CN103124703B - 用于制备永久韧性涂层的涂布剂 - Google Patents
用于制备永久韧性涂层的涂布剂 Download PDFInfo
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- CN103124703B CN103124703B CN201180045819.4A CN201180045819A CN103124703B CN 103124703 B CN103124703 B CN 103124703B CN 201180045819 A CN201180045819 A CN 201180045819A CN 103124703 B CN103124703 B CN 103124703B
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
- C04B24/06—Carboxylic acids; Salts, anhydrides or esters thereof containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/06—Quartz; Sand
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/06—Quartz; Sand
- C04B14/066—Precipitated or pyrogenic silica
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/10—Clay
- C04B14/104—Bentonite, e.g. montmorillonite
-
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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Abstract
本发明涉及基于一种或多种无机粘合剂、一种或多种聚合物、一种或多种填料和任选存在的一种或多种添加剂的涂布组合物。本发明的特征在于所述涂布组合物包含基于涂布组合物的干重为0.05‑5重量%的一种或多种增韧剂和基于聚合物和无机粘合剂的干重为至少55重量%的聚合物,所述增韧剂选自具有1‑25个碳原子的羟基化合物、具有1‑25个碳原子的羧酸化合物或其盐、具有1‑25个碳原子的羟基羧酸化合物或其盐、膦酸或其盐、以及磷酸或其盐。
Description
本发明涉及基于无机粘合剂、聚合物和填料的涂布组合物,用于制备涂层的方法,以及水再分散性分散粉末组合物,制备它们的方法以及其在上述涂布组合物中的用途。
用于制备韧性涂层的基于无机粘合剂、聚合物和填料的涂布组合物的用途在建造领域是公知的。该类涂布组合物例如如US6166113或DE-A19620817中所述用作薄浆。US4710526公开了用于制备具有良好粘合性质的韧性涂层的基于水泥和阳离子聚合物的砂浆组合物。KR100913255描述了粘性的、聚合物改性的砂浆组合物,其用于制备具有较好机械和化学耐受性的建筑产物。GB1236263公开了基于无机粘合剂、填料和聚合物以及添加剂的组合物,其中所述添加剂例如羟基-羧酸。US5543188推荐了包含注入了干拌水泥的聚合物层的膜。US2008/0060299和US2006/0054059描述了基于由塑料制成且具有韧性、粘性、聚合物改性涂层的垫的韧性膜。US5484478建议包含次磷酸单元的聚羧酸作为粘性薄泥浆的缓凝剂,以及其在石油提取中的用途。
然而,现有的涂布组合物导致涂层随着时间而慢慢变脆,因而不再是永久的韧性。所述脆变在涂层的断裂伸长率或裂纹桥联性(crake-bridgingability)变坏时而显而易见。然而为了保护涂布的基材,涂层的裂纹桥联性是重要的。由于地震、收缩过程、长度上的湿热变化或老化过程或者其他机械施加,而在诸如建筑物中,在基材中而形成裂纹。韧性的涂层用于使这种裂纹进行桥联,并因此防止了水渗透到基材中。然而,如果涂层目前变脆且因此不再韧性,则涂层本身随时间而趋于裂开,或者出现其他类型的损坏,因此水通过涂层而渗透到下面的基材中,结果是相应的水破坏。由于变脆,则涂层不再履行其功能,或者履行不足。当涂层在潮湿或者甚至湿的条件下,变脆的程度会增加。具有在永久韧性的涂层,即涂层具有持久的韧性,应该可以防止所述破坏。
根据该背景,目的是提供用于制备永久韧性涂层的涂布组合物,其中所述涂层特别在潮湿或湿度条件下不易变脆,因此具有持久的韧性。
本发明首先提供了基于一种或多种无机粘合剂、一种或多种聚合物、一种或多种填料和任选存在的一种或多种添加剂的涂布组合物,其特征在于所述涂布组合物包含基于涂布组合物的干重为0.05-5重量%的一种或多种增韧剂和基于聚合物和无机粘合剂的干重为至少55重量%的聚合物,其中所述增韧剂选自具有1-25个碳原子的羟基化合物、具有1-25个碳原子的羧酸化合物或其盐、具有1-25个碳原子的羟基羧酸化合物或其盐、膦酸或其盐、以及磷酸或其盐。
羟基化合物通常包含一个或多个醇基团,即一个或多个OH基团键接于碳原子上。如已知,羧酸化合物包含优选键接于碳原子上的一个或多个–COOH基团。羟基-羧酸化合物包含至少一个醇基团和至少一个COOH基团。羟基-羧酸化合物可以任选以己内酯的形式存在。己内酯为羟基-羧酸化合物的分子间的环状酯,其中羟基-羧酸化合物的醇基团和羧酸基团彼此连接以形成环,因此形成了酯基。羟基-羧酸化合物及其己内酯还可以彼此同时存在。羟基、羧酸或羟基-羧酸化合物可以任选带有其他基团,例如醛基或酮基。
所述羧酸化合物、羟基-羧酸化合物、膦酸或磷酸可以例如以它们的碱金属盐、碱土金属盐或铵盐的形式而存在,例如钠、钾、镁、钙或铵盐。
优选的增韧剂为羟基-羧酸化合物、膦酸或磷酸,或者它们各自的盐类。
所述羟基化合物、羧酸化合物或羟基-羧酸化合物包含优选2-10个碳原子,更优选2-8个碳原子,最优选2-6个碳原子。所述羟基化合物或羟基-羧酸化合物优选带有1-6个,更优选1-5个羟基。所述羧酸化合物或羟基-羧酸化合物优选带有1-3个羧酸基团。
合适的羧酸化合物的实例为草酸、酒石酸、葡糖酸、庚糖酸、没食子酸、柠檬酸、琥珀酸、癸二酸、水杨酸、庚二酸、血酸或苹果酸。优选酒石酸、葡糖酸和柠檬酸。
合适的羟基化合物的实例为季戊四醇、山梨糖醇、蔗糖、葡萄糖、果糖或二糖,如蔗糖。优选果糖和蔗糖(甘蔗糖)。
合适的膦酸或磷酸或其盐的实例为焦磷酸四钠和焦磷酸四钾以及六偏磷酸钠(Graham盐)。
增韧剂的最优选实例为葡糖酸、酒石酸和柠檬酸或者它们各自的盐。
所用聚合物通常为一种或多种烯键式不饱和单体(基础聚合物)的加成聚合物。优选的烯键式不饱和单体选自乙烯基酯、(甲基)丙烯酸酯、乙烯基芳族化合物、烯烃、1,3-二烯和乙烯基卤化物,以及任选存在的可与其共聚合的其他单体。
合适乙烯基酯例如为含有1-15个碳原子的羧酸酯。优选乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯、乙酸1-甲基乙烯酯、新戊酸乙烯酯及含有9-11个碳原子的α-支化的单羧酸的乙烯酯,例如VeoVa9R或者VeoVa10R(Resolution公司的商品名)。特别优选乙酸乙烯酯。
丙烯酸酯或甲基丙烯酸酯类的合适单体例如为含有1-15个碳原子的非支化或支化醇的酯。优选的甲基丙烯酸酯或丙烯酸酯为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸特丁酯、甲基丙烯酸特丁酯、丙烯酸2-乙基己基酯。特别优选的是丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸特丁酯和丙烯酸2-乙基己基酯。
优选的乙烯基芳族化合物为苯乙烯、甲基苯乙烯和乙烯基甲苯。优选的乙烯基卤化物为乙烯基氯化物。优选的烯烃为乙烯、丙烯,并且优选的二烯烃为1,3-丁二烯和异戊二烯。
任选地,可以具有基于单体混合物的总重量为0-10重量%的辅助单体进行共聚合。优选使用0.1-5重量%的辅助单体。辅助单体的实例为烯键式不饱和的单羧酸和二羧酸,优选丙烯酸、甲基丙烯酸、富马酸和马来酸;烯键式不饱和酰胺和腈,优选丙烯酰胺和丙烯腈;富马酸和马来酸的单酯和二酯,例如二乙基酯和二异丙基酯以及马来酸酐;烯键式不饱和磺酸和/或它们的盐,优选乙烯基磺酸、2-丙烯酰胺-2-甲基丙烷磺酸。其他实例为预交联的共聚单体,例如多烯键式不饱和共聚单体,实例为邻苯二甲酸二烯丙基酯、己二酸二乙烯基酯、马来酸二烯丙酯,甲基丙烯酸烯丙酯或氰尿酸三烯丙酯,或者后交联的共聚单体,例如丙烯酰胺基乙醇酸(AGA)、甲基丙烯酰胺基乙醇酸甲酯(MAGME)、N-羟甲基丙烯酰胺(NMA)、N-羟甲基-甲基丙烯酰胺、N-羟甲基氨基甲酸烯丙基酯、烷基醚,诸如N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺和N-羟甲基氨基甲酸烯丙基酯的异丁基醚或酯。合适还有环氧官能化的共聚单体,例如甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯。其他实例为硅官能化的共聚单体,例如丙烯酰氧基丙基三(烷氧基)-和甲基丙烯酰氧基丙基三(烷氧基)硅烷、乙烯基三烷氧基硅烷和乙烯基甲基二烷氧基硅烷,其中可能存在的烷氧基例如包括乙氧基基团和乙氧基丙二醇醚基。还可以提及具有羟基或CO基团的单体,实例为丙烯酸羟基烷基酯和甲基丙烯酸羟基烷基酯,例如羟乙基、羟丙基或羟丁基的丙烯酸酯或甲基丙烯酸酯,以及诸如双丙酮丙烯酰胺和乙酰基乙酰氧基乙基的丙烯酸酯或甲基丙烯酸酯的化合物。
优选为选自乙烯基酯均聚物、乙烯基酯共聚物、(甲基)丙烯酸酯的均聚物、(甲基)丙烯酸酯共聚物、诸如丁二烯或异戊二烯的均聚物和共聚物、以及诸如乙烯或丙烯的烯烃均聚物和共聚物、诸如苯乙烯、甲基苯乙烯、乙烯基甲苯的乙烯基芳族化合物的均聚物或共聚物、诸如氯代乙烯的乙烯基卤化物的均聚物或共聚物的一种或多种聚合物,其中所述乙烯酯共聚物包含一种或多种选自乙烯基酯、烯烃、乙烯基芳族化合物、乙烯基卤化物、丙烯酸酯、甲基丙烯酸酯、富马酸和/或马来酸的单酯或二酯的单体单元;其中所述(甲基)丙烯酸共聚物包含一种或多种选自甲基丙烯酸酯、丙烯酸酯、烯烃、乙烯基芳族化合物、乙烯基卤化物、富马酸和/或马来酸的单酯或二酯的单体单元;其中二烯可以与诸如苯乙烯、(甲基)丙烯酸酯或者富马酸或马来酸的酯进行共聚合;其中所述聚合物还可以含有辅助单体。
特别优选的是一种或多种乙烯基酯与1-50重量%乙烯的共聚物;乙酸乙烯酯与1-50重量%乙烯和1-50重量%的一种或多种选自在羧酸基团上具有1-12个碳原子的乙烯基酯(例如丙酸乙烯酯、月桂酸乙烯酯)、具有9-13个碳原子的α-支化的乙烯基酯(例如VeoVa9、VeoVa10、VeoVa11)的共聚单体的共聚物;一种或多种乙烯基酯与1-50重量%的乙烯和优选1-60重量%的具有1-15个C原子的未支化或支化醇的(甲基)丙烯酸酯的共聚物,其中所述酯更尤其是丙烯酸正丁酯或丙烯酸2-乙基己酯;以及与30-75重量%乙酸乙烯酯、1-30重量%月桂酸乙烯酯或者具有9-11个C原子的α-支化羧酸的乙烯基酯以及1-30重量%的具有1-15个C原子的未支化或支化醇的(甲基)丙烯酸酯的共聚物,其中所述酯更尤其是丙烯酸正丁酯或丙烯酸2-乙基己酯,其还可以含有1-40重量%的乙烯;与一种或多种乙烯基酯、1-50重量%乙烯和1-60重量%氯代乙烯的共聚物;所述共聚物还可以包含所述量的所述辅助单体,在每种情况下重量%的量相加为100重量%。
特别优选(甲基)丙烯酸酯聚合物,例如丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚物或甲基丙烯酸甲酯与丙烯酸正丁酯和/或丙烯酸2-乙基己基酯的共聚物;与一种或多种选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯的单体的苯乙烯-丙烯酸酯共聚物;与一种或多种选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯,丙烯酸2-乙基己酯和任选乙烯的单体的乙酸乙烯酯-丙烯酸酯共聚物;苯乙烯-1,3-丁二烯共聚物;所述聚合物还可以含有所述量的辅助单体,并且在每种情况下重量%的量相加为100重量%。
氯代乙烯共聚物的特别优选的共聚单体的实例为α-烯烃,例如乙烯或丙烯、和/或乙烯基酯,例如乙酸乙烯酯、和/或具有1-15个C原子的醇的丙烯酸酯或甲基丙烯酸酯,例如甲基丙烯酸酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、丙烯酸叔丁酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、丙烯酸2-乙基己酯、和/或富马酸和/或马来酸的单酯或二酯,例如马来酸或富马酸的各自的二甲基、甲基叔丁基、二正丁基、二叔丁基和二乙基酯。
最优选的是乙酸乙烯酯和5-50重量%的乙烯的共聚物、或者1-50重量%乙烯和1-50重量%的具有9-11个C原子的α-支化单羧酸的乙烯基酯与乙酸乙烯酯的共聚物、或者1-30重量%月桂酸乙烯酯或者具有9-11个C原子的α-支化羧酸的乙烯基酯以及1-30重量%具有1-15个C原子的未支化或支化醇的(甲基)丙烯酸酯与30-75重量%的乙酸乙烯酯的共聚物,其还含有1-40重量%乙烯、或者5-50重量%乙烯和1-60重量%氯代乙烯与乙酸乙烯酯的共聚物。
最优选的共聚物还为含有60-98重量%氯代乙烯单元和1-40重量%乙烯单元的氯代乙烯-乙烯共聚物,重量%的量是基于共聚物的总重量且在每种情况下相加为100重量%。该类氯代乙烯-乙烯聚合物在EP0 149 098A2中已知。
单体的选择和共聚单体的重量百分数的选择应使得到的玻璃化转变温度Tg为-50°C至+30°C,优选–40°C至+10°C,更优选-30°C至0°C。聚合物的玻璃化转变温度Tg可以以已知方式借助差热扫描量热法(DSC)测定。Tg还可以预选借助Fox方程而进行大约的计算。根据Fox T.G.,Bull.Am.Physics Soc.1,3,第123页(1956),如下方程:1/Tg=x1/Tg1+x2/Tg2+...+xn/Tgn,其中xn为单体n的质量分数(重量%),Tgn为以Kelvins计的单体n的均聚物的玻璃化转变温度。均聚物的Tg值列于PolymerHandbook,第二版,J.Wiley&Sons,New York(1975)中。
所述聚合物通常在含水介质中,优选通过例如在DE-A102008043988中所述的乳液或悬浮聚合物方法而制备。在这些情况下的聚合物以含水分散液的形式获得。如DE-A102008043988所述,在聚合过程中,可以使用常用的保护胶体和/或乳化剂。所述保护胶体可以为阴离子型或者优选阳离子型或非离子型。还优选阳离子型和非离子型保护胶体的组合物。优选的非离子型保护胶体为聚乙烯醇。优选的阳离子型保护胶体为携带一个或多个阳离子电荷的聚合物,例如如E.W.Flick,Water Soluble Resins–anIndustrial Guide,Noyes Publications,Park Ridge,N.J.,1991中所述。作为保护胶体,优选水解度为80-100mol%的部分水解或全部水解的聚乙烯醇,更尤其是水解度为80-94mol%且4%浓度的水溶液的粘度为1-30mPas(20°C下方法,DIN53015)的部分水解的聚乙烯醇。所述的保护胶体可以借助本领域熟练技术人员已知的方法而获得,并且以基于单体总重量通常为1-20重量%的总量而在聚合物中加入。
呈水再分散性聚合物粉末形式的聚合物可以通过使呈水分散液形式的聚合物进行干燥,然后任选添加作为干燥助剂的保护胶体而获得,干燥例如借助流化床干燥、冷冻干燥或喷雾干燥而进行。所述分散液优选通过喷雾干燥。喷雾干燥在常规的喷雾干燥装置中进行,在其中原子化可以借助一流体、两流体或多流体喷嘴或用旋转盘而进行。取决于装置、树脂的Tg和所需干燥程度,所选的出口温度通常为45-120°C,优选60-90°C。
通常而言,干燥助剂(保护胶体)的总用量基于分散液的聚合物成分为3-30重量%。优选基于聚合物级分而使用5-20重量%。
合适的干燥助剂为部分水解的聚乙烯醇;聚乙烯基吡咯烷酮;呈可溶于水形式的多糖,例如淀粉(直链淀粉和支链淀粉);纤维素以及其羧甲基、甲基、羟乙基和羟丙基衍生物;蛋白质,例如酪蛋白或酪蛋白酸盐、豆蛋白、明胶;木质素磺酸盐;合成聚合物,例如聚(甲基)丙烯酸、(甲基)丙烯酸酯与羧基-官能化的共聚单体单元的共聚物、聚乙烯基磺酸以及其可溶于水的共聚物,三聚氰胺-甲醛-磺酸盐、萘-甲醛-磺酸盐、苯乙烯-马来酸的共聚物以及乙烯基醚-马来酸共聚物。优选不使用除聚乙烯醇以外的任何保护胶体作为干燥助剂,优选作为保护胶体的聚乙烯醇还优选用作干燥助剂。
在进行喷雾而使聚合物水分散液进行干燥的过程中,通常已经证明基于基础聚合物为至多3重量%的抗发泡剂是有用的。为了通过改进结块稳定性而延长保存期,尤其是在具有低的玻璃化转变温度的聚合物粉末情况下,所得聚合物粉末可以加入基于聚合物成分总重量优选至多为30重量%的抗结块剂(抗结块剂)。抗结块剂的实例为Ca或Mg的碳酸盐、滑石、石膏、二氧化硅、高岭土、偏高岭土、煅烧的高岭土、以及粒径优选为10nm至100μm的硅酸盐。
要干燥的混合物的粘度以固含量计,以给出<1500mPas(在20转和23°C下Brookfield粘度),优选<500mPas的值。要干燥的混合物的固含量>35%,优选>40%。
为了改进性能,在干燥过程中可以加入其他助剂。在分散粉末组合物的优选实施方案中存在的其他成分例如为颜料、填料、泡沫稳定剂、疏水化剂或水泥增塑剂。
本发明还提供基于一种或多种烯键式不饱和单体的一种或多种聚合物(基础聚合物)的水再分散性分散粉末组合物,其特征在于存在一种或多种增韧剂。
增韧剂的比例基于分散粉末组合物的总重量优选0.025-12.5重量%,更优选0.05-7.5重量%,且最优选0.125-5重量%。
聚合物成分的比例基于分散粉末组合物的总重量优选50-99.75重量%,更优选70-99.95重量%,且最优选80-99.875重量%。聚合物成分包括基础聚合物和任选的保护胶体。
本发明额外还提供了借助一种或多种乙烯基单体在含水介质中的乳液聚合或悬浮聚合,然后将所得含水分散液干燥而制备所述水再分散性分散粉末组合物的方法,其特征在于混合了一种或多种增韧剂。
在此,所述乳液或悬浮聚合以及干燥可以如上述而进行。在本上下文中,还可以优选以上述量而相应使用上述保护胶体、乳化剂、干燥助剂、抗发泡剂、抗结块剂、助剂或其他成分。
可以在引发聚合以前将所述增韧剂与烯键式不饱和单体进行混合。或者,可以在烯键式不饱和单体的聚合过程中加入增韧剂。还可以在引发聚合以前,将部分增韧剂与烯键式不饱和单体混合,并且将剩余部分的增韧剂在烯键式不饱和单体的聚合中加入。
优选,在聚合结束以后将增韧剂加入相应的聚合物分散液之中。特别优选,在干燥聚合物分散液以前加入增韧剂。这通过将一种或多种增韧剂加入水性聚合物分散液,然后依据上述干燥方法而将所得混合物进行干燥。或者,特别优选的实施方案中,还可以在含水聚合物分散液的干燥过程中加入一种或多种增韧剂。
或者,还可以将已干燥的聚合物粉末与一种或多种增韧剂混合。这个方法在增韧剂以固体形式存在时特别适合。
所述包含增韧剂的水再分散性分散粉末组合物具有突出优点而适用于本发明的涂布组合物,这是因而所述聚合物和增韧剂可以作为单一组分而用于制备建筑工地和/或其他建筑物的干燥砂浆混合物的涂布组合物,而不再需要作为两个各自的组分而处理。这简化了(建筑工地)逻辑。
合适的无机粘合剂例如为水泥,更特别是硅酸盐水泥、铝酸盐水泥,特别是硫代铝酸钙水泥、火山土水泥、矿渣水泥、镁氧水泥、磷酸盐水泥和高炉水泥,以及混合的水泥、填料水泥、粉煤灰、微硅粉、矿渣砂、石灰或石膏。优选的无机粘合剂为水泥,更尤其是硅酸盐水泥、铝酸盐水泥,特别是硫代铝酸钙水泥、火山土水泥、矿渣水泥、镁氧水泥、磷酸盐水泥,和高炉水泥,以及混合的水泥、填料水泥。
铝酸盐水泥的比例基于无机粘合剂总重量优选为0-50重量%,更优选0-35重量%,非常优选0-25重量%,甚至更加优选0-10重量%,且最优选0-5重量%。在一个尤其优选的实施方案中,所述无机粘合剂不包含铝酸盐水泥。
合适的填料的实例是石英砂、微细研磨的石英、微细研磨的石灰石、碳酸钙、白云石、粘土、白垩、白消石灰、滑石或云母、粒状橡胶或硬质填料,诸如硅酸铝、刚玉、玄武岩、碳化物,诸如碳化硅或碳化钛,或具有火山灰反应的填料,诸如粉煤灰、偏高岭土、硅微粉。作为填料,优选石英砂、微细研磨的石英、微细研磨的石灰石、碳酸钙、碳酸钙镁(白云石)或白垩。填料优选不包含沙砾。沙砾通常具有≥4mm的平均粒径。
还可以使用任何所述填料的所需混合物。优选的混合物包含一种或多种硅酸盐填料,例如细沙,以及一种或多种选自碳酸钙、白垩、白云石和石灰石的碳酸盐填料。优选的混合物包含比例为1:1-4:1的一种或多种硅酸盐填料和一种或多种碳酸盐填料。
所述填料优选的平均粒径为0.01-4mm,更优选0.02-3mm,并且最优选0.03-2mm。
优选,至少50-100重量%的填料具有0.001-0.5mm的直径;更优选至少70-100重量%的填料具有0.01-0.3mm的直径;这些数字是基于每种情况下的所用总填料的干重而计。由于本发明的填料粒径,所述涂布组合物在制备永久韧性涂层的过程中,具有减小的收缩,这抵消了所述永久韧性涂层中的裂纹,并且导向裂纹桥联。
所述涂布组合物的典型配方优选包含10-60重量%,更优选20-55重量%,最优选30-50重量%的聚合物;优选2-30重量%,更优选2-20重量%,最优选3-15重量%的无机粘合剂;优选10-80重量%,更优选20-70重量%,最优选40-60重量%的填料;优选0.01-5重量%,更优选0.02-3重量%,最优选0.05-2重量%的增韧剂;此处,以重量%计的量涉及涂布组合物的干重,并且相加的总和为100重量%。
与聚合物相比,增韧剂在涂布组合物中优选以0.025-12.5重量%,更优选0.05-7.5重量%,最优选0.125-5重量%而存在。
聚合物在涂布组合物中优选以基于聚合物和无机粘合剂的干重为55-98重量%,更优选60-98重量%,最优选70-98重量%而存在。
所述涂布组合物优选呈干燥的混合物的形式。所述涂布组合物通常在其应用以前,通过添加水而直接转化为含水的涂布组合物。
含水的涂布组合物优选包含基于涂布组合物干重为15-50重量%,更优选20-40重量%的水。
所述涂布组合物的性能可以借助添加剂或助剂而得以改进。合适的添加剂的实例包括颜料,尤其是无机颜料,诸如氧化物颜料、氢氧化物颜料、硫化物颜料、硫硒化物颜料、碳酸盐颜料、铬酸盐颜料、混合相的铬酸盐-钼酸盐颜料、或者硅酸盐颜料。在本上下文中,优选颜料为包含有钛、铁、铬或镉的言论。最优选的颜料为二氧化钛。
合适的添加剂的实例为高分散的二氧化硅,简称为HDK,例如发烟二氧化硅或沉淀二氧化硅。高分散的二氧化硅在涂布组合物中优选以基于各自的涂布组合物的干重为0.1-3%,更优选0.1-1重量%而存在。通过使用高分散的二氧化硅,可以防止水向韧性涂层中的进一步渗透。此外,所述高分散二氧化硅还具有有利的加工性能的结果,这是由于对应的含水涂布组合物比较不粘,并且在无机粘合剂的固化过程中干燥更加快速。
优选的添加剂还有叶硅酸盐。包含叶硅酸盐的涂布组合物导致韧性涂层具有高度的不透水性。叶硅酸盐优选以基于涂布组合物的干重为0-3重量%,更优选以0.1-2重量%而存在。
优选的添加剂也是纤维。合适的纤维的实例为Kevlar、粘胶纤维、聚酰胺纤维、聚酯纤维、聚丙烯腈纤维、Dralon纤维、聚乙烯纤维、聚丙烯纤维、聚乙烯醇纤维、芳族聚酰胺纤维或碳纤维。纤维优选以基于涂布组合物的干重为0-3重量%,更优选0.1-2重量%而存在。纤维的使用导致涂层具有更强的裂纹桥联性。
用于所述涂布组合物的典型助剂为增稠剂,实例为多糖,例如纤维素醚和改性的纤维素醚、淀粉醚、瓜尔胶、黄原胶、聚羧酸,如聚丙烯酸和它们的偏酯、以及聚乙烯醇,任选可以缩醛化或进行疏水改性,以及酪蛋白和缔合增稠剂。常规的助剂还有交联剂,例如金属氧化物或半金属氧化物,更特别是硼酸或聚硼酸酯,或者二醛,如戊二醛。还可以提及下列助剂:防腐剂、成膜助剂、分散剂、泡沫稳定剂、消泡剂、增塑剂、流动控制剂和阻燃剂(例如氢氧化铝)。
通常而言,助剂在所述涂布组合物中的比例在每种情况下基于涂布组合物的干重而总共为0-20重量%,优选0.1-15重量%,更优选0.1-10重量%。
所述基于无机粘合剂、聚合物、填料和增韧剂和任选添加剂的涂布组合物的制备并不限于任何特别的步骤或混合装置。所述涂布组合物可以通过将配方中的各个成分在常规的粉末混合装置中混合并均质化而得到,例如借助砂浆搅拌机、混凝土搅拌机或石膏混合机或搅拌器。在混合阶段,通常以干燥形式而使用所述各成分。
所述聚合物可以以含水分散液的形式,优选以水再分散性粉末的形式或者水再分散性粉末组合物的形式而使用。
所述涂布组合物可以例如以单-组分体系或双-组分体系的形式而提供。单-组分体系包含涂布组合物的所有成分。使用单-组分体系时,配制剂通常为干燥的配制剂。单-组分系统通常通过将聚合物、增韧剂、任选的添加剂和任选的助剂进行预混合,并且在后面的时间点将无机粘合剂和填料混入而制备。为了制备含水的涂布组合物,可以在后面的任何时间点,通常在施用涂布组合物之前的不久,而将水混入。
双-组分体系包含第一个组合和第二个组分。第一个组分包含除聚合物以外的韧性涂布组合物的所有成分。第一个组分通常为干燥的配制剂。第二个组分包含优选呈含水分散液形式的聚合物。为了制备可以是含水的涂布组合物,将第一个组分和第二个组分混合,任选在添加水的情况下进行混合。
所述涂布组合物例如适用于薄浆、建筑胶粘剂、接缝灰浆、修补灰浆或抹灰。
本发明额外还提供通过将基于一种或多种无机粘合剂、一种或多种聚合物、一种或多种填料和任选的一种或多种添加剂的涂布组合物施加于基材上而制备永久韧性涂层的方法,其特征在于所述涂布组合物包含基于涂布组合物干重为0.05-5重量%的一种或多种增韧剂以及基于聚合物和无机粘合剂的干重为至少55重量%的聚合物,其中所述增韧剂选自具有1-25个碳原子的羟基化合物、具有1-25个碳原子的羧酸化合物或它们的盐、具有1-25个碳原子的羟基-羧酸化合物或者它们的盐、膦酸或其盐以及磷酸或其盐。
所述永久韧性涂层的涂层厚度优选1-10mm,更优选2-5mm,并且最优选2-3mm。
可以将这些涂布组合物施加于任何基材上。所述基材例如可以是有机的或无机的,天然的或合成的。天然基材的实例为地面、岩石、石头或砂浆层。合成基材的实例主要为来自建筑业的基材,例如基于包含无机粘合剂的组合物的基材,更尤其是混凝土或砂浆层,还有木材材料、塑料材料,更具体而言为聚氨酯泡沫板,或者金属,更具体而言为铝。优选来自建造业的基材。
所述含水的涂布组合物可以手动方法或机械方法而施加。在手动方法的情况下,将含水涂布组合物借助粗刷、细刷、辊、刀、镘刀、扁板或铲子而施加于基材上。在机械方法的情况下,将所述含水涂布组合物借助喷涂机、石膏混合机或机器人而施加于基材上。可以在一个上面施加另一个而得到涂层组合物的两个或更多层。优选仅向基材上施加一层涂布组合物。在将涂布组合物施加到基材上以后,可以例如使用打磨盘或板式打磨器而对所施加的涂层表面进行打磨。
通常在环境温度下施加涂布组合物,例如通常在0-50°C,更尤其在5-35°C的温度下。
在施加涂布组合物之前,可以将基材涂上底漆。合适的底漆的实例包括优选固含量为10-50%的上述聚合物的含水分散液。
最后,可以在本发明的永久韧性涂层上施加另一个涂层,例如,油漆涂层或包层,或者用于内部或外部的瓦片或厚片的覆盖物。也可以是地板填充化合物的涂层或者砂浆层。然而,在许多情况下,本发明的涂层构成了最上层或者面漆。
所述涂布组合物优选用于形成屋顶、沟渠、矿山、隧道、池塘或游泳池,更优选屋顶、沟渠或矿山的永久韧性涂层,最优选用于形成屋顶。
令人惊讶的是,本发明的涂布组合物形成永久韧性涂层,与传统的矿物涂层对比,其具有改进的断裂伸长率行为,因此,具有改进的裂纹桥联能力,这抵消了涂层的脆化。在涂层用于湿的或潮湿条件下时尤其如此。因此,可由本发明得到的涂层特别适合于保护建筑物结构例如防止水的渗透。
下面的实施例用于详细说明本发明,并且不应该理解为构成任何限制。
本发明实施例1(IEx.1):
所述涂布组合物通过在混合下以如下次序将如下所示配方中的各个成分加入Toni混合机(市购的实验室用混合机)中而制备:首先是硅酸盐水泥,然后是填料、分散粉末,最后是余下的添加剂。然后,在设置1下均匀混合15分钟。含水的涂布组合物由所得干燥混合物与配方所示的量的水以EN196-1所示方式而制备。
将含水涂布组合物以厚度为2mm的湿膜而施加于Teflon模板组件(基础面积:30×15cm)上。使用泥刀将所述湿膜进行平滑。在依据DIN50014的标准条件下保存24小时以后,膜进行了固化,由Teflon模板组件上除下以后,将膜在如下条件储存:
-将一个膜在标准条件(23°C/50%相对湿度)下储存28天(干储存);
-将另一个相同的膜在上述干燥储存以后,在自来水中在23°C下储存38天,然后在标准条件(23°C/50%相对湿度)下储存28天(湿储存)。
涂布组合物的配方:
10重量%硅酸盐水泥,CEM I42.5N,
40重量%分散粉末4040N(乙酸乙烯酯-乙烯共聚物,用聚乙烯醇和阳离子保护胶体进行稳定化),
0.5重量%高分散二氧化硅(Wacker HDK H15),
0.5重量%消泡剂(Agitan P800),
1.5重量%无机叶硅酸盐增稠剂(Optibent MF),
0.5重量%葡萄糖酸钠,
13.4重量%Omyacarb20BG(碳酸盐填料)和
33.6重量%细沙(0.063-0.3mm;硅酸盐填料)。
对于2kg的以上组分的干燥混合剂,使用640ml的水。
对比实施例2(CEx.2):
类似于本发明实施例1,不同之处为用于制备涂布组合物的配方和水的用量如下:
10重量%硅酸盐水泥CEM I42.5N,
20.5重量%分散粉末4040N(乙酸乙烯酯-乙烯共聚物,用聚乙烯醇和阳离子保护胶体进行稳定化),
20.5重量%分散粉末7055N(乙酸乙烯酯-乙烯基酯-乙烯三元聚合物,用聚乙烯醇进行稳定化),
0.5重量%高分散二氧化硅(Wacker HDK H15),
0.5重量%消泡剂(Silfoam SP15),
48重量%细沙(0.063-0.3mm;硅酸盐填料)。
对于2kg的以上组分的干燥混合剂,使用560ml的水。
对比实施例3(CEx.3):
类似于本发明实施例1,不同之处为用于制备涂布组合物的配方和水的用量如下:
10重量%硅酸盐水泥CEM I42.5N,
30重量%分散粉末4040N(乙酸乙烯酯-乙烯共聚物,用聚乙烯醇进行稳定化),
0.5重量%高分散二氧化硅(Wacker HDK H15),
0.5重量%消泡剂(Agitan P800),
1.5重量%无机叶硅酸盐增稠剂(Optibent MF),
57.5重量%碳酸盐和硅酸盐填料。
对于2kg的以上组分的干燥混合剂,使用600ml的水。
对比实施例4(CEx.4):
类似于本发明实施例1,不同之处为用于制备涂布组合物的配方和水的用量如下:
20重量%硅酸盐水泥CEM I42.5N,
20重量%分散粉末4040N(乙酸乙烯酯-乙烯共聚物,用聚乙烯醇进行稳定化),
0.5重量%高分散二氧化硅(Wacker HDK H15),
0.5重量%消泡剂(Agitan P800),
1.5重量%无机叶硅酸盐增稠剂(Optibent MF),
57.5重量%碳酸盐和硅酸盐填料。
对于2kg的以上组分的干燥混合剂,使用500ml的水。
性能测试
依据ISO527-3(8/1995),各自从本发明实施例1和对比实施例2-4在干储存和湿储存后得到的各个膜而冲击出2-4个1B型的标准杆。
然后借助依据ISO527-3(8/1995)的拉伸测试而测定标准杆的拉伸强度和断裂伸长率。以50mm/min的拉伸速度将标准杆拉到失效。测试结果示于表1。
令人惊讶的是,与干储存比较,本发明产品的湿储存并没有对断裂伸长率值造成任何显著的变化(本发明实施例1)。相反,在非本发明制备的产品的情况下,断裂伸长率值由于湿储存而显著变差(对比实施例2和3)。其中聚合物的量小于无机粘合剂的涂布组合物形成了甚至在干储存下断裂伸长率也不令人满意的产品(对比实施例4)。
表:涂层的测试:
*:n.d.:没有测定。
Claims (11)
1.基于一种或多种无机粘合剂、一种或多种聚合物、一种或多种填料和任选存在的一种或多种添加剂的涂布组合物,其特征在于所述涂布组合物包含:
基于涂布组合物的干重为0.05-5重量%的一种或多种增韧剂和基于聚合物和无机粘合剂的干重为60-98重量%的聚合物,所述增韧剂选自具有1-25个碳原子的羟基化合物、具有2-10个碳原子的羧酸化合物或其盐、具有2-10个碳原子的羟基羧酸化合物或其盐、膦酸或其盐、以及磷酸或其盐。
2.权利要求1的涂布组合物,其特征在于所述一种或多种增韧剂选自草酸、酒石酸、葡糖酸、庚糖酸、没食子酸、柠檬酸、琥珀酸、癸二酸、水杨酸、庚二酸、血酸、苹果酸以及前述酸的盐和季戊四醇、山梨糖醇、蔗糖、葡萄糖、果糖、二糖、焦磷酸四钠和焦磷酸四钾以及六偏磷酸钠(格雷姆盐)。
3.权利要求1或2的涂布组合物,其特征在于所述涂布组合物包含基于聚合物和粘合剂的干重为70-98重量%的聚合物。
4.权利要求1或2的涂布组合物,其特征在于所述聚合物能够通过一种或多种选自乙烯基酯、(甲基)丙烯酸酯、乙烯基芳族化合物、烯烃、1,3-二烯和乙烯基卤化物的烯键式不饱和单体以及任选存在的能够与其共聚合的其他单体的自由基引发聚合而得到。
5.权利要求1或2的涂布组合物,其特征在于所述涂布组合物包含基于涂布组合物的干重为10-60重量%的聚合物。
6.权利要求1或2的涂布组合物,其特征在于所述填料包含一种或多种硅酸盐填料与一种或多种碳酸盐填料的混合物。
7.权利要求1或2的涂布组合物,其特征在于所述涂布组合物包含一种或多种选自高分散二氧化硅、叶硅酸盐、颜料和纤维的添加剂。
8.权利要求1-7之一的涂布组合物作为建筑胶粘剂的用途。
9.权利要求1-7之一的涂布组合物用于制备用于屋顶、沟渠、矿山、隧道、池塘或游泳池的涂层的用途。
10.制备涂层的方法,其特征在于将一种或多种权利要求1-7的涂布组合物施加于基材上。
11.如权利要求10的制备涂层的方法,其特征在于所述涂层具有1-10mm的涂布厚度。
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DE10101314A1 (de) * | 2001-01-12 | 2002-08-01 | Wulff Gmbh U Co | Emissionsarme Ein-und Zwei-Komponenten-Klebstoffe |
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US9522845B2 (en) | 2016-12-20 |
WO2012038288A1 (de) | 2012-03-29 |
DE102010041293A1 (de) | 2012-03-29 |
EP2619152A1 (de) | 2013-07-31 |
US20130183448A1 (en) | 2013-07-18 |
CN103124703A (zh) | 2013-05-29 |
EP2619152B1 (de) | 2015-07-15 |
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