CN101939268A - 用于包含单糖和/或多糖和有机聚羧酸的矿棉的施胶组合物和所得绝缘产品 - Google Patents
用于包含单糖和/或多糖和有机聚羧酸的矿棉的施胶组合物和所得绝缘产品 Download PDFInfo
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Abstract
本发明涉及用于基于矿棉特别基于玻璃或岩石的绝缘产品的施胶组合物,其包含:至少一种单糖和/或至少一种多糖,和至少一种具有小于或等于1000的摩尔质量的有机聚羧酸。本发明的另一主题是基于由此获得的矿物纤维的绝缘产品及其制造方法。
Description
本发明涉及基于矿棉,特别是玻璃或岩石和基于无甲醛的有机粘合剂的热和/或声绝缘产品领域。
本发明更特别涉及能够交联形成所述有机粘合剂的施胶组合物,其包括至少一种单糖和/或一种多糖和至少一种具有小于1000的摩尔质量的有机聚羧酸,涉及所述施胶组合物的制备方法和由其制成的绝缘产品。
基于矿棉的绝缘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(centrifugationinterne ou externe)的纤维化技术进行。离心包括将熔融矿物材料(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细丝形式从中离开。在离开离心设备后,细丝被高温高速气流拉伸和运往向接收元件,以在此形成纤维(或矿棉)网。
为了使纤维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施胶组合物喷射到纤维上。在通常大于100℃的温度下对涂有施胶剂的纤维网施以热处理,以造成树脂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热和/或声绝缘产品。
要喷射到矿棉上的施胶组合物通常以包括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。该施胶组合物最通常通过喷雾施加到纤维上。
该施胶组合物的性质极大取决于树脂的特性。从应用角度看,该施胶组合物需要具有良好的喷雾能力并能够沉积在纤维表面以有效粘合纤维。
该树脂必须在用于形成施胶组合物之前的一定时期内是稳定的,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-和其必须在施胶阶段中或此后生成-尽可能少的可能有害人体健康或有害环境的化合物。
最常用的热固性树脂是属于可熔酚醛树脂族的酚醛树脂。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,并相对便宜。
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/酚摩尔比缩合而得,从而促进酚和甲醛之间的反应和降低该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相对不溶于水的长链。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,其存在是不希望的。
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。该树脂中脲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质量,而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-甲醛缩合物是不稳定的;它们分解同时再产生甲醛和脲,其又至少部分分解产生氨,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绝缘产品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。
替代施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 5340868中,该施胶剂包含聚羧酸聚合物、β-羟基酰胺和至少三官能单体羧酸。
已经提供包含聚羧酸聚合物、多元醇和催化剂的施胶组合物,该催化剂是含磷催化剂(US 5318990、US 5661213、US 6331350、US2003/0008978)、氟硼酸盐(US 5977232)或氰胺、二氰胺或氰基胍(US5932689)。
也已经描述了包含包括至少两个羟基的链烷醇胺和聚羧酸聚合物(US 6071994、US 6099773、US 6146746)以及共聚物(US6299936)的施胶组合物。
在US 2002/0091185中,该聚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不等的量使用。
在US 2002/0188055中,该施胶组合物包含聚羧酸聚合物、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,该施胶组合物包括聚羧酸聚合物、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施胶剂。
此外,可用作矿棉用施胶剂的基于可热交换的多糖的粘合剂组合物是已知的(US 5895804)。该组合物包含具有至少两个羧酸官能团和至少等于1000的分子量的聚羧酸聚合物和具有至少等于10000的分子量的多糖。
本发明的目的是提出用于基于矿棉的绝缘产品的施胶组合物,其不含甲醛,由此能够提供基于可熔酚醛树脂的施胶组合物的替代品。
另一目的是提供由来自可再生源,特别是植物源或通过微生物发酵产生的天然化合物制成的施胶组合物。
为了实现这些目的,本发明提出用于基于矿棉,特别基于玻璃或岩石的绝缘产品的施胶组合物,其包含:
-至少一种单糖和/或至少一种多糖,和
-至少一种具有小于或等于1000的摩尔质量的有机聚羧酸。
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100000,优选小于50000,有利地小于10000,更好大于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,这使得所述淀粉的成分直链淀粉和支链淀粉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键的淀粉酶,特别是微生物淀粉酶通过酶促途径来处理淀粉来获得糊精。处理(化学或酶促)和水解条件的性质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,来自水果,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的葡萄糖当量DE的糊精。
照惯例,葡萄糖当量DE通过下列关系式确定:断裂初始
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%的高糖类含量。蔗糖构成蜜糖糖类的主要部分。
本发明的蜜糖优选包括45至50重量%的以蔗糖表示的总糖类。
甜菜蜜糖特别优选。
术语“有机聚羧酸”被理解为是指包含至少两个羧基官能团,优选最多4个羧基官能团,有利地最多3个羧基官能团的有机酸。
该有机聚羧酸充当交联剂;其能够在热作用下与单糖和/或多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建立键。
该有机聚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的摩尔质量的有机聚羧酸。
该有机聚羧酸优选是饱和或不饱和的,和支链或非支链的脂环酸、环状酸或芳族酸。
该有机聚羧酸可以是二羧酸,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。
在该施胶组合物中,该单糖和/或多糖占由该单糖和/或多糖和有机聚羧酸构成的混合物重量的10至90%,优选20至85%,有利地30至80%。
该施胶组合物可另外包含特别具有调节交联开始温度的功能的酸或碱催化剂。
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,特别是碱金属四氟硼酸盐,如四氟硼酸钠或四氟硼酸钾,碱土金属四氟硼酸盐,如四氟硼酸钙或四氟硼酸镁、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。
引入到该施胶组合物中的催化剂的量可以构成该单糖和/或多糖和有机聚羧酸的重量的最多20%,优选最多10%,有利地至少等于1%。
本发明的施胶组合物可另外包含基于100重量份一种或多种单糖和/或一种或多种多糖和有机聚羧酸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份油,优选4至15份,
-0至30份脲和/或甘油,优选0至20份,
-0至5份硅酮,
-0至30份选自木质素衍生物,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;油是防尘和疏水剂;脲和甘油充当增塑剂并能够防止该施胶组合物的预胶凝;硅酮是疏水剂,其功能是降低该绝缘产品的吸水;“增量剂”是可溶于或可分散在水性施胶组合物中的有机填料,其特别能够降低该施胶组合物的成本。
根据所用的有机聚羧酸,该施胶组合物具有大约1至5,优选大于或等于1.5的酸性pH值。有利地,通过添加不能与该单糖和/或多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,以限制该施胶组合物的不稳定性和制造管路的腐蚀问题。含氨基化合物的量可构成单糖和/或多糖和有机聚羧酸总重量的最多30重量份。
该施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,该施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,随后在能使该施胶剂交联并形成难熔粘合剂的温度下处理该纤维网。本发明的施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。
由这些经施胶的纤维获得的声和/或热绝缘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,也是玻璃或岩石的纤维的纱(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,但不限制其。
在这些实施例中,测量下列:
-通过凝胶渗透色谱法(chromatographie par perméation de gel)在下列条件下测量的糊精的重均摩尔质量和数均摩尔质量;
洗脱剂:PBS缓冲剂(基于氯化钠和磷酸钠的盐水溶液,pH大约7.4)
-通过能够表征聚合材料的粘弹性行为的动态力学分析(DMA)法测量的交联开始温度(TR)和交联速率(V)。该程序如下:Whatmann纸样品用施胶组合物(有机固体含量为大约40%)浸渍,随后水平固定在两个叉钳之间。将配有用于以施加的形变的函数进行测量应力的设备的振荡部件置于该样品上表面上。该设备能够计算弹性模量E。将该样品以4℃/分钟的速率加热至20至250℃不等的温度。根据该测量,绘制作为温度(以℃计)的函数的弹性模量E(以MPa计)的变化曲线,该曲线的大致外观显示在图1中。在该曲线上测定以℃计的与交联开始温度(TR)对应的值和以MPa/℃计的与交联速率(V)对应的斜率。
图1
-该施胶组合物在玻璃支撑体上的接触角。
-在从绝缘产品上冲压切出的样品上根据标准ASTM C 686-71T的拉伸强度。该样品具有长122毫米、宽46毫米、外缘切口曲率半径等于38毫米且内缘切口曲率半径等于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(以克-力计),并计算通过断裂力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。
-该绝缘产品的初始厚度和以等于6/1(实施例22至24)或5/1(实施例25至34)的压缩度(定义为标称厚度与压缩后的厚度的比率)压缩1小时、24小时、30天和90天后的厚度。该厚度测量能够评测该产品的良好尺寸性能。
-以每平方米绝缘产品吸收的水的千克数表示的在标准EN 1609条件下的吸水。具有小于1千克/平方米的吸水的绝缘产品被视为具有低的短期(24小时)吸水;它们根据ACERMI认证属于“WS”类。
-根据标准EN ISO 1182测得的耐火性。属于“Euroclass A1”类的产品不造成火焰的产生(déclaration)和蔓延。
-以W/(m×°K)表示的根据标准EN 13162的导热系数λ。
-在标准ISO 16000-9的条件下和使用等于0.4的空气变化/室Q装料率的比率测试3天后该产品排放的甲醛量。根据标准ISO 16000-3中所述的方法测量甲醛量。结果以每平方米每小时排放的甲醛微克数表示。
实施例1至6
制备包含表1中所示的成分(以重量份表示)的施胶组合物。
蜜糖是工业用甜菜蜜糖(France Mélasses出售),其以包含43至53重量%糖(以蔗糖表示)的粘稠均匀液体形式存在。
通过在剧烈搅拌下向装有水的容器中相继引入蜜糖、柠檬酸和次磷酸钠(催化剂)直至成分完全溶解,制备施胶组合物。
与根据WO 01/96254A1的实施例2,试验1制成的包括甲醛-酚树脂和脲的传统施胶组合物(参照物)对比地评测表1中所示的施胶组合物的性质。
实施例1至6的施胶组合物在交联开始温度(TR)、粘度和接触角方面具有与参照物类似的性质。交联速率(V)仍低于参照物。
实施例7至21
在实施例1至6的条件下进行操作,改变在于使用具有下列特征的由玉米淀粉制成的糊精(麦芽糊精):
-重均摩尔质量等于5500,多分散指数IP等于9.5且葡萄糖当量DE为16.5至19.5(由Aldrich以419699为名出售;干提取物:100%):实施例7至12,
-重均摩尔质量等于1520,多分散指数IP等于5.72且葡萄糖当量DE等于62(由Roquette Frères以B6080S为名出售;干提取物:81%):实施例16至18,
-葡萄糖质量含量大于95%且葡萄糖当量DE等于99(由RoquetteFrères以葡萄糖浆74/为名出售;干提取物:75%):实施例19至21。
该施胶组合物的成分含量以重量份数列在表2中。
实施例8至15、18和21的施胶组合物有利地具有比参照物低的交联开始温度(TR)。实施例9的组合物中催化剂的存在能够与实施例7的组合物相比显著降低交联开始温度,但伴随着交联速率(V)的降低。
本发明的施胶组合物具有对于相同固体物质含量(40%)而言与参照物接近的低粘度,甚至较低,从而能够良好施加到矿物纤维上,特别是在其通过喷射进行施加时。
这些组合物还具有与参照物类似的接触角,这表明该施胶组合物对纤维的良好润湿性。
实施例22至24
使用实施例2、4和10的组合物以及甲醛-酚树脂(参照物)以形成基于玻璃棉的绝缘产品。
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对称性的轴旋转,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,施胶剂喷雾环位于纤维化盘下方,以将该施胶组合物规则地分布在刚形成的玻璃棉上。
将如此施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220℃的烘箱中,在此该施胶剂的成分聚合以形成粘合剂。
老化之前和之后的拉伸强度值、初始厚度和压缩24小时和30天后的厚度恢复值整理在表3中。
实施例25至34
这些实施例举例说明在工业生产线上制造绝缘产品。
在宽度2.40米的管线上在实施例22至24的条件下连续制造矿棉。涂有施胶组合物的矿棉随后连续送入290℃的烘箱。
在烘箱出口处获得的绝缘产品具有大约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。
在搅拌下通过将表4的成分引入到装有水的容器中,制备所用施胶组合物。
与实施例1至6中所述的参照施胶组合物(记为Réf.)对比地评测绝缘产品的性质。测量值显示在表4中。
表3
Claims (19)
1.用于基于矿棉特别基于岩石或玻璃的绝缘产品的施胶组合物,其特征在于其包含:
-至少一种单糖和/或至少一种多糖,和
-至少一种具有小于或等于1000的摩尔质量的有机聚羧酸。
2.如权利要求1中所述的组合物,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。
3.如权利要求2中所述的组合物,其特征在于该单糖是醛糖。
4.如权利要求3中所述的组合物,其特征在于该醛糖是己糖,如葡萄糖、甘露糖和半乳糖。
5.如权利要求1中所述的组合物,其特征在于该多糖具有小于1000000,优选小于50000,有利地小于10000,更好大于180的重均摩尔质量。
6.如权利要求5中所述的组合物,其特征在于该多糖由多于50%的葡萄糖单元构成。
7.如权利要求1至6之一中所述的组合物,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,特别是糊精和蜜糖。
8.如权利要求7中所述的组合物,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,更好小于100的葡萄糖当量。
9.如权利要求7中所述的组合物,其特征在于该蜜糖包含40至60重量%,优选45至50重量%的蜜糖。
10.如权利要求1至9之一中所述的组合物,其特征在于该有机聚羧酸包含至少两个羧基官能团,优选最多4个羧基官能团,有利地最多3个羧基官能团。
11.如权利要求10中所述的组合物,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。
12.如权利要求1至11之一中所述的组合物,其特征在于该有机聚羧酸是饱和或不饱和的,直链或支链的脂环酸、环状酸或芳族酸。
13.如权利要求1至12之一中所述的组合物,其特征在于该单糖和/或多糖占由该单糖和/或多糖和有机聚羧酸构成的混合物重量的10至90%,优选20至85%,有利地30至80%。
14.如权利要求1至13之一中所述的组合物,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。
15.如权利要求14中所述的组合物,其特征在于该催化剂构成该单糖和/或多糖和有机聚羧酸的重量的最多20%,优选最多10%,有利地至少1%。
16.如权利要求1至15之一中所述的组合物,其特征在于其另外以基于100重量份单糖和/或多糖和有机聚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份油,优选4至15份,
-0至30份脲和/或甘油,优选0至20份,
-0至5份硅酮,
-0至30份选自木质素衍生物,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”。
17.基于矿棉的声和/或热绝缘产品,特别基于玻璃或基于岩石的隔声和/或热绝缘产品,其使用如权利要求1至16之一中所述的施胶组合物施胶。
18.使用如权利要求1至16之一中所述的施胶组合物施胶的矿物纤维纱,特别是玻璃或岩石的纤维的纱。
19.如权利要求17中所述的基于矿棉的声和/或热绝缘产品或如权利要求18中所述的矿物纤维纱的制造方法,据此制造矿棉或矿物纤维,将施胶组合物喷射到所述矿棉或所述纤维上,和在能使该施胶剂交联和形成难熔粘合剂的温度下处理所述矿棉或所述纤维,其特征在于该施胶组合物包含:
-至少一种单糖和/或至少一种多糖,和
-至少一种具有小于1000的摩尔质量的有机聚羧酸。
Applications Claiming Priority (3)
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FR0759580A FR2924719B1 (fr) | 2007-12-05 | 2007-12-05 | Composition d'encollage pour laine minerale comprenant un monosaccharide et/ou un polysaccharide et un acide organique polycarboxylique, et produits isolants obtenus. |
FR0759580 | 2007-12-05 | ||
PCT/FR2008/052203 WO2009080938A2 (fr) | 2007-12-05 | 2008-12-04 | Composition d'encollage pour laine minerale comprenant un monosaccharide et/ou un polysaccharide et un acide organique polycarboxylique, et produits isolants obtenus |
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DE102005029479A1 (de) | 2005-06-24 | 2007-01-04 | Saint-Gobain Isover G+H Ag | Verfahren zur Herstellung von gebundener Mineralwolle und Bindemittel hierfür |
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-
2007
- 2007-12-05 FR FR0759580A patent/FR2924719B1/fr active Active
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2008
- 2008-12-04 CN CN200880126305.XA patent/CN101939268B/zh active Active
- 2008-12-04 ES ES08863743T patent/ES2697526T3/es active Active
- 2008-12-04 UA UAA201008243A patent/UA103014C2/ru unknown
- 2008-12-04 EA EA201070679A patent/EA019897B1/ru not_active IP Right Cessation
- 2008-12-04 DK DK08863743.4T patent/DK2231543T3/da active
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- 2008-12-04 EP EP18174640.5A patent/EP3415475A1/fr active Pending
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US9718729B2 (en) | 2009-05-15 | 2017-08-01 | Owens Corning Intellectual Capital, Llc | Biocides for bio-based binders, fibrous insulation products and wash water systems |
US11286204B2 (en) | 2009-10-09 | 2022-03-29 | Owens Coming Intellectual Capital, LLC | Bio-based binders for insulation and non-woven mats |
US10000666B2 (en) | 2009-10-09 | 2018-06-19 | Owens Corning Intellectual Capital, Llc | Insulative products having bio-based binders |
CN103476300A (zh) * | 2011-03-01 | 2013-12-25 | 欧文斯科宁知识产权资产有限公司 | 具有生物基粘结剂的隔离产品 |
CN102653901A (zh) * | 2011-03-01 | 2012-09-05 | 欧文斯科宁知识产权资产有限公司 | 具有生物基粘结剂的隔离产品 |
CN103443233A (zh) * | 2011-03-31 | 2013-12-11 | 松下电器产业株式会社 | 粘结组合物以及板 |
CN103443233B (zh) * | 2011-03-31 | 2016-08-24 | 松下电器产业株式会社 | 粘结组合物以及板 |
US10047210B2 (en) | 2011-04-07 | 2018-08-14 | Owens Corning Intellectual Capital, Llc | Bio-based binders including carbohydrates and a pre-reacted product of an alcohol or polyol and a monomeric or polymeric polycarboxylic acid |
US11066535B2 (en) | 2011-04-07 | 2021-07-20 | Owens Corning Intellectual Capital, Llc | Bio-based binders including carbohydrates and a pre-reacted product of an alcohol or polyol and a monomeric or polymeric polycarboxylic acid |
US9957409B2 (en) | 2011-07-21 | 2018-05-01 | Owens Corning Intellectual Capital, Llc | Binder compositions with polyvalent phosphorus crosslinking agents |
CN104350112A (zh) * | 2012-06-01 | 2015-02-11 | Stm技术公司 | 用于矿物纤维的不含甲醛的粘结组合物 |
CN106458739A (zh) * | 2014-04-15 | 2017-02-22 | 圣戈班伊索福公司 | 基于非还原糖和氢化糖的施胶组合物以及获得的隔绝产品 |
CN104775720A (zh) * | 2015-05-08 | 2015-07-15 | 南通启秀门窗有限公司 | 复合板门 |
CN109135618A (zh) * | 2018-07-25 | 2019-01-04 | 金隅微观(沧州)化工有限公司 | 一种保温材料用的无醛胶黏剂的制备方法 |
CN112778955A (zh) * | 2021-01-11 | 2021-05-11 | 黄山学院 | 一种低成本水性胶黏剂及其制备方法 |
Also Published As
Publication number | Publication date |
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US20120090505A1 (en) | 2012-04-19 |
CO6311013A2 (es) | 2011-08-22 |
PT2231543T (pt) | 2018-12-06 |
MX2010006224A (es) | 2010-08-11 |
AU2008339837A1 (en) | 2009-07-02 |
FR2924719B1 (fr) | 2010-09-10 |
KR101557845B1 (ko) | 2015-10-06 |
JP5575658B2 (ja) | 2014-08-20 |
KR20100094546A (ko) | 2010-08-26 |
CA2708079C (fr) | 2017-04-04 |
WO2009080938A2 (fr) | 2009-07-02 |
BRPI0820963A2 (pt) | 2015-07-14 |
EA019897B1 (ru) | 2014-07-30 |
EP2231543A2 (fr) | 2010-09-29 |
FR2924719A1 (fr) | 2009-06-12 |
WO2009080938A3 (fr) | 2009-09-17 |
JP2011506781A (ja) | 2011-03-03 |
EP3415475A1 (fr) | 2018-12-19 |
AU2008339837B2 (en) | 2015-01-15 |
EP2231543B1 (fr) | 2018-09-12 |
DK2231543T3 (da) | 2019-01-02 |
CA2708079A1 (fr) | 2009-07-02 |
US8197587B2 (en) | 2012-06-12 |
CN101939268B (zh) | 2015-06-03 |
EA201070679A1 (ru) | 2010-12-30 |
UA103014C2 (ru) | 2013-09-10 |
US20100282996A1 (en) | 2010-11-11 |
US8951341B2 (en) | 2015-02-10 |
ES2697526T3 (es) | 2019-01-24 |
PL2231543T3 (pl) | 2019-03-29 |
BRPI0820963B1 (pt) | 2019-11-19 |
NZ586577A (en) | 2012-09-28 |
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