple.Then, relatively this plays velvet apple and adds the linear phenol-aldehyde resin powder that comprises hexa (particle diameter: 20～30 μ m by 50 parts by mass separately in the mode that reaches 40 quality %, fusing point: 78 to 85 ℃) and the expanded graphite of 5 parts by mass (particle diameter: 70～80 μ m, the beginning temperature expands: 300 ℃, expansion rate: 300ml/g), and the average degree of polymerization of 45 parts by mass is n=10,30,40 APP (particle diameter: the mixture of being formed 50～75 μ m), and then divide and comb, mixing this rises after velvet apple forms long wool, it is thick to make 15mm with the two sides of these long wools of hot blast precuring of 150 ℃, and weight per unit area is 600g/m ²Flame-retardant fiber sheet.At last with 200 ℃ temperature with this flame-retardant fiber sheet of gained hot-forming 60 seconds, thereby make the thick article shaped of 5mm.

[comparative example 3]

Except with the APP among the embodiment 3 (particle diameter: average degree of polymerization 50～75 μ m) is set at n=5,8, other and embodiment 3 similarly carry out, and make the thick article shaped of 5mm.

[flame retardant test]

With the foregoing description 1,2,3 and comparative example 1, prepared article shaped is in normality in 2,3, and floods 1 in 25 ± 2 ℃ the water, after 3,7 days, in room temperature (25 ± 1 ℃), be dried 48 hours, and these article shaped are carried out flame retardant test separately, embodiment 1,2 and comparison 1,2 safe benchmark according to the automobile inside articles for use, the FMVSS-302 method, embodiment 3 and comparative example 3 are according to the UL94 specification.Its result is as shown in table 1.

[table 1]

	The degree of polymerization of APP (n)	During normality	Water resistant test (dipping fate)
						1 day	3 days	7 days
			Embodiment 1	10	Do not fire				Do not fire	Fire-retardant	After burning
30	Do not fire	Do not fire				Do not fire	Do not fire
				40	Do not fire			Do not fire	Do not fire	Do not fire
Comparative example 1	5	Fire-retardant				Burning	Burning				Burning
			8	Do not fire	Fire-retardant			Burning	Burning
	Embodiment 2	10				Do not fire	Do not fire			Do not fire	Fire-retardant
30			Do not fire	Do not fire	Do not fire			Do not fire
		40				Do not fire	Do not fire		Do not fire	Do not fire
Comparative example 2			5	Fire-retardant	Burning			Burning			Burning
	8	Do not fire				After burning	Burning		Burning
			Embodiment 3	10	V-0			V-0		V-2	V-2
30	V-0	V-0				V-0	V-1
				40	V-0			V-0	V-0	V-0
Comparative example 3	5	V-1				Burning	Burning				Burning
			8	V-0	V-2			Burning	Burning

The article shaped of embodiment as shown in Table 1, its resistance to water is all well, is article shaped in the comparative example of the APP below 10 and used average degree of polymerization (n), and its resistance to water is bad.

[embodiment 4]

(fiber number: 12dtex, fibre length: 60mm) making weight per unit area by needle point method is 100g/m with the polyester fiber of 100 quality % ²Fibre sheet material.Then, relatively this fibre sheet material in the mode of the coating weight that reaches 40 quality % with after being coated with the phenol-alkyl-resorcin-formaldehyde initial stage cocondensation compound (aqueous solution of 50 quality % solid constituents) of roller coat cloth impregnation as synthetic resin cement, again will be by this synthetic resin cement of 30 parts by mass at its back side, 0.5 the Sodium Polyacrylate of parts by mass, the APP of the average degree of polymerization n=15 of 20 parts by mass (particle diameter: 30～40 μ m), 49.5 the mixed liquor that the water of parts by mass is formed with its even dispersion, obtains the mixed liquor that viscosity is 0.3Pas with homogenizer.Relatively this fibre sheet material is that the mode of 30 quality % is coated with this mixed liquor with sprayer with solid constituent, then with 130～140 ℃ temperature drying precuring 1 minute, thereby makes flame-retardant fiber sheet.This flame-retardant fiber sheet as surface layer material, will be coated with glass wool raw cotton (the weight per unit area 700g/m of the uncured resol of 15 quality % ²) as base material,, and make the thick article shaped of 10mm again with the back side of this flame-retardant fiber sheet with the glass wool raw cotton is superimposed and with 200 ℃ temperature hot-forming 60 seconds.This article shaped when spraying because of evenly being coated with the mixed liquor that viscosity is 0.3Pas, so according to the FMVSS-302 method measured anti-flammability for not firing.

[comparative example 4]

Except the average degree of polymerization with the APP of the mixed liquor among the embodiment 4 is set at n=50, viscosity is beyond the 2.6Pas, and other and embodiment 4 carry out equally and make the thick article shaped of 10mm.Because of the viscosity abnormality of this mixed liquor increases to 2.6Pas, and can not evenly be coated with during spraying, make this article shaped generation uneven thickness, so the unstable after burning of being measured according to the FMVSS-302 method that mostly is of anti-flammability.

By embodiment 4 and 4 result relatively, when being APP more than 40 as using average degree of polymerization (n), then viscosity of mixed liquid increases unusually, occurs uneven thickness during coating, consequently is difficult to obtain sufficient anti-flammability.

[embodiment 5]

Will be by the P-F initial stage condensation product (aqueous solution of 50 quality % solid constituents) of 30 parts by mass, APP (average degree of polymerization: n=15 with 20 parts by mass, particle diameter: 60～70 μ m), the carbon black dispersion liquid of 1 parts by mass (30 quality % solid constituent), 0.5 the fluorine class water and oil repellent agent of parts by mass (20 quality % solid constituent), 48.5 after the mixed liquor that the water of parts by mass is formed evenly mixed with homogenizer, the mode that reaches 30 quality % with solid constituent was coated it by the prepared polyester nonwoven fabric of long fibers (weight per unit area: 30g/m of spunbond (spanbond) method by spraying ²) the back side, then 140～150 ℃ hothouse inner drying 2 minutes, and make flame-retardant fiber sheet.This flame-retardant fiber sheet as surface layer material, will be coated with glass wool raw cotton (the weight per unit area 600g/m of the uncured resol of 15 quality % ²) as base material,, and make the thick article shaped of 10mm again with the back side of this flame-retardant fiber sheet with the glass wool raw cotton is superimposed and with 200 ℃ temperature hot-forming 65 seconds.This article shaped is according to the safe benchmark of automobile inside articles for use, the FMVSS-302 method, and for not firing, and water-fast, the article shaped that weatherability is good.

[embodiment 6]

Use is by the polyester fiber (fiber number: 12dtex of 70 quality %, fibre length: 60mm), low melting point polyester fiber (softening point: 110 ℃ with 30 quality %, fiber number: 10dtex, fibre length: the 60mm) fiber web of being formed, and will contain this low melting point polyester fiber fusion in this fiber web, make the fiber bonding fibre sheet material (weight per unit area: 400g/m that makes mutually by this fused mass again ², thickness 40mm).Then, this fibre sheet material be impregnated in the used P-F initial stage condensation product by 30 parts by mass (aqueous solution of 50 quality % solid constituents) of embodiment 5, APP (average degree of polymerization: n=15 with 20 parts by mass, particle diameter: 60～70 μ m), the carbon black dispersion liquid of 1 parts by mass (30 quality % solid constituent), 0.5 the fluorine class water and oil repellent agent of parts by mass (20 quality % solid constituent), 48.5 in the mixed liquor that the water of parts by mass is formed, and contain with the impregnation amount that solid constituent reaches 40 quality % and to be dipped in this fibre sheet material, then in hothouse while bleeding with 100～110 ℃ temperature drying 3 minutes with this impregnation fibre sheet material of precuring, thereby make flame-retardant fiber sheet.This flame-retardant fiber sheet as base material, as surface layer material and superimposed, was shaped to the regulation shape in 60 seconds with 200 ℃ temperature hot pressing with flame-retardant fiber sheet made among the embodiment 4 again.This article shaped is according to the safe benchmark of automobile inside articles for use, the FMVSS-302 method, and for not firing, and water-fast, the article shaped that weatherability is good.

[embodiment 7]

To comb into cotton shape by polyester or the cotton regeneration chip branch of being formed by carding machine and make velvet apple.Then, relatively this plays velvet apple and adds the linear phenol-aldehyde resin powder that comprises hexa (particle diameter: 20～30 μ m by 50 parts by mass in the mode that reaches 30 quality %, fusing point: 78 to 85 ℃), the average degree of polymerization of 45 parts by mass is the APP (particle diameter: 30～40 μ m) of n=30, and the expanded graphite (particle diameter: 70～80 μ m of 5 parts by mass, the beginning temperature expands: 300 ℃, expansion rate: the 300ml/g) mixture of being formed, and then divide and comb, mixing this rises after velvet apple forms long wool, it is thick to make 15mm with these long wools of hot blast precuring of 150 ℃, and weight per unit area is 1000g/m ²Flame-retardant fiber sheet.At last with 200 ℃ temperature with this flame-retardant fiber sheet of gained hot-forming 60 seconds, thereby make the thick article shaped of 3mm.The anti-flammability of this article shaped is the V-0 of UL94 specification, resistance to water, and weatherability, rigidity is good, is suitable for to make arrangements for automotive doors ornamental strip, instrument board.

[embodiment 8]

Will be by the polyester fiber (fiber number: 10.5dtex of 80 quality %, fibre length 65mm), and the hollow polyester fibre of 20 quality % (hollow rate: 20%, fiber number: 12detx, fibre length: 60mm) to make weight per unit area by needle point method be 80g/m to the fiber of being formed ²Fibre sheet material.Then, modulation is by the methylated phenol-alkyl-resorcin of the sulfo group of 30 parts by mass-formaldehyde initial stage cocondensation compound (aqueous solution of 50 quality % solid constituents), the carbon black dispersion liquid of 1 parts by mass (30 quality % solid constituent), 1.5 the fluorine class water and oil repellent agent of parts by mass (20 quality % solid constituent), 67.5 the mixed liquor that the water of parts by mass is formed, again this fibre sheet material be impregnated in this mixed liquor, the impregnation amount that this mixed liquor reaches 40 quality % with solid constituent contain be immersed in the fibre sheet material after, will be by the polyamide powder (softening point: 130 ℃ as hot melt adhesives of 10 parts by mass, particle diameter: 40～50 μ m), the average degree of polymerization of 20 parts by mass is the APP (particle diameter: 30～40 μ m) of n=40, and the expanded graphite of 5 parts by mass (particle diameter: 70～80 μ m, the beginning temperature expands: 300 ℃, expansion rate: 150ml/g) and the mixed liquor formed of the water of 65 parts by mass, the mode that reaches 25 quality % with solid constituent is coated on the back side of this impregnation fibre sheet material with sprayer, again with 130～140 ℃ temperature drying 2 minutes, with this fibre sheet material of precuring, make the formed surface layer material of the flame-retardant fiber sheet that in this fibre sheet material, is adhesively fixed with hot melt adhesives and flame retardant particle simultaneously.Prepared flame-retardant fiber sheet among the embodiment 6 as base material, and at the surface layer material of its superimposed this flame-retardant fiber sheet in two sides, is shaped to the regulation shape in 60 seconds with 210 ℃ temperature hot pressing then, obtains the thing that is shaped.The aeration resistance of this article shaped is 40.5kPas/m, and anti-flammability is the V-0 of UL94 specification, the applicable sound absorption properties of doing, resistance to water, the automotive hood quieter material that weatherability is good or engine lower cover quieter material.

[embodiment 9]

Modulation by 40 parts by mass the methylated phenol-alkyl-resorcin of sulfino-formaldehyde initial stage cocondensation compound (aqueous solution of 45 quality % solid constituents), the carbon black dispersion liquid of 1 parts by mass (30 quality % solid constituent), the fluorine class water and oil repellent agent of 2 parts by mass (20 quality % solid constituent), the mixed liquor that the water of 57 parts by mass is formed again will be by prepared polyester nonwoven fabric of long fibers (the weight per unit area 50g/m of spun-bond process ²) impregnated in this mixed liquor, the impregnation amount that reaches 40 quality % with solid constituent with this mixed liquor contain be immersed in this nonwoven fabric after, to be by the average degree of polymerization of 20 parts by mass n=14 APP (particle diameter: 60～70 μ m) and the mixed liquor formed of the water of the 80 parts by mass mode that reaches 30 quality % with solid constituent be coated on the back side of this impregnation nonwoven fabric by sprayer, again with 130～140 ℃ temperature drying 2 minutes with precuring, make the anti-flammability surface layer material that in this impregnation nonwoven fabric, has been fixed with this APP simultaneously.Again will be by the kenaf (fibre length: 60mm) of 30 quality %, the nylon fiber of 60 quality % (fiber number: 7dtex, fibre length: 70mm), the aramid fibre of 10 quality % (fiber number: 15dtex) form and be 600g/m by the prepared weight per unit area of needle point method ²Fibre sheet material be immersed in that (average degree of polymerization is n=14 by the phenol-alkyl-resorcin-formaldehyde initial stage cocondensation compound (50 quality % solid constituent) of 30 parts by mass and the APP of 20 parts by mass, particle diameter: 60～70 μ m), the carbon black dispersion liquid of 1 parts by mass (30 quality % solid constituent), 0.5 the fluorine class water and oil repellent agent of parts by mass (20 quality % solid constituent), 48.5 what the water of parts by mass was formed contains in the immersion liquid, the impregnation amount that reaches 40 quality % with solid constituent with this mixed liquor contain be immersed in this fibre sheet material after, in hothouse,, make the anti-flammability base material with this impregnation fibre sheet material of precuring while bleeding with 100～120 ℃ temperature drying 3 minutes.Superimposed weight per unit area as hot melt adhesives is 15g/m on the two sides of this anti-flammability base material ²Polypropylene film, in the above that the back side of this anti-flammability surface layer material is superimposed on this polypropylene film again, at last be shaped to the regulation shape in 70 seconds, thereby make article shaped with 190 ℃ temperature hot pressing.The aeration resistance of this article shaped is 10.5kPas/m, and anti-flammability also is the V-0 of UL94 specification, the applicable sound absorption properties of doing, resistance to water, the instrument board quieter material of the automobile that weatherability is good or instrument board damping and silencing material.

[embodiment 10]

Will be by carding machine by the polyester fiber (fiber number: 12.5dtex of 60 quality %, fibre length: 55mm), low melting point polyester fiber (softening point: 120 ℃ with 10 quality %, fiber number: 15dtex, fibre length: 50mm), and the kenaf of 30 quality % (fibre length: the mixture of 60mm) being formed divides combs into cotton shape, then, will be by the linear phenol-aldehyde resin powder that the comprises hexa (particle diameter: 20～30 μ m of 50 parts by mass, fusing point: 78～85 ℃), with the average degree of polymerization of 30 parts by mass be the APP (particle diameter: 50～75 μ m) of n=20, and the expanded graphite of 20 parts by mass (particle diameter: 70～80 μ m, the beginning temperature expands: 300 ℃, expansion rate: mixture 300ml/g) adds in the mode of 30 quality % of the weight per unit area that reaches this cotton-like fiber, and then divide and comb, mix this cotton-like fiber and after forming long wool, it is thick to make 30mm with the two sides of these long wools of hot blast precuring of 150 ℃, weight per unit area is 700g/m ²Flame-retardant fiber sheet.Then, employed anti-flammability surface layer material among the embodiment 9 is superimposed on this flame-retardant fiber sheet, and be shaped to the regulation shape in 50 seconds with 200 ℃ temperature hot pressing, thus make article shaped.The aeration resistance of this article shaped is 5.5kPas/m, and anti-flammability also is the V-0 of UL94 specification, the applicable sound absorption properties of doing, resistance to water, the instrument board quieter material of the automobile that weatherability is good or instrument board damping and silencing material.

[embodiment 11]

(fiber number: 10.5dtex, fibre length: 65mm) weight per unit area that makes by needle point method is 80g/m with the polyester fiber of 100 quality % ²Fibre sheet material as surface layer material.This fibre sheet material is that modulation is by the methylated phenol-alkyl-resorcin of the sulfo group of 30 parts by mass-formaldehyde initial stage cocondensation compound (aqueous solution of 50 quality % solid constituents), the carbon black dispersion liquid of 1 parts by mass (30 quality % solid constituent), 1.5 the fluorine class water and oil repellent agent of parts by mass (20 quality % solid constituent), 67.5 the mixed liquor that the water of parts by mass is formed, this fibre sheet material be impregnated in this mixed liquor, the impregnation amount that reaches 40 quality % with solid constituent contains this mixed liquor and is immersed in the fibre sheet material again.Will be by the polyester powder (softening point: 120 ℃ as hot melt adhesives of 15 parts by mass, particle diameter: 40～50 μ m), the average degree of polymerization of 15 parts by mass is the APP (particle diameter: 30～40 μ m) of n=15, the acrylic based emulsion of 5 parts by mass (50 quality % solid constituent), and the mixed liquor formed of the water of the 60 parts by mass mode that reaches 25 quality % with solid constituent is coated on the back side of this impregnation fibre sheet material by sprayer, again with 130～140 ℃ temperature drying 2 minutes, with this fibre sheet material of precuring, making the flame-retardant fiber sheet that is adhesively fixed with hot melt adhesives and flame retardant particle in this fibre sheet material simultaneously is surface layer material.Then, this surface layer material is superimposed at polyurethane foam base material (the weight per unit area 200g/m through flame treatment ², thickness: two sides 30mm) was shaped to the regulation shape in 55 seconds with 180 ℃ temperature hot pressing then, thereby makes article shaped.The aeration resistance of this article shaped is 8.5kPas/m, and anti-flammability is the V-0 of UL94 specification, the applicable sound absorption properties of doing, resistance to water, automotive hood quieter material that weatherability is good or instrument board quieter material, instrument board damping and silencing material.

[embodiment 12]

Will be by the polyester fiber (fiber number: 10.5dtex of 70 quality %, fibre length: 65mm), with the hollow polyester fibre of 30 quality % (hollow rate: 20%, fiber number: 12dtex, fibre length: 60mm) form and be 80g/m by the weight per unit area that needle point method makes ²Fibre sheet material as surface layer material.Modulation is by the acrylic based emulsion (50 quality % solid constituent) of 5 parts by mass, the polyvinyl alcohol of the 20 parts by mass (aqueous solution of 10 quality % solid constituents, saponification degree: 99mol%), the carbon black dispersion liquid of 1 parts by mass (30 quality % solid constituent), 1.5 the fluorine class water and oil repellent agent of parts by mass (20 quality % solid constituent), the average degree of polymerization of 20 parts by mass is the APP (particle diameter: 30 to 40 μ m) of n=20,52.5 the mixed liquor that the water of parts by mass is formed, and the mode that reaches 30 quality % with solid constituent is coated on this mixed liquor at the back side of this fibre sheet material, again with 130～140 ℃ temperature drying 2 minutes, and make the flame-retardant fiber sheet surface layer material that is bonded with APP on this fibre sheet material surface.Then, will be by carding machine by the polyester fiber (fiber number: 1.5dtex of 70 quality %, fibre length: 55mm), glass fibre (fibre diameter: 0.01～0.06mm with 30 quality %, fibre length: mixture 50mm) divides combs into cotton shape to be used as base material, then, will be by the linear phenol-aldehyde resin powder that the comprises hexa (particle diameter: 20～30 μ m of 65 parts by mass, fusing point: 78～85 ℃), with the average degree of polymerization of 30 parts by mass be the APP (particle diameter: 50～75 μ m) of n=20, and the expanded graphite of 5 parts by mass (particle diameter: 70～80 μ m, the beginning temperature expands: 250 ℃, expansion rate: the mixture of being formed 300ml/g) is added in this cotton-like fiber in the mode that weight per unit area reaches 40 quality %, and divide again and comb, mix this cotton-like fiber with after forming long wool, it is thick with 200 ℃ hot blasts the phenolic resin curing in this long wool to be made 50mm, and weight per unit area is 1000g/m ²The flame-retardant fiber sheet base material.Across the fusing point as hot melt adhesives be 100 ℃ polyamide film (thickness: 0.01mm) with 150 ℃ temperature with hot-forming 2 minutes of this flame-retardant fiber sheet surface layer material of gained and this flame retardant type fibre sheet material base material, make it bonding and make laminated thing.The aeration resistance of this laminated thing is 30.5kPas/m, the good and sound absorption properties of anti-flammability, and resistance to water, weatherability, oil resistivity is good, around the engine applicable to compression pump or construction equipment, soundproof, the fire proofing of air conditioner equipment etc.

[embodiment 13]

Will be by the polyester fiber (fiber number: 10.5dtex of 70 quality %, fibre length: 65mm), with the low melting point polyester fiber of 30 quality % (softening point: 110 ℃, fiber number: 12dtex, fibre length degree: 60mm) form and be 80g/m by the weight per unit area that needle point method makes ²Fibre sheet material as surface layer material.Will by 20 parts by mass be used as hot melt adhesives polyester powder (softening point: 120 ℃, particle diameter: 40～50 μ m), the carbon black dispersion liquid of 1 parts by mass (30 quality % solid constituent), the fluorine class water and oil repellent agent of 3 parts by mass (20 quality % solid constituent), the average degree of polymerization of 20 parts by mass is the APP (particle diameter: 30～40 μ m) of n=20, the mixed liquor that the water of 56 parts by mass is formed, the mode that reaches 30 quality % with solid constituent is coated on the back side of this fibre sheet material by sprayer, again with 130～140 ℃ temperature drying 2 minutes, make on this fibre sheet material surface by hot melt adhesives bonding the surface layer material of flame-retardant fiber sheet of APP.Then, will be by carding machine by the polyester fiber (fiber number: 1.5dtex of 70 quality %, fibre length: 55mm), the low melting point polyester fiber of 10 quality % (softening point: 110 ℃, fiber number: 12dtex, fibre length: 60mm), and the kenaf (fibre diameter: 0.02～0.1mm of 20 quality %, fibre length: the mixture of 70mm) being formed divides to be combed into cotton shape and is used as base material, then with the linear phenol-aldehyde resin powder that the comprises hexa (particle diameter: 20～30 μ m of 65 parts by mass, fusing point: 78～85 ℃), with the average degree of polymerization of 30 parts by mass be the APP (particle diameter: 50～75 μ m) of n=40, and the expanded graphite of 5 parts by mass (particle diameter: 70～80 μ m, the beginning temperature expands: 350 ℃, expansion rate: mixture 300ml/g) is added in this cotton-like fiber in the mode that weight per unit area reaches 40 quality %, and divide again and comb, mix this cotton-like fiber with after forming long wool, it is thick to make 50mm with the two sides of these long wools of hot blast precuring of 150 ℃, and weight per unit area is 1000g/m ²The flame-retardant fiber sheet base material.This flame-retardant fiber sheet surface layer material of gained and this flame-retardant fiber sheet base material is superimposed, and be shaped to the regulation shape with 200 ℃ 70 seconds time of temperature hot pressing, thus make article shaped.The aeration resistance of this article shaped is 18.5kPas/m, the good and sound absorption properties of the anti-flammability of this article shaped, and resistance to water, weatherability, oil resistivity is good, around the applicable engine of making compression pump or construction equipment, soundproof, the fire proofing of air conditioner equipment etc.

[embodiment 14]

(fibre diameter: 0.01～0.05mm, fibre length: 70mm), (fiber number: 10.5dtex, fibre length: 65mm) form and make weight per unit area by needle point method is 600g/m to the polyester fiber of 70 quality % by the glass fibre of 30 quality % ²Fibre sheet material, modulation is by the methylated phenol-alkyl-resorcin of the sulfo group of 30 parts by mass-formaldehyde initial stage cocondensation compound (aqueous solution of 50 quality % solid constituents), the carbon black dispersion liquid of 1 parts by mass (30 quality % solid constituent), 1.5 the fluorine class water and oil repellent agent of parts by mass (20 quality % solid constituent), 67.5 the mixed liquor that the water of parts by mass is formed, again this fibre sheet material is immersed in this mixed liquor, the impregnation amount that reaches 40 quality % with solid constituent with this mixed liquor contain be immersed in this fibre sheet material after, modulate the polyvinyl alcohol (aqueous solution of 8 quality % solid constituents again by 20 parts by mass, saponification degree: 99mol%), the carbon black dispersion liquid of 1 parts by mass (30 quality % solid constituent), 1.5 the fluorine class water and oil repellent agent of parts by mass (20 quality % solid constituent), the average degree of polymerization of 20 parts by mass is the APP (particle diameter: 30～40 μ m) of n=10, the expanded graphite of 5 parts by mass (particle diameter: 70～80 μ m, the beginning temperature expands: 350 ℃, expansion rate: 200ml/g), 52.5 the mixed liquor that the water of parts by mass is formed, the mode that reaches 30 quality % with solid constituent is coated on this mixed liquor by sprayer the back side of this fibre sheet material again, again with 130～140 ℃ temperature drying with precuring 2 minutes, and make the thick flame-retardant fiber sheet of 15mm.At last, with 210 ℃ temperature this flame-retardant fiber sheet hot pressing was shaped to the regulation shape in 50 seconds and made article shaped.The aeration resistance of this article shaped is 10.5kPas/m, the good and sound absorption properties of the anti-flammability of this article shaped, and resistance to water, oil resistivity, weatherability is good, around the applicable engine of making compression pump or construction equipment, soundproof, the fire proofing of air conditioner equipment etc.

[embodiment 15]

Surperficial superimposed with the flame-retardant fiber sheet of the back side of the flame-retardant fiber sheet surface layer material of embodiment 12 gained and embodiment 14 gained, and be shaped to the regulation shape in 60 seconds and made article shaped with 210 ℃ temperature hot pressing.The aeration resistance of this article shaped is 12.3kPas/m, the good and sound absorption properties of the anti-flammability of this article shaped, and resistance to water, oil resistivity, weatherability is good, the applicable automotive hood quieter material of doing, cylinder cover cap quieter material, engine lower cover quieter material.

[embodiment 16]

Use is by the polyester fiber (fiber number: 2.0dtex of 80 quality %, fibre length: 55mm), (core: fusing point is 260 ℃ a polyester fiber to the low melting point polyester fiber of the core sheath structure of 20 quality %, sheath: fusing point is 120 ℃ a low melting point polyester fiber, fiber number: 15dtex, fibre length: the 50mm) fiber web of being formed, make fiber bonding fibre sheet material (the weight per unit area 400g/m that makes mutually again with the low melting point polyester fiber fusion of this contained in this fiber web core-sheath-type composite fibre, and by this fused mass ², thickness 20mm).Then, modulation is by the methylated phenol-alkyl-resorcin of the sulphur first-formaldehyde initial stage cocondensation compound (aqueous solution of 40 quality % solid constituents) of 30 parts by mass, the carbon black dispersion liquid of 1 parts by mass (30 quality % solid constituent), the fluorine class waterproof and oilproof of 2 parts by mass (20 quality % solid constituent), the average degree of polymerization of 20 parts by mass is the APP (particle diameter: 30～40 μ m) of n=25, the mixed liquor that the water of 47 parts by mass is formed, and the mode that reaches 80 quality % with solid constituent is coated on this mixed liquor on the fibre sheet material with being coated with the roller impregnation, again in hothouse while bleeding with 100～110 ℃ temperature drying 5 minutes, and the flame-retardant fiber sheet hot pressing of gained was shaped to the thick article shaped of 10mm in 60 seconds with 190 ℃ temperature.The aeration resistance of this article shaped is 0.02kPas/m, and anti-flammability also is the V-0 of UL94 specification, sound absorption properties, and resistance to water, weatherability is good, applicable automotive hood quieter material or the engine lower cover quieter material done.

[embodiment 17]

Use is by the polyester fiber (fiber number: 2.0dtex of 80 quality %, fibre length: 55mm), (core: fusing point is 260 ℃ a polyester fiber to the low melting point polyester fiber of the core sheath structure of 20 quality %, sheath: fusing point is 120 ℃ a low melting point polyester fiber, fiber number: 15dtex, fibre length: 50mm), kenaf (fibre length: the 55mm) fiber web of being formed with 60 quality %, make the fiber bonding fibre sheet material (weight per unit area: 600g/m that makes mutually again with the low melting point polyester fiber fusion of this contained in this fiber web core-sheath-type composite fibre, and by this fused mass ², thickness: 30mm).Then, modulation is by the methylated phenol-alkyl-resorcin of the sulfo group of 30 parts by mass-formaldehyde initial stage cocondensation compound (aqueous solution of 40 quality % solid constituents), the carbon black dispersion liquid of 1 parts by mass (30 quality % solid constituent), the fluorine class waterproof and oilproof of 2 parts by mass (20 quality % solid constituent), the average degree of polymerization of 20 parts by mass is the APP (particle diameter: 20～40 μ m) of n=15, the mixed liquor that the water of 47 parts by mass is formed, and the mode that reaches 100 quality % with solid constituent is coated on this mixed liquor on the fibre sheet material with being coated with the roller impregnation, again in hothouse while bleeding with 100～110 ℃ temperature drying 6 minutes, and the flame-retardant fiber sheet hot pressing of gained was shaped to the thick article shaped of 10mm in 70 seconds with 200 ℃ temperature.The aeration resistance of this article shaped is 0.08kPas/m, and anti-flammability also is the V-0 of UL94 specification, sound absorption properties, and resistance to water, weatherability is good, applicable automotive hood quieter material or the engine lower cover quieter material done.

[embodiment 18]

Will be by the polyester fiber (fiber number: 1.5dtex of 90 quality %, fibre length: 55mm), (core: fusing point is 260 ℃ a polyester fiber with the low melting point polyester fiber of the core sheath structure of 10 quality %, sheath: fusing point is 130 ℃ a low melting point polyester fiber, fiber number: 15dtex, fibre length: needle point method crosses in the blended fiber Netcom that 50mm) is formed, and to make weight per unit area be 100g/m ²Fibre sheet material.Then, the mode that reaches the coating weight of 20 quality % with solid constituent will be by the methylated phenol-alkyl-resorcin of the sulfo group of 30 parts by mass-formaldehyde initial stage cocondensation compound (aqueous solution of 40 quality % solid constituents) with being coated with roller, the carbon black dispersion liquid of 1 parts by mass (30 quality % solid constituent), the fluorine class water and oil repellent agent of 2 parts by mass (20 quality % solid constituent), after the mixed liquor impregnation that the water of 67 parts by mass is formed is coated on the fibre sheet material, again at its back side, the mode that reaches the coating weight of 40 quality with solid constituent is the APP (particle diameter: 30～40 μ m) of n=15 with the average degree of polymerization that sprayer is coated with by 20 parts by mass, the expanded graphite of 5 parts by mass (particle diameter: 70～80 μ m, the beginning temperature expands: 220 ℃, expansion rate: 200ml/g), the acrylic based emulsion of 15 parts by mass (50 quality % solid constituent), the mixed liquor that the water of 60 parts by mass is formed, and with 120～140 ℃ temperature drying 5 minutes, and with the flame-retardant fiber sheet of gained superimposed be the thick melamine foaming body (trade name: Basotect of 15mm in the thickness adjusted, BASF Japan Ltd system) two sides, last temperature hot pressing with 200 ℃ was shaped to the regulation shape in 60 seconds, thereby made article shaped.The anti-flammability of this article shaped is the V-0 of UL94 specification, sound absorption properties, and resistance to water, weatherability is good, the applicable soundproof fire retardant of making building or construction implement and automobile.

[embodiment 19]

The flame-retardant fiber sheet of embodiment 16 gained is bonded in the article shaped that the inboard of covering on the engine of being made up of the fire-resistant polyamide article shaped that is installed on automobile engine top makes by high frequency, sound absorption properties, sound insulation, anti-flammability is good, applicablely makes to cover on the engine quieter material.

[embodiment 20]

Use is by the polyester fiber (fiber number: 2.0dtex of 30 quality %, fibre length: 50mm), polyester fiber (fiber number: 6.0dtex with 20 quality %, fibre length: 50mm), the carding machine that passes through of 35 quality % divides the regeneration fragment velvet apple that rises of combing into cotton shape, and the low melting point polyester fiber (fusing point: 110 ℃ of the core sheath structure of 15 quality %, fiber number: 10dtex, fibre length: the 30mm) fiber web of being formed, and in 120 ℃～130 ℃ environment, make fiber bonding fibre sheet material (the weight per unit area 400g/m that makes mutually again with low melting point polyester fiber fusion contained in this fiber web, and by this fused mass ², thickness 20mm).Then, modulation is by the methylated phenol-alkyl-resorcin of the sulfo group of 40 parts by mass-formaldehyde initial stage cocondensation compound (aqueous solution of 50 quality % solid constituents), the carbon black dispersion liquid of 1 parts by mass (30 quality % solid constituent), the fluorine class water and oil repellent agent of 3 parts by mass (20 quality % solid constituent), the mixed liquor that the water of 56 parts by mass is formed, the mode that reaches the coating weight of 30 quality % with solid constituent is coated on this mixed liquor impregnation in the fibre sheet material with being coated with roller again, at the one side that contains the fibre sheet material that is soaked with this mixed liquor (back side), reach 200g/m then with solid constituent ²It is the APP (particle diameter: 20～40 μ m) of n=20 that the mode of De Tu cloth amount sprays by the average degree of polymerization of 15 parts by mass, the expanded graphite of 15 parts by mass (particle diameter: 70～80 μ m, the beginning temperature expands: 250 ℃, expansion rate: 200ml/g), the acrylic based emulsion of 10 parts by mass (50 quality % solid constituent), and the polyamide powder as hot melt adhesives of 5 parts by mass (softening point: 120 ℃, particle diameter: 40～50 μ m), the fire retardant mixed liquor of hot melt adhesives is formed and comprised to the water of 55 parts by mass, and while bleeding, thereby make flame-retardant fiber sheet with 130～140 ℃ temperature drying 5 minutes.Then, the fire retardant coated face (back side) of this flame-retardant fiber sheet of gained is superimposed with each other and overlaps, and be shaped to the regulation shape in 90 seconds with 200 ℃ temperature hot pressing.The aeration resistance of this article shaped is 5～20kPas/m, and anti-flammability also is the V-0 of UL94 specification, its sound absorption properties, and resistance to water, weatherability is good.

[embodiment 21]

Except in embodiment 20, use by the kenaf of 75 quality % (directly: 0.01～0.07mm, fibre length: 55mm) the regeneration fragment is divided the velvet apple that rises of combing into cotton shape with the carding machine that passes through of 10 quality %, and the low melting point polyester fiber (fusing point: 110 ℃ of the core sheath structure of 15 quality %, fiber number: 10dtex, fibre length: 30mm) beyond the fibre sheet material of being formed, other and embodiment 20 carry out and are shaped to the article shaped of regulation shape equally, its aeration resistance is 5～15kPas/m, and anti-flammability is the V-0 of UL94 specification also, and particularly thermal contraction is little, the excellent size stability of goods, sound absorption properties, resistance to water, weatherability is good.

Fibre sheet material of the present invention has high flame retardant, and is cheap and to the person poultry harmless.So the built-in material to for example automobile or building is exceedingly useful.

Claims (10)

1. a flame-retardant fiber sheet is characterized in that, contains average degree of polymerization and be 10～40 APP in fiber.

2. a flame-retardant fiber sheet is characterized in that, contains average degree of polymerization and be 10～40 APP and expanded graphite in fiber.

3. anti-flammability sheet material as claimed in claim 1 or 2 wherein, is mixed with fusing point and is the low-melting fiber below 180 ℃ in described fiber.

4. as each described flame-retardant fiber sheet in the claim 1～3, wherein, described fiber bonds and/or complexing by synthetic resin cement and/or acupuncture.

5. as the described anti-flammability sheet material of right claim 4, wherein, described synthetic resin adhesive is the aqueous solution or powder, when being the aqueous solution, disperseing average degree of polymerization in this aqueous solution is 10～40 APP or this APP and expanded graphite, and impregnation or coat in this fibre sheet material.

6. flame-retardant fiber sheet as claimed in claim 5 wherein, is dissolved with water-soluble resin in the described aqueous solution.

7. as claim 4,5 or 6 described flame-retardant fiber sheets, wherein, described synthetic resin cement is a phenolic resinoid.

8. flame-retardant fiber sheet as claimed in claim 7, wherein, processing that described phenolic resinoid has methylated through sulfo group and/or sulfino methylates.

9. an article shaped is characterized in that, this article shaped is to make by each described flame-retardant fiber sheet in the claim 1～8 is shaped to the regulation shape.

10. article shaped as claimed in claim 9, wherein, aeration resistance is 0.01～100kPas/m.

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