TWI284595B - Flame retardant sound insulating material - Google Patents

Abstract

The present invention provides a flame retardant sound insulating material with excellent inflammability and sound absorption, which is the sound insulating material of the hood silencer mounted beneath a hood panel for absorption of the noise produced by a car engine. Said flame retardant sound insulating material 1 consists of porous substrate 2 containing phenolic resin, wherein said porous substrate 2 is composed of fiber with fineness of 0.02 dtex to 50 dtex, and the content of said phenolic resin is adjusted to 50 to 200 mass% relative to the mass per unit area (g/m<2>) of porous substrate 2.

Description

[Brief Description of the Invention] [Technical Field] The present invention relates to a flame-retardant sound absorbing material for absorbing noise, which has flame retardancy for absorbing a hood silencer such as an automobile engine sound. "," [Prior Art] %· Previously under the engine cover of the car, in order to absorb the stand: a hood silencer (1P) is installed. The hood silencer (11>, as shown in Fig. 4, A polyester non-woven fabric (12p) such as PET is laminated on a glass wool _ (velvet) (2P) having excellent heat resistance and sound absorbing properties (for example, refer to Patent Document 1). [Patent Document 1] Japanese Patent JP-A-64-36433 SUMMARY OF THE INVENTION [Technical Problem to be Solved by the Invention] As described above, although glass (wool) (2P) can be used in the hood silencer H (lp), the glass wool is used. (velvet) (2p) is easy to handle and has poor workability, and the glass wool (4) (10) tends to have a problem of causing the micro-glass dust to deteriorate the working environment. In addition, the 'previous hood silencer (ιρ), in order to make = cotton (4) (10) is not exposed, it must be laminated on glass wool (wool) (10): cloth (1) P). The hood muffler using glass wool (velvet) cannot be burned due to glass wool (velvet), so disposal is difficult. (Technical solution for solving the problem) 'The present invention provides A flame retardant sound absorbing material is used to solve the above problems. The means of 315778 5 1284595 and the sound absorbing material (1) are composed of a porous substrate (2) containing a phenol resin, and the content of the phenol resin is 50 to 200% by mass of the mass per unit area (g/m2) of the porous substrate, the porous substrate is composed of fibers having a fineness of 2dtex to 5〇dtex. The phenolic resin is a phenol-alkyl group. a benzene diol; a phenol condensate is preferred, and the phenol-alkyl resorcinol cocondensate is formed by adding an alkyl resorcinol to the co-condensation of the initial condensate of the phenolic resin. It is more preferably produced. _ (Action) A fiber having a fineness of 0.02 dtex to 50 dtex is used as the porous substrate (2), and the porous substrate (2) contains a unit area of the porous substrate (2) 50 to 200% by mass of a non-flammable phenol-based resin having a mass (g/m2), which can be adjusted by the fineness of the fiber of the pericardial substrate (2) and the content of the phenolic resin in the porous substrate. The flame retardant and sound absorbing properties of the sound absorbing material (1). [Embodiment] The contents of the present invention will be described below. [Different Resin] The β phenol resin is obtained by condensing a phenol compound and an aldehyde and/or aldehyde donor. In order to impart water solubility, the desired resin may be subjected to acid group sulfonation and/or sulfinate group alkylation. The sizing resin of the present invention is impregnated into the porous substrate (2) by an initial condensate, and the initial condensate is usually prepared into an aqueous solution, but may be used as needed. decyl alcohol, ethanol, n-propanol, isopropanol, n-Butanol, isobutanol, first butanol, dibutyl, n-pentanol, isoamyl alcohol, n-hexanol, methyl hydrazine 315778 6 1284595 ethyl butanol, n-heptanol, n-octanol, trimethyl Alcohols such as decyl alcohol, cyclohexanol, sterol sterol, tetrahydrofurfuryl alcohol, rosinol, diacetone alcohol; acetamidine, alumina acetone methyl ethyl methacrylate, methyl propyl ketone, methyl positive Dibutyl ketone methyl isobutyl ketone, diethyl fluorenone, di-n-propyl methyl ketone, diisobutyl hydrazine, acetonyl acetonide, dimethyl ether, cyclohexanone, methylcyclohexane, = benzene, Camphor and other _ class; ethylene glycol, triethylene glycol, triethylene glycol: propylene glycol monomethylene alcohol, polyethylene glycol and other glycols; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether a glycol ether such as ethylene glycol isopropyl ether, diethylene glycol monomethyl ether or triethylene glycol monoterpene ether; ethylene glycol diacetate, an ester of the above diol or a derivative thereof ; 1,4 diethylene glycol monoethyl ether dioxane and other ethers, ethylene glycol diethyl ether (diethyl cell〇s〇lve), diethyl carbitol, ethyl lactate, isopropyl lactate, diethylene A water-soluble organic solvent such as alcohol diacetate or dimethyl decylamine. [Phase compound] The phenol compound used in the above phenol resin may be a mixture of a monohydric alcohol, a polyhydric alcohol, a monohydric alcohol, and a polyhydric alcohol, but when only a monohydric alcohol is used, it is easily released at the time of hardening and after hardening. Formaldehyde is thus preferred to use a multi-component or a mixture of a monohydric phenol and a polyhydric phenol. [One yuan] For the above-mentioned monohydric phenol, for example, phenol; or o-methyl hydrazine, m-methyl hydrazine, hydrazine, ethyl phenol, isopropyl phenol, dihydric phenol, 3,5-xylenol, butyl Alkylphenols such as phenol, tert-butylphenol, nonylphenol, o-fluorophenol, m-fluorophenol, p-fluorophenol, o-phenol, m-chlorophenol, p-phenol, o-bromophenol, m-bromophenol, Indifference, o-breaking, m-sulfonol, p-iodophenol, o-aminophenol, m-aminophenol, 7 315778 1284595 • on amine base, o-nitrogen age, inter-nitro-presence, on stone-based test, 2, 4 one or two nitro • 、, 2, 4, 6- three stone Xiao Kepan and other one yuan substitute; Cai 等 and other multi-ring one yuan - phenol, and these - hope can be used alone or in combination. - [Multiple] v The above-mentioned diverse hopes, for example, can be cited: inter-phenylene-prone, stupid in the base, two-dimensional m-tea, burning base, money, silk awakening, benzene, and double Hope, Sansi Cai and so on. These diversified hopes can be mixed alone or in combination of two or more. The better of the multi-diversity is the stupidity of the inter-phenylene-neutral group. The reaction speed is better than that of the meta-benzene. Resorcinol. Examples of the alkyl resorcinol include a 5-methylisophthalic acid test, a 5-ethylisophthalic acid test, a 5-propyl meta-phenylene bromide, and a n-butyl meta-phenylene phenol. 5_Dimethyl resorcinol, 2,5-dimethyl resorcinol, 4,5-diethyl resorcinol, 2, 5-diethyl resorcinol, 4 5_2 Propyl resorcinol, 2, 5-dipropyl resorcinol, 4-methyl-5-ethyl stilbene, 2-0 methoxy-5-ethyl resorcinol, 2_曱5-M-propyl resorcinol, 2,4,5-trimethyl resorcinol, 2,4, 5-triethyl resorcinol, and the like. By retorting the polyphenol mixture obtained from the oil shale made in Estonia, it is inexpensive and contains various alkyl resorcinols of the reaction enthalpy in addition to 5-methyl resorcinol. It is a special polyphenol raw material in the present invention. In the present invention, the phenolic compound is condensed with an aldehyde and/or aldehyde donor, and the aldehyde donor system refers to a compound or other mixture which can form a hydrazine when it is decomposed. Such aldehydes include, for example, formic acid, BJ 315778 8 1284595 propionic acid, gas acid, sputum plate, oxalic acid, n-butyric acid, hexanyl, benzophenanthrene, benzene, methyl, Bahe Road, acrylic plate, Examples of the aldehyde donor include phenylacetic acid, o-toluene, and sulphuric acid. Examples of the aldehyde donor include trioxane, trioxane (tnoxane), hexamethylenetetramine, and tetrakis (oxymethylene). Te^a〇x^ ethylene) and so on. As described in the above, in order to improve the stability of the water-soluble phenolic resin, the phenolic resin sulfonylmethylation (sulfomethylati〇n) and/or the linoleic acid methylation (sulfimethylati〇) n;) is preferred. [Sulphonic acid methylating agent] _ As a sulfonic acid methylating agent which can be used for improving the stability of the water-soluble phenol-based resin, for example, by sulfurous acid, acid sulfurous acid or partial acid Sulfuric acid, a water-soluble sulfite obtained by reacting a tertiary amine such as an alkali metal or trimethylamine or benzyltrimethylammonium or the like, or an aldehyde addition obtained by reacting such water-soluble sulfurous acid with a disk. One: said add-on m road, (four), test, sugar, Shiji =, n-butyraldehyde, hexanal, acrolein, benzaldehyde, crotonaldehyde, propylene • “phenylacetic acid, o-toluene disk, water A product obtained by an additional reaction of an acid such as a pan and the above-mentioned water-soluble sulfinic acid, for example, an addition of a methyl sulfite to a sulfite, is a hydroxymethanesulfonate. [Sulphonic acid methylating agent] 仏The sulfinic acid methylation of the stability of the water-soluble phenolic resin is improved, and the fate of the sulfinic acid group such as sodium sulfite (carved white powder, R〇ngaut), and the private sulfur (four) Group of (qua)sulfate alkali metal salts; sodium hydrogen sulfite and magnesium hydrogen sulfite, metal and soil test metals. 315778 9 1284595, hydrogen sulfate (dithionite); hydroxymethanesulfinic acid A hydroxyalkyl group such as a salt: a sulfonate or the like. ^ [Third component] When the phenolic resin is produced, if necessary, it can be mixed with the following materials as a catalyst or a pH adjuster. , sulfuric acid, (n-)phosphoric acid, (positive) • boric acid, oxalic acid, formic acid, acetic acid, butyric acid (propyl formate), benzenesulfonic acid, phenol , inorganic or organic acids such as sulfonic acid, p-toluenesulfonic acid, naphthalene-wan-sulfonic acid, naphthalene-stone monosulfonic acid; esters of organic acids such as dimethyl oxalate; cis-butenedic anhydride, hydrazine Anhydride such as β anhydride; ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium oxalate, ammonium acetate, ammonium phosphate, ammonium thiocyanate, ammonium imide sulfonate, etc.; monochloroacetic acid or its sodium salt 'α, α Organic halides such as di-propanol; hydrochlorides of amines such as triethanolamine hydrochloride and aniline hydrochloride; salicylic acid (o-hydroxybenzoic acid) urea adduct, stearic acid urea adduct, heptanoic acid urea Urea adduct such as adduct; acidic substance such as strontium-tri me thy 1 taurine, zinc hydride, gasified iron; ammonia; amine; sodium hydroxide, hydroxide An alkali metal or alkaline earth metal hydroxide such as potassium, barium hydroxide or calcium hydroxide; an alkaline earth metal oxide such as lime; an acid salt of an alkali metal such as sodium carbonate, sodium sulfite, sodium acetate or sodium phosphate. [Production of Phenolic Resin] The above-mentioned condensate (initial condensate) can be produced by a usual method. a method capable of condensing (a) a monohydric phenol and/or a polyhydric phenol with an aldehyde; (b) an initial condensate of an initial condensate and/or a polyphenol which is condensed with an aldehyde, and an initial condensate , a method of condensing a monohydric phenol and/or a polyphenol, '(c) an initial condensate of a condensed polyhydric phenol with an aldehyde, and a method of condensing a phenol of 10,315,778, 12,845,950 and/or a polyphenol; (d) An initial condensate of a condensation of a phenol with an aldehyde, and a method of condensing an initial condensate of a condensation of a polyphenol with an aldehyde; (e) an initial condensate of a condensation of a phenol with an aldehyde and/or a polyphenol and an aldehyde: The initial condensate is produced by a method of condensing a monohydric phenol with a polyhydric phenol and an aldehyde, etc. In the present invention, an optimum phenol-based resin is a phenol-alkyl resorcinol co-condensation compound. In the above phenol-alkyl resorcinol cocondensate, the cocondensate: (initial cocondensate) has good water solubility, and can be compared with a condensate formed only by age. The advantages of long-term preservation. Further, when the water 4 solution is impregnated into the porous base material (2) and pre-cured to the B state, not only the stability is good, but also the porous base material does not lose its formability even after long-term storage. Further, since the benzophenone has a high reactivity with the road and captures the free enthalpy and reacts, it has an advantage of reducing the free aldehyde in the resin. The phenol-alkyl-m-phenylene phenol co-condensate is preferably produced by first reacting a phenol with an aldehyde to produce an initial condensate of a phenolic resin, and then adding a benzoic acid to the initial condensate of the phenolic resin. It is necessary to add a brewing reaction method. ♦ a For example, in the condensation of the above (a) monohydric phenol and/or polyhydric phenol with aldehydes, the singularity of the above-mentioned (1) molars is expected to add 〇·2 to 3 moles of brewing, for ^莫^元龄/4 , 〇 · 1 to 〇 · 8 moles of the type, and if necessary, can add 刈 and the second component, the liquid temperature is 55 to i 〇〇 °c conditions for the heating reaction 20 i when the aldehyde It may be added all at the beginning of the reaction, or it may be dropped several times or continuously. The phenolic resin initial condensate sulfonate thiolation and/or sulfinic 315778 1284595 oxime methylation, and the sulfonate thiolating agent and/or subphase is added to the initial condensate at any stage. The sulfonic acid thiolating agent further methylates the phenolic compound and/or the initial condensate sulfonic acid group and/or the sulfinic acid group or the thiol group. The addition of the sulfonic acid methylating agent and/or the sulfinic acid sulfhydrating agent may be carried out before, during or after the condensation reaction.

The total addition of the sulfonic acid methylating agent and/or the sulfinic acid sulfhydrating agent is usually from 0. 001 to 1.5 moles for the 1 molar solvent. When the molar ratio is less than or equal to 0.001, the hydrophilicity of the phenol resin is insufficient. When the content is 1.5 or more, the water resistance of the phenol resin is poor. In order to maintain the properties such as the curability of the initial condensate produced and the physical properties of the resin after curing, it is preferably from 0. 01 to 〇 8 mol. a sulfonic acid methylating agent and/or a sulfinic acid methylating agent added to sulfonate sulfonate sulfonate and/or sulfinate methylation of the condensed resin initial condensate The hydroxymethyl group of the initial condensate and/or the aromatic reaction of the initial condensate is introduced into the initial condensate to introduce a rhegidylmethyl group and/or a benzylic acid methyl group. ~ In this way, the initial condensate of the phenolic resin which is methylated by sulfonic acid group and/or sulfinic acid group is water-soluble, and it is stable in a wide range from acidic (ρΗ1·〇) to alkaline. It can harden even in various ranges of acidity, neutrality and alkalinity. In particular, when it is acidic, once it is hardened, the residual methylol group is reduced, and there is no possibility that the hardened material decomposes to generate formaldehyde. Further, in the present invention, as the above phenol-based resin, if necessary, urea, sulfurized urea, melamine, thiomelamine, dicyanamide, guanidine, guanamine, guanamine-based guano may be added. An amine-based resin monomer of 2,6-315778 12 1284595 diamino-1,3 diamine and/or an initial condensate of the amine resin monomer, and The phenolic compound and/or the initial condensate are co-condensed and combined. Further, in the initial condensate of the phenol resin of the present invention (including the initial co-complex), a mixed aldehyde and/or aldehyde donor or a hydroxyalkylated triazone derivative may be further added. And other hardeners. Λ· The aldehyde and/or aldehyde donor may be the same as the aldehyde and/or aldehyde donor used in the production of the phenolic resin condensate (initial cocondensate). The ketone derivative is obtained by reacting a urea compound with an amine and an aldehyde and/or aldehyde donor. The above-mentioned urea-based compound used in the production of a hydroxyalkylated tricoterone derivative, for example, thiourea such as urea, thiourea or methyl urea, alkylthiourea such as methylthiourea, phenylurea or naphthalene A single substance such as urea, phenylated urea, and nitroalkyl urea, or a mixture of two or more thereof. Among them, the most preferred urea compound is urea or thiourea. Further, examples of the related amines include aliphatic amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, and pentylamine, decylamine, decylamine, and ethanolamine: ethylenediamine, hexamethylenediamine, and hexa. In addition to amines such as methylenetetramine, ammonia may be used as a mixture of two or more of them. The aldehyde and/or aldehyde donor used in the production of the burned monoketone ketone is the same as the aldehyde and/or aldehyde donor used in the production of the initial condensate of the phenolic resin. When synthesizing the above-mentioned hydroxyalkylated tricoterone derivative, it is usually carried out at a ratio of amines and/or ammonia Q1 to 12 moles and/or jun to U to 4.0 moles relative to the oxime urea compound. reaction. When the above reaction is carried out, although the best of these compounds continues, the optimum reaction is 315778 13 1284595 = the first step is to put the required amount of aldehyde and / or aldehyde donor, the same and eight sides in the reactor. ^ Maintain a temperature below 6 ° C, and gradually add the required amount of amines. / or ammonia, and then add the required amount of urea compound, and then heated and stirred under conditions of 800 to 9 ° C for 2 to 3 hours to react, as an aldehyde hydrazine and / or aldehyde donor, usually used 37 % formalin, but in order to increase the concentration of ruminants, the - part can also be replaced by trimeric furfural. X, such as; using methylenetetramine, a higher solids reaction product can be obtained. The reaction between the urea compound and the amine and/or ammonia and the aldehyde and/or aldehyde donor is usually carried out in water, but alcohol such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol or diethylene glycol may also be used. A single or a mixture of two or more of them may be substituted for a part or all of the water', and a single or a mixture of two or more kinds of ketones, such as acetone or mercaptoethyl ketone, may be added. The amount of the hardener added is 'in the case of an acid and/or an aldehyde donor, and is 10 to 10% in terms of 100 parts by mass of the initial condensate of the inventive resin (initial cocondensate). In the case of the alkylated trimethyl ketone derivative, the initial condensate (initial co-condensate) of the condensed resin of 1 part of the enamel is ίο to 500 parts by mass. [Porous substrate] The porous substrate (2) of the present invention is composed of a plastic foam having an organic fiber or a continuous cell structure. The porous substrate (2) composed of organic fibers is, for example, polyester fibers such as polyethylene terephthalate (pET) or polybutylene terephthalate (PBT); polyethylene fibers, Synthetic fibers such as polypropylene fiber, polyfluorene, amine fiber, acrylic fiber, urethane fiber, ethylene fiber fiber, partial gas ethylene fiber, acetate fiber, polyethylene fiber; rayon fiber 14 315778 1284595 dimension semi-synthetic An organic fiber such as a natural fiber such as a coconut fiber, a hemp fiber, a kenaf fiber or a bamboo fiber (a regenerated fiber obtained by disintegrating a fiber product made of the fiber); these fibers may be used singly or in combination of two or more kinds. Also, 'plastic foams, such as polyethylene terephthalate (PET), ♦ butyl terephthalate (pBT) and other polyester foams, polyethylene foams, polypropylene foams Polyamide foam, acrylic foam, urethane foam, ethylene foam, vinylidene chloride foam, acetate foam, and the like.

The mass per unit area (g/m2) of the porous substrate (2) used in the present invention is usually 200 g/m2 to 1 g/m2. Further, the above-mentioned fibers used in the porous substrate (2) of the present invention may be subjected to a flame-retardant treatment. The fineness of the fibers of the porous substrate (2) is preferably from 〇2dtex to 50 dtex, and more preferably from d1 tex1 dtex to 30 dtex. If the fineness is less than 0.02 dtex, the rigidity of the sound absorbing material (1) using the fiber of the fineness will be

Insufficient knowledge. However, if the fineness is more than 5 〇 dt ex, the sound absorbing effect of the sound absorbing material (1) will not be fully exerted. The initial condensate of the resin is impregnated into the porous substrate (2) by a spray method, a flow coating method, a roll coating method (r〇l 1 - c〇at, etc.). For example, as shown in Fig. 3, the porous substrate (2) is pulled out from the porous substrate (2) roll (2A), and introduced into the phenol system by the guide rolls (4, 5, 6). The initial condensate (aqueous solution S) of the resin is impregnated in the tank (7). The porous substrate (2) which has been impregnated with the initial condensate (2) is twisted by a wringer (8) to adjust the initial condensation. The amount of impregnation of the material. 315778 15 1284595 The phenolic resin is flame retardant, and the flame retardancy of the sound absorbing material (1) can be adjusted by adjusting the content of the phenolic resin in the porous substrate (2). The content, in terms of solid content, is 5 to 2% by mass, preferably 55 to 170% by weight, based on the mass per unit area (g/m2) of the porous base material (2). The content of the phenolic resin is less than 5% by mass of the mass per unit area of the porous substrate (2), and the resulting sound absorbing material (1) is flame retardant. Sex If the content is more than 200% by mass, the sound absorbing property of the sound absorbing material (1) will be poor. [Method for Producing Flame Retardant Sound Absorbing Material] Impregnation of a predetermined amount of condensed condensate of the phenol resin The porous substrate (2) after the porous soil material (2), g is dried and pre-cured. The drying step is carried out by blowing hot air or the like, and at this time, the surface decompression-surface blowing heat JL 〇, In the case of pre-curing, the initial condensate may be completely cured, but it is preferably in a ruthenium state. The porous base material (2) containing the initial condensate in the bismuth state has good forming properties and can be stored for a long period of time. After hardening, the porous substrate (2) is formed by hot pressing, and a sound absorbing material (1) can be obtained. "" For example, if an upper mold and a lower mold having a desired mold profile shape are used, The formed molding machine is subjected to hot pressurization to obtain a hood muffler (丨) having a predetermined shape as shown in the first drawing. The flame-retardant sound absorbing material (1) of the present invention does not need to be laminated to have a flame retardant treatment. The skin material can be used as the sound absorbing material (1) and the flame retardant of the present invention The sound absorbing material (1) is not limited to a single layer. The 315778 16 1284595 porous substrate (7) is also composed of a multilayer porous substrate (2). Further, the flame retardant sound absorbing layer of the present invention is required as needed. One or both sides of the material (1) may be laminated with a fiber sheet composed of the above synthetic fiber resin as a skin material and an inner surface material. Further, in the flame retardant sound absorbing material (1) of the present invention, Containing urea, thiourea, melamine, thiomelamine, dicyanamide, guanidine, guanamine, acetaminophen, guanamine, guanyl guanamine, 2,6-diamine-oxime, 3 An amine-based monovalent body such as an amine. The amine is a monolithic initial condensate; polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, vinyl acetate polymer, acrylate polymer, Thermoplastic resin such as styrene polymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-present ethylene copolymer, low melting point polyamine, low melting point polyester Latex or aqueous solution or powder; natural rubber and its derivatives; Acid feeding, carbonic acid town, sulfuric acid lock, sulfuric acid mother, sulfite mother, sulphuric acid, hydrogen hydroxide, oxidized town, aluminum hydroxide, magnesium oxide, titanium oxide, iron oxide, zinc oxide, aluminum oxide, aluminum oxide , Shiyuezao soil, dolomite (limestone), gypsum, talc, clay (soil), asbestos, mica, calcium citrate, bentonite (bentonite), white carbon, carbon black, iron powder, aluminum powder, glass powder , stone powder, synthetic resin powder, blast furnace slag (slag), fly ash (flying dust), cement, oxide knot, cotton linters, linen, sisal, wood flour, wheat flour, walnut powder, powder, coconut shell powder, Filling materials for rice flour, activated carbon, bark, bagasse, etc.; surfactant; hard S acid (n-octadecanoic acid), palmitic acid (hexadecanoic acid) and other higher fatty acids; palmitol, stearyl alcohol and other higher alcohols; Fatty acid esters such as butyl acrylate and glycerol monostearate; fatty acid 醯 17 315778 1284595 Amine, natural wax such as carnauba wax; synthetic wax; pigment; dye, difficult Fuel, fire retardant, anti-proof Insecticides, preservatives, anti-aging agents, UV absorbers (uv absorbers), fluorescent dyes, surfactants, foaming agents, oil repellents, plasticizers such as DOP, DBT, etc.; antioxidants, antistatic agents, crystals The third component such as a promoter. Further, these third components may be directly added or applied to the porous substrate (2) or added to the initial condensate of the above-mentioned antimony resin, and impregnated with the initial condensate of the viscous resin. Substrate (2). The flame-retardant sound absorbing material (1) of the present invention can be used for a cylinder head muffler for an automobile or the like, an engine bottom cover muffler, a cushioning material, an instrument panel silencer, an indoor heat insulating material, a ceiling material, a interior material, Building materials, etc. In particular, it is particularly useful as a hood silencer that requires flame retardancy (heat resistance) and sound absorbing properties when used. Hereinafter, the present invention will be described in detail by way of examples. However, the invention is not limited to the embodiments shown below. (Example 1) Impregnation of 6 Å in a sheet composed of polyethylene terephthalate and punctured by needle punching (denier 1 〇 dtex, mass per unit area: 400 g/m 2 , thickness 10 mm) Phenol·formaldehyde initial condensate of the % mass solids (initial condensate of the phenolic resin). The content of the initial condensate was adjusted so that the content of the phenol resin (solid content) was 50% by mass based on the mass per unit area of the sheet. The initial condensate of the impregnated phenolic resin was dried and pre-cured at a temperature of 150 ° C, and then subjected to a pre-hardened thin 315778 18 1284595 piece by 20 (TC x 60 seconds) to obtain a thickness of 5 mm. The molded article (Example 1). (Example 2 and Example 3) The initial condensate and the sheet of the expectant resin of the above Example 1 were used so that the content of the phenol resin (solid content) was the mass per unit area of the sheet. 100% by mass and 200% by mass, the initial condensate was impregnated into the sheet, and pre-cured in the same manner as in the above Example 1, and the sheet was heat-pressed to obtain a thickness of 5 mm each. Molded product (Example 2 and Example 3).

(Comparative Example 1 and Comparative Example 2) The initial condensate and the sheet of the phenol resin of the above Example 1 were used so that the content of the phenol resin (solid content) was 40 mass per unit area of the sheet. /In the case of 250% by mass, the initial condensate was impregnated into the sheet, and then pre-cured in the same manner as in the above Example 1, and the sheet was hot-pressed to obtain a molded article each having a thickness of 5 mm ( Comparative Example 2 and Comparative Example 3). [Combustion Test] The molded article burning tests of the above Examples 1 to 3 and Comparative Example 1 and Comparative Example 2 were carried out in accordance with the level test method of the FMVSS-302 method. The results are shown in Table 1. [Sound Absorption Test] The burning test of the molded articles of the above Examples 1 to 3 and Comparative Examples 1 and 2 was carried out in accordance with the horizontal test method of the FMVSS-302 method. The results are shown in Table 1. 19 315778 1284595

table

From the results of Table 1, it is understood that the content of the phenolic resin is 50 masses per unit area of the sheet in terms of the combustion result. /. 100% by mass, 2% by mass, and 250% by mass of the molded product are flame retardant or incombustible. Further, the molded article having a mass per unit area of 40% by mass of the sheet was delayed in ignitability. Further, as a result of the sound absorbing test, it was confirmed that the molded articles of Examples 丨 to 3 and Comparative Example 1 had predetermined sound absorbing properties, and the content of the phenolic resin was 250% by mass of the mass per unit area of the sheet (Comparative) Example 2), poor sound absorption.

As a result of the above test, the resin content is less than 50% by mass based on the mass per unit area of the sheet, and the molded article loses flame retardancy. If the content is more than 25 〇 mass%, the sound absorbing property of the molded article becomes poor. (Example 4) 55% impregnation in a sheet composed of polypropylene fibers and entangled by needle punching (denier: 〇.〇2dtex, unit area mass 300 g/m2, thickness: 15 mm) Phenol/alkyl resorcinol/furfural initial condensate of mass solids (initial condensate of phenolic resin). The impregnation amount of the initial condensate was adjusted so that the content of the phenol resin was 70% by mass based on the mass per unit area (solid content) of the sheet. 20 315778 1284595 The initial condensate of the impregnated phenol resin was dried and pre-cured at a temperature of 150 ° C, and the pre-hardened sheet was thermally pressed at 200 ° C for 45 seconds to obtain a molded product having a thickness of 7 mm ( Example 4). (Examples 5 and 6) Sheets composed of polypropylene fibers and entangled by needle punching ((fineness: 20 dtex, mass per unit area: 300 g/m 2 , thickness: 15 mm) and (The fineness: 50 dtex, mass per unit area: 300 g/m 2 , thickness: 15 mm)), the initial condensate of the phenol resin of the above Example 4 was impregnated to 70% by mass, and the same as in the above Example 4 The method was pre-hardened; the sheet was heat-pressed to obtain molded articles each having a thickness of 7 mra (Example 5 and Example 6). (Comparative Example 3 and Comparative Example 4) A sheet composed of polypropylene fibers and entangled by needle punching ((fineness: 〇· Oldtex, unit mass: 300 g/m 2 , thickness: 15 mm) And (the fineness: 6 〇 dtex, mass per unit area: 300 g/m 2 , thickness: 15 mm), impregnating the initial condensate of the phenol resin of the above Example 4 to a content of 7 〇 mass%, and further with the above examples (4) Pre-curing was carried out in the same manner, and the sheet was heat-pressed to obtain molded articles each having a thickness of 7 mm (Comparative Example 3 and Comparative Example 4). Example 4, Example 5, Example 6, Comparative Example 3 and the molded article of Comparative Example 4 were subjected to a rigidity test, a burning test, and a sound absorbing test. The results are shown in Table 2. The rigidity test was carried out in accordance with JIS-K6911 and the bending strength of 5.17 of the general test method for thermosetting plastics. The test and sound absorption test are the same as the combustion test and sound absorption test of 315778 21 1284595. Table 2 Shaped material (absorbent material) Rigidity test (N/mm2) Sound absorption rate of combustion test (%) 500Hz 1000 Hz 2000 Hz 4000 Hz Implementation Example 4 1. 5 Non-combustible 40 68 95 90 Example 5 1. 8 Non-combustible 33 60 90 83 Example 6 1· 7 Non-combustible 30 55 85 83 Comparative Example 3 0· 8 Non-combustible 42 70 95 92 Comparative Example 4 1· 5 Non-combustible 18 22 48 45 The results of the rigidity test showed that the molded articles (Example 4, Example 5, Example 6 and Comparative Example 4) were formed from sheets of fineness 〇·02dtex, 2〇dtex, 5〇dets P, and 60dtex. The molded article (Comparative Example 3) formed of the sheet having a fineness of 0·01 dtex was insufficient in rigidity. The results of the burning test showed that each of the molded articles (Example 4, Example-5, and implementation) Example 6, Comparative Example 3, and Comparative Example 4) were incombustible. - Sound Absorption Test Results The sound absorption of the molded articles (Example 4, Example 5, Example 6, and Comparative Example 4) made of a sheet having a fineness of 60 dtex was determined. Sex

The system is not sufficient. As a result of the above test, if the fineness of the fiber of the sheet is less than 0.02 dtex, the rigidity of the molded article becomes poor; if the fiber is more than 5 Odtex, the sound absorbing property of the molded article becomes poor. (Example 7) A sheet formed of polyester fibers ((40% by mass, denier 3dtex) and (60% by mass, fineness · 8dtex)) and entangled by needle punching ( In the mass per unit area of 60 g/m 2 ), the initial condensate of the phenol/alkyl benzophenan • hydrazine is impregnated with 60% by mass of the solid fraction and the diasteride derivative of the alkyl group 22 315778 1284595. The impregnation amount of the initial condensate was adjusted so that the content of the resin (solid content) was 100% by mass based on the mass per unit area of the sheet. As for the hydroxyalkylated tricoterone derivative, the initial condensate containing 60% by mass of the solid content is added in an amount of 50 parts by mass. The sheet which had been impregnated with the initial condensate was dried and pre-cured at a temperature of 120 ° C, and the pre-hardened sheet was thermally pressed at 200 ° C for 45 seconds to obtain a molded article having a thickness of 10 mm (Example 7) ). (Example 8 and Example 9) The initial condensate of the phenol resin of the above-mentioned Example 7 and the polyester fiber were used in the sheet formed of the fiber so that the phenol resin (solid content) contained the respective sheet. The initial condensate was impregnated in a manner of 1% by mass based on the mass per unit area, and pre-cured in the same manner as in the above Example 7, and the sheet was heat-pressed to produce a molded article each having a thickness of 1 〇min ( Example 8 and Example 9). (Comparative Example 5 to Comparative Example 1) The initial condensate of the phenolic resin of Example 7 was impregnated into the same sheet as the above Examples 7, 8 and 9, and the phenolic resin content was changed to the mass per unit area of the sheet. 30% by mass and 250% by mass of (mass area: 4〇g/m2, 10〇〇g/m2, and 8〇〇g/m2), and the respective thicknesses were 1 in the same manner as in the above-described Example 7. Molded product of 〇mm ((Comparative Example 5 (sheet unit area mass: 40 g/m2, resin impregnation amount: 30 mass%/.)), Comparative Example 6 ((Sheet unit area mass: 1〇〇g/m2) Resin impregnation amount··3〇% by mass)), Comparative Example 7 ((Sheet unit area mass: 8〇〇g/m2, resin impregnation amount: 30% by mass)), Comparative Example 8 ((Sheet unit area mass: 40 23 315778 1284595, W, resin impregnation amount: 250% by mass)), Comparative Example 9 ((sheet unit area, mass: 100 g/m 2 , resin impregnation amount: 250% by mass)), Comparative Example 10 ((sheet unit area) Mass: 800 g/m 2 , resin impregnation amount: 250% by mass)). Comparison of the above Examples 7 to 9 and Comparative Example 5 10; was molded stiffness test, combustion test and acoustic test system and test method for each test method described above results are similarly shown in Table 3...

As a result of the rigidity test, it was found that any of the molded articles of Examples 7 to 9 has sufficient rigidity as a sound absorbing material. As for the comparative examples, it was found that Comparative Examples 8 to 1 have sufficient rigidity, but Comparative Examples 5 to 7 do not have sufficient rigidity as a sound absorbing material. As a result of the burning test, it was found that any of the molded articles of Examples 7 to 9 was incombustible. As for the comparative examples, it was found that Comparative Example 8 to Comparative Example ι were incombustible, that is, the molded article having a phenolic resin content of 3 〇 mass% of the mass per unit area of the sheet was delayed in flame retardancy and was not flame retardant. 315778 24 1284595 It was found from the results of the sound absorbing test that the sound absorbing properties of the molded articles of Examples 7 to 9 were better at the sound absorbing properties of the molded articles of Comparative Examples 5 to 7 at any one frequency. Further, Comparative Example 8 to Comparative Example 1 were found, that is, a molded product having a phenolic resin content of 250% by mass based on the mass per unit area of the sheet, and the sound absorbing property was extremely poor. When the content of the phenolic resin is less than 50% by mass based on the unit area mass of the sheet, the molded article loses flame retardancy. If the content is more than 2% by mass, the sound absorbing property of the molded article becomes poor.

(Example 10) Impregnation in a sheet composed of polyester fibers having a denier of 1 Odtex and entangled by needle punching (mass area: 4 〇〇g/m 2 'thickness i 〇 mm) 6〇% by mass of the phenol formaldehyde initial work condensate (initial condensate of the resin) (see Fig. 3). The initial impregnation amount of the condensate was adjusted so that the content of the phenol resin (solid content) was 5% by mass based on the mass per unit area of the sheet. The initial condensate of the impregnated phenolic resin was dried at a degree of 150 C, and the crucible was changed to a crucible shape. Then, an upper mold having a predetermined mold surface and a molding machine were used, and the condition was 2 〇 rc x 60 seconds. The nipple of the predetermined shape as shown in Fig. 1 is obtained by heat-pressing the gusset of the pre-set, and the hood silencer (1) is attached to the automobile. The (4) cover silencer 11 (1) can be picked up by hand, and (4) work. In addition, the cover silencer (1) produces a front dust' so that it can maintain a good working environment. 315778 25 1284595 The hood silencer (1) is excellent in rigidity, sound absorption, and flame retardancy. (Example 11) Polyester fiber 4 of 30% by mass of polyester fiber having a fineness of 10dtex and a fineness of 10dtex;混合% by mass, a fine fiber of 20% by mass of 45 dtex, a fiber of 6 dtex, and a mixed fiber of a melting point U (5% of low-melting polyester fiber of Tc), which is melted in a thermostat of 13 ° C. The polyester fiber having a melting point is pressed into a sheet having a thickness of 15 minutes and a mass per unit area of #500 g/m2 on one side, and then mixed with a fluorine-based water repellent agent of 5% by mass and a phosphorus-based flame retardant of 3% by mass. The mass % solid phenol·alkyl resorcinol initial cocondensate is impregnated into the sheet, and the content of the phenol resin (solid content) is 70% by mass of the mass per unit area of the sheet. The sheet which had been impregnated with the initial co-condensate was dried-pre-hardened, and the pre-hardened sheet was heat-pressed at 200 ° C for 60 seconds to obtain a sound absorbing material (Example 11).

The sound absorbing material (1) is excellent in rigidity, sound absorbing property, and flame retardancy. (Example 12) A rayon fiber (30% by mass) having a fineness (K5dtex polypropylene fiber (4% by mass)), a fineness of 6 dtex, a polyamide fiber (20% by mass) having a fineness of 3 dtex, and a fineness of 45 dtex. a sheet made of kenaf fiber (25% by mass) and entangled by needle punching (mass area: 100 g/m 2 , thickness l 〇 mm), impregnated with 5% by mass of solid content and The initial co-condensation of the streptophenol in the desired phase of the sulfonate and the acid group, and the content of the lanthanide resin (solid content) is the mass per unit area of the sheet. 315778 26 1284595 9% by weight The temperature of 0 C is dried and pre-hardened by the sheet which has been impregnated with the initial cocondensate, and then three sheets of pre-hardened sheets are laminated, and then hot pressed under conditions of 2 〇〇 ° C , X 60 seconds, thereby A sound absorbing material was obtained (Example 12). The sound absorbing material was excellent in rigidity, sound absorbing property, and flame retardancy. (Example 13) / Polypropylene fiber (40% by mass) having a fineness of 0·5 dtex, fineness : 6dtex rayon fiber (3〇% by mass), 3dtex polyamide fiber (5 quality) %), a bamboo fiber (25 mass%) having a fineness of 45 dtex, and a sheet (unit mass l〇〇g/m2, thickness i〇min) which is entangled by needle punching. Impregnating a phenol-alkyl resorcinol initial cocondensate containing 5% by mass of a solid component and having been methylated by a sulfonic acid group, and a hydroxyalkylated triterpene ketone derivative, and phenolic resin (solid content) The content is 80% by mass based on the mass per unit area of the thin sheet. The hydroxyalkylated tricoterone derivative is 60 parts by mass relative to 100 parts by mass of the initial cocondensate containing 50% by mass of the solid content. Adding and mixing in proportion. The sheet which has been impregnated with the initial co-condensate is dried and pre-hardened at a temperature of 120 ° C, and then three pre-hardened sheets are laminated, and then 2 〇〇 ° C x 70 seconds The material is heat-pressed to obtain a sound absorbing material (Example 13). The sound absorbing material is excellent in rigidity, sound absorbing property, and flame retardancy. [Effect of the Invention] The flame retardant sound absorbing material of the present invention, the rigidity thereof, Sound absorption and flame retardancy are excellent. ' [Simple description], 315778 27 1 284595 Fig. 1 is a perspective view showing a squint sound absorbing material for a flame retardant sound absorbing material (engine moss silencer). Fig. 2 is a perspective view showing a flameproof (hood silencer) attached to the underside of the engine cover. Figure 3 shows the initial condensate impregnation step of the phenolic resin. Fig. 4 shows the part of the previous sound absorbing material (the hood silencer). [Main component symbol description]

Flame retardant sound absorbing material (hood silencer) : porous substrate 1 engine cover 315778 28

Claims (1)

1284595 X. Patent application scope: L - a kind of flame retardant sound absorbing material consisting of porous material containing (4) resin, characterized in that the content of the resin of the age is porous: the mass per unit area of the material (g 5ra to 2〇〇% by mass of the /ra", the secondary substrate is composed of fibers of 0-.02 dtex to 50 dtex. 2. The flame-retardant sound-absorbing material of the scope of the patent application, wherein : a phenolic resin-based phenol-housing resorcinol co-condensate. 3. A flame retardant sound absorbing material according to claim 2, wherein the phenol-alkyl resorcinol cocondensate is It is produced by adding an alkyl resorcinol to the initial condensate of a phenolic resin and co-condensing it.