WO2014075610A1 - 隔音材料组合物、车用隔音eva片材和汽车前围隔热垫 - Google Patents

隔音材料组合物、车用隔音eva片材和汽车前围隔热垫 Download PDF

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WO2014075610A1
WO2014075610A1 PCT/CN2013/087066 CN2013087066W WO2014075610A1 WO 2014075610 A1 WO2014075610 A1 WO 2014075610A1 CN 2013087066 W CN2013087066 W CN 2013087066W WO 2014075610 A1 WO2014075610 A1 WO 2014075610A1
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Prior art keywords
vacuum
material composition
insulating material
sound
eva
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PCT/CN2013/087066
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English (en)
French (fr)
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张晓宇
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深圳市比亚迪汽车研发有限公司
比亚迪股份有限公司
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Publication of WO2014075610A1 publication Critical patent/WO2014075610A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/08—Insulating elements, e.g. for sound insulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C08K7/20—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/28—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2268—Ferrous oxide (FeO)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/30—Applications used for thermoforming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Definitions

  • the invention belongs to the field of automobile parts, and particularly relates to a sound insulation material composition, a vehicle soundproof EVA sheet and an automobile front wall insulation mat. Background technique
  • the material for front and rear insulation pad of medium and high-grade vehicles at home and abroad is mainly EVA (ethylene-vinyl acetate copolymer) + PU (polyurethane) foam material, its function is to block the absorption of noise and heat from the engine, thus maintaining the car.
  • the EVA layer is a sound-insulating layer, and a plurality of thermoplastic resins such as EVA and a filler are mixed to form an EVA composite sound-insulating layer, which reflects noise transmitted by the engine; and the PU foam layer is a sound-absorbing layer, that is, absorbs noise from the engine.
  • the invention solves the technical problem that the sound insulation effect of the EVA sound insulation layer used in the front wall insulation pad of the automobile is poor and the material weight is large.
  • the present invention provides a sound insulating material composition
  • a sound insulating material composition comprising 10-40 parts by weight of a thermoplastic resin and 60-90 parts by weight of a filler and an auxiliary agent;
  • the thermoplastic resin contains an EVA resin,
  • the content of the EVA resin is 5-40% by weight based on the total mass of the sound insulating material composition;
  • the filler contains vacuum microbeads, and the content of the vacuum microbeads is 5-80 wt% based on the total mass of the sound insulating material composition.
  • the vacuum beads are vacuum ceramic beads and/or vacuum glass beads.
  • the present invention also provides a sound-insulating EVA sheet for a vehicle, which is obtained by the mixing, pressing and vacuum hot pressing of the sound insulating material composition provided by the present invention.
  • the present invention further provides a vehicle front wall insulation mat comprising the above-described vehicle soundproof EVA sheet and foamed PU foam on the surface of the vehicle soundproof EVA sheet.
  • the filler used is mainly vacuum microbeads.
  • the small specific gravity of the vacuum microspheres will greatly reduce the total weight of the material.
  • the sound transfer point is not present in the vacuum microbeads, the sound insulation effect is greatly improved.
  • the sound-insulating EVA sheet for a vehicle provided by the present invention is obtained by mixing, pressing and vacuum-pressing a sound-insulating material composition, and the EVA resin is cross-linked during hot pressing to enable EVA resin and filler, and thermoplastic resin. The combination is more tight, further improving the sound insulation effect, and the heat-resistant and mechanical properties of the EVA sheet which has been cross-linked by hot pressing are further improved. Therefore, the front compartment of the car using the EVA sheet The thermal pad has good sound insulation performance under the premise of being lightweight.
  • Fig. 1 shows the sound insulation performance test results of the vehicle front wall insulation pads B1-B5 and the vehicle standard front wall insulation pads in the embodiments 1-5. detailed description
  • the present invention provides a sound insulating material composition
  • a sound insulating material composition comprising 10-40 parts by weight of a thermoplastic resin and 60-90 parts by weight of a filler and an auxiliary agent;
  • the thermoplastic resin contains an EVA resin
  • the total mass of the sound insulating material composition is based on the reference, wherein the content of the EVA resin is 5-40% by weight;
  • the filler contains vacuum microbeads, and the content of the vacuum microbeads is 5 - based on the total mass of the sound insulating material composition.
  • the vacuum microbeads are vacuum ceramic microbeads and/or vacuum glass microbeads.
  • the filler used is mainly vacuum microbeads, and the specific gravity thereof is small, so that the amount thereof in the composition can be greatly increased, and the total weight of the material is not increased, thereby greatly Improve the sound insulation of soundproofing materials.
  • the sound transfer point is not present in the vacuum microbead, the sound insulation effect is greatly improved.
  • the main component of the thermoplastic resin is EVA, and optionally other thermoplastic resins, for example, one selected from the group consisting of EVA wax, LDPE (low density polyethylene), and EPDM (ethylene propylene diene monomer).
  • EVA wax can increase the fluidity in the subsequent molding process and increase the compatibility between the resin and the filler.
  • the inventors of the present invention have found that if the EVA content in the thermoplastic resin is too small, it is difficult to ensure good compatibility between the resin system and the filler system, and the sheet obtained after molding is too hard and lacks elasticity.
  • the EVA content should not be too high, otherwise the content of the filler will be relatively reduced, and the sound insulation performance will be relatively reduced.
  • the sheet after molding is too soft and difficult to maintain. Therefore, in the present invention, the content of the EVA resin is from 5 to 40% by weight based on the total mass of the sound insulating material composition.
  • the VA content in the EVA resin is 5 to 40% by weight.
  • the extruded sheet is too soft, and when the content is too low, the sheet lacks elasticity.
  • the density of the material can be increased, thereby increasing the sound insulating property.
  • the main component of the filler is vacuum microbeads, which have excellent sound insulation effects.
  • the content of the vacuum microbeads is from 5 to 80% by weight based on the total mass of the sound insulating material composition. The inventors have found that the content of the vacuum microbeads cannot be higher than 80% by weight, otherwise the sheet is difficult to be extruded.
  • the vacuum microbeads may be vacuum ceramic microbeads and/or vacuum glass microbeads.
  • the vacuum microbeads have a particle size of from 1 to 120 microns.
  • the inventors have found that the particle size of the vacuum microspheres is too large, and the compatibility with the resin is poor, and the amount of vacuum microbeads is also limited.
  • the particle size is too small, the vacuum volume is small, and the sound insulation effect is small. It will be relatively weak.
  • the density of the vacuum glass beads is slightly smaller than that of the vacuum ceramic beads, and the diameter of the vacuum glass beads is slightly larger than that of the vacuum ceramic beads.
  • the vacuum ceramic microspheres comprise aluminum oxide, such as basic aluminum oxide.
  • the vacuum glass microspheres comprise soda lime borosilicate glass.
  • the filler may contain other inorganic fillers having a hydroxyl group on the surface in addition to the vacuum microbeads.
  • the surface thereof has a hydroxyl group, it can react with a carboxyl group or a hydroxyl group on the EVA molecule, thereby providing good compatibility between the thermoplastic resin and the filler, so that it is not necessary to add a coupling agent in the improved sound insulating material composition of the present invention.
  • the inorganic filler having a hydroxyl group on the surface may be selected from one or more of calcium carbonate, aluminum oxide, reduced iron powder, and barium sulfate, but is not limited thereto.
  • the sound insulating material composition provided by the invention contains a thermoplastic resin, which can be cross-linked and cured in the later stage, which increases the compactness of the material and improves the heat resistance and mechanical properties of the material. Therefore, the auxiliary agent contains a crosslinking agent.
  • the crosslinking agent may be various materials which are commonly used in the prior art to crosslink the thermoplastic resin. For example, a peroxide crosslinking agent commonly used in the prior art may be used, and specifically, it may be selected from octyl peroxide.
  • the content of the crosslinking agent need not be too high, so that it can be sufficiently cured and crosslinked by the thermoplastic resin.
  • the content of the crosslinking agent is from 0.5 to 5% by weight based on the mass of the thermoplastic resin.
  • the auxiliary agent may further contain one or more of a lubricant, an antioxidant, and a plasticizer as needed.
  • a lubricant an antioxidant
  • a plasticizer an organic compound that is added to the lubricant.
  • the type of the lubricant, the antioxidant, the plasticizer, and the amount of the plasticizer are within the ordinary range of the art, and the present invention is not particularly limited and will not be described herein.
  • the present invention also provides a sound-insulating EVA sheet for a vehicle, which is obtained by the mixing, pressing and vacuum hot pressing of the sound insulating material composition provided by the present invention.
  • the vehicular soundproof EVA sheet provided by the present invention is obtained by mixing, pressing and vacuum hot pressing of a sound insulating material composition.
  • the EVA resin and other thermoplastic resins contained are cross-linked, which makes the resin and filler, and the thermoplastic resin more tightly combined, further improving the sound insulation effect, and the EVA sheet which has been subjected to hot pressing cross-linking is resistant. Thermal and mechanical properties are also further improved.
  • the organic component in the sound insulating material composition is premixed in a mixer, then the inorganic component is added, the mixing is continued, and then transferred to an internal mixer at a temperature lower than the EVA crosslinking temperature.
  • the mixture is subjected to mixing to uniformly mix the organic component and the inorganic component.
  • the conditions of the mixing include: the mixing temperature is below 100 ° C, and the mixing time is 40 to 60 minutes.
  • the mixing mixture is transferred to a tableting machine for pressing, and a sheet having a certain thickness is formed, and the obtained sheet is cut to a desired size, and then transferred to a laminating apparatus for vacuum heat. Pressure.
  • the vacuum hot pressing conditions include: vacuum hot pressing temperature of 135 ° C ⁇ 150 ° C, vacuum degree of -0.05 ⁇ - O.lMPa, vacuum hot pressing time of 15 ⁇ 25 minutes. After the vacuum hot pressing is completed, the vehicle soundproof EVA sheet is obtained.
  • the present invention further provides a vehicle front wall insulation mat comprising the above-described vehicle soundproof EVA sheet and foamed PU foam on the surface of the vehicle soundproof EVA sheet.
  • the automobile front wall insulation pad using the vehicle soundproof EVA sheet provided by the invention has good sound insulation performance under the premise of being lightweight.
  • the automobile front wall insulation pad can be prepared by: placing the vehicle soundproof EVA sheet in a foaming mold, and then performing a PU foam foaming process on the surface thereof to obtain a vehicle having a composite double layer structure. Front wall insulation pad.
  • EVA (with VA content of 19wt%) 870g, DCP 17.4g, put it in the drum mixer for mixing for 5 minutes, then add 900g of ultrafine barium sulfate (3000 mesh) to the mixer.
  • the EVA sheet A2 of the present embodiment and the automobile front wall insulation pad B2 were prepared by the same procedure as in Example 1, except that:
  • step (1) accurately weigh EVA (wherein VA content is 19wt%) 150g, DCP 1.5g, put it in the drum mixer for mixing for 5 minutes, then add 300g of heavy calcium carbonate to the mixer, oxidize Silicon-aluminum vacuum ceramic microbeads (particle size 50 microns) 2400 g, EVA wax 150 g, mixed for 10 minutes discharge.
  • the EVA sheet A3 of the present embodiment and the automobile front wall insulation pad B3 were prepared by the same procedure as in Example 1, except that:
  • step (1) accurately weigh EVA (wherein VA content is 19wt%) 1170g, DCP 11.7g, put it in the drum mixer for mixing for 5 minutes, then add alumina (2500 mesh) 300g to the mixer. , silica alumina vacuum ceramic microbeads (particle size 50 microns) 1500g, EVA wax 30g, mixed for 10 minutes discharge.
  • the EVA sheet A4 of the present embodiment and the automobile front wall insulation pad B4 were prepared in the same manner as in Example 1, except that:
  • the aluminum oxide vacuum ceramic microbeads of Example 1 were replaced with 300 g of vacuum glass microspheres having a particle size of 50 ⁇ m and composed of soda lime borosilicate glass.
  • the EVA sheet A4 of the present embodiment and the automobile front wall insulation pad B4 were prepared by the same procedure as in Example 2, except that:
  • vacuum glass beads 1200 g having a particle size of 50 ⁇ m and having a composition of soda lime borosilicate glass are used.
  • 1200 g of alkaline silica-alumina vacuum ceramic microbeads having a particle diameter of 50 ⁇ m were substituted for 2400 g of silica-alumina vacuum ceramic microbeads having a particle diameter of 50 ⁇ m in Example 2.
  • the sound-insulating EVA sheet formed by the sound insulating material composition provided by the present invention has a small density and a light weight, and is in line with the trend of light weight of automobiles.
  • the front wall insulation of the vehicle is improved by using the soundproof EVA sheet for a vehicle provided by the present invention.
  • the mat has good sound insulation performance under the premise of light weight, and fully meets the requirements of the current standard front wall insulation mat for vehicles.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Acoustics & Sound (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明提供了一种隔音材料组合物，所述隔音材料组合物包括10-40重量份的热塑性树脂和60-90重量份的填料和助剂。所述热塑性树脂中含有EVA树脂，以所述隔音材料组合物的总质量为基准，所述EVA树脂的含量为5-40wt%。所述填料中含有真空微珠，以所述隔音材料组合物的总质量为基准，所述真空微珠的含量为5-80wt%，所述真空微珠为真空陶瓷微珠和/或真空玻璃微珠。

Description

隔音材料组合物、 车用隔音 EVA片材和汽车前围隔热垫 技术领域
本发明属于汽车零部件领域， 尤其涉及一种隔音材料组合物、 车用隔音 EVA片材 和汽车前围隔热垫。 背景技术
目前国内外中高档车用前围隔热垫材料主要是 EVA (乙烯 -醋酸乙烯共聚物） +PU (聚氨酯）发泡材料， 其功能在于阻隔吸收由发动机传来的噪声、 热量， 从而保持车内 的安静舒适。 其中， EVA层为隔音层， 由 EVA等多种热塑性树脂与填料混合形成 EVA 复合材料隔音层， 反射由发动机传递过来的噪声； 而 PU发泡层为吸音层， 即吸收发动 机传来的噪声。 随着汽车工业的发展， 对隔音材料的隔音性能、 耐热性、 力学性能的要 求越来越高， 以往材料也越来越难以满足要求。
但目前， 传统配方的 EVA隔音层中的各种热塑性树脂分子之间结合不够紧密， 且 热塑性树脂与填料之间界面结合差， 不够密实， 难以达到理想的隔音效果。该隔音 EVA 层的隔音性能遵从质量定律， 由于大量无机填料的添加虽然提高了隔音性能， 但增大了 材料重量， 与汽车轻量化的趋势相背离。 发明内容
本发明解决了现有技术中汽车前围隔热垫采用的 EVA隔音层存在的隔音效果较差、 且材料重量较大的技术问题。
本发明提供了一种隔音材料组合物， 所述隔音材料组合物中含有 10-40重量份的热 塑性树脂和 60-90重量份的填料和助剂； 所述热塑性树脂中含有 EVA树脂， 以所述隔 音材料组合物的总质量为基准， EVA树脂的含量为 5-40wt% ; 填料中含有真空微珠， 以 所述隔音材料组合物的总质量为基准， 真空微珠的含量为 5-80wt%， 所述真空微珠为真 空陶瓷微珠和 /或真空玻璃微珠。
本发明还提供了一种车用隔音 EVA片材，所述车用隔音 EVA片材由本发明提供的 隔音材料组合物经密炼、 压制和真空热压得到。
本发明进一步提供了一种汽车前围隔热垫，所述汽车前围隔热垫包括上述车用隔音 EVA片材和位于所述车用隔音 EVA片材表面的发泡 PU泡沫。
本发明提供的隔音材料组合物中， 所采用的填料主要为真空微珠。 一方面， 真空微 珠的比重较小， 会大大降低材料总重量， 另外， 由于真空微珠内不存在声音传递质点， 因此其隔音效果得到大大提升。 同时， 本发明提供的车用隔音 EVA片材， 通过隔音材 料组合物密炼、 压制和真空热压得到， 在热压过程中 EVA树脂发生交联， 能使 EVA树 脂与填料、 以及热塑性树脂之间结合更加紧密， 进一步提高隔音效果， 且经过热压交联 的 EVA片材其耐热性和力学性能也进一步提高。 因此， 采用该 EVA片材的汽车前围隔 热垫， 在符合轻量化的前提下具有良好的隔音性能。 附图说明
图 1示出了实施例 1-5中的汽车前围隔热垫 B1-B5与车用标准前围隔热垫的隔声性 能测试结果。 具体实施方式
本发明提供了一种隔音材料组合物， 所述隔音材料组合物中含有 10-40重量份的热 塑性树脂和 60-90重量份的填料和助剂； 所述热塑性树脂中含有 EVA树脂， 以所述隔 音材料组合物的总质量为基准， 其中 EVA树脂的含量为 5-40wt% ; 填料中含有真空微 珠， 以所述隔音材料组合物的总质量为基准， 真空微珠的含量为 5-80wt%， 所述真空微 珠为真空陶瓷微珠和 /或真空玻璃微珠。
目前， 汽车内部的隔热隔音材料中， 可以在发泡材料中添加多孔陶瓷粒子来实现隔 音。 然而， 其隔音效果仍较差， 且发泡材料也达不到汽车前围隔热垫的结构要求。 而本 发明提供的隔音材料组合物中， 所采用的填料主要为真空微珠， 其比重较小， 因此其在 组合物中的用量可大大增加， 也不会增加材料的总重量， 从而可大大提高隔音材料的隔 音性能。 另外， 真空微珠内由于不存在声音传递质点， 因此其隔音效果得到大大提升。
本发明中， 所述热塑性树脂中主要组分为 EVA, 还可选择性含有其它热塑性树脂， 例如可选自 EVA蜡、 LDPE (低密度聚乙烯） 、 EPDM (三元乙丙橡胶） 中的一种或多 种。 其中 EVA蜡能增加后续成型过程中的流动性， 增加树脂与填料之间的相容性。
本发明的发明人发现， 热塑性树脂中 EVA含量若太少则难以保证树脂体系与填料 体系之间良好的相容性， 成型后得到的片材太硬缺少弹性。 EVA含量也不宜过高， 否则 填料的含量会相对降低， 隔音性能也相对降低， 同时成型后片材太软， 不易保型。 因此， 本发明中， 以所述隔音材料组合物的总质量为基准， 其中 EVA树脂的含量为 5-40wt%。
所述 EVA树脂中 VA含量为 5-40wt%。 VA含量过高时挤出片材太软， 含量过低时 片材缺少弹性。
本发明中， 在热塑性树脂中加入填料进行填充， 能提高材料的密度， 从而增加隔音 性能。 所述填料的主要组分为真空微珠， 其具有优异的隔音隔热效果。 优选情况下， 以 所述隔音材料组合物的总质量为基准， 真空微珠的含量为 5-80wt%。 发明人发现， 真空 微珠的含量不能高于 80wt%， 否则片材难以挤出成型。 本发明中， 所述真空微珠可以采 用真空陶瓷微珠和 /或真空玻璃微珠。 优选情况下， 所述真空微珠的粒径为 1-120微米。 发明人发现， 真空微珠的粒径太大， 其与树脂之间的相容性较差， 同时也限制了真空微 珠的添加用量； 而粒径太小时其真空体积也较小， 隔音效果则会相对较弱。 其中， 真空 玻璃微珠的密度相对真空陶瓷微珠密度稍小， 而真空玻璃微珠的粒径相对真空陶瓷微珠 稍大。 所述真空陶瓷微珠包括氧化硅铝， 例如碱性氧化硅铝。 所述真空玻璃微珠包括碱 石灰硼硅酸盐玻璃。 作为本发明的一种优选实施方式， 所述填料中除含有真空微珠之外， 还可含有其它 一些表面具有羟基的无机填料。 由于其表面具有羟基， 因此能与 EVA分子上的羧基、 羟基发生反应， 从而使热塑性树脂与填料之间具有良好的相容性， 使得本发明提高的隔 音材料组合物中无需添加偶联剂。 其中， 表面具有羟基的无机填料可选自碳酸钙、 氧化 铝、 还原铁粉、 硫酸钡中的一种或多种， 但不局限于此。
本发明所提供的隔音材料组合物中含有热塑性树脂， 其后期可发生交联固化， 增加 材料的密实度， 提高材料的耐热性和力学性能。 因此， 所述助剂中含有交联剂。 所述交 联剂可采用现有技术中常用的能够使热塑性树脂发生交联的各种物质， 例如可采用现有 技术中常用的过氧化物交联剂，具体可选自过氧化辛酰、过氧化月桂酰、过氧化硬脂酰、 过氧化对氯苯甲酰、 过氧化物二异丙苯 （DCP) 或过氧化苯甲酰 （BPO ) 中的一种或多 种， 优选采用过氧化物二异丙苯 （DCP) 。 所述交联剂的含量无需过高， 只需其能使热 塑性树脂充分固化交联即可。 优选情况下， 以所述热塑性树脂的质量为基准， 交联剂的 含量为 0.5-5wt%。
本发明中，所述助剂中还可根据需要含有润滑剂、抗氧剂、增塑剂中的一种或多种。 所述润滑剂、 抗氧剂、 增塑剂的种类以及用量在本领域的常规范围内即可， 本发明没有 特殊限定， 此处不再赘述。
本发明还提供了一种车用隔音 EVA片材，所述车用隔音 EVA片材由本发明提供的 隔音材料组合物经密炼、 压制和真空热压得到。
本发明提供的车用隔音 EVA片材， 通过隔音材料组合物密炼、 压制和真空热压得 到。 在热压过程中， EVA树脂以及含有的其它热塑性树脂均发生交联， 使树脂与填料、 以及热塑性树脂之间结合更加紧密， 进一步提高隔音效果， 且经过热压交联的 EVA片 材其耐热性和力学性能也进一步提高。
优选情况下， 可先将隔音材料组合物中的有机组分在混料机中进行预混合， 然后加 入无机组分， 继续混合， 然后转入密炼机中， 在低于 EVA交联温度的条件下进行密炼， 使有机组分与无机组分混合均匀。 优选情况下， 密炼的条件包括： 密炼温度为 100°C以 下， 密炼时间为 40~60分钟。
密炼完成后，趁热将密炼混合物转入压片机中进行压制，成型得到一定厚度的片材， 将得到的片材裁切至所需尺寸， 然后转入层压设备中进行真空热压。 真空热压的条件包 括： 真空热压温度为 135°C~150°C， 真空度为 -0.05〜- O.lMPa, 真空热压时间为 15〜25 分钟。 真空热压完成后， 即得到所述车用隔音 EVA片材。
本发明进一步提供了一种汽车前围隔热垫，所述汽车前围隔热垫包括上述车用隔音 EVA片材和位于车用隔音 EVA片材表面的发泡 PU泡沫。 采用本发明提供的车用隔音 EVA片材的汽车前围隔热垫， 在符合轻量化的前提下具有良好的隔音性能。
所述汽车前围隔热垫可通过如下方法制备得到： 将该车用隔音 EVA片材置于发泡 模具中， 然后在其表面进行 PU泡沫的发泡过程， 得到具有复合双层结构的汽车前围隔 热垫。 为了使本发明所解决的技术问题、 技术方案及有益效果更加清楚明白， 以下结合实 施例， 对本发明进行进一步详细说明。 应当理解， 此处所描述的具体实施例仅仅用以解 释本发明， 并不用于限定本发明。
实施例 1
( 1 )准确称量 EVA (其中 VA含量为 19wt% ) 870g、 DCP 17.4g, 置于滚筒混料机 中进行混合 5分钟，然后向混料机中加入超细硫酸钡（3000目） 900g，重质碳酸钙 900g， 氧化硅铝真空陶瓷微珠 （粒径为 50微米） 300g， EVA蜡 30g， 混合 10分钟出料。
( 2) 将上述混合好的料倒入已经升温至 90°C 的密炼机中进行密炼， 密炼转速为 50转 /分钟， 密炼时间为 60分钟。 密炼后趁热出料将物料转入双辊压片机压制成 2mm 厚的片材， 冷却后将其裁成 200mmX 200mm的尺寸， 并将其置于层压模具中在层压机 中进行真空热压， 热压温度为 140度， 真空度为 -0.1MPa， 热压时间为 20分钟。 热压完 成后得到本实施例的 EVA片材， 记为 Al。
( 3 ) 将 EVA片材 A1置于发泡模具中， 在其表面进行 PU泡沫的发泡， 泡沫密度 为 60kg/m3， 形成的发泡 PU层厚度为 20mm， 得到本实施例的汽车前围隔热垫， 记为 B i o
实施例 2
采用与实施例 1相同的歩骤制备本实施例的 EVA片材 A2和汽车前围隔热垫 B2， 不同之处在于：
步骤 （1 ) 中， 准确称量 EVA (其中 VA含量为 19wt% ) 150g、 DCP 1.5g， 置于滚 筒混料机中进行混合 5分钟，然后向混料机中加入重质碳酸钙 300g，氧化硅铝真空陶瓷 微珠 （粒径为 50微米） 2400g， EVA蜡 150g， 混合 10分钟出料。
实施例 3
采用与实施例 1相同的歩骤制备本实施例的 EVA片材 A3和汽车前围隔热垫 B3， 不同之处在于：
步骤 （1 ) 中， 准确称量 EVA (其中 VA含量为 19wt% ) 1170g、 DCP 11.7g， 置于 滚筒混料机中进行混合 5分钟， 然后向混料机中加入氧化铝（2500目） 300g， 氧化硅铝 真空陶瓷微珠 （粒径为 50微米） 1500g， EVA蜡 30g， 混合 10分钟出料。
实施例 4
采用与实施例 1相同的步骤制备本实施例的 EVA片材 A4和汽车前围隔热垫 B4， 不同之处在于：
步骤（1 )中，采用粒径为 50微米、组成为碱石灰硼硅酸盐玻璃的真空玻璃微珠 300g 取代实施例 1中的氧化硅铝真空陶瓷微珠。
实施例 5
采用釆用与实施例 2相同的歩骤制备本实施例的 EVA片材 A4和汽车前围隔热垫 B4, 不同之处在于：
步骤（1 )中，采用粒径为 50微米、组成为碱石灰硼硅酸盐玻璃的真空玻璃微珠 1200g 和粒径为 50微米的碱性氧化硅铝真空陶瓷微珠 1200g取代实施例 2中的 2400g粒径为 50微米的氧化硅铝真空陶瓷微珠。
性能测试
1、 按照 GBT 2413- 1980公开的方法测试各 EVA片材 A1-A5的密度。 测试结果如 表 1所示。
2、 按照 GB/T 18696.2-2002公开的方法测试各 EVA片材 A1-A5和车用标准前围隔 热垫样品 D的隔声性能， 测试结果如表 2和图 1所示。 表 1
Figure imgf000007_0001
表 2
Figure imgf000007_0002
从表 1 的测试结果可以看出， 采用本发明提供的隔音材料组合物形成的车用隔音 EVA片材的密度小、 质量轻， 符合汽车轻量化的趋势。
从表 2和图 1中可以看出， 釆用本发明提供的车用隔音 EVA片材的汽车前围隔热 垫在符合轻量化的前提下具有良好的隔音性能， 完全符合目前车用标准前围隔热垫的要 求。
以上所述仅为本发明的较佳实施例而已， 并不用以限制本发明， 凡在本发明的精神 和原则之内所作的任何修改、 等同替换和改进等， 均应包含在本发明的保护范围之内。

Claims

权利要求书
1. 一种隔音材料组合物， 包括
10-40重量份的热塑性树脂， 所述热塑性树脂中含有 EVA树脂， 以所述隔音材料组 合物的总质量为基准， 所述 EVA树脂的含量为 5-40wt% ; 和
60-90重量份的填料和助剂， 所述填料中含有真空微珠， 以所述隔音材料组合物的 总质量为基准， 所述真空微珠的含量为 5-80wt%，所述真空微珠为真空陶瓷微珠和 /或真 空玻璃微珠。
2. 根据权利要求 1所述的隔音材料组合物，其特征在于，所述热塑性树脂中还含有 EVA蜡、 LDPE、 EPDM中的一种或多种。
3. 根据权利要求 1或 2所述的隔音材料组合物，其特征在于，所述填料中还含有碳 酸钙、 氧化铝、 还原铁粉、 硫酸钡中的一种或多种。
4. 根据权利要求 1-3中任一项所述的隔音材料组合物， 其特征在于， 所述真空陶瓷 微珠包括氧化硅铝， 所述真空玻璃微珠包括碱石灰硼硅酸盐玻璃。
5. 根据权利要求 1-4中任一项所述的隔音材料组合物， 其特征在于， 所述真空微珠 的粒径为 1-120微米。
6. 根据权利要求 1-5中任一项所述的隔音材料组合物， 其特征在于， 所述 EVA树 月旨中 VA含量为 5-40wt%。
7. 根据权利要求 1-6中任一项所述的隔音材料组合物， 其特征在于， 所述助剂中含 有交联剂， 以所述热塑性树脂的质量为基准， 所述交联剂的含量为 0.5-5wt%。
8. 根据权利要求 7所述的隔音材料组合物，其特征在于，所述助剂中还含有润滑剂、 抗氧剂、 增塑剂中的一种或多种。
9. 一种车用隔音 EVA片材， 其特征在于， 所述车用隔音 EVA片材由权利要求 1-8 中任一项所述的隔音材料组合物经密炼、 压制和真空热压得到。
10. 根据权利要求 9所述的车用隔音 EVA片材， 其特征在于， 所述密炼的条件包 括： 密炼温度为 100°C以下， 密炼时间为 40-60分钟；
真空热压的条件包括： 真空热压温度为 135~150 °C， 真空度为 -0.05〜- O. lMPa, 真 空热压时间为 15〜25分钟。
11. 一种汽车前围隔热垫， 包括
权利要求 9或 10所述的车用隔音 EVA片材， 和
位于所述车用隔音 EVA片材表面的发泡 PU泡沫。
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