CN110167346A - 不含金属的抗微生物和uv防护添加剂 - Google Patents
不含金属的抗微生物和uv防护添加剂 Download PDFInfo
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Abstract
本发明涉及不含金属的抗微生物和UV防护添加剂,其可以用于建筑或装修材料,诸如石膏、灰浆、底漆、油漆和其他保护性或装饰性涂料,以消除细菌、真菌、藻类和地衣的生长并且保护材料免受紫外线(UV)辐射。该添加剂包含具有以下组分比率(重量%)的混合亲有机层伊利石‑蒙脱石、绿泥石、伊利石、碳酸盐岩、硅石和赤铁矿:从40%至70%的混层亲有机伊利石‑蒙脱石;从5%至10%的绿泥石;从5%至10%的伊利石;从0%至20%的碳酸盐岩;从5%至20%的硅石;从0%至3%的赤铁矿。该混层伊利石‑蒙脱石用季铵化合物亲有机化,这些季铵化合物以基于所需重量的该混层亲有机伊利石‑蒙脱石的从10%至30%的量使用。
Description
技术领域
本发明涉及不含金属的抗微生物和UV防护添加剂,其可以用于建筑或装修材料,诸如石膏、灰浆、底漆、油漆和其他保护性或装饰性涂料,以消除细菌、真菌、藻类和地衣的生长并且保护材料免受紫外线(UV)辐射。
背景技术
存在若干种已知的用于提供油漆、油墨和涂料的改善的流变特性的亲有机粘土组合物。
例如,存在已知的用有机酸衍生的酯季铵化合物制造的有机粘土组合物,其可以用于非水性流体系统(诸如油漆、油墨、和涂料)以提供改善的流变特性(US 5718841)。已知的亲有机粘土组合物包括以下物质的反应产物:蒙脱石类型粘土,其具有至少75毫当量/100克粘土的阳离子交换量;以及衍生自有机酸衍生的酯的季铵化合物,其量足以满足蒙脱石类型粘土的至少约75%的阳离子交换量。
存在已知的可倾倒的亲有机粘土聚酰胺组合物(US 5939475),其可以用于非水性流体系统(诸如油漆、油墨和涂料)以向该系统提供改善的流变特性。该组合物包含从5重量%至15重量%的亲有机改性的蒙脱石类型粘土;从25重量%至35重量%的一种或多种流变活性聚酰胺,以及从40重量%至60重量%的一种或多种有机溶剂,诸如正丙醇、甲苯和溶剂油。
存在已知的杀生物有机粘土(US 6165485),其通过将基于膨润土的有机粘土与在其结构内含有苄基分子的杀生物季铵混合来获得。已披露的是,当此有机粘土进一步用碘和碘化合物处理时,增强了其效率。
作为石膏、灰浆、底漆、油漆和其他保护性或装饰性涂料的添加剂的已知组合物的主要缺点在于,这些组合物不同时提供抗微生物特征和UV防护特征,或者旨在仅用于水性或非水性介质。
存在已知的多种用于油漆、水泥和其他材料的抗微生物添加剂,其包含金属,例如银、锌、铜和硫酸铜(WO 2013098774)。含有锌和铜的添加剂的缺点在于,它们不是环境友好的,而含有银的添加剂过于昂贵而不用于构造材料。
发明内容
提出了不含金属的抗微生物和UV防护添加剂,其包含混层伊利石-蒙脱石、绿泥石、伊利石、碳酸盐岩、硅石和赤铁矿。该添加剂含有以下比率的重量%的组分:从40%至70%的混层亲有机伊利石-蒙脱石;从5%至10%的绿泥石;从5%至10%的伊利石;从0%至20%的碳酸盐岩;从5%至20%的硅石;从0%至3%的赤铁矿。所述混层伊利石-蒙脱石预先用季铵化合物亲有机化,这些季铵化合物以基于所需重量的该混层伊利石-蒙脱石的从10%至30%的量使用。
该季铵化合物选自下组,该组由以下各项组成:一甲基、二甲基、三甲基取代的季铵盐。取代基是脂族或芳族(包括芳烷基)基团。根据优选的实施例,该季铵化合物至少具有一条具有8至18个碳原子的长脂族链。该季铵化合物优选地选自由氯化物或溴化物组成的卤化物的组。
碳酸盐岩优选地选自由方解石和白云石组成的组。
还提出了一种建筑或装修材料,诸如石膏、灰浆、底漆、油漆、保护性或装饰性涂料,其以从1:500至1:5的建筑或装修材料:抗微生物添加剂的比例(质量混合比率)包含所述抗微生物和UV防护添加剂。
附图说明
图1示出了涂覆有含有所提供的添加剂的油漆和没有添加剂的相同油漆的两个墙壁碎片的图片;这些图片示出了涂覆有没有添加剂的油漆的表面上藻类生长的动态以及涂覆有具有添加剂的油漆的表面上缺乏藻类。
图2–示出了比较由UV辐射导致的损坏的值变化的柱形图的图表;该柱形图示出了色差-ΔCIELAB,其比较在树脂中具有所提供的添加剂和没有添加剂的相同树脂的样品。
所要求保护的不含金属的抗微生物和UV防护添加剂可以例如通过已知的机械化学方法获得。
具体实施方式
本发明进一步通过以下实例解释,其中所提出的添加剂的一些可能的实施例以以下缩写描述:“P1/C1-10”,其中P1-P7是具有来自表1的比例的组合物混合物,并且“C1-10”(和其他)–具有来自表2的比例的季铵化合物的实例。
表1
抗微生物添加剂的组分(重量%)
表2
用于这些实例中的亲有机混层伊利石-蒙脱石的鎓基团化合物和重量%(重量%是基于所需重量的亲有机混层伊利石-蒙脱石计算的):
实例1–抗真菌特性
对于添加剂材料的抗真菌活性的确定,使用真菌菌株多主枝孢(Cladosporiumherbarum)MSCL 258、甘蓝链格孢菌(Alternaria brassicicola)MSCL 260。将真菌在22℃下在麦芽提取物琼脂(美国贝迪公司(Becton&Dickinson,USA))上培养48h。称重0.05g或0.5g的量的添加剂粉末并且置于培养皿(Petri plate)中。添加25ml的量的液化麦芽提取物琼脂,并且小心地与该粉末混合。这在培养基中产生0.2%或2.0%的粉末浓度。在培养基固化之后,将具有OD540=0.16±0.02浊度的真菌培养物的悬浮液均匀分散在培养皿上。基于在22℃下孵育4天之后真菌生长的抑制评估抗真菌活性,并且使用四点量度表示。结果在表3和表4中列出。
表3
添加剂变型P2/C2-11和P1/C1-23的抗真菌活性
样品-添加剂粉末变型 | P2/C<sub>2-11</sub> | P1/C<sub>1-23</sub> |
对照–0.0%粉末 | 4 | 4 |
0.2%粉末 | 2 | 2 |
2.0%粉末 | 2 | 2 |
1–未观察到生长。
2–仅少量小菌落。
3–真菌覆盖培养基的整个表面;培养基仅在某些地方是透明的。
4–真菌覆盖培养基的整个表面。
获得的结果显示0.2%和2.0%浓度的所提出的抗微生物和UV防护添加剂(粉末)等同地抑制真菌生长。
表4
添加剂(变型)的抗真菌活性
1–未观察到生长
2–仅少量小菌落
3–真菌覆盖培养基的整个表面,培养基仅在某些地方是透明的
4–真菌覆盖培养基的整个表面
*粉末是非常具有疏水性的,并且它不能均匀地悬浮在培养基中
获得的结果显示0.2%和2.0%浓度的P6/C5-13和P4/C6-15仅部分地抑制真菌生长。P1/C3-18在两种浓度下均完全抑制甘蓝链格孢菌,但是在0.2%浓度下部分抑制多主枝孢。P5/C4-10在两种浓度下均完全抑制两种真菌的生长。
实例2–抗细菌特性
对于所测试的抗微生物添加剂的粉末的抗细菌活性的确定,使用细菌菌株铜绿假单孢菌(Pseudomonas aeruginosa)MSCL 331和金黄色葡萄球菌(Staphylococcus aureus)MSCL 334。将细菌在37℃下在平板计数琼脂(法国伯乐生命医学产品公司(Bio-Rad,France))上培养24h。称重0.05g或0.5g的量的添加剂粉末样品并且置于培养皿中。添加25ml的量的液化Mueller-Hinton琼脂,并且小心地与该粉末混合。这在培养基中产生0.2%或2.0%的粉末浓度。在培养基固化之后,使用具有OD540=0.16±0.02浊度的细菌培养物的悬浮液,并且均匀分散在培养皿上。基于在37℃下孵育2天之后细菌生长的抑制评估抗细菌活性,并且使用四点量度表示。结果在表5中列出。
表5
抗细菌活性
1–未观察到生长
2–仅少量小菌落
3–细菌菌落覆盖培养基的整个表面,培养基仅在某些地方是透明的
4–细菌覆盖培养基的整个表面
获得的结果显示所有提出的添加剂都抑制细菌生长。在0.2%浓度的P1/C5-19的情况下观察到完全抑制,并且也在2.0%浓度的P6/C3-11和P4/C4-22的情况下观察到完全抑制。
实例3–非水性系统–亚麻籽油清漆的抗真菌特性
对于保护亚麻籽油清漆(linseed oil pernica)的所提出的抗微生物和UV防护添加剂的抗真菌活性的确定,使用真菌菌株多主枝孢MSCL 258。将真菌在22℃下在麦芽提取物琼脂(美国贝迪公司)上培养48h。将具有OD540=0.16±0.02浊度的真菌培养物的悬浮液分散在置于无菌培养皿中的层板样品上。基于在22℃下孵育7天之后真菌生长的抑制评估抗真菌活性,并且使用四点量度表示。结果在表6中列出。
表6
层板样品(P5/C1-15)的抗真菌活性
0–未观察到生长
1–仅少量小菌落
2–真菌覆盖培养基的表面,培养基仅在某些地方是透明的
3–真菌覆盖培养基的整个表面
获得的结果显示具有5%-10%浓度的所提出的抗微生物和UV防护添加剂的亚麻籽油完全抑制层板样品上的真菌生长。
实例4–水性系统–水泥-石灰基建筑材料的抗真菌特性
对于当混合到水泥-石灰基灰浆和石灰基油漆中时的所提出的抗微生物和UV防护添加剂的抗真菌活性的确定,将该添加剂与0%和2%质量比例的灰浆和油漆干燥部分混合,并且与表7中所述的不同组合进行比较。对于抗真菌活性的确定,使用真菌菌株多主枝孢MSCL 258和甘蓝链格孢菌MSCL 260。将真菌在22℃下在麦芽提取物琼脂(美国贝迪公司)上培养48h。使用具有OD540=0.16±0.02浊度的真菌培养物的悬浮液,并且均匀地分散在具有麦芽提取物琼脂的培养皿上。将所测试的材料放置在接种培养皿的表面上。基于在22℃下孵育2-7天之后所测试的材料周围抑制区域的大小评估抗真菌活性。结果以三点量度表示。结果在表7中列出。
表7
样品的抗真菌活性。
0–抑制区域超过1mm
1–抑制区域不超过1mm
2–未观察到抑制区域
获得的结果显示在石膏组合物和油漆两者中的所提出的抗微生物和UV防护添加剂均产生真菌生长的抑制。
实例5–水性系统–石灰基建筑材料的抗藻类特性
将没有和具有引入的添加剂(P4/C2-18)的历史石灰基油漆涂在没有其他处理的未整修建筑的北侧上。在注意到微生物物质在没有添加的添加剂的涂漆区域上生长之后,微生物涂片测试显示该微生物是绿藻门(Chlorophyta)绿藻。获得的结果(图1)显示所提出的添加剂产生藻类生长的抑制。
实例6–洗除测试
进行连续十个循环的测试运行。在每个循环中,将20克的抗微生物添加剂(P4/C1-23)混合到1升水中,混合4h,在70℃下干燥24h。在5个循环之后测量活性物质洗除–加热至450℃,并且计算加热质量损失的%。
10个循环之后观察到所提出的抗微生物和UV防护添加剂(封装的活性有机物质)的小于0.1%点的洗除倾向。
实例7–非水性系统–层板层合树脂膜的UV防护特性
对于添加剂的UV防护特性的确定,用UV辐射处理具有在树脂中的所提供的添加剂的层板的层合树脂膜,并且之后使用CIELAB(或CIE L*a*b*,CIE Lab)标准测试程序计算与未处理的层板膜的色差。将添加剂P4/C1-23的干燥粉末以0%、12%和20%的质量比例的树脂干燥部分混合在液体层合树脂中,以制备层合纸膜。将不同比例的所提供的添加剂等同地混合在树脂中。将层合纸浸渍到含有不同比例的所提供的添加剂的树脂中,干燥,并且之后使用热压法层合在层板上。含有不同比例的所提供的添加剂的层合树脂膜目测没有不同。在层合之后,选择含有0%和12%的层板样品来确定UV防护特性。将所制备的样品切成两个部分,并且通过用UV系统暴露处理样品一百次来将每个样品的一个部分用层板生产工艺中使用的UV线系统处理。基于使用CIELAB程序所计算的色差(Δ)评估UV防护特性。为了计算每个样品ΔCIELAB,从二十个点取数据,并且计算图2中所示的每个样品的平均ΔCIELAB。
获得的结果显示12%浓度的所提出的添加剂通过提高平均39%的ΔCIELAB系数(提高意指更小的Δ值)改善树脂膜(颜料颜色)对于由UV辐射导致的损坏的抗性。
所要求保护的不含金属的抗微生物和UV防护添加剂可以从1:500至1:5的流体系统:抗微生物添加剂的比例(质量混合比率)用于水性系统(诸如油漆、石膏、灰浆、油墨、涂料)和非水性流体系统(诸如油漆、树脂、油、油墨、生物聚合物)以及其他涂料。
所要求保护的添加剂的存在有利地确保对应的水性或非水性介质的UV防护特性,并且保护涂料和建筑材料,从而防止细菌、真菌、藻类和地衣的生长。
该添加剂还改善材料的粘附性和颜色表面质量,从而使其更光滑。包含添加剂的涂料适于冲洗-在与水接触的情况下仍保留物理和抗微生物特性。≤150μm的磨粒有助于与其他原材料的均匀混合。作为干燥粉末,便于在材料生产期间并在施工工艺中使用。该添加剂适合于干磨和湿磨(≥5μm)以及在干混合物和湿混合物中分散。加热至高达约170℃不影响物理和功能产品特征。
因此,所要求保护的添加剂可以帮助保护表面或物体的初始特性和体积美学外观,这些表面或物体即油漆、石膏、灰浆、塑料、树脂、密封剂、生物复合材料粘合剂以及粘结剂、纸材、艺术品、砖石结构、复合材料、或其他构造材料,包括木材。该添加剂由于耐浸出微结构而是无害的、人类健康和环境友好的。
Claims (6)
1.一种抗微生物和UV防护添加剂,其包含混层伊利石-蒙脱石、绿泥石、伊利石、碳酸盐岩、硅石和赤铁矿,其中,该添加剂含有以下比率的重量%的组分:
-从40%至70%的混层伊利石-蒙脱石,
-从5%至10%的绿泥石,
-从5%至10%的伊利石,
-从0%至20%的碳酸盐岩,
-从5%至20%的硅石,
-从0%至3%的赤铁矿,
其中该混层伊利石-蒙脱石预先用季铵化合物亲有机化,这些季铵化合物以基于所需重量的该混层伊利石-蒙脱石的从10重量%至30重量%的量使用。
2.根据权利要求1所述的抗微生物添加剂,其中,碳酸盐岩选自由方解石和白云石组成的组。
3.根据权利要求1或2所述的抗微生物添加剂,其中,该季铵化合物选自下组,该组由以下各项组成:一甲基、二甲基、三甲基或它们的具有脂族或芳烷基基团的取代物。
4.根据权利要求1或2所述的抗微生物添加剂,其中,该季铵化合物具有至少一条具有8至18个碳原子的长脂族链。
5.根据权利要求1或2所述的抗微生物添加剂,其中,该季铵化合物选自由氯化物和溴化物组成的卤化物的组。
6.一种建筑或装修材料,诸如石膏、灰浆、底漆、油漆、保护性或装饰性涂料,其以从1:500至1:5的建筑或装修材料:该添加剂的比例(质量混合比率)包含根据任何前述权利要求所述的抗微生物和UV防护添加剂。
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LT3562304T (lt) | 2021-12-10 |
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BR112019013826A2 (pt) | 2020-01-28 |
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JP6892150B2 (ja) | 2021-06-23 |
US20190357540A1 (en) | 2019-11-28 |
KR102307544B1 (ko) | 2021-10-01 |
MX2019008193A (es) | 2019-09-11 |
HRP20211961T1 (hr) | 2022-03-18 |
BR112019013826B1 (pt) | 2022-08-02 |
PL3562304T3 (pl) | 2022-01-31 |
HUE057089T2 (hu) | 2022-04-28 |
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