Process to manufacture three dimensionally shaped substrate for sound abatement

[0001] [Technical field to which the invention belongs] The present invention relates to a method for producing a three-dimensional composite material having structural and acoustic (or acoustic) properties. The method of the present invention is to supply a polyurethane resin, coat the polyurethane resin on the first surface (or first side surface) of the substrate, and then shape (or shape) the substrate into a desired three-dimensional shape. ) Consists of that. Further, the method of the present invention includes, for example, a three-dimensional dashboard, a fire wall (or fire wall) insulation (insulation, insulation material, sound insulation material or sound insulation material: insulation or insulator) on the indoor and engine side. Automotive acoustic sounds (acoustic or acoustic) such as engine side hood (bonnet or roof) insulation, interior wheel room insulation, and trunk compartment trim (or compartment trim) insulation. Sufficient for: acoustically sound) Regarding the manufacture of parts (or parts). [0002] [Conventional technology] The interior of a car is usually insulated (sound-insulated or soundproofed) from sounds (or noise) transmitted through the frame of the car, such as tire sounds, road surface sounds, wind sounds, engine sounds, and sounds from other parts of the car. ) Has been done. Numerous substrates are known in the art to reduce the noise that enters the interior of the vehicle from the outside of the vehicle. For example, it is known in the art to supply a fibrous material between the sound outside the vehicle and the interior. The material reduces sound propagation and vibration. A wide variety of damping materials, such as non-woven and foamed polyurethane materials, such as shoddy pads (or shoddy pads), are known in the art. It is also conventionally known to attach a soundproofing barrier to the damping material via an adhesive. Such mounting is usually performed on the carpet of an automobile (see, for example, Patent Documents 1 to 4). However, such acoustic damping materials are heavy. [0003] Further, it is known in the art to manufacture a needled composite acoustic barrier in which the need for an adhesive is limited (see Patent Document 5). In addition, a structure formed from a porous core coated on both sides with a skin made of a pile of synthetic or inorganic fiber fabrics soaked in thermoplastics that can withstand heavy loads and dampen acoustics. It is known in the art to supply panels with target and acoustic properties or similar elements (see Patent Document 6). [0004] Two methods are known in the art for manufacturing dashboard insulation for automotive firewalls to absorb and / or block the sound (or noise) generated by the engine. Generally, these dashboard barriers are made from cast polyurethane foam, skived polyurethane foam, polyester or natural fibers. Includes EVA or PVC filled with barium sulphate or vacuum-formed heavy layers of injection-molded TPO skins and decouplers, such as mat) and shody pads. For fiber mats, a phenolic binder is applied. [0005] A known dashboard insulation manufacturing process involves heating a sheet of vinyl resin, then transferring the vinyl resin to a molding tool, and subsequently vacuum forming the vinyl resin. If the barrier is cast foam, the liquid foam is applied to the vinyl resin made of the tool by the operation of the open or closed tool, and then the applied foam. Remove from mold and trim (finish or shape: trim). If the barrier is a fiber or shody mat (or shoddy mat), the vinyl resin formed is transferred to another molding tool, the fiber or shody mat is added, molded and cured. [0006] The barrier formed from this process is the sound that penetrates through the steel of the firewall from the heavy layer (second wall) by using a flexible, flexible and absorbent material such as the foam or mat mentioned above. It has a double wall effect by separating vibration. The barrier containing the resin-impregnated phenolic shody pad acts primarily as an absorber that absorbs the sound that enters through the firewall or is reflected from the interior of the vehicle. [0007] [Patent Document 1] U.S. Patent Specification No. 4,056,161 [Patent Document 2] U.S. Patent Specification No. 4,966,799 [Patent Document 3] U.S. Patent Specification No. 5,266,143 [Patent Document 4] U.S. Patent Specification No. 5,068,001 [Patent Document 5] U.S. Patent Specification No. 6,109,389 [Patent Document 6] U.S. Patent Specification No. 5,888,610 [0008] [Problems to be Solved by the Invention] However, there is a conventional method (or process) for producing a three-dimensionally molded (or shaped) composite containing a substrate whose one side is coated (coated or coated) with a polyurethane resin. Needs remain. In particular, the conventional need to supply lightweight, acoustically and structurally sufficient three-dimensional insulation (soundproofing or soundproofing) parts (or parts) for automobiles remains. [0009] [Means for solving problems] By applying polyurethane resin to the first surface (or first side surface) of the substrate and then molding the resin-coated substrate, a three-dimensional acoustical sound (acoustic or acoustically sufficient) : acoustically sound) It was found that automobile parts can be manufactured. [0010] Automotive parts (or parts) manufactured under the present invention are lighter than conventional foams and heavy layered composites and are more than cast foam or slabstock foam of the same thickness. Provides good sound absorption (or sound absorption). [0011] The present invention also directs a method (or process) of manufacturing a three-dimensional acoustical sound dash mat. [0012] The dash mat manufactured according to the present invention is self-supporting for easy installation. [0013] BEST MODE FOR CARRYING OUT THE INVENTION The present invention directs a method of manufacturing a three-dimensional composite material for reducing (or attenuating) sound. In particular, the present invention is a step of mixing a two-component polyurethane resin containing a polyol blend (or a compound) and an isocyanate, and then applying (coating) the resin to the first surface (or first side surface) of the base material. Or coat), then transfer the resin-coated substrate to a hot molding tool, mold (or shape) the resin-coated substrate into a composite, and finally the composite. It aims at a method of manufacturing a three-dimensional composite material that absorbs sound, including the step of removing the composite material from the tool and trimming (or finishing) the composite material after curing. Further, based on the present invention, the three-dimensional composite material may be coated with a resin on both sides (or both sides) of the base material in some cases. [0014] The polyurethane resin used in the present invention can be processed in a wide range of polyol / isocyanate ratios. Preferably, the polyurethane resin used according to the present invention has an NCO index in the range of 90-130, more preferably 100-120. The polyurethane blend preferably comprises from about 30 to about 60% by weight of polyol blend and from about 25 to about 55% by weight of isocyanate. [0015] The polyurethane resin used in the present invention includes a polyol blend. In general, the polyol blends of the present invention contain at least one polyol or isocyanate-reactive component. The first polyol is generally present in the range of about 30 to about 80% by weight, preferably 45 to about 65% by weight of the total blend. The second polyol is generally present in the range of about 10 to about 64% by weight, preferably in the range of about 27 to about 47% by weight. Optionally, the polyol blend further comprises from about 0 to about 20% by weight of fatty acids, preferably from about 3 to about 10% by weight of fatty acids. The polyol blend may comprise from about 0 to about 5% by weight, preferably from about 0.2 to about 1% by weight of the catalyst. [0016] The polyol blend may further comprise a filler present in an amount of about 0 to about 20% by weight, preferably about 1 to about 5% by weight. If necessary, the black pigment can be added to the polyol blend in an amount ranging from 0 to 5% by weight, preferably about 0.5 to 2% by weight. Carbon black is widely used as a pigment in this industrial field, but organic dyes (or pigments) can also be used. In some cases, in order to improve the wettability of urethane to various mats, a wetting agent in an amount of 0 to 5% by weight, preferably 0.1 to 2% by weight based on the total amount of the polyol blend can also be used. Further, based on the total amount of the polyol blend, it is preferable that the polyol blend contains about 1 to about 20% by weight of fatty acid, about 1 to about 2% by weight of a catalyst, and about 1 to about 10% by weight of a filler. [0017] Generally, the isocyanate-reactive compound includes, for example, a hydroxyl group-containing compound. These materials can typically be divided into two groups, high molecular weight compounds with a molecular weight of 500 to 10,000 and low molecular weight compounds with a molecular weight of 62 to 499. Preferred polyols of the present invention include commonly used initiators such as 4,4'-dihydroxydiphenylpropane, sucrose, aniline, ammonia, toluenediamine, monoethanolamine, propylene glycol, ethylene glycol, trimethylolpropane, ethylenediamine and the like. It is a low molecular weight polyether derived using. [0018] Polyethers modified with vinyl polymers, such as the types of polyethers formed by polymerizing styrene or acrylonitrile in the presence of the polyether (eg, US Pat. Nos. 3,383,351; 3,304,273; 3,523,093; and Nos. 3,110,695: US Patents Nos. 3,383,351; 3,304,273; 3,523,093; and 3,110,695; German Patent No. 1,152,536: German Patent 1,152,536) is also appropriate, as is OH group-containing polybutadiene. In addition, suitable hydroxyl group-containing polyols include ethylene glycol, 1,2-propylene diol, 1,3-propylene diol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1, Includes 6-hexanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, glycerol and trimethylolpropane. [0019] Polyols useful in the present invention include those used in the art of producing polyester polyols, such as adipic acid, phthalic acid or other aliphatic dicarboxylic acids or aromatic dicarboxylic acids or their acid anhydrides, such as propylene glycol. , Dipropylene glycol, tripropylene glycol, or tetrapropylene glycol or ethylene glycol and their oligomers, butanediol, hexanediol or other aliphatic diols, bisphenol A or other aromatic diols. Includes polyester polyol. In addition, polycaprolactam or polylactide may also be present in the polyol blends of the present invention. Naturally occurring polyester polyols such as castor oil or modified soybean oil, rapeseed oil, or linseed oil, or ricinoleic acid or condensates of polyricinoleic acid and butanediol or polyricinoleic acid can also be used in the polyol blends used in this invention. May be used to form. [0020] The polyol blend of the present invention may also contain fatty acids. Suitable fatty acids include, for example, fatty acids as shown by (Chemical Formula 1). [Chemical 1] R (CO₂H)_n :( conversion 1) [In (Chemical formula 1), n is 1, 2 or 3. R contains at least 10 carbon atoms. R is an alkyl group (cyclic or chain may have branches), an alkylaryl group, an arylalkyl group or an aryl group, which may be saturated or unsaturated. ] [0021] [0021] Examples of useful acids include, for example, n-decanoic acid, neodecanoic acid, lauric acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid and the like. Oleic acid is a preferred fatty acid. [0022] Other additives that may be used in the present invention include, for example, various organic metal compounds such as tin (II) salt of carboxylic acid, dialkyl tin salt of carboxylic acid, dialkyl tin mercaptide, dialkyl tin dithioester, and the like. For example, dimethylcyclohexylamine (ie, Polycat 8: Polycat 8), pentamethyldiethylenetriamine (ie, Polycat 5: Polycat 5), potassium acetate (ie, Polycat 45: Polycat 45), bis [2- (dimethylamino). ) Ethyl] Ether (Niax A-1: Niax Includes catalysts for tertiary amines such as A-1), dimethylethanolamine (DMEA), and Dabco WT. Of course, any catalyst known to those skilled in the art of polyurethane chemistry can be used. [0023] Suitable fillers and reinforcing agents that may be included in the polyol blends as described above include, for example, fibrous, flake, cut fiber, or microsphere shaped glass; mica ( Or mica), wollastonite; carbon fiber; carbon black; carbon black paste; talc; and both organic and inorganic compounds such as calcium carbonate. For example, recrushed polyurethane with a particle size of 100 μm or less from the manufacturing trim of seat cushions and SRIM (or structural reaction injection molding) or RIM (or reaction injection molding) parts is used as the filler. You can do it. [0024] The starting polyisocyanate component used in the present invention is an aliphatic, alicyclic, aromatic aliphatic, aromatic and heterocyclic polyisocyanate, for example, Justus Levichs anaren der Chemie by W. Ziefken, No. 562. Volume, pp. 72-136 (W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 72 to 136). Examples of these compounds 1 include ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate; 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate; cyclohexane-1,3-and. Includes 1,4-diisocyanate and mixtures of these isomers. [0025] Further examples include 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane (German Patent Specification 1,202,785: German Auslegeschrift No. 1,202,785, US Patent Specification 3,401,190: US). Patent No. 3,401,190), 2,4- and 2,6-hexahydrotolylene diisocyanate and mixtures of these isomers. Hexahydro-1,3- and / or -1,4-phenylenediocyanate; perhydro-2,4'-and / or -4,4'-diphenylmethane diisocyanate; 1,3- and 1,4-phenylrangedisocyanate Mixtures of 1,4- and 2,5-tolylene diisocyanates and their isomers are also suitable in the present invention. [0026] Diphenylmethane-2,4- and / or -4,4'-diisocyanate; naphthylene-1,5-diisocyanate; triphenylmethane-4,4', 4 "-triisocyanate; phosgenate after condensing aniline with formaldehyde The type of polyphenylpolymethylene polyisocyanate thus obtained, for example, those described in British Patent Nos. 874,430 and 848,671 (British Patent Nos. 874,430 and 848,671) can also be used in the present invention. [0027] U.S. Patent Specification No. 3,454,606 (US) M- and p-isocyanato-phenylsulfonyl isocyanate based on Patent No. 3,454,606); for example, described in German Auslegeschrift No. 1,157,601, US Patent No. 3,277,138: US Patent No. 3,277,138). Type of perchlorinated aryl polyisocyanate; containing carbodiimide groups of the type described in German Patent No. 1,902,007 (German Patent No. 1,902,007, US Patent No. 3,152,162: US Patent No. 3,152,162) Polyisocyanate; the type of diisocyanate described in US Patent No. 3,492,330; and, for example, British Patent No. 993,890, Belgian Patent No. 761,626 ( Belgian Patent No. The types of allophanate (or allophanate) group-containing polyisocyanates described in 761,626) and published Dutch Patent Application No. 7,102,524 (published Dutch Patent Application No. 7,102,524) are also examples of even more suitable isocyanates. Is. [0028] Further, for example, the type of isocyanerate group-containing polyisocyanate described in US Patent No. 3,001,973 (US Patent No. 3,001,973), German Patent Specification Nos. 1,929,034 and 2,004,408 (German Offenlegungsschriften Nos. 1,929,034 and 2,004,408). For example, Belgian Patent No. 752,261 or US Patent No. 3,394,164 (US Patent No.). Urethane group-containing polyisocyanates of the type described in 3,394,164); acylated urea group-containing polyisocyanates under German Patent No. 1,230,778, and, for example, German Patent Specification 1,102,394. (German Patent No. 1,101,394, US Patent No. 3,124,605 and 3,201,372: US Patent Nos. 3,124,605 and 3,201,372) and British Patent No. 889,050 (British Patent No. 889,050) containing biuret groups of the type described. Polyisocyanates are also suitable. [0029] It is preferred to use a liquid aromatic polyisosinate at the production (or treatment) temperature. Preferred starting polyisocyanates are derivatives of 4,4'-diisocyanato-diphenyl-methane that are liquid at room temperature, such as German Patent No. 1,618,380 (German Patent No. 1,618,380, US Patent Specification 3,644,457: US). Patent No. Includes urethane group-containing liquid polyisocyanates of the type that can be obtained based on 3,644,457). These may be produced, for example, by reacting 1 mol of 4,4'-diisosianato-diphenylmethane with 0.05 to 0.3 mol of low molecular weight diol or triol, preferably polypropylene glycol having a molecular weight of 700 or less. [0030] Preferably, the aromatic polyisocyanate used in the present invention has a content of 2,4-diphenylmethane diisocyanate in the range of about 1 to about 16% by weight, more preferably in the range of about 2 to about 12% by weight. [0031] In some cases, based on the present invention, a prepolymer can be used as a component of the polyurethane resin. Based on the present invention, in order to produce a prepolymer, the polyol component can be reacted with the polyisocyanate in the absence of a catalyst. To produce a polyurethane resin, the remainder of the polyol can be added and reacted together in the presence of a catalyst and other suitable additives. Other additives may be added to the prepolymer, the rest of the polyol, or both before mixing the components to give the polyurethane resin at the end of the reaction. [0032] Suitable substrates used in the present invention consist of flax, flax-sisal (or flax-sisal), hemp, jute, polyurethane foam granules or mixtures thereof. Includes fiber mats, natural and synthetic mats containing hemp and polypropylene or polyether fibers, polyether fibers, shody pads, and synthetic mats made from soft or hard moldable polyurethane foam. Preferably, the substrate is 400-1200 g / m.²Has the weight of. The fiber mat may consist of about 0.01 to about 50% by weight polypropylene or polyester. When the fiber mat is a flexible polyurethane foam, about 12 to about 75 kg / m³If the fiber mat is a rigid moldable foam, it may have a density of about 10 to about 40 kg / m.³May have a density of. [0033] The above-mentioned two-component polyurethane resin is applied to a substrate by any conventionally known method, preferably by spraying, brushing, rake, or using a roller coater. Can be coated (or coated) on. More preferably, a two-component polyurethane resin is sprayed onto a high pressure spray using a low pressure device (pressure &lt;150 psi) with a static mixer on the spray head or using impingement mixing. Spray (or spray) onto the first side (or first side) of the substrate using a head (pressure&gt; 500 psi). [0034] Generally, polyurethane resin is 150 to about 1500 g / m.²Can be applied to the substrate in the amount of. The composition based on the present invention can be molded (or shaped) using conventional manufacturing (or processing) techniques. Generally, the substrate is molded with a mold (or mold) or tool (or tool) at a temperature between 90 and 130 ° C. for about 60 to about 120 seconds at conventional pressure. In some cases, to improve strength, a paper honeycomb sheet (paper honeycomb sheet) is placed under (or in resin) a resin-coated substrate before molding the composite. It may be placed on the second side (or second side) of the coated substrate. [0035] Acoustical sound automotive parts manufactured under the present invention include three-dimensional dashmat, interior and engine side fire wall insulation (insulation or sound insulation), engine side hood insulation, etc. Includes interior wheel compartment insulation and trunk compartment trim (or trunk compartment trim) insulation.<u style="single">The main aspects of the present invention are illustrated below.</u><u style="single">1.</u><u style="single">A step of mixing a two-component polyurethane resin containing a polyol blend and an isocyanate or a prepolymer, a step of coating a polyurethane resin on the first surface of a substrate, a step of transferring a resin-coated substrate to a hot molding tool, A method for producing an acoustic three-dimensional composite material, which comprises a step of molding a resin-coated base material into a composite material, a step of taking out the composite material from a molding tool, and a step of trimming the composite material.</u><u style="single">2.</u><u style="single">A dash insulator manufactured by the method described in 1 above.</u><u style="single">3.</u><u style="single">A food insulator manufactured by the method according to claim 1.</u><u style="single">4.</u><u style="single">A three-dimensional composite material containing a base material and a polyurethane resin, in which the polyurethane resin is coated on the first surface of the base material, and the base material coated with the resin is molded.</u>[0036] The present invention will be further described by the following examples, but it does not limit the present invention in any way. In the examples, all parts and% are by weight unless otherwise indicated. [0037] [Example] General procedure The isocyanates and polyols below are examples of polyurethane resin components useful in the present invention: Commercially available aromatic polymeric (or polymer) diphenylmethane diisocyanates containing 2,4-MDI isomers with a content in the range of 1: 1 to 7% by weight of isocyanates; Isocyanate 2: Reaction mixture (or prepolymer) of about 80 to about 100% by weight of isocyanate 1 and about 0.01 to about 20% by weight of a commercially available oleic acid / adipic acid / pentaerythritol mixture; Isocyanate 3: Commercially available aromatic polypeptide 2,4-diphenylmethane diisocyanate; Polyol A: Sucrose / Polyglycol / Water, a polyether with a molecular weight of about 440 produced from the initiator; Polyol B: A polyether with a molecular weight of approximately 240, made from a monoethanolamine initiator. [0038] [table 1]<img file="JP4375985B2_D0001.tif" />[0039] Example 1 About 1000g / m²A piece of flux-sisal mat (50% flux, 50% sisal) with a weight per square meter was placed on a horizontal support. The size of the mat was based on the dimensions of the molding tool (or secondary molding tool: forming tool). The mat should cover all parts of the tool (or tool) during the molding process. The polyol blends listed in Table 1 are combined with isocyanate 2 (polyol / isocyanate has a mixing ratio of 100: 139.4) on the top surface of the mat using a low pressure mixing head with an internal static mixer. Painted. Equipment useful for this type of coating is commercially available, for example, from Langemann. The typical pressure was 300 psi and the throughput was adjusted to about 20 g / s. The total amount of polyurethane resin sprayed (or sprayed) on the mat is about 500 g / m.²Met. [0040] The substrate was then transferred into an aluminum molding tool heated to 90 ° C. The substrate was placed on the male part of the mold in such a way that the male part of the mold (or mold) was coated with resin so that the surface was facing. As a result, the polyurethane layer of the finished part was directed toward the sound source. Molding because the mold used to manufacture the parts mentioned above was designed to mold a conventional dash insulator consisting of a heavy layer of vinyl resin and a molded (or molded) polyurethane soft foam. The support layer of the shody pad (thickness when uncompressed is about 5 cm, density is about 70 kg / m) to provide the required pressure during operation.³) Was placed on the substrate. The mold was closed and the resin was cured in 120 minutes. The part was then removed from the mold and trimmed (shaped or finished), with the support layer's shody pad removed. [0041] Impedance tube test An impedance tube test was performed on the base material produced in Example 1 and the conventional insulating material. ASTM E1050 (Standard Test Method for Impedance and Absorption of Acoustical Materials Using a Tube, Two Microphones, Two Microphones, Standard Test Method for Impedance and Absorption of Acoustical Materials Using a Tube, Two Microphones, and a Digital Frequency Analysis System) is the method used to collect the data in Figures 2-4. [0042] The arrangement of the two microphones and the impedance tube test device is schematically shown in Fig. 1. Bruel and Kujael (or including impedance tubes, two 1/4 condenser microphones, power amplifiers, fast Fourier transform multi-channel analyzers (or analyzers), and computers with Bruel &amp; Kjaer software. Bruel &amp; Kjaer) system was used. Two different sized tubes were used to measure in different frequency ranges. Larger tubes (100 mm diameter) were used at frequencies from 100 Hz to 1600 Hz. Small tubes. (29 mm diameter) was used at frequencies of 500 Hz to 6400 Hz. [0043] The speaker placed at one end of the tube generates a wide band constant acoustic plane wave in the tube. Test sample with hard piston lining (piston) Place it on the opposite end with backing). Broadband waves are separated into incident and reflective components by using a transfer function relation between sound pressures at two locations on the wall of the tube. The analyzer calculates the magnitude of the reflection coefficient R from the amplification ratio of the reflection pressure to the incident pressure at each of the frequencies of interest. The frequency-dependent SA coefficient (or sound absorption coefficient) is given by the following equation [Equation 1]: [Number 1] α (f) = 1-R (f)²[0044] The ASTM method recommends testing at least two 29 mm samples and at least two 100 mm samples cut from the same block of material. Averaging these results will give a more accurate assessment of the performance of the material, as the inherent changes in the part can be taken into account. [0045] As described in comparison with FIGS. 2, 3 and 4, polyurethane resin components (or components) manufactured according to the present invention have low densities and other sound insulators known in the art. , Soundproofing material or soundproofing material) has higher sound absorption. [0046] Although described in detail to illustrate the invention, such detailed description is solely for that purpose and, except that it may be limited by the claims, will be appreciated by those skilled in the art. It should be understood that changes can be made without departing from the spirit and scope of the invention. [Simple explanation of drawings] FIG. 1 shows an outline of an impedance tube test apparatus. [Figure 2] Figure 2 shows the sound absorption coefficient of a 7.62 mm thick slab stock foam from a commercially available dash insulator in the frequency range of 100 to 6400 Hz. FIG. 3 shows the sound absorption coefficient of a Ford Taurus Ultralite Dash Insulator in the frequency range of 100 to 6400 Hz. FIG. 4 shows the sound absorption coefficient of a polyurethane coated (or coated) flux sisal fiber mat according to the present invention for conventional polyurethane foam in the frequency range of 100 to 6400 Hz. Shown by comparison.