CN109715740A - 用于硅酸盐油漆的稳定剂 - Google Patents

用于硅酸盐油漆的稳定剂 Download PDF

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CN109715740A
CN109715740A CN201780009072.4A CN201780009072A CN109715740A CN 109715740 A CN109715740 A CN 109715740A CN 201780009072 A CN201780009072 A CN 201780009072A CN 109715740 A CN109715740 A CN 109715740A
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R·库普费尔
J·皮塔奇罗派兹
C·索芬
J·鲁格
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Abstract

本发明的主题是硅酸盐涂料，其包含(A)至少一种式(I)的化合物，其中R1表示H、C1‑C4‑烷基、CH2CH2OH或CH2CH(CH3)OH，(B)至少一种硅酸盐粘结剂，(C)任选的一种或更多种聚合物粘结剂，(D)任选的另外的用于制备硅酸盐涂料的常规添加物，和(E)水。

Description

用于硅酸盐油漆的稳定剂
技术领域
本发明的主题是用于硅酸盐油漆和分散性硅酸盐油漆的稳定剂，其降低油漆的触变性和粘度。
背景技术
根据DIN 18363的硅酸盐油漆和分散性硅酸盐油漆可以包含多达5重量％的有机级分，以及具有>5重量％有机份额的有机硅酸盐油漆越来越令人感兴趣，因为它们由于它们的高pH值不需要或者需要很少的杀生物剂。根据现有技术，在含水的硅酸盐油漆和分散性硅酸盐油漆中使用稳定剂，所述稳定剂阻碍水玻璃在容器中过早硅化，使得涂料在储存期间并不胶凝并且保持可应用。
WO 9418277描述了气相二氧化硅，其表面用表面活性剂改性并且可以作为流变学添加剂和增稠剂使用。对此作为表面活性剂尤其适合的是叔烷基胺和季烷基胺，包括其烷氧基化物和二聚体。
WO 0073237和EP 1222234二者都描述了硅酸盐涂料，其使用双羟基季铵盐作为稳定剂。
EP 1431354教导了作为水玻璃体系的稳定剂的叔二胺。
DE 102006045853教导了由含氮化合物和烷基硅醇盐组成的含硅酸盐的制剂的组合物，其具有改进的粘度稳定化。
S.Weber(Farbe und Lacke，2007，第5卷，第173-174页)教导了工业上得到证实有用的用于硅酸盐油漆和有机硅酸盐油漆的稳定剂基于季铵化合物和胺衍生物。S.Weber尤其强调，两种稳定剂的组合导致在储存期间的降低的增稠。
EP 0614881、US 5449770和US 2016962描述了从葡萄糖出发制备葡糖胺的方法。
EP 1676831一般性地描述了叔二烷基葡糖胺如二乙基葡糖胺的制备及其作为表面活性剂在水性涂漆中的用途，然而没有记载任何具体实例。
根据现有技术描述的硅酸盐涂料在实践中具有高触变性，这使得用户的操作变得困难，因为涂料看起来像布丁。因此，必须将硅酸盐涂料和分散性硅酸盐涂料在使用前强烈搅拌，以破坏触变性并且使其能够流动，从而可以均匀地施加油漆并且产生更好的流平。此外，硅酸盐涂料通常显示出在储存期间增稠的倾向，这根据现有技术借助溶液仅部分地得以解决。
发明内容
本发明的任务因此在于发现用于硅酸盐尤其和分散性硅酸盐油漆的稳定剂，所述稳定剂降低粘度和触变性，以改进硅酸盐油漆和分散性硅酸盐油漆的操作和可应用性以及改进其储存稳定性。
出人意料地发现，这采用基于可再生原料葡萄糖的胺而成为可能。
本发明的主题因此是硅酸盐涂料，其包含
(A)至少一种式(I)的化合物
其中，R1表示H、C1-C4-烷基、CH2CH2OH或CH2CH(CH3)OH，
(B)至少一种硅酸盐粘结剂，
(C)任选的一种或更多种聚合物粘结剂，
(D)任选的另外的用于制备硅酸盐涂料的常规添加物，
和
(E)水。
化合物(I)为多羟基胺，其中R1可以为H、C1-C4-烷基、CH2CH2OH或CH2CH(CH3)OH。优选地，R1为H、甲基或CH2CH2OH。
多羟基单元为己糖，优选差向异构体葡萄糖。
用于制备式(I)的烷基葡糖胺的方法是本领域技术人员充分已知的。对于其中R＝C1-至C4-烷基的化合物，这例如根据在EP 1676831中给出的方法，通过N-烷基多羟基胺与醛或酮在氢气和过渡金属催化剂存在下的还原烷基化来进行。羟乙基-N-甲基-葡糖胺和羟丙基-N-甲基-葡糖胺可以通过N-甲基葡糖胺与氧化乙烯或者氧化丙烯在水溶液中反应而制备。可以将式(I)的化合物作为纯物质或作为水溶液使用。因为叔胺如二甲基葡糖胺，羟乙基-N-甲基葡糖胺和羟丙基-N-甲基-葡糖胺不太易于形成亚硝胺，所以它们对于根据本发明的硅酸盐涂料而言是优选的。
硅酸盐粘结剂，即组分(B)优选为沉淀的碱金属硅酸盐、水玻璃或硅溶胶。
聚合物粘结剂，即组分(C)优选为烯属不饱和单体的均聚物或共聚物。优选的烯属不饱和单体例如为
-乙烯基单体，如乙烯醇的羧酸酯，例如乙酸乙烯酯、丙酸乙烯酯，异壬酸或异癸酸(也被称为C9和C10-叔羧酸)的乙烯基醚，
-芳基取代的烯烃，如苯乙烯和茋，
-烯属不饱和羧酸酯，如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸戊酯、丙烯酸己酯、丙烯酸2-乙基己酯、丙烯酸十三烷基酯、丙烯酸硬脂基酯、丙烯酸羟乙酯、丙烯酸羟丙酯以及对应的甲基丙烯酸酯，
-烯属不饱和二羧酸酯，如马来酸二甲酯、马来酸二乙酯、马来酸二丙酯、马来酸二丁酯、马来酸二戊酯、马来酸二己酯和马来酸2-乙基己酯，
-烯属不饱和羧酸和二羧酸，如丙烯酸、甲基丙烯酸、衣康酸、马来酸和富马酸，及其钠、钾和铵盐，
-烯属不饱和磺酸和膦酸及其碱金属盐和铵盐，如乙烯基磺酸、乙烯基膦酸、丙烯酰氨基甲基丙磺酸及其碱金属盐和铵盐、烷基铵盐和羟烷基铵盐，烯丙基磺酸及其碱金属盐和铵盐，丙烯酰氧乙基膦酸及其铵盐和碱金属盐以及相应的甲基丙烯酸衍生物，
-烯属不饱和胺、铵盐、腈和酰胺，如丙烯酸二甲氨基乙酯、丙烯酰氧乙基三甲基卤化铵、丙烯腈、丙烯酰胺、甲基丙烯酰胺、N-甲基丙烯酰胺、N-乙基丙烯酰胺、N-丙基丙烯酰胺、N-羟甲基丙烯酰胺以及相应的甲基丙烯酸衍生物和乙烯基甲基乙酰胺。
常规添加物，即组分(D)可以为：颜料，其中术语“颜料”既意指颜料，又在更宽的意义上意指填料，和助剂。助剂尤其可以为润湿剂和分散剂、消泡剂、杀生物剂、聚结剂、碱以及流变学添加剂。
合适的颜料是细分散的、有机或无机白色颜料或彩色颜料或各种这样的颜料的混合物。
作为特别优选的有机颜料的示例性选择，在此列举炭黑颜料，例如气黑或炉黑；单偶氮颜料和双偶氮颜料，尤其是染料索引颜料颜料黄1、颜料黄3、颜料黄12、颜料黄13、颜料黄14、颜料黄16、颜料黄17、颜料黄73、颜料黄74、颜料黄81、颜料黄83、颜料黄87、颜料黄97、颜料黄111、颜料黄126、颜料黄127、颜料黄128、颜料黄155、颜料黄174、颜料黄176、颜料黄191、颜料黄213、颜料黄214、颜料红38、颜料红144、颜料红214、颜料红242、颜料红262、颜料红266、颜料红269、颜料红274、颜料橙13、颜料橙34或颜料棕41；萘酚颜料和萘酚AS颜料，尤其是染料索引颜料颜料红2、颜料红3、颜料红4、颜料红5、颜料红9、颜料红12、颜料红14、颜料红53:1、颜料红112、颜料红146、颜料红147、颜料红170、颜料红184、颜料红187、颜料红188、颜料红210、颜料红247、颜料红253、颜料红254、颜料红256、颜料橙5、颜料橙38或颜料棕1；色淀偶氮颜料和金属络合物颜料，尤其是染料索引颜料颜料红48:2、颜料红48:3、颜料红48:4、颜料红57:1、颜料红257、颜料橙68或颜料橙70；苯并咪唑啉颜料，尤其是染料索引颜料颜料黄120、颜料黄151、颜料黄154、颜料黄175、颜料黄180、颜料黄181、颜料黄194、颜料红175、颜料红176、颜料红185、颜料红208、颜料紫32、颜料橙36、颜料橙62、颜料橙72或颜料棕25；异吲哚啉酮颜料和异吲哚啉颜料，尤其是染料索引颜料颜料黄139或颜料黄173；酞菁颜料，尤其是染料索引颜料颜料蓝15、颜料蓝15:1、颜料蓝15:2、颜料蓝15:3、颜料蓝15:4、颜料蓝15:6、颜料蓝16、颜料绿7或颜料绿36；蒽嵌蒽二酮颜料、蒽醌颜料、喹吖啶酮颜料、二噁嗪颜料、靛蒽醌颜料、二萘嵌苯颜料、芘酮颜料和硫靛颜料，尤其是染料索引颜料颜料黄196、颜料红122、颜料红149、颜料红168、颜料红177、颜料红179、颜料红181、颜料红207、颜料红209、颜料红263、颜料蓝60、颜料紫19、颜料紫23或颜料橙43；三芳基正碳颜料，尤其是染料索引颜料颜料红169、颜料蓝56或颜料蓝61。
合适的无机颜料为例如二氧化钛、锌硫化物、锌氧化物、铁氧化物、磁铁矿、锰铁氧化物、铬氧化物、群青、镍或铬锑钛氧化物、锰钛金红石、钴氧化物、钴和铝的混合氧化物、金红石混合相颜料、稀土的硫化物、钴与镍和锌的尖晶石、基于铁和铬与铜锌以及锰的尖晶石、钒酸铋以及体质颜料，尤其使用染料索引颜料颜料黄184、颜料黄53、颜料黄42、颜料黄棕24、颜料红101、颜料蓝28、颜料蓝36、颜料绿50、颜料绿17、颜料黑11、颜料黑33以及颜料白6；还有被称为填料的碳酸钙，如天然存在的白垩和沉淀碳酸钙、白云石，天然二氧化硅(石英粉)，气相和沉淀二氧化硅，硅藻土，铝氧化物，铝氢氧化物，滑石，高岭土，云母(钾-铝硅酸盐水合物)，硫酸钡如天然存在的重晶石和沉淀Blanc Fix。优选地还经常使用无机颜料的混合物。同样经常使用有机与无机颜料的混合物。
合适的润湿剂和分散剂优选为聚丙烯酸盐，丙烯酸酯和MAS共聚物，烷基酚乙氧基化物和烷基份乙氧基化物替代物，如Guerbet衍生物，脂肪酸衍生物和脂肪醇衍生物，尤其是其烷氧基化物，以及EO/PO均聚物和嵌段共聚物和聚硅氧烷醚。
合适的消泡剂优选为矿物油消泡剂及其乳液，硅油消泡剂和硅油乳液，聚亚烷基二醇，聚亚烷基二醇脂肪酸酯，脂肪酸，较高元的醇，磷酸酯，疏水改性的二氧化硅，三硬脂酸铝，聚乙烯蜡和酰胺蜡。
用于防止细菌、藻类和真菌的不受控的增殖的合适的杀生物剂为甲醛、甲醛给体化合物、甲基异噻唑啉酮、氯甲基异噻唑啉酮、苯并异噻唑啉酮、溴硝丙二醇、二溴二氰基丁烷和经氯化银涂覆的二氧化钛。
合适的聚结剂为酯和酮，如苯甲酸酯和丁酸酯，以及醚醇和二醇。尤其列举2,2,4-三甲基-戊烷-1,3-二醇单异丁酸酯、丁基乙二醇、丁基二乙二醇、丁基二丙二醇、丙二醇丁醚和二丙二醇丁醚作为聚结剂。
合适的碱为一价、二价或三价金属离子的金属氢氧化物。优选的碱为氢氧化钠或氢氧化钾以及其水溶液。
作为用于调节粘度的试剂的合适的流变学添加剂例如为淀粉衍生物和纤维素衍生物，和疏水改性的乙氧基化的氨基甲酸酯(HEUR)增稠剂，碱可溶胀的丙烯酸酯增稠剂，疏水改性的丙烯酸酯增稠剂，黄原胶，层状硅酸盐，丙烯酰氨基甲基丙磺酸的聚合物或气相二氧化硅。
常规助剂的概述由Wernfried Heilen等人在由Vincentz Network,2009出版的“Additive fürLacksysteme”中给出。
用于制备根据本发明的硅酸盐涂料的水，即组分(E)优选以蒸馏水或脱盐水的形式使用。也可以使用饮用水(自来水)和/或天然来源的水。
在本发明的一个优选实施方案中，组分(A)以0.01至10重量％，尤其是0.02至5.0重量％的量包含于根据本发明的组合物中。
在本发明的一个优选实施方案中，组分(B)以0.1至40重量％，尤其是0.5至25重量％的量包含于根据本发明的组合物中。
在本发明的一个优选实施方案中，组分(C)以0.1至70重量％，尤其是0.5至50重量％的量包含于根据本发明的组合物中。
如果根据本发明的组合物包含归入组分(D)的一种或更多种成分，则使用这样的成分的以下优选的量：
-10至70重量％的量的白色颜料或彩色颜料
-0.01至10重量％的量的润湿剂或分散剂
-0.01至5重量％的量的消泡剂
-0.01至5重量％的量的杀生物剂
-0.01至5重量％的量的聚结剂
-0.1至10重量％的量的流变学添加剂
-0.01至10重量％的量的碱。
在本发明的一个优选实施方案中，组分(E)以1至80重量％，尤其是加至100重量％的量包含于根据本发明的组合物中。
以重量百分比计的数据基于涂料组合物的总重量计。
在另一优选的形式中，将组分(A)，即式(I)的化合物与季铵化合物组合。在另一优选的形式中，季铵化合物为式(II a)或(II b)的化合物，
其中
R3、R4、R5和R8彼此独立地表示C1-C6-烷基；
R2表示C1-C2-烷基、CH2CH2OH或CH2CH(CH3)OH；
R6和R7表示H或C1-C4-烷基；和
n、x和y彼此独立地表示介于1和10之间的数。
X为阴离子，选自卤离子、亚硝酸根、硝酸根、碳酸根、磷酸根、膦酸根、氢氧根、硫酸根或磺酸根。
在特别优选的形式中，以0.5:1至1:0.5的比例使用式(I)和(II)的化合物。在一个特别优选的形式中，式(I)和(II)的化合物的比例介于0.75:1至1:0.75之间。
根据本发明的硅酸盐涂料适合于制备所有类型的涂料。根据本发明的硅酸盐涂料特别适合于制备硅酸盐油漆、分散性硅酸盐油漆和有机硅酸盐油漆和内部和外部的灰泥，以及模塑料、粘合料和填充料。
本发明的另一主题是式(I)的化合物作为硅酸盐尤其、分散性硅酸盐油漆和有机硅酸盐油漆和内部和外部的灰泥，以及模塑料、粘合料和填充料的稳定剂的用途。
实施例
如果没有另外指出，则在本说明书中的百分比数据为基于总组合物的重量计的重量百分比。
在对比序列中，对表1的含氮化合物在硅酸盐涂料中关于它对流变学的影响进行研究。经过储存时间的粘度和粘度改变显示了增稠的程度。流动界限(Flieβgrenze)和触变面积(Thixotropie-)显示了为了使硅酸盐涂料变得能流动以可以均匀地施涂油漆所需要的力。经过储存时间的改变显示了多快重新建立触变性并且因此防止均匀的流平。
流变学测量在流变仪HAAKE MARS III(Thermo Scientific)上进行。在每次测量时使用填充有水的溶剂阱和样品封闭罩。
采用锥/板测量几何(1°60mm)在20℃测量粘度。测量具有介于1和200s-1之间的剪切速率规格的旋转斜坡并且在60s-1的剪切速率读取粘度的值。
触变性的确定通过具有介于0.1和1000s-1之间剪切速率规格的介于向上旋转斜坡与向下旋转斜坡之间的滞后面积的评价来进行。所述测量采用锥/板测量几何(1°60mm)在23℃进行。
在流动界限测定之前，将样品施涂在测量板上，在0.1s-1下剪切5分钟，并且静置5分钟(结构恢复阶段)。然后以介于0.01和80Pa之间的剪切应力规格进行旋转斜坡。流动界限的确定按照切线法在测量曲线的双对数图中进行。所述测量采用板-板几何(35mm–间隙1mm)在23℃进行。
表1：所使用的稳定剂
表2：硅酸盐油漆以重量％计的组成
项目 原料 功能 重量％
1 水 溶剂 24.5
2 Tylose H 30000P2 纤维素增稠剂 0.4
3 Sapetin D27 润湿剂 0.2
4 DispersogenSPS 稳定剂(季铵化合物) 1
5 Agitan E 256 消泡剂 0.15
6 Tiona 595 白色颜料 10
7 Finntalc M30SL 填料 5
8 Omyacarb 2GU 填料 10
9 Omyacarb 5GU 填料 16
10 Omyacarb extra GU 填料 3.7
11 水 溶剂 1
12 Mowilith LDM 6119 粘结剂 9
13 水 溶剂 1
14 Silres BS 1306 硅油 0.65
15 Betolin K28 碱 16
16 根据表1的稳定剂 稳定剂 0.2
17 水 溶剂 0.2
18 Agitan E 256 消泡剂 0.15
19 水 溶剂 0.85
总计 100
根据表2组成硅酸盐油漆。为此将组分1-5在室温通过连续添加在100至300转/min下借助于Firma Getzmann公司的具有锯齿搅拌器的溶解器而均质化。然后将组分6-10在高剪切速率(1000-1300转/min)下分散。最后在1300转/min连续添加和均质化组分11至19。
表3示出了当根据表1添加稳定剂时，根据表2的硅酸盐油漆的性质。
表3：实施例1(V)至3于硅酸盐油漆中
表3实施例1(V)显示出相对于本发明(实施例2和3)更高的粘度和更强的粘度升高。实施例2和3的更小的触变面积和流动界限显示出硅酸盐油漆的更容易的操作。
表4：有机硅酸盐油漆以重量％计的组成
项目 原料 功能 重量％
1 水 溶剂 20
2 Tafigel PUR 40 PU-增稠剂 0.3
3 Tylose MH 6000YG8 纤维素增稠剂 0.08
4 Lopon 890 润湿剂 0.3
5 Dispersogen SPS 稳定剂(季铵化合物) 0.16
6 Agitan E 256 消泡剂 0.4
7 Wükonil HB 3000 蜡 2
8 Tiona 595 白色颜料 17.5
9 Finntalc M30SL 填料 5
10 Omyacarb 2GU 填料 8.5
11 Omyacarb 5GU 填料 6.5
12 Omyacarb extra GU 填料 12
13 水 溶剂 1
14 Mowilith LDM 1828 粘结剂 17
15 水 溶剂 1
16 Tafigel PUR 44 PU-增稠剂 0.5
17 氢氧化钾溶液(10％) Alkali 1
18 Betolin K28 水玻璃 3.5
19 根据表1的稳定剂 稳定剂 0.2
20 水 溶剂 0.2
21 Agitan E 256 消泡剂 0.15
22 水 溶剂 1.67
总计 100
根据表4组成有机硅酸盐油漆。为此将组分1-7在室温通过连续添加在100至300转/min下借助于Firma Getzmann公司的具有锯齿搅拌器的溶解器而均质化。然后将组分8-13在高剪切速率(1000-1300转/min)下分散。最后在1300转/min连续添加和均质化组分14至22。
表5示出了当根据表1添加稳定剂时，根据表4的有机硅酸盐油漆的性质。
表5：实施例4(V)至6于有机硅酸盐油漆中
表5实施例4(V)显示出相对于本发明(实施例5和6)更高的粘度和更强的粘度升高。实施例5和6的更小的触变面积和流动界限显示出有机硅酸盐油漆的更容易的操作。

Claims (30)

1.分散体，其包含
(A)至少一种式(I)的化合物
其中，R1表示H、C1-C4-烷基、CH2CH2OH或CH2CH(CH3)OH，
(B)至少一种硅酸盐粘结剂，
和
(E)水。
2.根据权利要求1所述的分散体，其另外包含作为组分(C)的一种或更多种聚合物粘结剂。
3.根据权利要求1和/或2所述的分散体，其另外包含作为组分(D)的一种或更多种成分，选自颜料、分散剂、消泡剂、聚结剂、流变学添加剂、杀生物剂、润湿剂和碱。
4.根据权利要求1至3中一项或多项所述的分散体，其中R1为H、甲基或CH2CH2OH。
5.根据权利要求1至3中一项或多项所述的分散体，其中R1为H或甲基。
6.根据权利要求1至5中一项或多项所述的分散体，其中式(I)的化合物的浓度为0.01至10重量％。
7.根据权利要求1至5中一项或多项所述的分散体，其中式(I)的化合物的浓度为0.02至5％。
8.根据权利要求1至7中一项或多项所述的分散体，所述分散体包含季铵化合物。
9.根据权利要求8所述的分散体，其中所述季铵化合物选自式(II a)和(II b)的化合物
其中，
R3、R4、R5和R8彼此独立地表示C1-C6-烷基；
R2表示C1-C2-烷基、CH2CH2OH或CH2CH(CH3)OH；
R6和R7彼此独立地表示H或C1-C4-烷基；
n、x和y彼此独立地表示介于1和10之间的数，和
X为阴离子，选自卤离子、亚硝酸根、硝酸根、碳酸根、磷酸根、膦酸根、氢氧根、硫酸根或磺酸根。
10.根据权利要求9所述的分散体，其中以0.5:1至1:0.5的比例使用式(I)和(II)的化合物。
11.根据权利要求9所述的分散体，其中以0.75:1至1:0.75的比例使用式(I)和(II)的化合物。
12.根据权利要求1至11中一项或多项所述的分散体，其以10至70重量％的量包含白色颜料或彩色颜料。
13.根据权利要求1至12中一项或多项所述的分散体，其以0.01至10重量％的量包含润湿剂或分散剂。
14.根据权利要求1至13中一项或多项所述的分散体，其以0.01至5重量％的量包含消泡剂。
15.根据权利要求1至14中一项或多项所述的分散体，其以0.01至5重量％的量包含杀生物剂。
16.根据权利要求1至15中一项或多项所述的分散体，其以0.01至5重量％的量包含聚结剂。
17.根据权利要求1至16中一项或多项所述的分散体，其以0.1至10重量％的量包含流变学添加剂。
18.根据权利要求1至17中一项或多项所述的分散体，其以0.01至70重量％的量包含聚合物粘结剂。
19.根据权利要求1至17中一项或多项所述的分散体，其以0.5至50重量％的量包含聚合物粘结剂。
20.根据权利要求1至19中一项或多项所述的分散体，其0.01至10重量％以的量包含碱。
21.根据权利要求1至20中一项或多项所述的分散体，其中包含0.1至40重量％的成分(B)。
22.根据权利要求1至20中一项或多项所述的分散体，其中包含0.5至25重量％的成分(B)。
23.根据权利要求1至22中一项或多项所述的分散体，其中包含1至80重量％的水。
24.根据权利要求1至23中一项或多项所述的分散体，其中式(I)的化合物衍生自葡萄糖。
25.至少一种式(I)的化合物作为用于硅酸盐涂料的稳定剂的用途
其中，R1表示H、C1-C4-烷基、CH2CH2OH或CH2CH(CH3)OH，所述硅酸盐涂料包含至少一种硅酸盐粘结剂和水。
26.根据权利要求25所述的用途，其中将所述式(I)的化合物与至少一种季铵化合物组合。
27.根据权利要求26所述的用途，其中所述季铵化合物对应于式(II a)和/或(II b)
其中，
R3、R4、R5和R8彼此独立地表示C1-C6-烷基；
R2表示C1-C2-烷基、CH2CH2OH或CH2CH(CH3)OH；
R6和R7彼此独立地表示H或C1-C4-烷基；
n、x和y彼此独立地表示介于1和10之间的数，和
X表示阴离子，选自卤离子、亚硝酸根、硝酸根、碳酸根、磷酸根、膦酸根、氢氧根、硫酸根或磺酸根。
28.根据权利要求27所述的用途，其中以0.5:1至1:0.5的比例使用式(I)和(II)的化合物。
29.根据权利要求27所述的用途，其中以0.75:1至1:0.75的比例使用式(I)和(II)的化合物。
30.根据权利要求25至29中一项或多项所述的用途，其中所述硅酸盐涂料另外包含至少一种聚合物粘结剂。
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