CN1445068A - 用于消音的三维成型基材的制造方法 - Google Patents
用于消音的三维成型基材的制造方法 Download PDFInfo
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- CN1445068A CN1445068A CN03107344A CN03107344A CN1445068A CN 1445068 A CN1445068 A CN 1445068A CN 03107344 A CN03107344 A CN 03107344A CN 03107344 A CN03107344 A CN 03107344A CN 1445068 A CN1445068 A CN 1445068A
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Abstract
本发明涉及三维汽车隔音配件的制造方法。具体而言,所述方法包括以下步骤:混合双组份聚氨酯树脂,将该树脂施加到基材上,将所述基材成型然后清理该施加了树脂的基材的表面并使其脱模。
Description
技术领域
本发明涉及具有结构和消音性能的三维组合材料的制造方法。本发明的方法包括以下步骤:制备聚氨酯树脂并将该树脂施加到基材的第一个侧面上,然后将该基材成型为希望的三维形状。进而,本发明涉及汽车消音零部件的制造,如三维仪表盘,内部和引擎侧面隔火板隔音材料,侧引擎罩隔音材料,内部齿轮箱隔音材料和行李箱密封面隔音材料。
背景技术
通常,汽车内部与汽车框架所传导的声音是隔绝开的,这些声音源自轮胎,道路噪声,风噪声,引擎噪声,和来自汽车其它机械部件的噪声。在本领域内已知有很多基材用来减弱来自汽车外部传向汽车内部的声音。例如,在外部噪声和汽车内部之间安装纤维材料,这在本领域内是已知的。该材料抑制了声音的传导和振动。有多种在本领域内已知的阻尼材料,例如非织造织物,如长弹毛垫和发泡聚氨酯材料。用胶将隔音层施加到阻尼材料上在本领域内也是已知的。这样的应用一般出现在汽车的地毯上。参见,例如美国专利Nos.4,056,161;4,966,799;5,266,143和5,068,001。然而这些隔音材料很重。
另外,在本领域内已知一种针状复合材料隔音层,该隔音层限制了对胶的需要。参见例如美国专利No.6,109,389。另外,在蜂窝状心层两侧贴合由矿物纤维或合成纤维浸渍了热塑性树脂的织物层外皮,来为仪表盘或类似的元件提供结构和消音性能,这在本领域内是已知的,所述仪表盘或类似元件可抗重负载并实现对声音的衰减。参见例如美国专利No.5,888,610。
在本领域内还已知两种制备仪表盘隔音材料的方法,所述仪表盘隔音材料安装在汽车的隔火板上以阻挡和吸收引擎发出的声音。通常这些仪表盘隔音层包括一个真空形成的重层-硫酸钡填充的EVA或PVC或注射成型的TPO外皮和减震剂,如流延聚氨酯泡沫塑料,屑状聚氨酯泡沫塑料,由聚酯纤维或天然纤维制成的纤维垫和长弹毛垫。在使用纤维垫的情况下,要施加酚醛树脂粘合剂。
已知仪表盘隔音材料的制造方法涉及以下步骤:加热乙烯基片材,然后将该乙烯基材料转移至成型工具,接下来将该乙烯基材料真空成型。如果隔音层为流延泡沫塑料,则在开放式或封闭式工具操作中向所述工具成型的乙烯基材料施加液态泡沫塑料,然后使所施加的泡沫塑料脱模并清理修饰其表面。如果该隔音层是纤维或长弹毛垫,则将所述成型的乙烯基材料转移至另一成型工具且加入所述纤维或长弹毛垫并成型和固化。
经此方法成型的隔音层通常具有双倍的屏蔽效果,该效果是用柔软有韧性的吸收性材料如上述泡沫塑料或垫,通过减弱来自重层(第二隔热板)并穿透过隔火板钢材的声音和振动来获得的。包含树脂处理的苯酚长弹毛垫的隔音层主要作为吸收器,用来吸收透过隔火板或从客舱反射来的声音。
然而,在本领域内仍需要一种制造三维成型复合材料的方法,所述复合材料包含在一侧涂布有聚氨酯树脂的基材。具体而言,在本领域内仍需要为汽车提供一种轻质的、从声学上和三维结构上均合理的配件。
发明内容
已经发现三维隔音汽车配件可以这样制造:向基材的第一个侧面施加聚氨酯树脂,然后成型该施加了树脂的基材。
本发明制造的汽车配件比通常的泡沫塑料和重层复合材料轻并且比相同厚度的流延泡沫塑料或柔性板料泡沫塑料具有更好的吸声性能。
本发明还涉及一种制造三维隔音仪表盘的方法。
本发明所制造的仪表盘为易于安装的自承式。
附图说明
图1简要说明了阻抗管测试设备。
图2说明了厚度为7.62毫米的板料泡沫塑料的吸声系数,数据来自于在100-6,400Hz的频率范围对一商用仪表盘隔音板的测量。
图3说明了Ford Taurus_Ultralite Dash Insulator在100-6,400Hz的频率范围内的吸声系数。
图4把本发明的涂布了聚氨酯的亚麻剑麻纤维垫与通常的聚氨酯泡沫塑料在100-6,400Hz的频率范围内的吸声系数作了对比说明。
具体实施方式
本发明涉及一种用于消音的三维复合材料的制造方法。具体而言,本发明涉及一种吸声三维复合材料的制造方法,其包括以下步骤:将包含多元醇混合物和异氰酸酯的双组份聚氨酯树脂混合,然后将该树脂施加到基材的第一侧面上,接下来将涂布了树脂的基材转移至一台热成型工具内,将所述涂布了树脂的基材模铸成型为复合材料,在固化后将所述复合材料从工具中取出并清理修饰其表面。进而,根据本发明,该三维复合材料可将树脂任选地施加到基材的两个侧面上。
本发明中使用的聚氨酯树脂可以在宽范围的多元醇/异氰酸酯比值内加工。优选地,本发明中使用的聚氨酯的NCO指数为90-130,更优选为100-120。
用于本发明的聚氨酯含有多元醇混合物。通常,本发明的多元醇混合物含有至少一种多元醇或者异氰酸酯反应性组份。通常第一多元醇存在的量为总混合物的约30-约80wt%,优选约45-约65wt%。通常第二多元醇存在的量为约10-约64wt%,优选为约27-约47wt%。任选地,该多元醇混合物还包含约0~20wt%的脂肪酸,优选为约3-约10wt%的脂肪酸。该多元醇混合物还可以包含约0-约5wt%的催化剂,优选为约0.2-约1%。另外,该多元醇混合物还可以包含填料,其存在的量为约0-约20wt%,优选为约1-约5wt%。此外,根据要求可以向该多元醇混合物中加入黑色颜料,加入的量为0-5wt%,优选为约0.5-2%。在工业中碳黑被广泛地用作颜料,然而,也可以使用有机染料。还可以使用任选的湿润剂,基于该多元醇混合物的总重计,其量为0-5wt%,优选为0.1-2wt%,以进一步提高氨基甲酸酯对各种垫的润湿作用。
通常,异氰酸酯反应性化合物包括,例如,含羟基的化合物。这些材料一般可分为两组:分子量为500-10,000的高分子量化合物和分子量为62-499的低分子量化合物。本发明优选的多元醇为由常用原料如4,4’-二羟基-二苯基丙烷,蔗糖,苯胺,氨,甲苯二胺,单乙醇胺,丙二醇,乙二醇,三羟甲基丙烷和1,2-乙二胺衍生的低分子量聚醚。
例如在聚醚存在下使苯乙烯或丙烯腈聚合形成的经乙烯基聚合物改性的聚醚(美国专利3,383,351;3,304,273;3,523,093;和3,110,695;和德国专利1,152,536)也是合用的,含OH基的聚丁二烯也是如此。另外,合用的含羟基多元醇包括乙二醇,1,2-和,1,3-丙二醇,1,3-和1,4-和2,3-丁二醇,1,6-己二醇,1,10-癸二醇,二甘醇,三甘醇,四甘醇,双丙二醇,三丙二醇,甘油和三羟甲基丙烷。
本发明中有用的多元醇包括从缩合作用衍生得到的聚酯型多元醇,所述缩合作用发生在例如己二酸,苯二甲酸或其它脂肪族或芳族二羧酸或它们的酸酐与低分子量的二醇如丙二醇,双丙二醇,三丙二醇,或四丙二醇或乙二醇及其低聚物,丁二醇,己二醇或其它脂肪族二醇,双酚-A或其它用于制造聚酯型多元醇的芳香族二醇之间。另外,聚己内酰胺或聚交酯可以存在于本发明多元醇组合物中。天然的聚酯型多元醇如蓖麻油或改性大豆油,菜子油,或亚麻子油或蓖麻油酸和丁二醇或聚蓖油酸的缩合产品也可以用来配制本发明使用的多元醇混合物。
用于本发明的多元醇混合物还可以包括一种脂肪酸。适用的脂肪酸包括,例如脂肪酸,如分子式:R(CO2H)n表示的酸,其中n是1,2或3,且其中R含有至少10个碳原子。R可以是烷基(即环形的,直链的或支链的),烷芳基,芳烷基,或芳基,饱和的或不饱和的均可。有用的酸的例子包括,例如,正癸酸,新癸酸,月桂酸,棕榈酸,硬脂酸,异硬脂酸,油酸,亚麻酸等。油酸是优选的脂肪酸。
其它可用于本发明的添加剂包括催化剂如,例如各种有机金属化合物,包括例如锡(II)的羧酸盐,羧酸的二烷基锡盐,二烷基锡硫醇盐,二烷基锡二硫代酯和叔胺如,例如二甲基-环己胺(即Polycat8),五甲基亚乙基三胺(即Polycat 5),乙酸钾(即Polycat45),二[2-(二甲氨基)-乙基]醚(Niax A-1),二甲基-乙醇胺(DMEA),Dabco WT等。当然,聚氨酯化学领域的技术人员所熟知的任意催化剂也是可能使用的。
如上所述,可包含于多元醇混合物中的填料和增强剂包括有机和无机化合物,例如,诸如玻璃的化合物,其形式为纤维,薄片,切段纤维或微球体;云母,硅灰石;碳纤维;碳黑;碳黑膏体;滑石和碳酸钙。也可将经再次研磨的聚氨酯与颗粒尺寸小于100微米、来自于制造座垫和SRIM或RIM配件的下脚料颗粒一起作为填料使用。
用于本发明的原料多异氰酸酯组份包括例如W.Siefken在JustusLiebigs Annalen der chemie,562,第72-136页中所描述的种类的脂肪族,脂环族,芳脂族,芳族的和杂环的多异氰酸酯化合物。这些化合物的具体实例是二异氰酸亚乙酯,1,4-四亚甲基二异氰酸酯,1,6-亚己基二异氰酸酯;1,12-十二烷基二异氰酸酯,环丁烷-1,3-二异氰酸酯;环己烷-1,3-和-1,4-二异氰酸酯及其同分异构体的混合物。另外的例子是1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合-甲基环己烷(German Auslegeschrift No.1,202,785,美国专利No.3,401,190),2,4-和2,6-六氢-甲苯二异氰酸酯及其同份异构体的混合物。六氢-1,3-和/或-1,4-苯二异氰酸酯;全氢化-2,4’-和或-4,4-二苯甲烷二异氰酸酯;1,3-和1,4-苯二异氰酸酯;1,4-和2,5-甲苯二异氰酸酯及其同份异构体的混合物也适用于本发明。二苯基-甲烷-2,4-和/或-4,4’-二异氰酸酯;亚萘基-1,5-二异氰酸酯;三苯基甲烷-4,4’-4”-三异氰酸酯;通过将苯胺和甲醛缩合并随后经光气化作用获得并描述于例如英国专利Nos.874,430和848,671中的多苯基多亚甲基多异氰酸酯化合物也可用于本发明;根据美国专利3,454,606的m-和p-异氰酸根合-苯磺酰基-异氰酸酯化合物;例如GermanAuslegeschrift No.1,157,601(美国专利3,277,138)中所描述类型的全氯代芳基多异氰酸酯化合物;德国专利No.1,902,007(美国专利No.3,152,162)中所描述类型的含碳二亚胺基团的多异氰酸酯;美国专利No.3,492,330中所描述类型的二异氰酸酯化合物;和例如英国专利No.993,890,比利时专利No.761,626和已出版荷兰专利申请No.7,102,524中所描述类型的含脲基甲酸酯基团的多异氰酸酯化合物是合用的异氰酸化合物的更多实例。此外,例如美国专利No.3,001,973,German offenlegungsschriften Nos.1,929,034和2,004,408中所描述类型的含异氰脲酸酯基团的多异氰酸酯化合物;例如比利时专利No.752,261或美国专利No.3,394,164中所描述类型的含氨基甲酸乙酯基团的多异氰酸酯化合物;根据德国专利No.1,230,778的含酰化脲基团的多异氰酸酯化合物和例如德国专利No.1,101,394(美国专利Nos.3,124,605和3,201,372)和英国专利No.889,050中所描述类型的含缩二脲基团的多异氰酸酯化合物也是合用的。
优选使用在加工温度下是液态的芳族多异氰酸酯化合物。优选的原料多异氰酸酯化合物包括在室温下为液态的4,4’-二异氰酸根合-二苯基-甲烷的衍生物,例如,可根据德国专利No.1,618,380(美国专利No.3,644,457)获得的含氨基甲酸乙酯基团的液态多异氰酸酯化合物。这些化合物可通过,例如,使1摩尔的4,4’-二异氰酸根合-二苯甲烷与0.05-0.3摩尔的低分子量二醇或三醇,优选分子量低于700的聚丙二醇进行反应来制备。
本发明使用的芳香族多异氰酸酯化合物的2,4-二苯基甲烷二异氰酸酯的含量优选为约1-约16wt%,更优选为约2-约12wt%。
根据本发明,预聚体可以任选地用作聚氨酯树脂的组份。根据本发明,多元醇组份可以在不存在催化剂的情况下与多异氰酸酯反应来制备预聚体。为了制备聚氨酯树脂,可加入剩余部分的多元醇并使各组份在催化剂和其它适当添加剂存在的条件下一起反应。其它添加剂可以在各组份混合前加入到预聚体或剩余的多元醇中或者在二者中都加入,这样,在反应结束时就获得了聚氨酯树脂。
适用于本发明的基材包括由亚麻,亚麻-剑麻,***,黄麻,聚氨酯泡沫塑料颗粒或其混合物组成的纤维垫,天然纤维垫和由***加上聚丙烯或聚醚纤维组成的合成纤维垫,由聚醚纤维制成的合成垫,长弹毛垫,柔性的或刚性的可成型聚氨酯泡沫塑料。所述基材重量优选为400-1200克/米2。所述纤维垫可包含约0.01-约50wt%的聚丙烯或聚酯。如果所述纤维垫是柔性聚氨酯泡沫塑料,其密度可以是约12-约75千克/米3,如果所述纤维垫是刚性可成型泡沫塑料,其密度可以是约10-约40千克/米3。
上述双组份聚氨酯树脂可以通过本领域内任意已知方式向基材施加;优选通过刷涂,刮涂或使用辊涂机。更优选的是采用高压喷头(压力>500psi),应用撞击式混合技术或采用在喷头中带有静态混合器的低压力设备(压力<150psi),将所述双组份聚氨酯树脂喷涂在基材的第一侧面上。
通常,向基材施加的聚氨酯树脂的量为150-约1500克/米2。本发明的组合物可以采用常规的加工技术成型。通常,采用常规的压力下,在模具或工具中,于90-130℃的温度下,经约60-约120秒使基材成型。任选地,在成型所述复合材料前可以将一蜂窝状纸质片材放置在树脂涂布过的基材下面,以提高强度。
根据本发明制造的隔音汽车部件包括三维仪表盘,内部和引擎侧面隔火板隔音材料,引擎侧盖隔音材料,内部齿轮箱隔音材料,及行李箱封面隔音材料。
本发明将通过以下实施例进一步说明,但并非仅限于这些实施例,其中的份数和百分数除另有说明外均以重量计。
实施例
通用程序
以下的异氰酸酯化合物和多元醇是用于本发明的聚氨酯树脂各组份的实例:
异氰酸酯1:一种商购的芳香族聚合二苯甲烷二异氰酸酯,其2,4MDI同分异构体的含量为1-7wt%。
异氰酸酯2:由约80-约100wt%的异氰酸酯1和约0.01-约20wt%的商购油酸/己二酸/季戊四醇的混合物反应后得到的混合物(或预聚体)。
异氰酸酯3:一种商购的芳族聚合2,4二苯甲烷二异氰酸酯。
多元醇A:由蔗糖/聚乙二醇/水作为原料制成的聚醚,其分子量为约440。
多元醇B:由原料单乙醇胺制得的聚醚,其分子量为约240。
表1
多元醇混合物 | |
组分 | wt.% |
多元醇A | 55 |
多元醇B | 37 |
油酸 | 5 |
乙酸钾(Polycat 45,AirProducts) | 0.5 |
黑膏体 | 2.5 |
实施例1
将单位面积重量为约1000克/米2的亚麻-剑麻垫(50%亚麻,50%剑麻)片材放置在水平支承夹具上。所述垫的大小取决于成型工具的尺寸。所述垫在成型步骤中应覆盖所述工具的所有部份。采用装有内置静态混合器的低压力-混合头将根据表1的多元醇制剂与异氰酸酯2一起,按混合比为POLYOL/ISO为100∶139.4施涂到所述垫的上表面。用于此类型施涂的设备可从例如Langemann商购。典型压力为300psi,将物料的通过量调节至约20克/秒,在所述垫上喷涂的聚氨酯树脂的总量为约500克/米2。
接下来将基材转移到一个加热到90℃的铝制成型工具内。按照树脂处理过的一面朝着模具的阳模部份的方式将基材放置在模具的阳模上。这样,成品零件的聚氨酯层朝向声源。因为用来制造上述配件的模具是为将包含乙烯基材料重层和铸塑聚氨酯柔性泡沫塑料的常规仪表盘隔音板进行成型而设计的,所以要在所述基材顶部放置一个长弹毛垫的支承层(未压缩厚度为约5厘米,密度为约70千克/米3)以在成型操作期间提供必要的压缩力。将模具关闭并使树脂固化120秒。然后从模具中取出配件,将其从支承性长弹毛垫上清理下来并整洁其表面。
阻抗管测试
对实施例1制备的基材和常规隔音板进行阻抗管测试。ASTME1050(采用阻抗管,两个麦克风和一个数字频率分析***测试消音材料的阻抗和吸收性的标准测试方法)是用来产生图2-4中数据的步骤。
双麦克风、阻抗管法测试装置简要地示于图1。使用Bruel &kjaer***,其包含一个阻抗管,两个1/4英寸的电容器麦克风,一个功率放大器,一个快速付立叶转变多频道分析器和一个装有Bruel &Kjaer软件的计算机。使用两个不同尺寸的管来进行不同频率范围的测量。大管(100毫米直径)用于100Hz-1600Hz的频率,小管(29毫米直径)用于500Hz-6400Hz的频率。
位于阻抗管末端的扬声器在管中发出宽波段平面声学驻波。测试样品与一个刚性活塞背衬一起位于对面的末端。应用在管壁上两个位置间的声压传递函数关系将该宽波段波分离成入射和反射组份。分析器由每个有关频率上反射对入射压的放大比计算出反射系数的大小。然后,频率依赖SA系数由下式给出:
α(f)=1-R(f)2
ASTM方法建议至少要对从同一块材料上割下来的两块29毫米和两块100毫米的样品进行测试。由于要考虑到该配件的一些固有的差异,将这些结果进行平均将能对材料性能提供更好的评估。
如在图2、3和4中所做的对比性说明,根据本发明制备的聚氨酯组份比其它的本领域内已知的隔音板的密度小并具有更高的声吸收。
尽管为了说明的目的已在前面对本发明进行了详细阐述,但应理解为该详述只是为了说明的目的,并且本领域技术人员可以在不背离本发明的精神和范围的情况下对其做出改动,但权利要求书中已作出限制的除外。
Claims (23)
1.一种制造消音三维复合材料的方法,其包括以下步骤:将包含多元醇混合物和异氰酸酯或预聚体的双组份聚氨酯树脂混合,然后将该树脂施加到基材的第一侧面上,将涂布了树脂的基材转移至一台热成型工具,将所述涂布了树脂的基材成型为复合材料,将所述复合材料从工具中取出并清理修饰其表面。
2.权利要求1的方法,其中所述的树脂通过喷涂、刷涂或辊压法进行施加。
3.权利要求2的方法,其中所述的树脂通过采用撞击式混合的高压头来进行喷涂。
4.权利要求2的方法,其中所述的树脂采用带有静态混合器的低压头来进行喷涂。
5.权利要求2的方法,其中所述的树脂喷涂的量为约150-约1500克/米2。
6.权利要求1的方法,其中所述的基材选自天然纤维垫,合成纤维垫,长弹毛垫,柔性聚氨酯泡沫塑料,刚性可成型聚氨酯泡沫塑料及它们混合物。
7.权利要求6的方法,其中所述基材的重量为约400-约1200克/米2。
8.权利要求6的方法,其中所述的纤维垫包含约0.01-约50%的聚丙烯或聚酯,其中所述的纤维垫的单位面积重量为约400-约1200克/米2。
9.权利要求6的方法,其中所述的柔性聚氨酯泡沫塑料的密度为约12-约75千克/米3。
10.权利要求6的方法,其中所述的刚性可成型聚氨酯泡沫塑料的密度为约10-约40千克/米3。
11.权利要求1的方法,其中所述的聚氨酯混合物包含约30-约60wt.%的所述多元醇混合物和约25-约55wt.%的异氰酸酯。
12.权利要求1的方法,其进一步包括的步骤是在所述的树脂基材成型前将蜂窝状纸质片材放置在基材的第二侧面上。
13.权利要求1的方法,其中所述的多元醇混合物还包含脂肪酸,催化剂和填料。
14.权利要求1的方法,其中所述的多元醇混合物包含第一种多元醇的量为约30-约80wt.%,第二种多元醇的量为约10-约64wt.%,其中的重量百分比基于所述多元醇混合物的总重量计。
15.根据权利要求13的方法,其中所述的脂肪酸存在的量为约1-约20wt.%,其中所述的催化剂存在的量为约1-约2wt.%,其中所述的填料存在的量为约1-约10wt.%,其中的重量百分比基于所述多元醇混合物的总重量计。
16.权利要求1的方法获得的仪表盘隔音板。
17.权利要求1的方法获得的引擎罩隔音板。
18.权利要求1的方法,其中所述的聚氨酯树脂的NCO指数为90-130。
19.权利要求1 8的方法,其中所述的聚氨酯树脂的NCO指数为100-120。
20.一种包含基材和聚氨酯树脂的三维复合材料,其中所述的聚氨酯树脂施加在所述基材的第一侧面上并将施加了树脂的基材进行了成型。
21.权利要求20的三维复合材料,其中所述的聚氨酯树脂施加在所述基材的第一和第二侧面上。
22.权利要求20的三维复合材料,其中在成型前向所述基材的第二侧面上施用蜂窝状纸质片材。
23.权利要求20的三维复合材料,其中所述的聚氨酯树脂的NCO指数为90-130。
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- 2003-03-07 DE DE2003605765 patent/DE60305765T2/de not_active Expired - Lifetime
- 2003-03-07 AT AT03004921T patent/ATE328723T1/de not_active IP Right Cessation
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- 2003-03-19 KR KR1020030017010A patent/KR101005985B1/ko not_active IP Right Cessation
- 2003-03-20 CN CNB031073441A patent/CN1313258C/zh not_active Expired - Fee Related
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CN102529840A (zh) * | 2010-12-23 | 2012-07-04 | 上海新安汽车隔音毡有限公司 | 一种多层结构的汽车用隔音垫及其制造方法 |
CN102529840B (zh) * | 2010-12-23 | 2014-05-14 | 上海新安汽车隔音毡有限公司 | 一种多层结构的汽车用隔音垫及其制造方法 |
CN105383135A (zh) * | 2014-09-02 | 2016-03-09 | 现代自动车株式会社 | 具有透气性的多层吸音隔音材料 |
CN107000311A (zh) * | 2014-10-16 | 2017-08-01 | 陶氏环球技术有限责任公司 | 增材制造方法 |
CN104987702A (zh) * | 2015-06-29 | 2015-10-21 | 青岛海信电器股份有限公司 | 一种聚氨酯泡棉及其制备方法 |
CN110799689A (zh) * | 2017-06-30 | 2020-02-14 | 沙特基础工业全球技术有限公司 | 增强纸、制造增强纸的方法以及包含增强纸的制品 |
CN112638718A (zh) * | 2018-10-26 | 2021-04-09 | MT-Tec合同会社 | 汽车用隔音材料 |
CN110229498A (zh) * | 2019-06-17 | 2019-09-13 | 韧泉智能科技(上海)有限公司 | 一种声学材料的制备方法及应用 |
CN110229498B (zh) * | 2019-06-17 | 2021-05-18 | 韧泉智能科技(上海)有限公司 | 一种声学材料的制备方法及应用 |
CN114573788A (zh) * | 2020-12-02 | 2022-06-03 | 上海东大聚氨酯有限公司 | 高强度耐冲击聚氨酯内墙装饰板原料组合物、内墙装饰板及其制备方法 |
CN114573788B (zh) * | 2020-12-02 | 2023-08-04 | 上海东大聚氨酯有限公司 | 高强度耐冲击聚氨酯内墙装饰板原料组合物、内墙装饰板及其制备方法 |
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Publication number | Publication date |
---|---|
DE60305765T2 (de) | 2007-06-14 |
ATE328723T1 (de) | 2006-06-15 |
JP2003291166A (ja) | 2003-10-14 |
ES2266656T3 (es) | 2007-03-01 |
CA2421884C (en) | 2011-10-18 |
JP4375985B2 (ja) | 2009-12-02 |
US7285316B2 (en) | 2007-10-23 |
CA2421884A1 (en) | 2003-09-20 |
HK1056853A1 (en) | 2004-03-05 |
KR20030076362A (ko) | 2003-09-26 |
US20030180500A1 (en) | 2003-09-25 |
EP1346819A1 (en) | 2003-09-24 |
EP1346819B1 (en) | 2006-06-07 |
CN1313258C (zh) | 2007-05-02 |
US20040212125A1 (en) | 2004-10-28 |
US6773756B2 (en) | 2004-08-10 |
KR101005985B1 (ko) | 2011-01-05 |
MXPA03002320A (es) | 2004-10-29 |
CN101025916A (zh) | 2007-08-29 |
DE60305765D1 (de) | 2006-07-20 |
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