CN105579543B - 粘合剂组合物和由其制成的涂层组合物 - Google Patents
粘合剂组合物和由其制成的涂层组合物 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/16—Cyclodextrin; Derivatives thereof
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- Materials Engineering (AREA)
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- Engineering & Computer Science (AREA)
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Abstract
一种新颖粘合剂组合物，其包含根据所述粘合剂组合物的总干燥重量以干燥重量计，i)93％到99.96％的聚合物粒子，所述聚合物粒子包含根据所述聚合物粒子的总重量以干燥重量计，25％到95％的乙酸乙烯酯；和5％到75％的叔碳酸的乙烯酯和/或2‑乙基己酸的乙烯酯作为聚合单元；和ii)0.04％到7％的低水溶性环糊精。
Description
技术领域
本发明涉及一种粘合剂组合物和由其制成的涂层组合物，所述涂层组合物具有减少的气味和挥发性有机化合物(VOC)释放。
背景技术
粘合剂常用于内墙和外墙涂层中。工业中需要低VOC和低气味粘合剂和涂层产品。对于壁涂层涂覆，广泛使用包含乙酸乙烯酯的粘合剂，尤其在内墙涂层中，因为其低廉，除乙酸外的VOC杂质相对低且气味少。
併入叔碳酸的乙烯酯的乙酸乙烯酯粘合剂具有改进的性能，例如水和碱抗性、UV抗性和污渍抗拒性。
目前，越来越多的涂层包括乙酸乙烯酯与叔碳酸的乙烯酯。然而，叔碳酸的乙烯酯是具有臭味的化合物且挥发到空气中。所述气味和其向空气中的释放极难以克服，因为叔碳酸的乙烯酯的化合物具有高沸点。
因此，所属技术领域中仍需要由叔碳酸的乙烯酯的化合物制成的涂层组合物，其具有减少的气味和挥发性有机化合物(VOC)释放。亦希望此粘合剂组合物是基于叔碳酸的乙烯酯的粘合剂。
发明内容
本发明提供一种粘合剂组合物，其包含根据粘合剂组合物的总干燥重量以干燥重量计，i)93％到99.96％的聚合物粒子，所述聚合物粒子包含根据聚合物粒子的总重量以干燥重量计，25％到95％的乙酸乙烯酯；和5％到75％的叔碳酸的乙烯酯和/或2-乙基己酸的乙烯酯作为聚合单元；和ii)0.04％到7％的低水溶性环糊精。
在一个优选实施例中，聚合物粒子进一步包含根据聚合物粒子的总干燥重量以干燥重量计，0.1％到50％的(甲基)丙烯酸酯单体作为聚合单元。
在一个优选实施例中，聚合物粒子进一步包含根据聚合物粒子的总干燥重量以干燥重量计，0.01％到2％的稳定剂单体作为聚合单元。
在一个优选实施例中，粘合剂组合物进一步包含根据聚合物粒子的总干燥重量以干燥重量计0.01％到5％的胶体稳定剂。
本发明进一步提供一种涂层组合物，其包含所述粘合剂组合物。
具体实施方式
本发明的粘合剂组合物包含根据粘合剂组合物的总干燥重量以干燥重量计，93％到99.96％、优选97％到99.94％且更优选98％到99.92％的聚合物粒子；0.04％到7％、优选0.06％到3％且更优选0.08％到2％的低水溶性环糊精。
聚合物粒子
聚合物粒子包含根据聚合物粒子的总干燥重量以干燥重量计，25％到95％、优选40％到80％且更优选55％到70％的乙酸乙烯酯；和5％到75％、优选10％到50％且更优选15％到30％的叔碳酸的乙烯酯和/或2-乙基己酸的乙烯酯作为聚合单元。
叔碳酸的乙烯酯是具有式(I)的化合物：
其中R1或R2各自独立地是C1-C10烷基。适合实例包括式(I)化合物，其中R1和R2是各自总共含有6个碳原子的烷基，和式(I)化合物，其中R1和R2是各自总共含有7个碳原子的烷基，所述式(I)化合物分别可以商标VEOVATM 10和VEOVA 9从迈图化工企业管理(上海)有限公司(Momentive Specialty Chemicals Management(Shanghai)Co.，Ltd)购得。
2-乙基己酸的乙烯酯是具有式(II)的化合物：
其中R1是C4烷基，且R2是C2烷基。适合实例可以商标VEOVA EH从迈图化工企业管理(上海)有限公司购得。
在一个优选实施例中，本发明的聚合物粒子进一步包含根据聚合物粒子的总干燥重量以干燥重量计，0.1％到50％、优选1％到30％且更优选5％到20％的(甲基)丙烯酸酯单体作为聚合单元。
(甲基)丙烯酸酯单体的适合实例包括(甲基)丙烯酸丁酯、(甲基)丙烯酸乙基己酯、(甲基)丙烯酸乙酯、甲基丙烯酸甲酯、(甲基)丙烯酸正庚酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸月桂酯、顺丁烯二酸酐以及丙烯腈。
在一个优选实施例中，聚合物粒子进一步包含根据聚合物粒子的总干燥重量以干燥重量计，0.01％到2％、优选0.05％到1.5％且最优选0.1％到1％的稳定剂单体作为聚合单元。
在一个优选实施例中，粘合剂组合物进一步包含根据聚合物粒子的总干燥重量以干燥重量计，0.01％到5％、优选0.05％到3％且最优选0.1％到2％的胶体稳定剂。
胶体稳定剂的适合实例包括羟基乙基纤维素(HEC)和其衍生物以及聚乙烯醇(PVOH)。
稳定剂单体的适合实例包括苯乙烯磺酸钠(SSS)、乙烯基磺酸钠(SVS)、2-丙烯酰胺基-2-甲基丙烷磺酸(AMPS)、丙烯酰胺(AM)、丙烯酸(AA)、甲基丙烯酸(MAA)以及衣康酸(IA)。
聚合物粒子的聚合可以是所属领域中已知的任何方法，包括乳液聚合、微乳液聚合以及机械分散技术。聚合方法的适合实例包括US 7,579,081B2、US 7,357,949B2和WO2010074865 A1中所公开的方法。
低水溶性环糊精
本发明中所用的低水溶性环糊精可以是含有六到十二个葡萄糖单元的已知环糊精中的任一种，例如α-环糊精、β-环糊精、γ-环糊精和其衍生物，例如乙基-β-环糊精、乙酰基-β-环糊精、三乙酰基-β-环糊精和叔丁基-β-环糊精以及其混合物。
优选实例是β-环糊精和其衍生物。
涂层组合物-颜料和增量剂
本发明的粘合剂组合物可以通过向粘合剂组合物中添加颜料、增量剂和添加剂制成涂层组合物。
本发明的颜料通常是无机颜料粒子，且优选是能够显著促成涂层的不透明性或遮盖能力的颗粒无机材料。此类材料的折射率通常等于或大于1.8，且其包括二氧化钛(TiO2)、氧化锌、硫化锌、硫酸钡以及碳酸钡。二氧化钛(TiO2)为优选的。
增量剂通常是折射率小于或等于1.8且大于1.3的颗粒无机材料，且包括碳酸钙、粘土、硫酸钙、铝硅酸盐、硅酸盐、沸石、云母、硅藻土、实心或空心玻璃以及瓷珠。
涂层组合物-添加剂
本发明的涂层组合物可以进一步含有至少一种常规涂层添加剂，例如聚结剂、共溶剂、表面活性剂、缓冲剂、中和剂、增稠剂、非增稠流变改性剂、分散剂、保湿剂、润湿剂、防霉剂、杀生物剂、塑化剂、防泡剂、消泡剂、防结皮剂、着色剂、流动剂、交联剂以及抗氧化剂。这些添加剂的使用是所属领域中已知的。
涂层组合物的制备
涂层组合物的制备涉及以下方法：选择且以恰当比例混合适当涂层成分以提供具有特定加工和处理特性的涂层以及具有所需特性的最终干燥涂层膜。
涂层组合物的涂覆
涂层组合物可以通过常规涂覆方法涂覆，例如涂刷、辊涂和喷雾方法，例如空气雾化喷雾、空气辅助喷雾、无空气喷雾、高体积低压喷雾和空气辅助无空气喷雾。
适合衬底包括混凝土、水泥板、中等密度纤维板(MDF)和粒子板、石膏板、木材、石头、金属、塑料、壁纸以及纺织物等。优选地，所有衬底由水性或溶剂型底漆预先底涂。
实例
I.原材料
表1a
表1b缩写
II.测试程序
总VOC检测(根据中国标准GB 18582-2008)
在安捷伦(Agilent)7890-5975C气体色谱-质谱仪(安捷伦技术公司(Agilenttechnologies))上进行粘合剂和涂层样品的定量和定性分析。
将2g(精确记录)均质化样品的等分试样称量到20ml离心小瓶中。将乙腈溶剂溶液添加到小瓶中且记录其精确重量。乙腈溶液包含以重量计5000ppm 2(2-乙氧基乙氧基)乙醇作为内标，且以重量计1000ppm草酸乙酯作为VOC标记物。将小瓶涡流离心，振荡1min且保持5min，随后再次涡流离心且振荡1min以使样品与标记物混合。随后将小瓶在4000rpm下涡流离心20min。取出混合物的上清液且经由0.45μm针筒过滤器过滤。随后将滤液注射到安捷伦7890-5975C气体色谱-质谱仪中。注射体积是1μl。
气味检测
气味检测测试由8个组员的裸鼻进行。记录平均值。
III.实例
聚合物粒子的分散液
分散液1
单体乳液通过首先混合336.11g DI水、55.17g A-102和23.66g 15-S-40，继而添加13.26g SVS、1310.70g VA、331g VEOVA10、16.71g丙烯酰胺和690g DI水来制备。将乳液馈入配备有机械搅拌器、氮气层、温度计、冷凝器、加热套和温度控制器的5L 4-颈圆底烧瓶中。将***内含物在氮气氛围下加热到81℃。将10g FeSO47H2O(0.2wt％)、2.1g EDTA(1％)、3.75g SPS在21g DI水中的溶液和80.90g E-1476添加到搅拌烧瓶中。用30g DI水冲洗烧瓶。随后在180分钟内将单体乳液、3.75g SPS溶解在70.46g DI水中的溶液和0.80IAA和2.00g乙酸钠溶解在70.46g DI水中的溶液添加到烧瓶中。维持反应温度在75℃下。接着，使用38g DI水冲洗***乳液进料管线。***内含物冷却到70℃后，将1.18g t-BHP在7.00g DI水中的溶液和1.18g IAA在30g DI水中的溶液添加到烧瓶中。保持烧瓶10分钟。将烧瓶温度冷却到65℃，随后将0.71g t-BHP在7g DI水中的溶液和0.71g IAA在19g DI水中的溶液添加到烧瓶中。保持烧瓶10分钟。烧瓶温度接近60℃前，将0.71g t-BHP在7g DI水中的溶液和0.71g IAA在19g DI水中的溶液添加到烧瓶中。保持烧瓶10分钟。
在烧瓶温度冷却到低于50℃时，通过添加27.56g NaOH溶液(5.66wt％)将***内含物中和到4.64的pH值。之后，将10.86g KATHONTM LXE杀生物剂在8g DI水中的溶液和1.00g NOPCOTMNDW消泡剂添加到烧瓶中。通过过滤器移除凝胶，且所得分散液具有52.31％固体和366nm粒度。
分散液2
以类似于制备分散液1中的程序，由含有1244.19g VA、416.40g VEOVA 10和10.88g SVS的单体混合物制备分散液2。所得分散液2具有57.31wt％固体和402nm粒度。
分散液3
以类似于制备分散液1中的程序，由含有978.03g VA、662g VEOVA 10、13.26g SVS和16.71g丙烯酰胺的单体混合物制备分散液3。所得分散液3具有52.52wt％固体和360nm粒度。
分散液的组成概括在表2中。
表2
粘合剂组合物
粘合剂1
将0.191wt％β-CD在搅拌下缓慢添加到分散液1中以制备粘合剂组合物1，且测试所制备的粘合剂1的总VOC。
粘合剂2-9
除β-CD负载不同且如表3中所列以外，粘合剂2-9以类似于制备粘合剂1的程序制备。
在VOC测试前用DI水将粘合剂1-9调节到相同固体含量。
使用常见配方将粘合剂1-3制成涂层1-3且测试涂层1-3的气味释放。
粘合剂组合物如表4中所示。
表4
i涂层在30％乳胶负载和70％Zero-VOC研磨浆下制备。
*比较实例。
上表中的结果表明粘合剂1和2相较于粘合剂3，粘合剂4和5相较于粘合剂6以及粘合剂7和8相较于粘合剂9具有较高的β-CD负载，因此具有较低的VOC和气味。
Claims (8)
1.一种粘合剂组合物，其包含根据所述粘合剂组合物的总干燥重量以干燥重量计，
i)93％到99.96％的聚合物粒子，所述聚合物粒子包含根据所述聚合物粒子的总重量以干燥重量计，25％到95％的乙酸乙烯酯；和5％到75％的叔碳酸的乙烯酯和/或2-乙基己酸的乙烯酯作为聚合单元；和
ii)0.04％到7％的低水溶性环糊精；
其中所述叔碳酸的乙烯酯是具有式(I)的化合物：
其中R1或R2各自独立地是C1-C10烷基；且所述2-乙基己酸的乙烯酯是具有式(II)的化合物：
其中R1是C4烷基，且R2是C2烷基。
2.根据权利要求1所述的粘合剂组合物，其中所述聚合物粒子包含根据所述聚合物粒子的总干燥重量以干燥重量计，40％到80％的所述乙酸乙烯酯；和10％到50％的所述叔碳酸的乙烯酯作为聚合单元。
3.根据权利要求1到2中任一项所述的粘合剂组合物，其中式(I)的R1和R2是各自总共含有6个碳原子的烷基或各自总共含有7个碳原子的烷基。
4.根据权利要求1到2中任一项所述的粘合剂组合物，其中所述低水溶性环糊精是β-环糊精或其衍生物。
5.根据权利要求1所述的粘合剂组合物，其中所述聚合物粒子进一步包含根据所述聚合物粒子的总干燥重量以干燥重量计，0.01％到2％的稳定剂单体作为聚合单元。
6.根据权利要求1所述的粘合剂组合物，其中其进一步包含根据所述聚合物粒子的总干燥重量以干燥重量计，0.01％到5％的胶体稳定剂。
7.根据权利要求1所述的粘合剂组合物，其中所述聚合物粒子进一步包含根据所述聚合物粒子的总干燥重量以干燥重量计，0.1％到50％的(甲基)丙烯酸酯单体作为聚合单元。
8.一种涂层组合物，其包含根据权利要求1到7任一项所述的粘合剂组合物。
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