CN110191931A - 用于混凝土结构的涂布剂 - Google Patents

用于混凝土结构的涂布剂 Download PDF

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CN110191931A
CN110191931A CN201880007069.3A CN201880007069A CN110191931A CN 110191931 A CN110191931 A CN 110191931A CN 201880007069 A CN201880007069 A CN 201880007069A CN 110191931 A CN110191931 A CN 110191931A
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concrete structure
smears
component
mass parts
silicon atom
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森秀之
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DuPont Toray Specialty Materials KK
Dow Toray Co Ltd
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Abstract

本发明的用于混凝土结构的涂布剂包含：(A)在两个分子末端经硅烷醇基或硅原子键合的可水解基团封端的二有机聚硅氧烷；(B)每分子具有至少两个硅原子键合的可水解基团的硅烷化合物或其部分水解的缩合物；(C)固化催化剂；和(D)气相二氧化硅；并且形成与混凝土结构牢固粘合的硅酮膜，并且能够通过所述硅酮膜直观地确认所述混凝土结构的表面状态。

Description

用于混凝土结构的涂布剂
技术领域
本发明涉及一种用于混凝土结构的涂布剂。
背景技术
人们担心，由于地震、振动、地面沉降、过载等引起的中和和内部开裂，混凝土结构的部分如隧道内壁或桥梁可能由于表面开裂而脱落和掉落，并且可能会落到在所述结构下方通过的车辆或导航船上。因此，已经提出了将透明或半透明树脂涂布到混凝土结构表面上的方法(参见专利文献1至3)。
作为在此类方法中使用的涂布剂，使用诸如环氧树脂、丙烯酸树脂、聚氯酯树脂或聚酯树脂的有机树脂。
然而，此类有机树脂的耐候性差，因此，此类有机树脂不足以作为用于隧道、桥梁和暴露于恶劣环境的其它此类混凝土结构的涂布剂。另一方面，通过水分固化的硅酮橡胶组合物在固化时不需要加热或类似处理，并且可以形成具有优异耐候性的硅酮固化产物，且因此，此类组合物已作为用于混凝土结构的涂布剂进行考查。然而，硅酮橡胶组合物的问题是对混凝土结构的粘合性不足。
[现有技术文件]
[专利文件]
专利文件1：JP 2001-355343 A
专利文件2：JP 2006-342538 A
专利文件3：JP 2009-150085 A
发明内容
[本发明要解决的问题]
本发明的一个目的是提供一种用于混凝土结构的涂布剂，所述涂布剂形成与混凝土结构牢固粘合的硅酮膜，并且能够通过所述硅酮膜直观地确认混凝土结构的表面状态。
[解决问题的手段]
本发明的用于混凝土结构的涂布剂包含：
(A)100质量份的在两个分子末端经硅烷醇基或硅原子键合的可水解基团封端的二有机聚硅氧烷；
(B)1至25质量份的每分子具有至少两个硅原子键合的可水解基团的硅烷化合物或其部分水解的缩合物；
(C)0.5至10质量份的固化催化剂；以及
(D)15至40质量份的气相二氧化硅。
组分(A)中的硅原子键合的可水解基团优选为烷氧基。
组分(B)优选为由以下通式表示的烷氧基硅烷：
R1 aSi(OR2)(4-a)
(其中，R1是具有1至6个碳原子的一价烃基；R2是具有1至3个碳原子的烷基；并且“a”是0或1)
或其部分水解的缩合物。
组分(C)优选是有机钛化合物。
组分(D)优选是通过用有机硅化合物表面处理BET比表面积为50至400m2/g的气相二氧化硅而获得的气相二氧化硅。
所述组合物可进一步包含(E)所期望量的有机溶剂。
此外，根据本发明的用于涂布混凝土结构的方法的特征在于将底涂剂施加到混凝土结构的表面上，之后施加如上所述的用于混凝土结构的涂布剂。
[发明效果]
根据本发明的用于混凝土结构的涂布剂，形成了与混凝土结构牢固粘合的硅酮膜，并且可以通过所述硅酮膜直观确认混凝土结构的表面状态。
附图说明
图1是绘示用本发明的用于混凝土结构用涂布剂涂布混凝土结构的方法的实施例的步骤图。
具体实施方式
将详细描述本发明的用于混凝土结构的涂布剂。
组分(A)是在两个分子末端具有硅原子键合的羟基(所谓的硅烷醇基)或硅原子键合的可水解基团的二有机聚硅氧烷。硅原子键合的可水解基团的实例包括：烷氧基，如甲氧基、乙氧基和丙氧基；肟基，如乙酰肟基和甲基乙基酮肟基；氨基，如二甲氨基和二乙氨基；酰胺基，如N-甲基乙酰胺基；氨基氧基，如二乙氨基氧基；和烯基氧基，如异丙烯氧基；且其中，烷氧基是优选的。此类烷氧基可以在每个分子末端直接键合到硅原子上，并且可以键合到通过亚烷基键合到分子末端的硅原子上的硅原子上。亚烷基的实例包括甲基亚甲基、亚乙基、甲基亚乙基和亚丙基。与组分(A)中的硅原子键合的其它基团的实例包括：烷基，如甲基、乙基、丙基和丁基；烯基，如乙烯基和烯丙基；芳基，如苯基、甲苯基和萘基；芳烷基，如苄基、苯乙基和苯丙基；以及卤代烃基，如氯甲基、三氟丙基和氯丙基；且其中，甲基是尤其优选的。
组分(B)是每分子具有至少两个硅原子键合的可水解基团的硅烷化合物，或者是其部分水解的缩合物。硅原子键合的可水解基团的实例包括：烷氧基，如甲氧基、乙氧基和丙氧基；肟基，如乙酰肟基和甲基乙基酮肟基；氨基，如二甲氨基和二乙氨基；酰胺基，如N-甲基乙酰胺基；氨基氧基，如二乙氨基氧基；和烯基氧基，如异丙烯氧基；且其中，烷氧基是优选的。与(B)组分中的硅原子键合的其它基团的实例包括：烷基，如甲基、乙基、丙基和丁基；烯基，如乙烯基和烯丙基；芳基，如苯基、甲苯基和萘基；芳烷基，如苄基、苯乙基和苯丙基；以及卤代烃基，如氯甲基、三氟丙基和氯丙基；且其中，甲基是尤其优选的。
组分(B)优选为由以下通式表示的烷氧基硅烷：
R1 aSi(OR2)(4-a)
或者是其部分水解产物。在所述式中，R1是具有1至6个碳原子的一价烃基，并且实例包括：烷基，如甲基、乙基、丙基或丁基；烯基，如乙烯基或烯丙基；和苯基。此外，在所述式中，R2是具有1至3个碳原子的烷氧基，并且实例包括甲氧基、乙氧基和丙氧基。在所述式中，“a”是0或1。
组分(B)的烷氧基硅烷的实例包括甲基三甲氧基硅烷、甲基三乙氧基硅烷、乙基三甲氧基硅烷、乙烯基三甲氧基硅烷、苯基三甲氧基硅烷、甲基三甲氧基乙氧基硅烷、四甲氧基硅烷和四乙氧基硅烷；组分(B)的肟硅烷的实例包括甲基三(甲基乙基酮肟)硅烷和乙烯基三(甲基乙基酮肟)硅烷；组分(B)的氨基硅烷的实例包括甲基三(二甲基氨基)硅烷；组分(B)的酰胺硅烷的实例包括甲基三(N-甲基乙酰胺)硅烷；且组分(B)的氨基氧基硅烷的实例包括甲基三(二甲基氨基)硅烷。组分(B)可以独立地使用这些化合物或者作为其中两种或更多种的混合物使用。
组分(B)的含量在每100质量份组分(A)1至25质量份的范围内，并且优选在2至10质量份的范围内。这是因为当组分(B)的含量不低于上述范围的下限时，涂布剂的储存稳定性提高，而另一方面，当含量不高于上述范围的上限时，涂布剂的固化性提高。
组分(C)是固化催化剂，且实例包括有机钛化合物和有机锡化合物。有机钛化合物的实例包括四(异丙氧基)钛、四(正丁氧基)钛、四(叔丁氧基)钛和其它钛酸酯；二(异丙氧基)双(乙基乙酰乙酸)钛、二(异丙氧基)双(甲基乙酰乙酸)钛、二(异丙氧基)双(乙酰丙酮)钛和其它钛螯合物。有机锡化合物的实例包括二月桂酸二丁基锡、二乙酸二丁基锡和二辛酸二丁基锡。
组分(C)的含量在每100质量份组分(A)0.5至10质量份的范围内，并且优选在1至5质量份的范围内。这是因为当组分(C)的含量不低于上述范围的下限时，促进了涂布剂的固化性，而另一方面，当含量不超过上述范围的上限时，涂布剂的储存稳定性提高。
组分(D)是气相二氧化硅，用于改良本发明涂布剂的粘合性并改良所得硅酮膜的机械特性。这种类型的组分(D)优选是通过用有机硅化合物表面处理BET比表面积在50至400m2/g范围内、在100至400m2/g范围内、或在200至400m2/g范围内的气相二氧化硅而得到的气相二氧化硅。有机硅化合物的实例包括六甲基二硅烷、六甲基环三硅氮烷和其它此类硅氮烷化合物；三甲基氯硅烷、二甲基二氯硅烷和其它此类卤代硅烷化合物；甲基三甲氧基硅烷、二甲基二甲氧基硅烷和其它此类烷氧基硅烷化合物；和甲基氢聚硅氧烷和其它此类有机聚硅氧烷。
相对于100重量份的组分(A)，组分(D)的含量在15至40质量份范围内，并且优选在20至40质量份范围内，在25至40质量份范围内，或在30至40质量份范围内。这是因为当组分(D)的含量不低于上述范围的下限时，涂布剂的粘合性提高，而另一方面，当含量不超过上述范围的上限时，涂布剂的施加容易性提高。
本发明的涂布剂可包含例如在不妨碍本发明目的的范围内的有机溶剂、防霉剂、阻燃剂、耐热剂、增塑剂、触变性赋予剂、粘合赋予剂、固化促进剂和颜料。有机溶剂的实例包括正己烷、甲苯、二甲苯和乙酸溶纤剂，其混合量是任选的，且考虑到施加本发明涂布剂的容易性和所得硅酮的膜厚度，可以混合所期望的量。
施加涂布剂的混凝土结构的实例包括公路或铁路隧道、公路或铁路桥梁等。图1a是绘示在施加本发明涂布剂之前的混凝土结构的横截面图。混凝土结构1的表面优选预先用底涂剂以分层方式涂布。当施加本发明涂布剂时，此底涂剂改良了底涂层强化性和粘合性。图1b是表面上形成有底涂剂层2的混凝土结构1的横截面图。
接下来，如图1c中所示，将涂布剂施加到底涂剂层2的表面上。施加后，可以通过在室温下放置来固化涂布剂。当使用本发明涂布剂时，不需要在硅酮固化产物层3的表面上进一步施加面涂布剂，且因此可以显著缩短施工时间。另外，由于硅酮固化产物层3是透明或半透明的，因此即使在其中存在开裂时也可以在施加后直观确认混凝土结构1的表面，且因此可以更有效地进行检查工作。另外，即使发生混凝土结构1的开裂，硅酮固化产物层3也具有足够的粘合性、弹性和强度，且因此，可以追踪开裂并支撑混凝土结构1的表面，并且可以防止混凝土长时间剥落。
应注意，网状剥落防止材料可以以分层的方式安置在底涂剂层2的表面上，以改良混凝土防剥落性能。防剥落材料不受限制，并且可使用各种形状的片材(平面成形体)，如织造片状片材(如纤维片材)、非织造片材和网状或筛状片材(有时称为“网状片材”)。此外，各种纤维，如碳纤维、塑料纤维(例如芳族聚酰胺纤维、维尼纶纤维、聚乙烯纤维片(特别是由高冲击型聚乙烯制成的纤维片)和聚酰亚胺纤维片等)和玻璃纤维可以用作防剥落的材料。
[实例]
将使用实例详细描述本发明的用于混凝土结构的涂布剂。应注意，粘度是25℃时的值。此外，涂布剂的固化产物相对于混凝土结构的粘合强度和固化产物的可见性评估如下。
[粘合性]
通过以下“表面涂布材料的粘合强度的测试方法(Method for Testing theAdhesion Strength of a Surface Coating Material)”评估涂布剂的固化产物对混凝土结构的粘合性。
[表面涂布材料的粘合强度的测试方法]
根据日本土木工程师学会(Japan Society of Civil Engineers)发布的混凝土结构标准规范(Standard Specifications for Concrete Structure)的JSCE-K531-2013“表面涂布材料的粘合强度测试方法”的规定测量粘合强度。具体地，如下进行测量。根据JIS R5201 10.4规定的方法使用内部尺寸为70mm×70mm×20mm的混凝土试件。在混凝土试件上以100g/m2施加底涂剂(可获自道康宁东丽有限公司(Dow Corning Toray Co.，Ltd.)的密封底涂剂B)并干燥。随后，涂布剂根据JIS A 1439规定的固化条件在23±2℃、50±5％RH环境中施加并固化14天，然后在30±2℃的烘箱中固化14天。2℃。在所得试件的表面上，使用粘合剂(Cemedine PPX)将JSCE-K 531-2013规定的上部张紧钢夹具粘合到涂布剂的固化产物的表面上，然后放置在23±2℃、50±5％RH气氛中24小时。接下来，插入40mm×40mm的方形切口，直到围绕上部张紧钢夹具的衬底粘合到测试件上。通过使用JSCE-K 531-2013中所述的用于较低拉伸测试的钢夹具和钢接触板，并使用autograph(可获自岛津制作所(Shimadzu Corporation))在竖直方向上施加拉伸力，对最大拉伸载荷(N/mm2)进行测定。应注意，破损前的加载速率为1750N/分钟。
[可见性]
评估通过涂布剂的固化产物确认混凝土试件的表面状态的能力，且能够确认的情况用“o”表示，难以确认的情况用“Δ”表示，而无法确认的情况用“×”表示。
[实例1]
硅酮橡胶基础化合物通过以下方式制备：将100质量份在两个分子末端经羟基封端且粘度为15,000mPa·s的二甲基聚硅氧烷与35质量份通过用六甲基二硅氮烷表面处理BET比表面积为220m2/g的气相二氧化硅而获得的气相二氧化硅混合。接下来，在水分阻挡下，用于混凝土结构的涂布剂(I)通过以下方式制备：将10质量份甲基三甲氧基硅烷和0.7质量份四(叔丁氧基)钛与此硅酮橡胶基础化合物混合。然后将涂布剂以1.0mm的厚度施加到混凝土试件上以制备试件。评估结果如表1所示。
[实例2]
用于混凝土结构的溶剂型涂布剂(II)通过以下方式制备：将100质量份实例1中制备的用于混凝土结构的涂布剂(I)与100质量份正己烷掺合。然后将涂布剂以0.5mm的厚度施加到混凝土试件上以制备试件。评估结果如表1所示。
[比较实例1]
除了将气相二氧化硅的混合量变为10质量份之外，以与实例1相同的方式制备用于混凝土结构的涂布剂(III)。然后将涂布剂以1.0mm的厚度施加到混凝土试件上以制备试件。评估结果如表1所示。
[比较实例2]
当将实例1的气相二氧化硅的混合量变为45质量份时，不能制备均匀的基础化合物，且因此不能制备均匀的涂布剂。
[比较实例3]
基础化合物通过以下方式制备：将100质量份在两个分子末端经羟基封端且粘度为15,000mPa·s的二甲基聚硅氧烷与17质量份的已经硬脂酸处理的沉淀碳酸钙(SolvaySA产品名称：Socal 312N)混合。接下来，在水分阻挡下，用于混凝土结构的涂布剂(IV)通过以下方式制备：将10质量份甲基三甲氧基硅烷和0.7质量份四(叔丁氧基)钛与此基础化合物混合。然后将涂布剂以1.0mm的厚度施加到混凝土试件上以制备试件。评估结果如表1所示。
[表1]
[工业适用性]
由于本发明的用于混凝土结构的涂布剂通过水分固化形成具有高耐候性的硅酮膜，因此本发明的涂布剂适合作为用于隧道、桥梁以及暴露于恶劣环境的其它此类混凝土结构的涂布剂。
[附图标号]
1：混凝土结构
2：底涂剂层
3：硅酮固化产物层

Claims (7)

1.一种用于混凝土结构的涂布剂，所述涂布剂包含：
(A)100质量份的在两个分子末端经硅烷醇基或硅原子键合的可水解基团封端的二有机聚硅氧烷；
(B)1至25质量份的每分子具有至少两个硅原子键合的可水解基团的硅烷化合物或其部分水解的缩合物；
(C)0.5至10质量份的固化催化剂；以及
(D)15至40质量份的气相二氧化硅。
2.根据权利要求1所述的用于混凝土结构的涂布剂，其中组分(A)中的所述硅原子键合的可水解基团是烷氧基。
3.根据权利要求1所述的用于混凝土结构的涂布剂，其中组分(B)是由以下通式表示的烷氧基硅烷：
R1 aSi(OR2)(4-a)
(其中，R1是具有1至6个碳原子的一价烃基；R2是具有1至3个碳原子的烷基；并且“a”是0或1)
或其部分水解的缩合物。
4.根据权利要求1所述的用于混凝土结构的涂布剂，其中组分(C)是有机钛化合物。
5.根据权利要求1所述的用于混凝土结构的涂布剂，其中组分(D)是通过用有机硅化合物表面处理BET比表面积为50至400m2/g的气相二氧化硅而获得的气相二氧化硅。
6.根据权利要求1至5中任一项所述的用于混凝土结构的涂布剂，其进一步包含(E)所期望量的有机溶剂。
7.一种用于涂布混凝土结构的方法，所述方法包含将底涂剂施加到混凝土结构的表面上，且随后施加根据权利要求1至6中任一项所述的用于混凝土结构的涂布剂。
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JP7121661B2 (ja) 2022-08-18
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