CN1849422A - Flame-retardant sheet and formed article therefrom - Google Patents
Flame-retardant sheet and formed article therefrom Download PDFInfo
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- CN1849422A CN1849422A CN 200480025193 CN200480025193A CN1849422A CN 1849422 A CN1849422 A CN 1849422A CN 200480025193 CN200480025193 CN 200480025193 CN 200480025193 A CN200480025193 A CN 200480025193A CN 1849422 A CN1849422 A CN 1849422A
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Abstract
The object of the present invention is to provide a highly fire resistant fiber sheet and a molded fiber sheet thereof. The fibers of the fire resistant sheet of the present invention contain expandable graphite. When said expandable graphite is exposed to high temperatures, it will expand, giving self-extinguishing properties to said fiber sheet. Since said fire resistant molded fiber sheet is highly fire resistant and nontoxic to humans and animals, it is useful for car or building interiors, and the like.
Description
Technical field
The present invention relates to the flame-retardant fiber sheet and the article shaped thereof of a kind of built-in material that is used for automobile and building etc.
Background technology
In the past, as this fibre sheet material, provide a kind of needle punched non-woven fabrics that forms by needle point method complexing fiber mat or Nomex, and (reference example such as spy open flat 11-61616 communique, the spy opens flat 8-39596 communique) such as braided fabrics of the resin nonwoven fabric that forms by synthetic resin viscose fibre net sheet or resin felt, fiber.
For this fiber, requiring to have soundproof property and thermal insulation De Tong Time, also require to have anti-flammability.In order to give this fibre sheet material anti-flammability, be to make tetrachlorophthalic acid in the past, the tetrabromo phthalandione, tetrabromobisphenol A, antimony trioxide, fire retardants such as chlorinated paraffin wax contain in this fibre sheet material.
Even but use above-mentioned fire retardant, fire-retardantization of fibre sheet material is also insufficient, and the toxigenous problem of fire retardant is also arranged.
Summary of the invention
As solution to the problems described above, the invention provides a kind of flame-retardant fiber sheet that in fiber, contains expanded graphite.
This fiber is preferably doughnut or wherein is mixed with doughnut, and more preferably being mixed with fusing point in this fiber is 180 ℃ or following low-melting fiber.
With the fibre sheet material moulding time, preferably this fiber bonds by synthetic resin cement.At this moment, preferably this synthetic resin cement is the aqueous solution, is scattered in this expanded graphite in this aqueous solution and it be impregnated in this fibre sheet material, and preferably be dissolved with water-soluble resin in this aqueous solution.And preferably this synthetic resin cement is a phenolic resin, and has methylated through sulfo group and/or sulfino (the ス Le Off イ メ チ Le that methylates
).
The present invention provides a kind of article shaped that above-mentioned flame-retardant fiber sheet is shaped to the regulation shape again.The aeration resistance of this article shaped is preferably 0.1～100kPas/m.
And the present invention provide again a kind of on the one or both sides of above-mentioned flame-retardant fiber sheet across the porous thermoplastic film and the stacked sandwich of other fibre sheet material, and the article shaped that this sandwich is shaped to the regulation shape.The aeration resistance of this article shaped is preferably 0.1～100kPas/m.
Flame-retardant fiber sheet of the present invention is as being exposed under the high temperature, and the expanded graphite that is then contained produces expansion and gives this fibre sheet material self-extinguishment.This fiber is if doughnut or wherein be mixed with doughnut, and then the rigidity of fibre sheet material improves.Have, as being that 180 ℃ or following low-melting fiber are blended in this fiber with fusing point, or fiber bonds by synthetic resin cement again, and then this fibre sheet material can obtain mouldability.Usually synthetic resin cement is the aqueous solution, be dispersed in this expanded graphite in this aqueous solution and it be impregnated in this fibre sheet material, as being dissolved with water-soluble resin, this aqueous solution then can prevent the precipitation of expanded graphite through tackify in the aqueous solution, and improves the adhesive force of expanded graphite to fiber.And this water-soluble resin also becomes releasing agent, when the extrusion forming flame-retardant fiber sheet, can improve the release property of article shaped.
Fibre sheet material of the present invention has high flame retardant, and to the person poultry harmless.
Description of drawings
Fig. 1 represents the key diagram of the measuring principle of aeration resistance.
The specific embodiment
Below explain the present invention.
[fiber]
As employed fiber among the present invention, for example: 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 (ガ マ Xian Victoria), paper pulp, cotton, cocoanut fiber, flax fibre, bamboo fibre, natural fabrics such as kenaf, artificial silk (artificial schappe silk, staple fibre), koplon, copper ammonia fibre, acetic acid esters, cellulose family artificial fibres such as triacetate, glass fibre, carbon fiber, ceramic fibre, inorfils such as asbestos fibre, and the chip 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, poly--1, and thermoplastic resins such as polyolefin such as polyamide, polyethylene, polypropylene, acrylic acid, polyurethane, polyvinyl chloride, Vingon, acetic acid esters such as polyester such as 4-dimethyl cyclohexane terephthalate, nylon 6, nylon 66, nylon 46, nylon 10 are formed.These doughnuts can use separately, also can two kinds or more kinds of being used in combination.
This doughnut is by melt spinning method, or removes side one-tenth in 2 kinds of polymer gained of the composite spinning fiber known method manufacturing of grading by preferential wash-out.
This doughnut has the hollow tube portion of 1,2 or shapes such as more a plurality of cross sections circle, ellipticalness, and 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.
When above-mentioned doughnut and other mixed with fibers are used, above-mentioned doughnut preferably mix 30 quality % or more than.
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 180 ℃ or following low-melting fiber.As this low-melting fiber, for example: TPO fibers such as polyethylene, polypropylene, vinyl-vinyl acetate copolymer, 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.
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.
[expanded graphite]
Employed expanded graphite among the present invention, be by in mixed liquors such as sulfuric acid, nitric acid, flooding native graphite, and oxidants such as interpolation hydrogen peroxide or hydrochloric acid obtain, the beginning temperature that expands is about 150 ℃～300 ℃, allowance for expansion is about 30～300ml/g, and particle diameter is about 300～30 sieve meshes.
When in fibre sheet material, adding expanded graphite, expanded graphite can be dispersed in (latex in the synthetic resin cement, latex etc.) add with synthetic resin cement, in addition also can be after fibre sheet material flood synthetic resin, preparation has disperseed the partly-hydrolysed thing of Sodium Polyacrylate, polyacrylate, polyvinyl alcohol, carboxymethyl cellulose, methylcellulose, ethyl cellulose, the hydroxyethylcellulose of expanded graphite in addition; And latex, the aqueous solution of acrylate and/or alkali soluble resins such as the copolymer of methacrylate and acrylic acid and/or methacrylic acid or little cross-linking agent of this copolymer etc., and fibre sheet material is coated with, floods with these latexes, the aqueous solution.
Homogenizer, ultrasonic emulsification device etc. are preferably used in the dispersion of expanded graphite in synthetic resin, latex, the aqueous solution.
When using the ultrasonic emulsification device, the expanded graphite refinement also is scattered in the aqueous solution, the latex equably.As the even synthetic resin cement of expanded graphite that disperseed is immersed in the fibre sheet material, expanded graphite just is penetrated into fibre sheet material inside easily, thereby improves the anti-flammability of fibre sheet material.
[thermal expansivity granule]
In the present invention, also can in fibre sheet material, add the thermal expansivity granule during use.As this thermal expansivity granule, for example formed by thermoplastic resin with low softening point and low boiling point solvent.As thermoplastic resin with low softening point, for example: 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-Octyl Nitrite, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, the methacrylic acid stearyl, aliphatic or ring-type acrylate and/or methacrylates such as lauryl methacrylate, ethylene methacrylic (base) ether, ethylethylene (base) ether, n-pro-pyl ethene (base) ether, normal-butyl ethene (base) ether, ethene (base) ethers such as isobutyl group ethene (base) ether, 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, atropic acid, α such as lemon 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 vinyl pyrrolidone, vinylpyridine, water-soluble monomers such as vinylcarbazole, also has above-mentioned γ-(methacryloxy) propyl trimethoxy silicane, vinyltriacetoxy silane, right-trimethoxy silane base styrene, right-triethoxysilicane alkyl styrene, right-trimethoxy silane base-α-Jia Jibenyixi, right-triethoxysilicane alkyl-α-Jia Jibenyixi, γ-(acryloxy) propyl trimethoxy silicane, vinyltrimethoxy silane, N-β (N-vinyl benzyl amido ethyl-γ-aminocarbonyl propyl) trimethoxy silane hydrochloride etc. contains a kind of of vinyl monomer of water-disintegrable silylation etc., two kinds or more kinds of polymer or above-mentioned polymer are by divinylbenzene, multicomponent methacrylate or methacrylates such as diacrylate binaryglycol ester, dially phthalate, the polymer that crosslinking agents such as allyl glycidyl ether are crosslinked, the low softening point polyamide, low-softening point polyesters etc. are preferably the thermoplastic resin with 180 ℃ or following softening point.As low boiling point solvent, for example: boiling points such as n-hexane, cyclohexane, pentane, isopentane, normal butane, iso-butane, normal heptane, normal octane, isooctane, gasoline, ether, acetone, benzene are 150 ℃ or following organic solvent.And the thermal expansivity granule by the foaminess bead that in above-mentioned thermoplastic resin particle body, is impregnated with above-mentioned low boiling point solvent, and in the shell of above-mentioned low softening point thermoplastic resin filling the institutes such as microcapsules of above-mentioned low boiling point solvent form.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 natural glass matter hollow microsphere.
[fibre sheet material]
Fibre sheet material of the present invention is by following method manufacturing: the method for utilizing needle point method complexing fiber mat or fiber mat; Or by dipping in fiber mat or fiber mat or mix low-melting fiber or synthetic resin cement bonds, or flood the method that synthetic resin cement bonds afterwards with needle point method complexing fiber mat or fiber mat; And the method for braided fiber etc.
Above-mentioned expanded graphite or thermal expansion granule were blended in the fiber before fiber is made into sheet material or pad usually, but in sheet material or pad dipping or when mixing synthetic resin cement, also can be blended in this synthetic resin cement.Blending ratio can be arbitrarily, but adds this expanded graphite 0.5～50 quality % with respect to fiber usually.When using this thermal expansion granule, add this granule 0.1～50 quality %.
In the fiber of this sheet materialization, behind dipping or the mixing synthetic resin solution, this sheet material chemical fibre dimension is carried out drying.When being contained in synthetic resin cement in this sheet material chemical fibre dimension and being heat-curing resin, just but as make this resin reach B state long preservation, but and low temperature short time moulding.
[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, vinyl-vinyl acetate copolymer, polyvinyl chloride, Vingon, polystyrene, polyvinyl acetate, fluororesin, thermoplastic acrylic resin, thermoplastic polyester, polyamide thermoplastic, TPU(Thermoplastic polyurethanes), acrylonitrile-butadiene copolymer, Styrene-Butadiene, acrylonitrile-butadiene-styrene copolymer, ethylene-propylene copolymer, the ethylene-propylene ter-polymers, thermoplasticity synthetic resin such as vinyl-vinyl acetate copolymer, polyurethane resin, melamine resin, thermal-curable acrylic resin, urea resin, phenol resin, epoxy resin, thermoset synthetic resins such as heat curing-type polyester etc. also can use the polyurethane resin performed polymer that generates this synthetic resin, epoxy prepolymer, the melamine resin prepolymer, the urea resin prepolymer, the phenol resin prepolymer, the dially phthalate prepolymer, the acrylic acid oligomer, multicomponent isocyanate, methacrylate monomers, prepolymers such as dially phthalate monomer, oligomer, the precursor of synthetic resin such as monomer.Above-mentioned synthetic resin also can use separately, also can two kinds or more kinds of being used in combination, use as latex, latex, the aqueous solution, organic solvent etc. usually.
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 acrylate and/or methacrylate and acrylic acid and/or methacrylic acid or the alkali-soluble Trees fat such as little cross-linking agent of this copolymer.Above-mentioned copolymer or micro-crosslinked copolymer provide as latex usually.
As in above-mentioned synthetic resin aqueous solution, adding the above-mentioned water-soluble resin of dissolving, be dispersed in this aqueous solution expanded graphite then since its tackify effect or dispersion effect be difficult for precipitating, thereby obtain uniform maceration extract.And this water-soluble resin can strengthen the adhesive force of expanded graphite to fiber, prevents that effectively this expanded graphite breaks away from from fibre sheet material.
Above-mentioned water-soluble resin uses in the above-mentioned aqueous solution about 0.1～20 quality % usually with solid component meter.
When making in the fiber of above-mentioned sheet materialization impregnation synthetic resin, normally this sheet material chemical fibre of dipping is tieed up in aqueous synthetic resin or synthetic resin solution, or by spraying, blade coating, roller coat, flow coat etc. this sheet material chemical fibre dimension is coated with aqueous synthetic resin or synthetic resin solution.
For regulating dipping or having mixed synthetic resin amount in the sheet material chemical fibre dimension of synthetic resin, be at dipping or after mixing synthetic resin, use compression roller or platen with the extruding of sheet material chemical fibre dimension.At this moment, though the thickness of sheet material chemical fibre dimension reduces, rigidity is higher when containing doughnut in this sheet material chemical fibre dimension, after the extruding, and thickness elastic recovery, thereby maintenance thickness to a certain degree.When particularly containing low-melting fiber in this sheet material chemical fibre dimension, preferably in advance with this fibre sheet materialization, heating makes the low-melting fiber fusion, and by this fused mass fiber is bondd.So, the intensity and the rigidity of this fibre sheet material further improve, and the operability when synthetic resin floods also improves, and the recovery of the thickness after the extruding also becomes obvious.
As mentioned above, fiber of the present invention is containing doughnut and during sheet material, sheet material becomes high rigidity, and can make the content of synthetic resin cement in the sheet material chemical fibre dimension be less than the content of synthetic resin cement in the sheet material chemical fibre dimension that does not contain doughnut.
Preferably in this aqueous synthetic-resin latex, add expanded graphite when synthetic resin cement is the aqueous synthetic-resin latex and apply ultrasonic wave it is disperseed.At this moment, hyperacoustic wavelength is preferably 10～700kHz.As apply ultrasonic wave, but just miniaturization of expanded graphite, thus it can be impregnated into the inside of fibre sheet material.
As synthetic resin cement used in the present invention, be preferably phenolic resin.Below describe phenolic resin used in the present invention in detail.
Phenolic resin obtains by making phenolic compound and aldehyde and/or the condensation of aldehyde donor.Water-soluble for it is had, also can be to the processing of carrying out that sulfo group methylates and/or sulfino methylates of this phenolic resin.
Phenolic resin of the present invention is immersed in the sheet substrate with the form of the aqueous solution (initial stage condensation product liquid) of initial stage condensation product.This initial stage condensation product liquid also can use following water-miscible organic solvent as required: alcohols such as 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, diacetone alcohol; Ketones such as 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, dimethyl ether, cyclohexanone, methyl cyclohexanone, acetophenone, camphor; Ethylene glycol, diethylene glycol (DEG), triethylene glycol, propylene glycol, 1, glycolss such as ammediol, polyethylene glycol; Glycol ethers such as glycol monoethyl ether, ethylene glycol monoethyl ether, glycol isopropyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether; The ester class or derivatives thereof of above-mentioned glycolss such as ethylene acetate, 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.
[phenolic compound]
As employed phenolic compound in the above-mentioned phenolic resin, can be monohydric phenol or polyhydric phenols, or the mixture of monohydric phenol and polyhydric phenols, 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, the 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, between iodophenol, to iodophenol, o-aminophenol, m-aminophenol, para-aminophenol, o-nitrophenol, between-nitrophenol, 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 two or more mix use.Preferred resorcinol or alkyl-resorcin among these polyhydric phenols, especially preferably with the reaction speed of aldehyde than resorcinol alkyl-resorcin faster.
As alkyl-resorcin, for example have: oreinol diphenol, 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.
It is cheap to carry out the polyhydric phenols mixture price that destructive distillation obtains by the oil shale that Estonia is produced, and contain to volume the reactive high various alkyl-resorcins except that the oreinol diphenol, so be particularly preferred polyhydric phenols raw material among the present invention.
Among the present invention, above-mentioned phenolic compound and aldehyde and/or aldehyde donor (aldehydes) are carried out condensation, above-mentioned aldehyde donor is meant to generate when decomposing and provides the compound of aldehyde or their mixture.As such aldehyde, can example illustrate: formaldehyde, acetaldehyde, propionic aldehyde, chloral, furfural, glyoxal, hutanal, hexanal, allyl aldehyde, benzaldehyde, crotonaldehyde, acrolein, phenylacetaldehyde, tolualdehyde, salicylide etc., as the aldehyde donor, can example for example illustrate: paraformaldehyde, trioxane, hexa, tetramethyl aldehyde (tetraoxymethylene) etc.
As mentioned above, in order to improve the resinoid stability of water-soluble phenolic, the processing of preferably above-mentioned phenolic resin being 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 resinoid stability, can example for example illustrate: quaternary amines such as sulfurous acid, acidic sulfurous acid or meta-acid formula sulfurous acid and alkali metal or trimethylamine and benzyltrimethylammon.um or quaternary ammonium are reacted and aldehyde adducts that the water-soluble sulfite that obtains and the reaction by these water-soluble sulfites and aldehyde obtain.
This aldehyde adducts be meant formaldehyde, acetaldehyde, propionic aldehyde, chloral, furfural, glyoxal, aldehyde such as hutanal, hexanal, allyl aldehyde, benzaldehyde, crotonaldehyde, acrolein, phenylacetaldehyde, tolualdehyde, salicylide and above-mentioned water-soluble sulfurous acid carries out the material of addition reaction gained, for example the formed aldehyde adducts of formaldehyde and sulphite is the hydroxyl mesylate.
[sulfino methylating agent]
As the sulfino methylating agent that can be used for improveing water-soluble phenolic resinoid stability, the alkali metal sulphoxylic acid salt of aliphatic such as formaldehyde sodium sulfoxylate (rongalite), benzaldehyde sodium hydrosulfide and aromatic aldehyde can example be shown; The bisulfites of alkali metal such as sodium hydrogensulfite, magnesium bisulfite and alkaline-earth metal (dithionite) class; Hydroxyl alkane sulfinates such as hydroxyl methane inferior sulfonate etc.
When making above-mentioned phenolic resin; need by it; following alkaline matter can be adjusted agent as catalyst or pH and mix; for example: hydrochloric acid; 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 anhydride; ammonium chloride; ammonium sulfate; ammonium nitrate; ammonium oxalate; ammonium acetate; ammonium phosphate; ammonium thiocyanate; ammonium salts such as imino group ichthyodin; monochloro acetate or its 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 stearic acid urea adduct; 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 and alkaline-earth metal; the oxide of alkaline-earth metals such as lime; sodium carbonate; sodium sulfite; sodium acetate; alkali-metal weak acid salt such as sodium phosphate etc.
(manufacturing of phenolic resin)
Above-mentioned phenolic resin (initial stage condensation product) can be made according to usual method, can make by following method particularly: (a) make monohydric phenol and/or polyhydric phenols and aldehydes carry out the method for condensation, (b) make monohydric phenol and aldehydes condensation and the initial stage condensation product and/or polyhydric phenols and aldehydes condensation and the initial stage condensation product, the method of carrying out condensation with monohydric phenol and/or polyhydric phenols, (c) make monohydric phenol and polyhydric phenols and aldehydes condensation and the initial stage condensation product, the method of carrying out condensation with monohydric phenol and/or polyhydric phenols, (d) make monohydric phenol and aldehydes condensation and the initial stage condensation product, with polyhydric phenols and aldehydes condensation and the initial stage condensation product method of carrying out condensation, (e) make monohydric phenol and aldehydes condensation and the initial stage condensation product and/or polyhydric phenols and aldehydes condensation and the initial stage condensation product, with monohydric phenol and polyhydric phenols and aldehydes condensation and the initial stage condensation product method etc. of carrying out condensation.
Preferred phenolic resin is phenol-alkyl-resorcin cocondensation compound among the present invention.The aqueous stability of above-mentioned phenol-alkyl-resorcin cocondensation compound (initial stage condensation product) is good, and compares with having only the formed condensation product of phenol (initial stage condensation product), has advantage with long preservation period under normal temperature condition.And this aqueous solution impregnated in the sheet substrate and the having good stability of precuring and the fibre sheet material that obtains, even this fibre sheet material long preservation is not lost mouldability yet.Have again, alkyl-resorcin because of and aldehyde reactive higher, catch free aldehyde and reaction, so also have advantages such as the quantitative change of free aldehyde in the resin is few.The preferable production process of above-mentioned phenol-alkyl-resorcin cocondensation compound is, at first make phenol and aldehyde reaction make phenolic resin initial stage condensation product, then, in this phenolic resin initial stage condensation product, add alkyl-resorcin, if necessary, add aldehyde and make the method for its reaction again.
For example, in the condensation of above-mentioned (a) monohydric phenol and/or polyhydric phenols and aldehydes, usually with respect to 1 mole of monohydric phenol, add 0.2～3 mole aldehydes, with respect to 1 mole of polyhydric phenols, adding 0.1～0.8 mole of aldehydes, 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, aldehydes can all add when the reaction beginning, and also graded adds or drips continuously.
The initial stage condensation product of above-mentioned phenolic resin 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, reacted arbitrary stage carries 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 0.001 mole or when following, the hydrophily of phenolic resin is insufficient, and at 1.5 moles or when above, the resistance to water variation of phenolic resin.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, be preferably 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 should react by initial stage condensation product aromatic rings, thus 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 resin of sulfino, and is stable in the broad range of acid (pH1.0)～alkalescence, even all curable in acid, neutrality and alkaline each scope.It is solidified, and remaining methylol reduces, and decomposes and the worry of generation formaldehyde with regard to not having solidfied material.
Among the present invention, as above-mentioned phenolic resin, also can add urea, thiocarbamide, melamine, sulfo-melamine, dicyandiamide, guanidine, guanamines, methyl guanamines, phenyl guanamines, 2 if needed, the 6-diaminostilbene, the initial stage condensation body that the amine resins monomer of 3 diamines and/or this amine resins monomer form makes itself and phenolic compound and/or initial stage condensation product carry out cocondensation.
In addition, in phenolic resin of the present invention initial stage condensation product (comprising initial stage cocondensation compound), also can add curing agent such as aldehyde and/or aldehyde donor or hydroxyalkylation triazinone derivative again.
As above-mentioned aldehyde and/or aldehyde donor, employed aldehyde and/or the same material of aldehyde donor in the time of can using and make the initial stage condensation product (initial stage cocondensation compound) of phenolic resin, hydroxyalkylation triazinone derivative can obtain by the reaction between urea compound, amine and aldehyde and/or the aldehyde donor.Employed above-mentioned urea compound during as manufacturing hydroxyalkylation triazinone derivative can example illustrate: independent a kind, the mixture of two or more of alkyl thioureas such as ureine, methylthiourea such as urea, thiocarbamide, methyl urea, phenylurea, naphthyl urea, halogenation phenylurea and nitration ureine etc.Particularly preferred urea compound is urea or thiocarbamide.As amine except amines such as aliphatic amines such as methylamine, ethamine, propylamine, isopropylamine, butylamine, amylamine, benzylamine, chaff amine, monoethanolamine, ethylenediamine, hexamethylene diamine, hexa, can also ammonia be shown example, they can use separately, also can use the mixture of two or more.Employed aldehyde and/or aldehyde donor are and the initial stage of making phenolic resin employed aldehyde and/or the same material of aldehyde donor during condensation product when making above-mentioned hydroxyalkylation triazinone derivative.
During 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 aldehyde and/or aldehyde donor are 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 aldehyde and/or the aldehyde donor 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.As aldehyde and/or aldehyde donor, use 37% formalin usually, 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.Reaction between urea compound, amine and/or ammonia and aldehyde and/or the aldehyde donor is carried out in the aqueous solution usually, but independent a kind of alcohols such as also available methyl alcohol, ethanol, isopropyl alcohol, n-butanol, ethylene glycol, diethylene glycol (DEG), two or more mixture replace water part or all, and also can add independent a kind, the mixture of two or more of water-miscible organic solvents such as ketone such as using acetone, methyl ethyl ketone.The addition of above-mentioned curing agent, under the situation that is aldehyde and aldehyde donor, initial stage condensation product (initial stage cocondensation compound) with respect to the phenolic resin of the present invention of 100 parts by mass is 10～100 parts by mass, under the situation that is hydroxyalkylation triazinone derivative, be 10～500 parts by mass with respect to the initial stage condensation product (initial stage cocondensation compound) of the above-mentioned phenolic resin of 100 parts by mass.
In the employed in the present invention synthetic resin cement, also can add inorganic fillers such as mixed calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, calcium sulfite, 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, zirconia again; The natural rubber or derivatives thereof; Synthetic rubber such as SBR styrene butadiene rubbers, acrylonitrile-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, isoprene rubber, isoprene-isobutene rubber; Water soluble polymer and natural rubber classes such as polyvinyl alcohol, mosanom, starch, starch derivatives, gelatine, gelatin, blood meal, methylcellulose, carboxymethyl cellulose, hydroxyethylcellulose, polyacrylate, polyacrylamide; Fillers such as calcium carbonate, talcum, gypsum, carbon black, wood powder, English walnut powder, coconut shell flour, wheat flour, ground rice; Surfactant; Higher alcohols such as senior aliphatic acid such as stearic acid, palmitic acid, palmityl alcohol, stearyl alcohol; Fatty acid ester such as butyl stearate, glycerin monostearate; The fatty acid acyl amine; Natural waxes, synthetic wax classes such as Brazil's cocoanut tree wax; Releasing agents such as paraffin class, paraffin oil, silicone oil, silicone resin, fluororesin, polyvinyl alcohol, lubricating grease; Azodicarboamide, dinitropentamethylenetetramine, P, P '-OBSH, azodiisobutyronitrile organic foaming agents such as (ア ゾ PVC ス-2,2 '-(2-メ チ Le グ ロ ピ オ ニ ト リ Le)); Inorganic foaming agents such as sodium bicarbonate, saleratus, carbonic hydroammonium; Hollow particle bodies such as natural glass matter hollow microsphere, perlite, glass marble, foamed glass, hollow ceramic; Plastic foam material or expanded beads such as polyethylene foamed, expanded polystyrene (EPS), expanded polypropylene; Fire retardant, fireproof agent, waterproofing agent, oil-proofing agent, insect-proof agent, preservative agent, wax class, lubricant, age resister, ultra-violet absorbers such as pigment, dyestuff, antioxidant, antistatic agent, crystallization promoter, Phosphorus compound, nitrogen compound, sulphur compounds, boron compound, bromine compounds, guanidine compound, phosphoric acid salt compound, phosphate compounds, amine resins; DOP, DBP, the phthalate plasticizer as dicyclohexyl phthalate and other is as plasticizer such as phosphoric acid trimethylbenzene phenolic ester etc.
Fibre sheet material of the present invention is shaped to tabular or regulation shape, usually applied heat is molded, 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.As one side limited thickness on one side this fibre sheet material is heated to this thermal expansivity granule that is contained expansion temperature or more than, then this thermal expansivity granule expands.As mentioned above, because of having limited the thickness of this fibre sheet material, so by the expansion of this particle fiber on every side is compressed, the density of pars fibrosa uprises, and 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.Also denumerable overlapping use of fibre sheet material of the present invention.
Fibre sheet material of the present invention for example can be used as: the base material of built-in materials such as the roof material of automobile, instrument board quieter material, hood quieter material, engine lower cover quieter material, cylinder head cover quieter material, damping and silencing material, carpet, instrument board, door trim bar, be layered in reinforcing material on the base material or sound-absorbing material, 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 (Pa.s/m) is the yardstick of the ventilation degree of expression aeration material.The mensuration of this aeration resistance R is measured mode by the current stabilization differential pressure and is carried out.As shown in Figure 1, configuration test film T in vent passage W cylindraceous, under the state of 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
2And there are the relation of C=1/R in aeration resistance R (Pas/m) and venting quality C (m/Pas) .s).
Aeration resistance for example can pass through aeration testing machine (goods name: KES-F8-AP1, Kato-tech Co., Ltd. makes, current stabilization differential pressure mensuration mode) and measure.
Aeration resistance is in the article shaped of 0.1～100kPas/m scope, and its sound absorption properties is good.
And, also can other materials such as this fibre sheet material and skin material, inner lining material, core is stacked.
At the one or both sides of fibre sheet material of the present invention, also can form sandwich across folded other fibre sheet material of porous layer thermoplastic film.
This porous thermoplastic film, the film of forming by for example polyolefin resins such as polyethylene, polypropylene, vinyl-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer (modifier that comprises polyolefin resin), polyvinyl chloride, polyurethane, polyester, polyester copolymer, polyamide, polyamide copolymer etc. a kind, two or more mixture.
Above-mentioned sandwich for example is pressed on the flame-retardant fiber sheet by the layer thermoplastic film that will be extruded from mold T, more stacked other fibre sheet material and through hot-forming and make on this fibre sheet material.
Above-mentioned porous thermoplastic film also can be predisposed to the film of porous, also can be behind this film of lamination on the flame-retardant fiber sheet, offer porous by pin etc., but fibre sheet material for example: the layer thermoplastic film of the thermoplastic state that is in that will be extruded from mold T is pressed, once extruding, just on this film, form fine porous.This porous is that the fine hair by the fibre sheet material surface forms.In the method, need not film is carried out the operation of porous, and fine porous there is desirable influence to the sound absorption properties of goods.
The aeration resistance that above-mentioned sandwich is shaped to the sandwich of regulation shape gained is preferably 0.1～100kPas/m.Aeration resistance is in the article shaped of 0.1～100kPas/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]
Use is by the polyester fiber (fiber number: 12dtex of 80 quality %, fibre length: 52mm) and the low melting point polyester fiber of 20 quality % (softening point: 110 ℃, fiber number: 8dtex, fibre length: the 54mm) fiber web of being formed, and make the sheet material chemical fibre by needle point method and tie up (weight per unit area: 500g/m
2, thickness: 15mm).The expanded graphite of interpolation mixing 20 parts by mass in the P-F initial stage of 80 parts by mass condensation product (50% quality solid constituent) (the beginning temperature expands: 300 ℃～320 ℃, and expansion rate: 100 times) and make maceration extract.The viscosity of this maceration extract is 100mPas.Use this maceration extract, be immersed in the above-mentioned sheet material chemical fibre dimension, so that solid constituent reaches the content of 50 quality %, make fibre sheet material with 100～120 ℃ temperature drying 3 minutes with this sheet material chemical fibre dimension of precuring while in hothouse, bleed then.With this fibre sheet material hot-forming 60 seconds of 200 ℃ temperature after, make the thick article shaped of 10mm with precuring.Use aeration testing machine (goods name: KES-F8-AP1, Kato-tech Co., Ltd. system, V=4 * 10
-2(m/s)) measure the aeration resistance (embodiment 2 after too) of this article shaped.The aeration resistance of this article shaped is 3.5kPas/m.
[embodiment 2]
Add the P-F initial stage condensation product (50% quality solid constituent) that mixes 60 parts by mass, polyvinyl alcohol (the 10% quality solid constituent of 20 parts by mass, saponification degree: 98.5mol%) and the expanded graphite of 20 parts by mass (the beginning temperature expands: 300 ℃～320 ℃, expansion rate: 100 times) and make maceration extract.The viscosity of this maceration extract is 250mPas.Except using this maceration extract to replace the maceration extract among the embodiment 1 and embodiment 1 same compression moulding, thereby make the thick article shaped of 10mm, the aeration resistance of this article shaped is 4.1kPas/m.
[embodiment 3]
Add the P-F initial stage condensation product (50% quality solid constituent) that mixes 60 parts by mass, polyvinyl alcohol (the 10% quality solid constituent of 15 parts by mass, saponification degree: 98.5mol%), 4 parts by mass be PRIMAL as the ethyl acrylate of alkali-soluble tackifier and the back cross-linked copolymer latex of methacrylic acid, (Rohm and Haas company makes ASE-60, trade name), 27 quality % ammoniacal liquor of expanded graphite of 20 parts by mass (the beginning temperature expands: 300 ℃～320 ℃, expansion rate: 130 times) and 1 parts by mass and make maceration extract.The viscosity of this maceration extract is 950mPas.Except using this maceration extract to replace the maceration extract among the embodiment 1 and embodiment 1 same compression moulding, make the thick article shaped of 10mm, the aeration resistance of this article shaped is 4.6kPas/m.
[comparative example 1]
, nitrogen based flame retardant phosphorous except using replaces the expanded graphite among the embodiment 1 and embodiment 1 similarly floods, precuring and compression moulding, makes the thick article shaped of 10mm, and the aeration resistance of this article shaped is 3.3kPas/m.
To the foregoing description 1,2,3 and comparative example 1 carry out the flame retardant test of the stability and the article shaped of maceration extract, its result is as shown in table 1.
Anti-flammability
UL94: according to the UL94 specification is benchmark, is that 125mm, thickness are that the size of 10mm is carried out with length.
FMVSS-302:, be that 350mm, width are that 100mm, thickness are that the size of 10mm is carried out with length according to the FMVSS-302 method.
The stability of maceration extract
The stability of the maceration extract that investigation is at room temperature placed.The assessment benchmark as described below.
◎: also be stabilized uniform solution in 7 days or more days even if place.
Expanded graphite begins to separate after zero: 2～3 days.
*: made after the maceration extract 10～20 minutes, the expanded graphite precipitation is also separated.
Table 1
| Anti-flammability | The stability of maceration extract | ||
| UL94 | FMVSS-302 | ||
| Embodiment 1 | V-0 | Do not fire | × |
| Embodiment 2 | V-0 | Do not fire | ○ |
| Embodiment 3 | V-0 | Do not fire | ◎ |
| Embodiment 4 | Defective | Do not fire | ◎ |
[embodiment 4]
Use is by the hollow polyester fibre (hollow rate: 20% of 50 quality %, fiber number: 7dtex, fibre length: 60mm), the vinylon fiber (fiber number: 12dtex of 20 quality %, fibre length: 45mm) and the flax fibre of 30 quality % (fiber number: 20dtex, fibre length: the 40mm) fiber web of being formed, and make sheet material chemical fibre dimension (weight per unit area: 450g/m by needle point method
2, thickness: 15mm).Add in the phenol-alkyl-resorcin-formaldehyde initial stage cocondensation compound (50% quality solid constituent) of 50 parts by mass, the carboxymethyl cellulose of 17 parts by mass (1 quality % solid constituent), 5 parts by mass as employed PRIMAL among the embodiment 3 of tackifier, ASE-60, (expanded graphite of 27 parts by mass expands the beginning temperature: 300 ℃, expansion rate: 150 times) and 27 quality % ammoniacal liquor of 1 parts by mass, make the maceration extract that viscosity is 2000mPas, this maceration extract is immersed in the above-mentioned sheet material chemical fibre dimension, so that solid constituent reaches 40 quality %, then in hothouse while bleeding with 100 ℃ temperature drying 3 minutes with this sheet material chemical fibre dimension of precuring, make fibre sheet material.With 60 seconds of this fibre sheet material after the hot-forming precuring of 220 ℃ temperature, thereby make the thick article shaped of 10mm.The anti-flammability of this article shaped is the V-0 of UL94 specification.In addition, there is no the precipitation of expanded graphite in this maceration extract, operability is good.The aeration resistance of this article shaped is 7.5kPas/m.
[embodiment 5]
Use is by the hollow polyester fibre (hollow rate: 20% of 60 quality %, fiber number: 25dtex, fibre length: 50mm), the kenaf (fiber number: 30dtex of 10 quality %, fibre length: 45mm) and the low melting point polyester fiber of 30 quality % (softening point: 120 ℃, fiber number: 7dtex, fibre length: the 45mm) fiber web of being formed, and make sheet material chemical fibre dimension (weight per unit area: 400g/m by needle point method
2, thickness: 25mm).Add the sulfo group methylated phenol-alkyl-resorcin-formaldehyde initial stage cocondensation compound (55% quality solid constituent) that mixes 20 parts by mass, the carbon black dispersion liquid of 1 parts by mass (30 quality % solid constituent), the zirconium class waterproofing agent of 3 parts by mass (40 quality % solid constituent), the polyvinyl alcohol of 20 parts by mass (6 quality % solid constituents, saponification degree: 99mol%), the PRIMAL as tackifier of 5 parts by mass, TT-615 (Rohm and Haas Gong Si System, trade name), (expanded graphite of 3 parts by mass expands the beginning temperature: 220 ℃, expansion rate: 200 times), 0.5 the 27 quality % ammoniacal liquor of parts by mass and the water of 47.5 parts by mass make the maceration extract that viscosity is 840mPas.Use this maceration extract, be immersed in the above-mentioned sheet material chemical fibre dimension, so that solid constituent reaches the content of 40 quality %, while in hothouse, bleed then with 100～120 ℃ temperature drying 3 minutes with this sheet material chemical fibre dimension of precuring, thus make fibre sheet material.In addition, as skin material, will be immersed in the polyester non-woven fabric (weight per unit area of making by spun-bond process: 30g/m by the maceration extract that the water of phosphorous, the nitrogen based flame retardant of the fluorine class water and oil repellent agent (20 quality % solid constituent) of the carbon black dispersion liquid (30 quality % solid constituent) of the sulfo group methylated phenol-alkyl-resorcin-formaldehyde initial stage cocondensation compound (55% quality solid constituent) of 30 parts by mass, 1 parts by mass, 2 parts by mass, 3 parts by mass and 64 parts by mass is formed
2) in, so that solid constituent reaches the content of 30 quality %, while in hothouse, bleed then with 130～150 ℃ temperature drying 2 minutes with this nonwoven fabric of precuring, thus make the nonwoven fabric skin material.Then, the nonwoven fabric skin material after stacked this precuring on the above-mentioned fibre sheet material, and when being shaped to the regulation shape, obtained shape good and water and oil-resistant and all good article shaped of rigidity with 60 seconds of temperature hot pressing of 200 ℃.When article shaped and forming operation etc., compare simultaneously with glass wool in the past, not from the dust of glass disperse or glass is stabbed the situation of human body, thereby operability is good.Also have, the anti-flammability of this article shaped is the V-0 of UL94 specification, is useful article shaped as the hood quieter material.The aeration resistance of this article shaped is 20.5kPas/m.
[embodiment 6]
With the hollow polyester fibre (hollow rate: 25% of 180 ℃ temperature heating by 80 quality %, fiber number: 6dtex, fibre length: 55mm) and the low melting point polyester fiber (softening point: 120 ℃ of 20 quality %, fiber number: 3dtex, fibre length: the 45mm) fiber web of being formed, make this low melting point polyester fiber fusion that is contained in this fiber web, and make the bonding mutually sheet material chemical fibre dimension (weight per unit area: 400g/m that makes of fiber by this fused mass
2, thickness: 30mm).Produce sulfino methylated phenol-alkyl-resorcin-formaldehyde initial stage cocondensation compound (50% quality solid constituent) by 30 parts by mass, 0.5 the carbon black dispersion liquid of 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 acrylic resin latex of 5 parts by mass (50 quality % solid constituent), employed PRIMAL among the embodiment 3 of 3 parts by mass, ASE-60, thermal expansivity granule (the capsule-type of 5 parts by mass, マ ッ モ ト マ イ Network ロ ス Off エ ア-F-100: the trade name of Matsumoto Yushi-Seiyaku Co., Ltd.'s system, the shell softening temperature is 135～145 ℃), the expanded graphite of 3 parts by mass (the beginning temperature expands: 200 ℃, and expansion rate: 150 times), 0.1 the cataloid of parts by mass, 0.5 the viscosity that the 27 quality % ammoniacal liquor of parts by mass and the water of 50.9 parts by mass are formed is the maceration extract of 850mPas.Use this to contain immersion liquid, be immersed in the above-mentioned sheet material chemical fibre dimension, so that solid constituent reaches the content of 40 quality %, while in hothouse, bleed then with 100～110 ℃ temperature drying 3 minutes with this sheet material chemical fibre dimension of precuring, thus make fibre sheet material.Be shaped to the regulation shape 60 seconds with the fibre sheet material after this precuring of temperature hot pressing of 180 ℃ again, on one side and on one side limited thickness the thermal expansivity granule is expanded and makes article shaped.The sound absorption properties of this article shaped, rigidity, water and oil-resistant are good.The anti-flammability of this article shaped is the V-0 of UL94 specification, can obtain as the instrument board quieter material of car body and damping and silencing material and useful article shaped.The aeration resistance of this article shaped is 30.3kPas/m.
[embodiment 7]
In embodiment 6, as skin material, to be immersed in the weight per unit area of making by needle point method by the maceration extract that the water of the methylcellulose (the 4 quality % aqueous solution) of the carbon black dispersion liquid (30 quality % solid constituent) of the fluorine class water and oil repellent agent (15 quality % solid constituent) of the phenol-alkyl-resorcin-formaldehyde initial stage cocondensation compound (55% quality solid constituent) of 60 parts by mass, 2 parts by mass, 1 parts by mass, the expanded graphite of 0.5 parts by mass (the beginning temperature expands: 200 ℃, expansion rate: 150 times), 10 parts by mass and 26.5 parts by mass is formed is 80g/m
2The polyester non-woven fabric sheet material in, make the solid constituent in this polyester non-woven fabric reach 25 quality %, the polyamide powder (by 200 sieve meshes) that with fusing point is 120 ℃ then is as hot melt adhesives, with 5g/m
2Coating weight be coated on the back side of this nonwoven fabric sheet, then in hothouse with 130～140 ℃ temperature drying 2 minutes so that this hot melt adhesives is attached to the back side of this nonwoven fabric sheet, precuring simultaneously and make skin material.This skin material is layered among the embodiment 6 on the fibre sheet material after the prepared precuring, and is shaped to the regulation shape 60 seconds with 180 ℃ temperature hot pressing, on one side and on one side limited thickness the thermal expansivity granule is expanded and makes article shaped.The sound absorption properties of this article shaped, rigidity, water and oil-resistant are good.Anti-flammability is the V-0 of UL94 specification also, can be used for the moulding roof material of automobile.The aeration resistance of this article shaped is 31.0kPas/m.
[embodiment 8]
Use is by the polyester fiber (fiber number: 1.5dtex of 60 quality %, fibre length: 45mm), the low melting point polyester fiber (softening point: 110 ℃ of 10 quality %, fiber number: 3dtex, fibre length: 54mm) and the hollow polyester fibre of 30 quality % (hollow rate: 25%, fiber number: 3dtex, fibre length: the 50mm) fiber web of being formed, and make sheet material chemical fibre dimension (weight per unit area: 350g/m by needle point method
2, thickness: 20mm).Make sulfo group methylated phenol-alkyl-resorcin-formaldehyde initial stage cocondensation compound (50% quality solid constituent) again by 40 parts by mass, 0.5 the carbon black dispersion liquid of parts by mass (30 quality % solid constituent), the fluorine class water and oil repellent agent of 3 parts by mass (15 quality % solid constituent), the polyvinyl alcohol of 20 parts by mass (8 quality % solid constituents, saponification degree: 99.5mol%), as employed PRIMAL among the embodiment 3 of 2 parts by mass of tackifier, ASE-60 (Rohm and Haas corporate system, trade name) employed PRIMAL and among the embodiment 5 of 1 parts by mass, TT-615 (Rohm and Haas corporate system, trade name), 0.2 (the expanded graphite A of parts by mass expands the beginning temperature: 130 ℃～150 ℃, expansion rate: 150 times), (the expanded graphite B of 7 parts by mass expands the beginning temperature: 300 ℃～320 ℃, expansion rate: 150 times), 0.5 27 quality % ammoniacal liquor of parts by mass, 0.1 2 of parts by mass, the viscosity that the water of 6-di-t-butyl-paracresol class antioxidant and 25.7 parts by mass is formed is the maceration extract of 1200mPas.Use this maceration extract, be immersed in the above-mentioned sheet material chemical fibre dimension, so that solid constituent reaches the content of 40 quality %, while in hothouse, bleed then with 100～110 ℃ temperature drying 3 minutes with this sheet material chemical fibre dimension of precuring, thus make fibre sheet material.And, as skin material, will be immersed in a bit-type aromatic polyamide fibre nonwoven fabric sheet (weight per unit area: 40g/m by the maceration extract that the fluorine class water and oil repellent agent (15 quality % solid constituent) of the carbon black dispersion liquid (30 quality % solid constituent) of the sulfo group methylated phenol-alkyl-resorcin-formaldehyde initial stage cocondensation compound (55% quality solid constituent) of 40 parts by mass, 1 parts by mass and 2 parts by mass is formed
2Fiber number: 5dtex), so that the solid constituent in this aromatic polyamide fibre nonwoven fabric sheet reaches the content of 20 quality %, then in hothouse with 140～150 ℃ temperature drying 2 minutes with this aromatic polyamide fibre nonwoven fabric sheet of precuring, thereby make skin material.Then, stacked this skin material on above-mentioned fibre sheet material, and be shaped to the regulation shape 60 seconds with 210 ℃ temperature hot pressing, on one side and on one side limited thickness expanded graphite A in this fibre sheet material is expanded and makes article shaped.The sound absorption properties of this article shaped, rigidity, heat resistance, water and oil-resistant are good.Anti-flammability is the V-0 of UL94 specification also, can be used for the hood quieter material or the engine lower cover quieter material of automobile.The aeration resistance of this article shaped is 10.2kPas/m.
[embodiment 9]
At the felt (weight per unit area: 800g/m that uses regenerated fiber and bond with synthetic resin
2Thickness: 25mm), employed maceration extract among the dipping embodiment 4 is so that the solid constituent in this felt reaches 10 quality %, then in hothouse with 100～130 ℃ temperature drying 2 minutes to remove moisture, again with 200～230 ℃ temperature hot briquetting 3 minutes and make fibre sheet material.This fibre sheet material anti-flammability is good, and its article shaped can be used for the carpet of automobile.The aeration resistance of this article shaped is 6.6kPas/m.
[embodiment 10]
With the kenaf (fiber number: 30dtex of 180 ℃ temperature heating by 70 quality %, fibre length: 40mm) and the polypropylene fibre (softening point: 140 ℃ of 30 quality %, fiber number: 1.5dtex, fibre length: the 40mm) fiber web of being formed, make this polypropylene fibre fusion that is contained in this fiber web, the mutual bonding sheet material chemical fibre that makes of fiber is tieed up (weight per unit area: 500g/m by this fused mass
2, thickness: 15mm).Use to add and mixed the acrylic resin latex (50 quality % solid constituent) of 85 parts by mass, the expanded graphite of 5 parts by mass (expansion beginning temperature: 300 ℃, expansion rate: 150 times) and the polyvinyl alcohol water solution of 10 parts by mass (10 quality % solid constituents, saponification degree: maceration extract 85mol%), be immersed in the above-mentioned sheet material chemical fibre dimension, so that solid constituent reaches 30 quality %, 100～130 ℃ hothouse inner drying 2 minutes, make fibre sheet material then.Again this fibre sheet material was placed 5 minutes in 150～180 ℃ hothouse, make this polypropylene fibre fused mass fusion after, cold pressing and make the article shaped that thickness is 5mm.Rigidity, the anti-flammability of this article shaped are good.The door panel that can be used for automobile.The aeration resistance of this article shaped is 90.5kPas/m.
[embodiment 11]
Use is by the polyester fiber (fiber number: 1.5dtex of 95 quality %, fibre length: 36mm) and the low melting point polyester fiber (softening point: 110 ℃ of 5 quality %, fiber number: 4dtex, fibre length: the 40mm) fiber web of being formed, and make sheet material chemical fibre dimension (weight per unit area: 80g/m by needle point method
2, thickness: 2mm).Use to add and mixed the phenol-alkyl-resorcin-formaldehyde initial stage cocondensation compound (50% quality solid constituent) of 65 parts by mass, the water-soluble epoxy resin of 10 parts by mass (60 quality % solid constituent), (expanded graphite of 3 parts by mass expands the beginning temperature: 300 ℃, expansion rate: 150 times), the polyvinyl alcohol water solution of 22 parts by mass (5 quality % solid constituents, saponification degree: maceration extract 99.5mol%), and it is coated on the above-mentioned sheet material chemical fibre dimension by spraying process, so that solid constituent reaches 40 quality %, then 150～180 ℃ hothouse inner drying 2 minutes, and with the gained fibre sheet material as the moulding roof of the automobile of forming by hard polyurethane foams and skin material reinforcing material with base material.This fibre sheet material can be used as the reinforcing material that rigidity is good and anti-flammability is good.
[embodiment 12]
Acrylic based emulsion (50% quality solid constituent) with 30 parts by mass, the polyvinyl alcohol of 15 parts by mass (10% quality solid constituent, saponification degree: 98.5mol%), the PRIMAL of 10 parts by mass, ASE-60 (Rohm and Haas corporate system, trade name), (expanded graphite of 20 parts by mass expands the beginning temperature: 300～320 ℃, expansion rate: 130 times, particle diameter: 80 sieve meshes), the 27 quality % ammoniacal liquor of 1 parts by mass and the water of 24 parts by mass mix, and carry out ultrasonic wave and stir (frequency: 30kHz, 5 minutes), on one side the expanded graphite of refinement on one side makes its dispersion then.This viscosity in aqueous solution is 840mPas.
The above-mentioned aqueous solution is immersed in the sheet material chemical fibre dimension (weight per unit area: 50g/m of embodiment 1
2, thickness: in the time of 15mm), expanded graphite has been impregnated into the inside of this sheet material chemical fibre dimension.This is interpreted as: owing to hyperacoustic stirring makes the expanded graphite refinement, thereby the dispersiveness of the particle diameter of this expanded graphite becomes good.
[embodiment 13]
Use is by the polyester fiber (fiber number: 5dtex of 40 quality %, fibre length: 25mm), the low melting point polyester fiber (softening point: 110 ℃ of 20 quality %, fiber number: 2.5dtex, fibre length: 20mm) and the kenaf of 40 quality % (fiber number: 40detx, Xian Wei Long degree: the 30mm) fiber web of being formed, make this low melting point polyester fiber fusion that is contained in this fiber web, and the mutual bonding sheet material chemical fibre that makes of fiber is tieed up (weight per unit area: 250g/m by this fused mass
2, thickness: 30mm).The maceration extract that use is made up of the water of the fluorine class water and oil repellent agent (20 quality % solid constituent) of the carbon black dispersion liquid (30% quality solid constituent) of the sulfo group methylated phenol-alkyl-resorcin-formaldehyde initial stage cocondensation compound (50% quality solid constituent) of 40 parts by mass, 1 parts by mass, 2 parts by mass and 57 parts by mass, be immersed in the above-mentioned sheet material chemical fibre dimension, so that solid constituent reaches the content of 40 quality %, then in hothouse with 140～150 ℃ temperature drying 10 minutes.Then, by spray pattern the expanded graphite dispersion liquid of gained among the embodiment 12 is coated on the two sides of above-mentioned sheet material chemical fibre dimension, so that the amount of expanded graphite on each face is 40g/m
2, and then be dried 5 minutes with 140～150 ℃ temperature, thus make the precuring fibre sheet material that has been coated with expanded graphite.Formed by polyester fiber and be 50g/m then by the weight per unit area that spun-bond process is made
2The back side of nonwoven fabric, the thickness polyethylene extrusion with 20 μ m makes the nonwoven fabric through lamination.Use this nonwoven fabric, with in the above-mentioned maceration extract of 98 parts by mass, add the phosphorus mixed 2 parts by mass, the fire retardant of nitrogen based flame retardant cooperates maceration extract to be immersed in this nonwoven fabric, so that solid constituent reaches the content of 45 quality %, in hothouse,, make skin material with 140～150 ℃ 30 seconds of temperature drying.Stacked this skin material on above-mentioned precuring fibre sheet material again, and make article shaped hot-forming 45 seconds with 200 ℃ temperature.The aeration resistance of this article shaped is 58.3kPas/m.And the anti-flammability of this article shaped is the V-0 of UL94 specification, can be used for the instrument board sound-absorbing material and the damping and silencing material of the good car body of sound absorption properties.
Fibre sheet material of the present invention has high flame retardant, and to the person poultry harmless, so exceedingly useful to built-in material of for example automobile and building etc.
Claims (12)
1, a kind of flame-retardant fiber sheet is characterized in that, contains expanded graphite in fiber.
2, flame-retardant fiber sheet as claimed in claim 1, wherein, described fiber is doughnut or wherein is mixed with doughnut.
3, flame-retardant fiber sheet as claimed in claim 1 or 2, wherein, being mixed with fusing point in described fiber is 180 ℃ or following low-melting fiber.
4, as each described flame-retardant fiber sheet of claim 1～3, wherein, described fiber bonds by synthetic resin cement.
5, flame-retardant fiber sheet as claimed in claim 4, wherein, described synthetic resin cement is the aqueous solution, is scattered in described expanded graphite in the described aqueous solution and it be impregnated in the described fibre sheet material.
6, anti-flammability sheet material as claimed in claim 5 wherein, is dissolved with water-soluble resin in the described aqueous solution.
7, as claim 5 or 6 described flame-retardant fiber sheets, wherein, described synthetic resin cement is a phenolic resin, and has methylated and/or sulfino methylates through sulfo group.
8, a kind of article shaped is characterized in that, this article shaped obtains by each described flame-retardant fiber sheet in the claim 1～7 is shaped to the regulation shape.
9, article shaped as claimed in claim 8, wherein, aeration resistance is 0.1～100kPas/m.
10, a kind of sandwich is characterized in that, on the one or both sides of each described flame-retardant fiber sheet, is laminated with other fibre sheet material across the porous thermoplastic film in claim 1～7.
11, a kind of article shaped is characterized in that, this article shaped obtains by the described sandwich of claim 10 is shaped to the regulation shape.
12, article shaped as claimed in claim 11, wherein, aeration resistance is 0.1～100kPas/m.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003310590 | 2003-09-02 | ||
| JP310590/2003 | 2003-09-02 | ||
| JP408019/2003 | 2003-12-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1849422A true CN1849422A (en) | 2006-10-18 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480025193 Pending CN1849422A (en) | 2003-09-02 | 2004-08-20 | Flame-retardant sheet and formed article therefrom |
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| Country | Link |
|---|---|
| CN (1) | CN1849422A (en) |
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| CN102822412A (en) * | 2010-03-10 | 2012-12-12 | 名古屋油化株式会社 | Flame-retardant fibrous material and process for production thereof |
| CN102912624A (en) * | 2011-08-02 | 2013-02-06 | 上海优先装饰材料有限公司 | Foamed-type textile product flame retardant and preparation method thereof |
| CN105263999A (en) * | 2013-08-27 | 2016-01-20 | 株式会社Sh能源化学 | Adiabatic expandable polystyrene particles and method for manufacturing adiabatic expandable polystyrene particles |
| CN105902045A (en) * | 2016-04-25 | 2016-08-31 | 江苏恒康家居科技股份有限公司 | Polyurethane fiber and polyurethane mixed mattress and preparation method thereof |
| CN106393916A (en) * | 2015-07-28 | 2017-02-15 | 佛吉亚汽车工业公司 | Thread, and associated equipment piece of a vehicle, formation process to make a thread and fabrication method for making a piece of automotive vehicle |
| CN107500711A (en) * | 2014-12-24 | 2017-12-22 | 中国建筑材料科学研究总院 | Engine expansion plugging heat-barrier material |
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| CN109320132A (en) * | 2018-10-19 | 2019-02-12 | 江苏大利节能科技股份有限公司 | A kind of sound-absorbing insulation material |
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| CN102822412A (en) * | 2010-03-10 | 2012-12-12 | 名古屋油化株式会社 | Flame-retardant fibrous material and process for production thereof |
| CN102912624A (en) * | 2011-08-02 | 2013-02-06 | 上海优先装饰材料有限公司 | Foamed-type textile product flame retardant and preparation method thereof |
| TWI617567B (en) * | 2012-06-28 | 2018-03-11 | Daihachi Chemical Industry Co Ltd | Flame retardant, flame retardant aqueous resin composition containing the flame retardant, flame retardant urethane resin composition, and uses thereof |
| US10000625B2 (en) | 2012-06-28 | 2018-06-19 | Daihachi Chemical Industry Co., Ltd. | Flame retarding agent, flame-retardant aqueous resin composition and flame-retardant urethane resin composition containing said flame-retarding agent, and use therefor |
| CN105263999A (en) * | 2013-08-27 | 2016-01-20 | 株式会社Sh能源化学 | Adiabatic expandable polystyrene particles and method for manufacturing adiabatic expandable polystyrene particles |
| CN105263999B (en) * | 2013-08-27 | 2018-02-09 | 株式会社Sh能源化学 | A kind of thermal insulation expanded polystyrene particle and preparation method thereof |
| CN107500711B (en) * | 2014-12-24 | 2019-09-10 | 中国建筑材料科学研究总院 | Engine expansion plugging heat-barrier material |
| CN107500711A (en) * | 2014-12-24 | 2017-12-22 | 中国建筑材料科学研究总院 | Engine expansion plugging heat-barrier material |
| CN106393916A (en) * | 2015-07-28 | 2017-02-15 | 佛吉亚汽车工业公司 | Thread, and associated equipment piece of a vehicle, formation process to make a thread and fabrication method for making a piece of automotive vehicle |
| CN105902045A (en) * | 2016-04-25 | 2016-08-31 | 江苏恒康家居科技股份有限公司 | Polyurethane fiber and polyurethane mixed mattress and preparation method thereof |
| CN109320132A (en) * | 2018-10-19 | 2019-02-12 | 江苏大利节能科技股份有限公司 | A kind of sound-absorbing insulation material |
| CN109320132B (en) * | 2018-10-19 | 2021-10-15 | 江苏大利节能科技股份有限公司 | Sound-absorbing heat-insulating material |
| CN110256107A (en) * | 2019-07-18 | 2019-09-20 | 西华大学 | A kind of polyurethane foam insulation decorative integrated plate and preparation method thereof |
| CN112779670A (en) * | 2020-12-30 | 2021-05-11 | 杭州朝盛塑业有限公司 | Needled heat-insulation non-woven fabric and production process thereof |
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