CN1035871C - 玻璃浆料组合物、涂布玻璃纤维和增强热塑性塑料 - Google Patents

玻璃浆料组合物、涂布玻璃纤维和增强热塑性塑料 Download PDF

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CN1035871C
CN1035871C CN92115127A CN92115127A CN1035871C CN 1035871 C CN1035871 C CN 1035871C CN 92115127 A CN92115127 A CN 92115127A CN 92115127 A CN92115127 A CN 92115127A CN 1035871 C CN1035871 C CN 1035871C
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D·W·加列特
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Abstract

用于玻璃纤维的水性浆料组合物，它包括三聚氰胺甲醛树脂，苯氧基树脂和环氧偶联剂，它们是热塑性塑料非常适宜的玻璃纤维增强物。特别地，覆有这种浆料的短玻璃纤维对增强缩醛复合材料很有用。

Description

玻璃浆料组合物、涂布玻璃纤维和增强热塑性塑料
本发明涉及一种浆料组合物，涂布玻璃纤维和增强热塑性塑料。这些浆料对于增强缩醛树脂尤其有用。
目前已有大量的热塑材料包括聚烯烃、聚醛聚酰胺(尼龙)、聚碳酸酯、聚苯乙烯、苯乙烯-丙烯腈共聚物、丙烯腈-丁二烯-苯乙烯共聚物(ABS)和聚氯乙烯(PVC)。热塑树脂和玻璃纤维通过加热和加压的方法制成各种有用的形状。制作方法包括将热树脂注入模具、挤压和挤拉成型。其余方法包括热轧光、浇铸、真空成型等等。在这些制造方法中加入短玻璃纤维以增强和硬化所得的复合材料。
本发明包含一种浆料，它含有：
.三聚氰胺甲醛树脂
.苯氧基树脂
.环氧硅烷偶联剂
由所得的涂布玻璃纤维获得了抗拉强度较高的玻璃纤维增强热塑性塑料。作者发现了对于缩醛树脂的复合抗拉性有特别惊人的效果。
本发明的玻璃浆料组合物与长丝玻璃很有用，对本领域的专业人员来说长丝玻璃是很熟悉的。不同种类的玻璃丝，如“E”型玻璃及其它已知类型的玻璃可归入作者所指的浆料。该浆料对不同直径的玻璃丝都有用，且可用于玻璃丝上，不管它们是否编织成纤维绳子、粗纱、纱线等等。
作者所用的三聚氰胺甲醛树脂是带有N-羟甲基官能团或N-CH2-OR官能团的化合物，其中R为烷基。它是一种甲醛氨基塑料树脂，带或不带醚键(多氧烷基化)。例如：三聚氰胺-甲醛树脂、脲醛树脂、酰胺基-甲醛树脂或可任意挑选地，一种氨基塑料树脂；或这些树脂的混合物，不管它们是否共聚。
作者所用的苯氧基树脂是任何适宜的水可分散苯氧基树脂。例如，该水可分散苯氧基树脂可以是羧基改性的聚羟基醚。苯氧基树脂述于美国专利No.4711924。一种特别适宜的水可分散苯氧基树脂为可由Union Carbide商购的PKHW-35。
本发明的水性浆料合成物中的偶联剂成分含有有机硅烷，该硅烷的硅原子有一容易水解的键或是由此产生的水解产物。有机硅烷可以有一环氧基，即环氧乙烷，通过非水解键与一硅原子连接。该有机硅烷也可以有一个通过非水解键与有机硅烷的硅原子连接的丙烯基或甲基丙烯基。优选的丙烯或甲基丙烯基团是丙烯基氧基或甲基丙烯基氧基基团。该有机硅烷含有R′Si(OR)2结构的甲硅烷，其中R′实际上可是任何有机基团，但低级烷基基团如甲基或乙基则尤其方便且令人满意。该有机硅烷的一个例子是缩水甘油氧基聚亚甲基三烷氧基硅烷，如3-缩水甘油氧基-1-丙基三甲氧基硅烷。另一个例子是丙烯酰氧基或甲基丙烯酰氧基聚亚甲基三烷氧基硅烷，如3-甲基丙烯酰氧基-1-丙基三甲氧基硅烷。作者优选一种有机硅烷如γ-缩水甘油氧基丙基三甲氧基硅烷(A-187 Union Carbide)。另一种适宜的偶联剂是γ-甲基丙烯酰氧基丙基三甲氧基硅烷(A-174 Union Carbide)。
本发明的水性浆料组合物中的润滑剂组分可以是任意适宜于润滑的一般性液体或固体润滑材料。这样的材料包括植物和矿物油，各种蜡以及也有表面活性剂效果的特定物质，如聚亚烷基二醇的脂肪酸单酯。其它润滑剂为乙氧基化的脂肪酸或二元酸，一种乙氧基化的壬烷基苯酚，以及一种乙氧基化的辛烷基苯酚。
往浆料中加酸主要是为了控制pH值。所加的酸的数量足以使浆料的pH达到5.5或更低，但酸的数量可增加，使得浆料的pH值在约3至4范围之间。
以惯用的数量使用浆料的各组分。
浆料最好包含下列物质(重量比)：
                      重量百分比
三聚氰胺甲醛树脂      0.5-14.0
苯氧基树脂            1.0-33.0
环氧硅烷偶联剂        0.1-3.5
润滑剂                0.01-0.2
酸                    0.001-0.1
水                    余下的部分
优选的总固体含量为从约1至约25％(重量)，更加优选的为从约3至约10％重量。
该浆料按如下配比(重量百分比)更佳：
                    重量百分数
三聚氰胺甲醛树脂    1.5-5.5
苯氧基树脂          3.5-13.5
环氧硅烷偶联剂      0.4-1.5
润滑剂              0.02-0.1
酸                  0.01-0.1
水                  余下的部分
本发明的水性浆料组合物可用下列被普遍接受的混合程序制作。使用常用的方法，这些浆料组合物可应用于玻璃纤维。所使用的水性浆料组合物的数量并不严格地限制，但最好能加以控制以使沉积在玻璃纤维上的浆料覆膜含有本发明水性浆料组合物的干残条物的数量为玻璃重量的约0.25％至约2％，这是因为考虑到水性浆料组合物中的非挥发性组分的稀释及一些水性组分在干燥前施用于玻璃时的机械损失。
该水性浆料组合物可应用于玻璃纤维，通过喷涂、浸渍或其它适宜的方法，将纤维绕在用水性浆料组合物润湿或溢流过的卷筒垫子或其它适宜的表面上。水性浆料组合物中的非挥发性组分的总浓度可根据下列各条件在很大范围内调整：应用的方法，所上浆的纤维的特性，即其直径和组成，以及欲用于上浆纤维的干浆料涂层的重量。
本发明上浆后的玻璃纤维可加入可固化基体树脂中，该待增强基体树脂最后成为固化树脂状物件，上浆的玻璃纤维可以取单丝或多丝股，或以长的基本上是连续的单元或短切断的碎毛的形式，这取决于欲形成的物件的形状和制作方法。本发明的浆料玻璃纤维特别适用于短玻璃纤维形式。在这种增强中主要是那些直径约为0.0064至0.019厘米及长度为约0.33至约5.08厘米的玻璃纤维。
如前所述，这种浆料对增强热塑性树脂很有帮助，但我们发现用于缩醛树脂特别有用。这种工程塑料在汽车、家用电器和管道工业上有很多用途。缩醛树脂聚合形成聚甲醛热塑性塑料，该塑料有着-O-CH2-O-CH2-O-CH2-重复单元。
实施例I：
一种优选的水性浆料组合物有着如下的配方：
                            重量百分数
甲基化三聚氰胺甲醛树脂，
美国，Cyanamid Cymel 373       4.6
水可分散性苯氧基树脂，
Union Carbide PKHW-35          11.4
γ-缩水甘油氧基丙基三甲氧基硅烷
Union Carbide A-187            1.2
聚氧化乙烯(20)脱水山梨醇
润滑剂，美国ICI，吐温65     0.07
氯化铵                      0.12
乙酸                        0.025
水                          剩余的部分
该水溶液的固体含量为8.44％(重量百分比)及pH为5.5或更低。该浆料以常用的使用方法应用于玻璃纤维单丝上，且使得股绳固体(干重)的数量达约2％(重量百分比)。
含有标准长度短玻璃纤维的玻璃纤维其平均长度为约0.318厘米且从股绳中可产出约0.00089至0.00099厘米直径的纤维。
实施例II：
评估该上浆纤维模塑试样机的械特性并与一种商业上可获得的试样相比较。每一次试验的结果示于下表。复合树脂为取自Celanese，Celcon M-90C/360的缩醛树脂。
试样   A    B    C    D   对照组   对照组
挤塑机温度(℃)   227    260    227    260    227    260
抗拉(108帕)   1.32    1.37    1.22    1.25    1.25    1.19
无缺口冲击强度IZOD(m-kg/cm)   0.642    0.535    0.491    0.432    0.492    0.373
缺口冲击强度IZOD(m-kg/cm)   0.105    0.118    0.104    0.110    0.113    0.105
耐屈挠性(108帕)   1.89    2.16    1.91    1.89    1.89    1.72
％玻璃   24.7    25.4    24.5    24.7    25.0    24.9
以上数据表明，用本发明的浆料上浆后的玻璃相比，有着比对照组样品更大的机械强度。抗拉与耐层挠性比对照样品有特别明显的改进。当与对照样品相比较时，在色彩方面模塑试样也有很大的改进。

Claims (13)

1.一种用于玻璃纤维的水性浆料组合物，它含有：
带有N-羟甲基官能团或N-CH2-OR官能团或两者都有的化合物，R为烷基；
羧基改性聚羟基醚；
环氧硅烷偶联剂。
2.一种用于玻璃纤维的水性浆料组合物，它含有：
三聚氰胺甲醛树脂、脲醛树脂、酰胺基甲醛树脂、或氨基塑料树脂；苯氧基树脂；和
环氧硅烷偶联剂，它有一个经非水解键与一硅原子相连的环氧乙烷基团。
3.一种用于玻璃纤维的水性浆料组合物，它含有：
三聚氰胺甲醛树脂；水可分散性苯氧基树脂；含有低级烷基的环氧硅烷偶联剂；
润滑剂；
酸。
4.权利要求2的浆料组合物，它含有(重量百分比)：
                   重量百分比：
三聚氰胺甲醛树脂    1.5-5.5
苯氧基树脂          3.5-13.5
环氧硅烷偶联剂      0.4-1.5
润滑剂             0.02-0.1
酸                 0.01-0.1
水                 余下的部分。
5.一种用于玻璃纤维的水性浆料组合物，它含有(重量百分比)：
                                 重量百分比：
甲基化三聚氰胺甲醛树脂             4.6
水可分散性苯氧基树脂               11.4
γ-缩水甘油氧基丙基三甲氧基硅烷     1.2
聚氧化乙烯脱水山梨醇润滑剂          0.07
氯化铵                            0.12
乙酸                              0.025
水                                余下的部分。
6.有着一层浆料覆膜的玻璃纤维，它含有权利要求1中水性组合物的干残余物。
7.有着一层浆料覆膜的玻璃纤维，它含有权利要求5中水性组合物的干残余物。
8.权利要求6所述的玻璃纤维，其中纤维为短玻璃纤维。
9.权利要求7所述的玻璃纤维，其中纤维为短玻璃纤维。
10.玻璃纤维增强热塑性塑料，其中玻璃纤维为权利要求6中的纤维。
11.玻璃纤维增强热塑性塑料，其中玻璃纤维为权利要求8中的短纤维。
12.玻璃纤维增强缩醛复合材料，其中玻璃纤维为权利要求7的纤维。
13.玻璃纤维增强缩醛复合材料，其中玻璃纤维为权利要求9中的短玻璃纤维。
CN92115127A 1991-12-19 1992-12-18 玻璃浆料组合物、涂布玻璃纤维和增强热塑性塑料 Expired - Fee Related CN1035871C (zh)

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EP1812843A4 (en) * 2004-08-31 2014-08-27 Miller Herman Inc DESIGN-BASED PROTOCOL SYSTEMS FOR CONVERTING TAX RELATIONS BETWEEN EQUIPMENT
US8211974B2 (en) 2005-10-07 2012-07-03 Johns Manville Curable fiberglass binder comprising a polyacetal or polyketal
KR101404296B1 (ko) * 2010-06-07 2014-06-09 (주)엘지하우시스 직물 표면을 갖는 ｐｌａ 바닥재
WO2014028333A1 (en) 2012-08-15 2014-02-20 3M Innovative Properties Company Sized short alumina-based inorganic oxide fiber, method of making, and composition including the same
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JP2015034097A (ja) * 2013-08-07 2015-02-19 信越化学工業株式会社 水性シランカップリング剤組成物及びその製造方法、表面処理剤並びに物品
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