CN102459112A - 包含糖、有机多元羧酸和反应性硅酮的用于矿棉的上胶组合物和由所述组合物获得的隔离性产品 - Google Patents
包含糖、有机多元羧酸和反应性硅酮的用于矿棉的上胶组合物和由所述组合物获得的隔离性产品 Download PDFInfo
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- CN102459112A CN102459112A CN2010800341754A CN201080034175A CN102459112A CN 102459112 A CN102459112 A CN 102459112A CN 2010800341754 A CN2010800341754 A CN 2010800341754A CN 201080034175 A CN201080034175 A CN 201080034175A CN 102459112 A CN102459112 A CN 102459112A
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Abstract
本发明涉及用于基于矿棉,特别基于玻璃棉或岩石棉的隔离性产品的上胶组合物,其包含:-至少一种单糖,-至少一种具有小于或等于1000的摩尔质量的有机多元羧酸,和-至少一种反应性硅酮。本发明还涉及基于获得的矿物纤维的隔离性产品及其制造方法。
Description
本发明涉及基于矿棉(特别是玻璃棉或岩石棉)和基于无甲醛的有机粘合剂的隔热和/或隔音产品领域。
本发明更特别涉及能够交联形成所述有机粘合剂的上胶组合物,其包括至少一种糖和至少一种具有小于1000的摩尔质量的有机多元羧酸和至少一种反应性硅酮,涉及所述上胶组合物的制备方法和由其制成的隔离性产品(produits isolants)。
基于矿棉的隔离产品的制造通常包括矿棉本身的制造阶段,这可以通过各种方法,例如根据通过已知的内部或外部离心(centrifugation interne ou externe)的纤维化技术进行。该离心在于将熔融矿物材料(玻璃或岩石)引入到包含多个小孔的离心设备中,该材料在离心力作用下投向该设备的周壁并以长丝形式从中离开。在离心设备出口处,长丝被高温高速气流拉伸和夹带向接收元件,以在此形成纤维(或矿棉)网。
为了使纤维彼此集合在一起和为了使该网具有内聚力,在离心设备出口到接收元件的途中将包含热固性树脂的上胶组合物喷射到纤维上。在通常大于100℃的温度下对涂有上胶剂的纤维网施以热处理,以造成树脂的缩聚和由此获得具有特定性质,特别是尺寸稳定性、拉伸强度、压缩后的厚度恢复性和均匀颜色的隔热和/或隔音产品。
要喷射到矿棉上的上胶组合物通常以包含热固性树脂和添加剂,如树脂交联催化剂、粘合硅烷促进剂、防尘矿物油等的水溶液形式提供。该上胶组合物最通常通过喷雾施加到纤维上。
该上胶组合物的性质极大取决于树脂的特性。从应用角度看,该上胶组合物需要具有良好的雾化能力并能够沉积在纤维表面以有效粘合它们。
该树脂必须在用于形成上胶组合物之前的给定时期内是稳定的,通常在使用时通过将该树脂与上述添加剂混合来制备该组合物。
在规章层面上,该树脂必须被认为是非污染性的,即其必须包含――和其必须在上胶阶段中或此后生成――尽可能少的可有害于人体健康或有害于环境的化合物。
最常用的热固性树脂是属于可熔酚醛树脂类的酚醛树脂。除了它们在上述热条件下的良好的交联能力外,这些树脂可溶于水,具有对矿物纤维,特别是玻璃纤维的良好亲合力,并是相对便宜的。
这些可熔酚醛树脂通过酚和甲醛在碱性催化剂存在下以大于1的甲醛/酚摩尔比的缩合而得,从而促进酚和甲醛之间的反应和降低该在树脂中的残留酚含量。在限制单体缩合程度的同时进行酚和甲醛之间的缩合反应以避免形成降低可稀释度的较不溶于水的长链。因此,该树脂包含一定比例的未反应单体,特别是甲醛,由于其已知的有害作用,甲醛的存在是不希望的。
因此,基于可熔酚醛的树脂通常用脲处理,脲通过以非挥发性脲-甲醛缩合物形式捕获甲醛来与游离甲醛反应。脲在该树脂中的存在还由于其低成本而带来一定的经济优点,因为可以相对大量引入脲而不影响树脂的使用品质,特别是不损害最终产品的机械性质,这显著降低该树脂的总成本。
但是,已经观察到,在为了获得树脂的交联而对该网施加的温度条件下,该脲-甲醛缩合物不是稳定的;它们分解同时再产生甲醛和脲,其又至少部分地分解为氨,被释放到工厂大气中。
日益严格的关于环境保护的规章迫使隔离产品的制造商寻找能够进一步降低不合意排放物,特别是甲醛的浓度的解决方案。
替代在上胶组合物中的可熔酚醛树脂的解决方案是已知的,并基于使用羧酸聚合物,特别是丙烯酸聚合物。
在US 5 340 868中,该上胶剂包含多元羧酸聚合物、β-羟基酰胺和至少三官能单体羧酸。
已经提供了包含多元羧酸聚合物、多元醇和催化剂的上胶组合物,该催化剂是含磷的催化剂(US 5 318 990、US 5 661 213、US 6331 350、US 2003/0008978)、氟硼酸盐(US 5 977 232)或氨氰、二氰胺或氰基胍(US 5 932 689)。
也已经描述了包含与共聚物(US 6 299 936)组合的包括至少两个羟基的链烷醇胺和多元羧酸聚合物(US 6 071 994、US 6 099 773、US 6 146 746)的上胶组合物。
在US 2002/0091185中,该多元羧酸聚合物和多元醇以使得OH基团的当量数与COOH基团的当量数的比率为0.6/1至0.8/1的量使用。
在US 2002/0188055中,该上胶组合物包含多元羧酸聚合物、多元醇和阳离子型、两性或非离子型表面活性剂。
在US 2004/0002567中,该上胶组合物包括多元羧酸聚合物、多元醇和硅烷型偶联剂。
在US 2005/0215153中,描述了由包含羧酸与多元醇的聚合物的预粘合剂和作为辅助粘合剂的糊精形成的上胶剂。
此外,可用作矿棉用上胶剂的基于可热交联的多糖的粘合剂组合物是已知的(US 5 895 804)。该组合物包含具有至少两个羧酸官能团和至少等于1000的分子量的多元羧酸聚合物和具有至少等于10 000的分子量的多糖。
用上胶剂粘合的基于矿棉的隔离产品还必须满足特别地规定优良耐老化性(特别地在潮湿环境中)的标准。因此重要的是,隔离性产品的吸水能力是尽可能低的。
本发明的目的是提出用于基于矿棉的隔离产品的上胶组合物,其不含甲醛,并且其为隔离性产品提供最低的吸水能力。
为了实现这种目的,本发明提出用于基于矿棉,特别基于玻璃棉或岩石棉的隔离性产品的上胶组合物,其包含:
- 至少一种糖,
- 至少一种具有小于或等于1000的摩尔质量的有机多元羧酸,
- 和至少一种反应性硅酮。
该糖可以是单糖、多糖或这些化合物的混合物。
该单糖选自包括3至8个碳原子的单糖,优选醛糖,有利地包含5至7个碳原子的醛糖。特别优选的醛糖是天然醛糖(属于D系列),特别是己糖,如葡萄糖、甘露糖和半乳糖。
本发明的多糖选自具有小于100 000,优选小于50 000,有利地小于10 000,且更好地大于180的重均摩尔质量的多糖。
有利地,该多糖具有小于或等于10的由重均摩尔质量/数均摩尔质量的比率定义的多分散指数(IP)。
该多糖优选包括至少一个选自上述醛糖,有利地葡萄糖的单元。特别优选主要(多于50重量%)由葡萄糖单元构成的多糖。
根据一个优选实施方案,本发明使用特别获自植物的单糖和/或多糖的混合物,尤其是糊精或蜜糖(mélasse)。
糊精是通过淀粉的部分水解获得的符合通式(C6H10O5)n的化合物。糊精制备方法是已知的。例如,可以通常在酸性催化剂存在下通过加热淀粉或通过将淀粉干燥至干来制备糊精,这使得构成所述淀粉的直链淀粉和支链淀粉的分子断裂成具有较低摩尔质量的产物。也可以用一种或多种能够水解淀粉的键的淀粉酶,特别是微生物淀粉酶通过酶促途径处理淀粉来获得糊精。处理的性质(化学或酶促)和水解条件对糊精的平均摩尔质量和摩尔质量分布具有直接影响。
本发明的糊精可获自各种植物来源的淀粉或淀粉衍生物,例如来自块茎,如马铃薯、木薯、竹芋和甘薯,来自谷物,如小麦、玉米、黑麦、稻米、大麦、黍、燕麦和高粱,来自果实,如栗子、板栗和榛子,或来自豆科植物,如豌豆和云豆。
特别优选的是具有大于或等于5,优选大于或等于10,有利地大于或等于15,更好小于100的右旋糖当量DE(英文为“Dextrose Equivalent”)的糊精。
照惯例,右旋糖当量DE通过下列关系式定义:
蜜糖是特别从甘蔗和甜菜中提取的糖的精炼的残渣,其包含大约40至60重量%的高糖素含量。蔗糖构成蜜糖糖素的主要部分。
本发明的蜜糖优选包括45至50重量%的以蔗糖表示的总糖素。
甜菜蜜糖是特别优选的。
术语“有机多元羧酸”被理解为是指包含至少两个羧酸官能团,优选最多4个羧酸官能团,有利地最多3个羧酸官能团的有机酸。
该有机多元羧酸充当交联剂;其能够在热量作用下与糖反应以形成导致在最终粘合剂中获得聚合网络的酯键。所述聚合网络能够在矿棉中纤维的接合点处形成键。
该有机多元羧酸选自具有小于或等于1000,优选小于或等于750,有利地小于或等于500的摩尔质量的有机多元羧酸。
该有机多元羧酸优选是饱和或不饱和的,和支化或非支化的脂环酸,环状酸或芳族酸。
该有机多元羧酸可以是二羧酸,例如草酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、苹果酸、酒石酸、丙醇二酸、天冬氨酸、谷氨酸、富马酸、衣康酸、马来酸、愈伤酸、樟脑酸、邻苯二甲酸及其衍生物(特别包含至少一个硼或氯原子)、四氢化邻苯二甲酸及其衍生物(特别包含至少一个氯原子,如氯菌酸)、间苯二甲酸、对苯二甲酸、甲基反丁烯二酸和柠康酸,或二羧酸前体,特别是酸酐,如马来酸酐、琥珀酸酐和邻苯二甲酸酐;三羧酸,例如柠檬酸、丙三羧酸、1,2,4-丁-三羧酸、乌头酸、苯连三酸、苯偏三酸和苯均三酸;或四羧酸,例如1,2,3,4-丁四羧酸和苯均四酸。
在该上胶组合物中,该糖占由该糖和有机多元羧酸构成的混合物的重量的10至90%,优选20至85%,有利地30至80%。
措辞“反应性硅酮”理解为表示带有至少一个能够与该上胶组合物的至少一种组分反应的羟基、羧基或酸酐、胺、环氧或乙烯基官能团的聚硅氧烷。
反应性硅酮在环境温度下是液体;它属于在英语中被称为“硅酮液”的硅酮种类。它的平均分子量通常小于或等于50000,优选地小于或等于10000。
该反应性硅酮由这样的主链构成,该主链由有机硅氧烷残基(特别地烷基硅氧烷残基,优选地二甲基硅氧烷残基)和任选的苯基硅氧烷残基(特别地甲基苯基硅氧烷残基)以相对于该硅酮的重量优选地不超过20%,特别地不超过10%重量的苯基硅氧烷单元的比例组成。所述主链在末端位置(在该链的自由端之一上)或在侧基(或接枝)上带有至少一个反应性羟基、羧基或酸酐、胺、环氧或乙烯基官能团。优选地,反应性硅酮包含至少两个末端官能团,有利地羟基官能团。
该反应性硅酮的反应性羟基、羧基或酸酐、胺、环氧或乙烯基官能团可以用保护基封端,该保护基在热量作用下释放所述反应性官能团。反应性官能团的封端保证该反应性硅酮在用于在烘箱中交联该胶料的热处理之前不反应。作为这种保护性封端作用的实例,可以设想该羟基至少部分地为醚化形式,或用保护基(特别地酰基或碳酸酯基)封端。
反应性硅酮在该上胶组合物中的比例为对于100重量份糖和有机多元羧酸有0.1-5重量份,优选地0.3-3重量份,有利地0.5-2重量份,更好是0.7-1.8重量份的反应性硅酮。
该上胶组合物可另外包含特别具有调节交联起始温度的功能的酸或碱性催化剂。
该催化剂可以选自路易斯碱和酸,如粘土、胶态或非胶态二氧化硅、有机胺、季胺、金属氧化物、金属硫酸盐、金属氯化物、脲硫酸盐、脲氯化物和基于硅酸盐的催化剂。
该催化剂还可以是含磷化合物,例如碱金属次磷酸盐、碱金属亚磷酸盐、碱金属聚磷酸盐、碱金属磷酸氢盐、磷酸或烷基膦酸。该碱金属优选是钠或钾。
该催化剂还可以是包含氟和硼的化合物,例如四氟硼酸或该酸的盐,特别是碱金属(如钠、钾)的四氟硼酸盐,碱土金属(如钙或镁)四氟硼酸盐,四氟硼酸锌和四氟硼酸铵。
该催化剂优选是次磷酸钠、亚磷酸钠和这些化合物的混合物。
引入到该上胶组合物中的催化剂的量可以占该糖和有机多元羧酸的重量的最多20%,优选最多10%,且有利地至少等于1%。
本发明的上胶组合物可另外包含基于100重量份糖和有机多元羧酸进行计算的下列比例的下列传统添加剂:
- 0至2份硅烷,特别是氨基硅烷,
- 0至20份,优选4至15份油,
- 0至30份,优选0至20份脲和/或甘油,
- 0至30份选自木素衍生物,如木素磺酸铵(LSA)或木素磺酸钠,和动物或植物蛋白质的“增量剂”。
添加剂的作用是已知的并简要重述:硅烷是纤维和粘合剂之间的偶联剂,也充当抗老化剂;油是防尘剂和疏水剂;脲和甘油充当增塑剂并能够防止该上胶组合物的预胶凝;“增量剂”是可溶于或可分散在含水上胶组合物中的有机填料,其特别能够降低该上胶组合物的成本。
非反应性硅酮可以任选地与反应性硅酮一起共同存在,特别地由于配制原因或为了提供补充疏水作用;它的存在优选地被限制在基于100重量份糖和有机多元羧酸低于2重量份,更好是低于1重量份,特别地低于0.5重量份。
根据所用的有机多元羧酸,该上胶组合物具有大约1至5,优选大于或等于1.5的酸性pH值。有利地,借助于添加不能与该糖反应的含氨基化合物,例如叔胺,特别是三乙醇胺,使pH保持在至少等于2的值,以限制该上胶组合物的不稳定性问题和制造管线的腐蚀问题。含氨基化合物的量可构成糖和有机多元羧酸总重量的最多30重量份。
该上胶组合物用于施加到矿物纤维,特别是玻璃或岩石纤维上。
照惯例,该上胶组合物在离心设备出口处和在矿物纤维以纤维网(nappe de fibres)形式收集在接收元件上之前喷射到该矿物纤维上,随后在允许该上胶剂交联并形成难熔粘合剂的温度下处理该纤维网。本发明的上胶剂的交联在与传统甲醛-酚树脂(résine formophénolique)相当的温度下,在大于或等于110℃,优选大于或等于130℃,有利地大于或等于140℃的温度下发生。
由这些经上胶的纤维获得的隔声和/或隔热产品也构成本发明的主题。
这些产品通常以矿棉、玻璃棉或岩石棉的垫或毡,或矿物纤维纱,也是玻璃纱或岩石纱(voile)(特别用于形成所述垫或毡的表面涂层)的形式存在。
下列实施例能够例证本发明,但不限制本发明。
在这些实施例中,测量下列:
-测量在制备之后和在使用等于6/1(实施例1-3)的压缩度(被定义为标称厚度与在压缩下厚度的比率)或如表2所示(实施例4-8)不同压缩时间之后的隔离产品的厚度。厚度的测量可以评价该产品的优良的尺寸稳定性。
- 在从隔离产品中冲压切出的样品上测量根据标准ASTM C 686-71T的拉伸强度。该样品具有长122毫米、宽46毫米、外缘切割曲率半径(rayon de courbure de la découpe)等于38毫米且内缘切割曲率半径等于12.5毫米的环面形状。
将该样品置于试验机的两个圆柱心轴之间,其中一个心轴是活动的并恒速移动。测量该样品的断裂力F(以克-力计),并计算由断裂力F与样品质量的比率所定义的拉伸强度RT。
在制成后(初始拉伸强度)和在高压釜中在105℃、100%相对湿度下加速老化15分钟(RT 15)后测量拉伸强度。
- 以每平方米隔离性产品吸收的水的kg表示的在标准EN 1609条件下的水吸收。具有小于1千克/平方米的水吸收的隔离产品被视为具有低的短期(24小时)水吸收;它们根据ACERMI认证属于“WS”级。
实施例1至3
制备包含在表1中显示的组分的上胶组合物,比例以重量份表示。
该上胶组合物通过在强烈搅拌下(直至组分完全地溶解)连续地在含水容器中引入糖,然后其它组分进行制备。
还根据WO01/96254A1的实施例2、测试1制备包括酚醛树脂和脲的传统上胶组合物(参照)。
上胶组合物用来使基于玻璃棉的隔离产品成型。
玻璃棉在2.4m宽生产线上连续进行制备。该玻璃棉通过内部离心技术制造,其中借助被称作离心盘的工具将熔融的玻璃组合物转化成纤维,该工具包含形成熔融组合物的接收室的篮和被刺穿多个孔的外周带:该盘围绕其垂直设置的对称性轴旋转,该组合物在离心力作用下穿过这些孔被射出,并借助拉制气流将离开孔的材料拉制成纤维。
照惯例,上胶剂喷雾环位于纤维化盘下方,以将该上胶组合物规则地分布在刚形成的玻璃棉上。
将如此上胶的矿棉收集在配有内部吸气箱的带式输送机上,内部吸气箱使矿棉以毡或网形式留在该输送机表面上。切割该毡或网,随后放在保持290℃的烘箱中(对于参照产品为260℃),在此该上胶剂的成分聚合以形成粘合剂。
在烘箱出口处获得的隔离产品具有大约82毫米的厚度,等于17.5千克/立方米的密度和等于5%的烧失量。
隔离产品的性质在下面表1中给出。
表1
n.d.:未测定
(1)衍生自玉米淀粉的糊精;重均分子量:3510;右旋糖当量DE:30;以商标Roclys?C3072S由ROQUETTE FRERES销售;
(2)具有末端反应性羟基官能团的聚二甲硅氧烷;以商标DOW CORNING?1581由DOW CORNING销售;
(3)反应性聚二甲硅氧烷;以商标SILRES?BS10421581由WACKER SILICONES销售。
可以看出,根据本发明的隔离性产品特别地具有低的水吸收,其与用于实施例2的由参照酚-甲醛上胶组合物得到的产品的水吸收相当并比由用于实施例1和3的上胶组合物得到的产品分别地降低32%和90%。
实施例4-8
上胶组合物在实施例1-3的条件下由在表2中显示的组分以指出的比例(表示为重量份)进行制备。
这些组合物用来在实施例1-3中描述的条件下制备基于矿棉的隔离产品。获得的产品具有不同的标称厚度(60、100或160mm)和等于19kg/m3的密度。
隔离产品的性质在下面表2中给出。
包含反应性硅酮的根据本发明的产品具有最多等于0.6kg/m2的水吸收。
实施例4和5的产品具有比对比实施例1和2的包含非反应性硅酮的产品更低的吸水能力。
Claims (25)
1.用于基于矿棉,特别地岩石棉或玻璃棉的隔离性产品的上胶组合物,其特征在于其包含:
- 至少一种糖,
- 至少一种具有小于或等于1000的摩尔质量的有机多元羧酸,和
- 至少一种反应性硅酮。
2.如权利要求1的组合物,其特征在于所述糖为单糖、多糖或这些化合物的混合物。
3.如权利要求2的组合物,其特征在于该单糖选自包括3至8个碳原子,优选5至7个碳原子的单糖。
4.如权利要求3的组合物,其特征在于该单糖是醛糖。
5.如权利要求4的组合物,其特征在于该醛糖是己糖,如葡萄糖、甘露糖和半乳糖。
6.如权利要求2的组合物,其特征在于该多糖具有小于1 000 000,优选小于50 000,有利地小于10 000,更好大于180的重均摩尔质量。
7.如权利要求6的组合物,其特征在于该多糖由多于50%的葡萄糖单元构成。
8.如权利要求1至7之一的组合物,其特征在于其包含一种或多种单糖和/或一种或多种多糖的混合物,它们选自糊精和蜜糖。
9.如权利要求8的组合物,其特征在于该糊精具有大于或等于5,优选大于或等于10,有利地大于或等于15,且更好小于100的右旋糖当量。
10.如权利要求8的组合物,其特征在于该蜜糖包含40至60重量%,优选45至50重量%的糖素。
11.如权利要求1至10之一的组合物,其特征在于该有机多元羧酸包含至少两个羧酸官能团,优选最多4个羧酸官能团,有利地最多3个羧酸官能团。
12.如权利要求11的组合物,其特征在于该酸具有小于或等于750,优选小于或等于500的摩尔质量。
13.如权利要求1至12之一的组合物,其特征在于该有机多元羧酸是饱和或不饱和的,支化或非支化的脂环酸、环状酸或芳族酸。
14.如权利要求1至13之一的组合物,其特征在于该糖占由该糖和有机多元羧酸构成的混合物的重量的10至90%,优选20至85%,有利地30至80%。
15.如权利要求1至14之一的组合物,其特征在于该反应性硅酮的摩尔质量小于或等于50000,优选地小于或等于10000。
16.如权利要求1至15之一的组合物,其特征在于该反应性硅酮由这样的主链构成,该主链由有机硅氧烷残基,特别地烷基硅氧烷残基,优选地二甲基硅氧烷残基,和任选的苯基硅氧烷残基,特别地甲基苯基硅氧烷残基构成。
17.如权利要求1至16之一的组合物,其特征在于所述反应性硅酮在末端位置或在侧基上带有至少一个反应性羟基、羧基或酸酐、胺、环氧或乙烯基官能团,优选至少两个末端官能团。
18.如权利要求17的组合物,其特征在于至少两个末端官能团为羟基官能团。
19.如权利要求1至18之一的组合物,其特征在于反应性硅酮的比例为每100重量份糖和有机多元羧酸有0.1-5重量份,优选地0.3-3重量份,有利地0.5-2重量份,更好是0.7-1.8重量份反应性硅酮。
20.如权利要求1至19之一的组合物,其特征在于其另外包含选自路易斯酸和碱、含磷化合物和含氟和硼的化合物的催化剂。
21.如权利要求20的组合物,其特征在于该催化剂占该糖和有机多元羧酸的重量的最多20%,优选最多10%,并有利地至少1%。
22.如权利要求1至21之一的组合物,其特征在于其另外以基于100重量份糖和有机多元羧酸计算的下列比例包含下列添加剂:
- 0至2份硅烷,特别是氨基硅烷,
- 0至20份,优选4至15份油,
- 0至30份,优选0至20份脲和/或甘油,
- 0至30份选自木素衍生物,如木素磺酸铵(LSA)或木素磺酸钠,和动物或植物蛋白质的“增量剂”。
23.基于矿棉的隔音和/或隔热产品,特别基于玻璃棉或基于岩石棉的隔音和/或隔热产品,其使用如权利要求1至22之一的上胶组合物进行上胶。
24.使用如权利要求1至22之一的上胶组合物进行上胶的矿物纤维纱,特别是玻璃或岩石的纤维纱。
25.如权利要求23的基于矿棉的隔音和/或隔热产品或如权利要求24的矿物纤维纱的制造方法,据该方法制造矿棉或矿物纤维,将上胶组合物喷射到所述矿棉或所述纤维上,和在能使该上胶剂交联并形成难熔粘合剂的温度下处理所述矿棉或所述纤维,其特征在于该上胶组合物包含:
- 至少一种糖,
- 至少一种具有小于1000的摩尔质量的有机多元羧酸,和
- 至少一种反应性硅酮。
Applications Claiming Priority (3)
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FR0902705 | 2009-06-04 | ||
FR0902705A FR2946352B1 (fr) | 2009-06-04 | 2009-06-04 | Composition d'encollage pour laine minerale comprenant un saccharide, un acide organique polycarboxylique et un silicone reactif, et produits isolants obtenus |
PCT/FR2010/051075 WO2010139899A1 (fr) | 2009-06-04 | 2010-06-02 | Composition d ' encollage pour laine minerale comprenant un saccharide, un acide organique polycarboxylique et un silicone reactif, et produits isolants obtenus a partir de ladite composition |
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CN102459112B CN102459112B (zh) | 2016-11-16 |
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Also Published As
Publication number | Publication date |
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EP2438129B1 (fr) | 2018-08-22 |
US9562150B2 (en) | 2017-02-07 |
EP2438129A1 (fr) | 2012-04-11 |
UA106497C2 (uk) | 2014-09-10 |
KR20120034075A (ko) | 2012-04-09 |
ES2698371T3 (es) | 2019-02-04 |
CA2763970A1 (fr) | 2010-12-09 |
AU2010255574B2 (en) | 2015-06-25 |
BRPI1011135B1 (pt) | 2019-10-08 |
CA2763970C (fr) | 2017-12-05 |
KR101769360B1 (ko) | 2017-08-18 |
FR2946352A1 (fr) | 2010-12-10 |
TR201816331T4 (tr) | 2018-11-21 |
BRPI1011135A2 (pt) | 2018-02-06 |
JP2012528948A (ja) | 2012-11-15 |
WO2010139899A1 (fr) | 2010-12-09 |
PL2438129T3 (pl) | 2019-02-28 |
RU2539982C2 (ru) | 2015-01-27 |
CN102459112B (zh) | 2016-11-16 |
RU2011154198A (ru) | 2013-07-20 |
DK2438129T3 (da) | 2018-12-17 |
AR079590A1 (es) | 2012-02-08 |
FR2946352B1 (fr) | 2012-11-09 |
AU2010255574A1 (en) | 2012-02-02 |
JP5875977B2 (ja) | 2016-03-02 |
US20120070645A1 (en) | 2012-03-22 |
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