CN104987821A - Environment-friendly water-borne polyurethane interior wall latex paint and preparation method thereof - Google Patents

Environment-friendly water-borne polyurethane interior wall latex paint and preparation method thereof Download PDF

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CN104987821A
CN104987821A CN201510451144.3A CN201510451144A CN104987821A CN 104987821 A CN104987821 A CN 104987821A CN 201510451144 A CN201510451144 A CN 201510451144A CN 104987821 A CN104987821 A CN 104987821A
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emulsion paint
glycol
acid
latex paint
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CN104987821B (en
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乔义涛
王萃萃
李坤
吕洪朋
张洁
孙家宽
华卫琦
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Guangdong Co Ltd
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Abstract

本发明涉及一种环保水性聚氨酯内墙乳胶漆，以水性聚氨酯分散体、水、颜料和填料为主要原料，添加润湿剂、分散剂、增稠剂、消泡剂、防腐剂、pH调节剂等助剂加工制备而成。本发明还公开了环保水性聚氨酯内墙乳胶漆的制备方法。采用本发明制备的水性聚氨酯内墙乳胶漆具有超低绝对VOC含量、无气味、绿色环保、耐擦洗性能优异、手感好、装饰性能好的特点。The invention relates to an environmentally friendly water-based polyurethane interior wall latex paint, which uses water-based polyurethane dispersion, water, pigments and fillers as main raw materials, and adds wetting agent, dispersant, thickener, defoamer, antiseptic and pH regulator And other additives processing preparation. The invention also discloses a preparation method of the environment-friendly water-based polyurethane interior wall latex paint. The water-based polyurethane interior wall latex paint prepared by the invention has the characteristics of ultra-low absolute VOC content, no odor, environmental protection, excellent scrub resistance, good hand feeling and good decorative performance.

Description

一种环保水性聚氨酯内墙乳胶漆及其制备方法A kind of environment-friendly waterborne polyurethane interior wall latex paint and preparation method thereof

技术领域technical field

本发明涉及建筑涂料领域，更具体的涉及一种水性聚氨酯内墙乳胶漆。The invention relates to the field of architectural coatings, in particular to a water-based polyurethane interior wall latex paint.

背景技术Background technique

在我国，内墙乳胶漆经历了多年的发展，正在越来越多的应用于内墙建筑装饰装修中。但是某些内墙乳胶漆在生产、施工和应用过程中会释放出如甲醛和苯类物质等有害物质，容易诱发呼吸道疾病和白血病，因此近年来人们更加关注内墙乳胶漆的绿色环保性能如VOC含量。In my country, interior wall latex paint has experienced many years of development, and is being more and more used in interior wall building decoration. However, some interior wall latex paints will release harmful substances such as formaldehyde and benzene substances during production, construction and application, which can easily induce respiratory diseases and leukemia. Therefore, in recent years, people have paid more attention to the green environmental protection performance of interior wall latex paints. VOC content.

VOC为可挥发性有机化合物，不同国家和地区对于VOC的定义存在差异，如我国规定VOC为利用Tenax GC和Tenax TA采样，非极性色谱柱(极性指数小于10)进行分析，保留时间在正己烷和正十六烷之间的挥发性有机化合物；德国标准则定义常压下，沸点或初馏点低于或等于250℃的任何有机化合物为VOC。以上标准定义的均为相对VOC，而绝对VOC还包括沸点高于250℃的可挥发性有机化合物。如常用成膜助剂OE-300醇酯(伊士曼)的沸点为281℃，其不属于相对VOC，但属于绝对VOC。VOC is a volatile organic compound, and there are differences in the definition of VOC in different countries and regions. For example, my country stipulates that VOC is sampled by Tenax GC and Tenax TA, analyzed by non-polar chromatographic columns (polarity index less than 10), and the retention time is between Volatile organic compounds between n-hexane and n-hexadecane; German standards define any organic compound with a boiling point or initial boiling point lower than or equal to 250°C under normal pressure as VOC. The above standards define relative VOC, while absolute VOC also includes volatile organic compounds with a boiling point higher than 250°C. For example, the boiling point of OE-300 alcohol ester (Eastman), a commonly used film-forming aid, is 281°C, which is not a relative VOC, but an absolute VOC.

市场上所售的零VOC/净味水性丙烯酸乳胶漆，其乳液相对VOC含量通常大于1000ppm，绝对VOC含量则更高，因为水性丙烯酸乳液在自由基聚合过程中引入难以彻底清除的小分子有机化合物，包括未反应单体、由单体引入的有机杂质、由表面活性剂或引发剂分解产生的有机物。且因水性丙烯酸乳液自身结构特点，在乳胶漆配方中需平衡成膜助剂和防冻助剂的选择，不加成膜助剂则存在漆膜发粘、耐沾污性能差的缺点，而加入成膜助剂后乳胶漆的绝对VOC含量大于10000ppm。For the zero-VOC/clean-odor water-based acrylic latex paints on the market, the relative VOC content of the emulsion is usually greater than 1000ppm, and the absolute VOC content is higher, because the water-based acrylic emulsion introduces small molecular organic compounds that are difficult to completely remove during the free radical polymerization process. , including unreacted monomers, organic impurities introduced by monomers, and organic substances produced by the decomposition of surfactants or initiators. And because of the structural characteristics of water-based acrylic emulsion, it is necessary to balance the selection of film-forming aids and antifreeze aids in the formulation of latex paint. Without film-forming aids, there will be disadvantages of sticky paint film and poor stain resistance. Adding The absolute VOC content of latex paint after coalescent is greater than 10000ppm.

CN1414045A公开了一种零VOC的环保纯丙乳胶漆，低温成膜性良好，相对VOC含量较低，但其手感发粘，且冻融稳定性差。CN101343451A公开了一种零VOC健康内墙乳胶漆，但是其配方中引入成膜助剂，因此难以达到超低的绝对VOC含量。因此，开发一种绝对VOC含量接近零、无气味、健康环保的水性聚氨酯内墙乳胶漆，势必将进一步提升整个行业的环保水平。CN1414045A discloses a kind of zero-VOC environment-friendly pure acrylic latex paint, which has good low-temperature film-forming properties and relatively low VOC content, but it feels sticky and has poor freeze-thaw stability. CN101343451A discloses a kind of zero-VOC healthy interior wall latex paint, but introduces film-forming aid in its formula, so it is difficult to reach ultra-low absolute VOC content. Therefore, the development of a water-based polyurethane interior wall latex paint with an absolute VOC content close to zero, odorless, healthy and environmentally friendly will certainly further enhance the environmental protection level of the entire industry.

发明内容Contents of the invention

本发明的目的在于提供一种环保水性聚氨酯内墙乳胶漆，采用的成膜物质水性聚氨酯分散体通过缩合聚合制备得到。无需加入成膜助剂即可在5℃成膜，且漆膜表面滑爽、耐污渍性能及耐沾污性能优异，本发明提供的聚氨酯内墙乳胶漆绝对VOC含量极低，具有无气味、健康环保、耐擦洗性能优异、手感佳、装饰性能佳的优点。The object of the present invention is to provide a kind of environment-friendly water-based polyurethane interior wall latex paint, and the film-forming substance water-based polyurethane dispersion used is prepared by condensation polymerization. Films can be formed at 5°C without adding film-forming aids, and the surface of the paint film is smooth, with excellent stain resistance and stain resistance. The polyurethane interior wall latex paint provided by the invention has extremely low absolute VOC content, and has odorless, It has the advantages of health and environmental protection, excellent scrub resistance, good hand feeling and good decoration performance.

本发明还提供一种所述环保水性聚氨酯内墙乳胶漆的生产方法。The invention also provides a production method of the environment-friendly water-based polyurethane interior wall latex paint.

为实现以上技术目的，本发明采用如下技术方案：To achieve the above technical purpose, the present invention adopts the following technical solutions:

一种环保水性聚氨酯内墙乳胶漆，其包括：基于乳胶漆总重计，A kind of environment-friendly water-based polyurethane interior wall latex paint, it comprises: Based on the total weight of latex paint,

优选的，本发明所述乳胶漆，包括：基于乳胶漆总重计，Preferably, the latex paint of the present invention includes: based on the total weight of the latex paint,

本发明所述的水性聚氨酯分散体中的聚氨酯为包含以下组分制备得到的产物：The polyurethane in the aqueous polyurethane dispersion of the present invention is the product that comprises following component preparation:

(a1)10wt％-35wt％，优选15wt％-35wt％的多异氰酸酯单体，(a1) 10wt%-35wt%, preferably 15wt%-35wt% polyisocyanate monomer,

(a2)50wt％-85wt％，优选60wt％-80wt％的多元醇，(a2) 50wt%-85wt%, preferably 60wt%-80wt% polyhydric alcohol,

(a3)0.1wt％-8wt％，优选0.1wt％-6wt％的扩链剂，(a3) 0.1wt%-8wt%, preferably 0.1wt%-6wt% chain extender,

(a4)0.1wt％-5wt％，优选0.1wt％-3wt％的非离子亲水性单体,(a4) 0.1wt%-5wt%, preferably 0.1wt%-3wt% of non-ionic hydrophilic monomers,

(a5)0.1wt％-5wt％，优选0.5wt％-3wt％的离子型亲水单体；各组分含量均基于所述(a)水性聚氨酯分散体的聚氨酯的重量计算。(a5) 0.1wt%-5wt%, preferably 0.5wt%-3wt% ionic hydrophilic monomer; the content of each component is calculated based on the weight of polyurethane in the (a) aqueous polyurethane dispersion.

本发明所述的水性聚氨酯分散体的不挥发物成分即聚氨酯的含量为30wt％-70wt％，其余组成为水。The non-volatile component of the water-based polyurethane dispersion of the present invention, that is, the content of polyurethane is 30wt%-70wt%, and the rest is composed of water.

本发明所述多异氰酸酯单体选自芳香族、芳脂族、脂肪族和脂环族多异氰酸酯中的一种或两种或多种；合适的多异氰酸酯单体的例子有1,6-六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、双-(4,4’-异氰酸根合环己基)甲烷(HMDI)、4,4’-二苯基甲烷二异氰酸酯(MDI)。The polyisocyanate monomer of the present invention is selected from one or two or more of aromatic, araliphatic, aliphatic and alicyclic polyisocyanates; examples of suitable polyisocyanate monomers include 1,6-hexa Methylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), bis-(4,4'-isocyanatocyclohexyl)methane (HMDI), 4,4' - Diphenylmethane diisocyanate (MDI).

本发明所述多元醇选自聚醚多元醇、聚酯多元醇和聚碳酸酯多元醇中的一种或两种或多种。所述多元醇具有2个以上官能度，分子量为500-5000。The polyol in the present invention is selected from one or two or more of polyether polyols, polyester polyols and polycarbonate polyols. The polyol has more than two functionalities, and the molecular weight is 500-5000.

优选的，本发明所述多元醇选自聚酯二元醇、聚醚二元醇和聚碳酸酯二元醇中的一种或两种或多种。Preferably, the polyol in the present invention is selected from one or two or more of polyester diol, polyether diol and polycarbonate diol.

所述聚醚二元醇优选聚乙二醇、聚丙二醇和聚四氢呋喃醚二醇中的一种或两种或多种。The polyether diol is preferably one or two or more of polyethylene glycol, polypropylene glycol and polytetrahydrofuran ether diol.

所述聚酯二元醇由二元羧酸或二元羧酸酐与二元醇反应制得或者由内酯制备，所述内酯优选但不限于己内酯。The polyester diol is prepared by reacting dibasic carboxylic acid or dibasic carboxylic acid anhydride with dibasic alcohol or prepared from lactone, and the lactone is preferably but not limited to caprolactone.

优选的，所述聚酯二元醇基于己二酸、邻苯二甲酸、间苯二甲酸和对苯二甲酸和邻苯二甲酸酐中的一种或两种或多种与乙二醇、1,4-丁二醇、1,3-丁二醇、1,6-己二醇和新戊二醇中的一种或两种或多种制备。Preferably, the polyester diol is based on one or two or more of adipic acid, phthalic acid, isophthalic acid and terephthalic acid and phthalic anhydride with ethylene glycol, Preparation of one or two or more of 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol and neopentyl glycol.

更优选的，本发明所述多元醇为基于己二酸、1,6-己二醇和新戊二醇制备的聚酯二元醇(PNHA)和聚四氢呋喃醚二醇的混合物，其中所述基于己二酸、1,6-己二醇和新戊二醇制备的聚酯二元醇的数均分子量500-3000，优选1000-2000，聚四氢呋喃醚二醇的数均分子量为500-3000，优选1000-2000；所述基于己二酸、1,6-己二醇和新戊二醇制备的聚酯二元醇和聚四氢呋喃醚二醇的质量比为9:1-1:1，优选9:1-7:3。More preferably, the polyhydric alcohol of the present invention is based on the mixture of polyester diol (PNHA) and polytetrahydrofuran ether diol prepared based on adipic acid, 1,6-hexanediol and neopentyl glycol, wherein said based on The number average molecular weight of the polyester diol prepared by adipic acid, 1,6-hexanediol and neopentyl glycol is 500-3000, preferably 1000-2000, and the number average molecular weight of polytetrahydrofuran ether diol is 500-3000, preferably 1000-2000; the mass ratio of the polyester diol and polytetrahydrofuran ether diol prepared based on adipic acid, 1,6-hexanediol and neopentyl glycol is 9:1-1:1, preferably 9:1 -7:3.

进一步优选的，所述基于己二酸、1,6-己二醇和新戊二醇制备的聚酯二元醇中新戊二醇用量为1,6-己二醇和新戊二醇总质量的5wt％～100wt％，优选10wt％～80wt％。Further preferably, the amount of neopentyl glycol in the polyester diol prepared based on adipic acid, 1,6-hexanediol and neopentyl glycol is 1,6-hexanediol and neopentyl glycol total mass 5wt%-100wt%, preferably 10wt%-80wt%.

本发明所述的聚酯多元醇能有效提高漆膜的强度，且提供良好的手感，同时基于己二酸、1,6-己二醇与新戊二醇的聚酯二元醇，结构中引入非对称的新戊二醇，有效降低聚酯结构的对称性，降低聚氨酯中软段结构自身的相互作用，提升其与颜料、填料的结合。同时，聚四氢呋喃醚二醇内聚力小，抗水解能力强，有效提升漆膜的耐久性。聚四氢呋喃醚二醇和聚酯二元醇的特定比例混合使用，可进一步降低多元醇间的相互作用，增强聚氨酯与颜料、填料的结合，有效提升乳胶漆的耐久性、抗开裂效果及与耐擦洗性能，在保证乳胶漆环保性能的同时，提升乳胶漆的整体应用性能。The polyester polyol of the present invention can effectively improve the strength of the paint film, and provide a good feel. At the same time, the polyester diol based on adipic acid, 1,6-hexanediol and neopentyl glycol, in the structure The introduction of asymmetric neopentyl glycol can effectively reduce the symmetry of the polyester structure, reduce the interaction of the soft segment structure in polyurethane, and improve its combination with pigments and fillers. At the same time, polytetrahydrofuran ether glycol has low cohesion and strong hydrolysis resistance, which can effectively improve the durability of the paint film. The mixed use of polytetrahydrofuran ether diol and polyester diol in a specific ratio can further reduce the interaction between polyols, strengthen the combination of polyurethane with pigments and fillers, and effectively improve the durability, anti-cracking effect and scrub resistance of latex paint Performance, while ensuring the environmental protection performance of latex paint, improve the overall application performance of latex paint.

本发明所述扩链剂选自低分子多元醇、低分子多元胺和低分子醇胺中的一种或两种或多种；合适的扩链剂的例子有1,3-丙二醇、1,4-丁二醇(BDO)、新戊二醇、一缩二乙二醇、1,6-己二醇、1,4-环己烷二甲醇、乙二胺、六亚甲基二胺、五亚甲基二胺、二亚乙基三胺、异佛尔酮二胺、4,4’-二苯基甲烷二胺、单乙醇胺、二乙醇胺。The chain extender of the present invention is selected from one or two or more of low-molecular polyols, low-molecular polyamines and low-molecular alcohol amines; examples of suitable chain extenders are 1,3-propanediol, 1, 4-butanediol (BDO), neopentyl glycol, diethylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, ethylenediamine, hexamethylenediamine, Pentamethylenediamine, Diethylenetriamine, Isophoronediamine, 4,4'-Diphenylmethanediamine, Monoethanolamine, Diethanolamine.

优选，本发明所述扩链剂选自至少一种低分子多元醇和至少一种低分子多元胺。Preferably, the chain extender in the present invention is selected from at least one low molecular polyol and at least one low molecular polyamine.

本发明所述非离子亲水性单体,其具有异氰酸酯反应性基团的官能度为1或2，所述具有异氰酸酯反应性基团选自羟基、氨基等。The non-ionic hydrophilic monomer of the present invention has an isocyanate-reactive group with a functionality of 1 or 2, and the isocyanate-reactive group is selected from hydroxyl, amino and the like.

优选的，本发明所述非离子亲水性单体选自单官能聚环氧烷和/或含有聚环氧烷侧链的双官能度分子。Preferably, the nonionic hydrophilic monomer in the present invention is selected from monofunctional polyalkylene oxide and/or bifunctional molecules containing polyalkylene oxide side chains.

本发明所述含有聚环氧烷侧链的双官能度分子优选主链碳数为2-20个，侧链含有聚环氧乙烷醚或者含有环氧乙烷链段的分子，所述聚环氧烷侧链的双官能度分子的数均分子量为200-2000，优选数均分子量为500-1500。According to the present invention, the bifunctional molecules containing polyoxyalkylene side chains preferably have 2-20 carbon atoms in the main chain, and the side chains contain polyethylene oxide ether or molecules containing ethylene oxide segments. The number-average molecular weight of the bifunctional molecule of the alkylene oxide side chain is 200-2000, preferably the number-average molecular weight is 500-1500.

本发明所述单官能聚环氧烷优选数均分子量为200-3000的端羟基聚环氧乙烷单甲醚和/或端氨基聚环氧乙烷单甲醚。The monofunctional polyalkylene oxide in the present invention is preferably hydroxyl-terminated polyethylene oxide monomethyl ether and/or amino-terminated polyethylene oxide monomethyl ether with a number average molecular weight of 200-3000.

本发明所述离子型亲水单体是含亲水稳定性基团的二元醇、二元胺和醇胺中的一种或两种或多种，所述亲水稳定性基团选自羧基、磺酸基、磷酸根基团、叔胺基团或季铵基团。The ionic hydrophilic monomer of the present invention is one or two or more of diols, diamines and alcohol amines containing hydrophilic stabilizing groups, and the hydrophilic stabilizing groups are selected from Carboxyl, sulfonic acid, phosphate, tertiary amine or quaternary ammonium groups.

优选的，本发明所述离子型亲水单体选自二羟甲基丙酸(DMPA)、1,3-二羟基丁烷-1-羧酸、1,2-二羟基丁烷-1-磺酸、1,3-二羟基丁基-三甲基铵氯化物和中的一种或两种或多种，其中m，n相互独立的为1-20的自然数；更优选其中m，n相互独立的为1-6的自然数；进一步优选N-(2氨基乙基)-2-氨基乙磺酸的钠盐和/或N-(2-氨基乙基)-2-氨基丙磺酸的钠盐。Preferably, the ionic hydrophilic monomer of the present invention is selected from dimethylolpropionic acid (DMPA), 1,3-dihydroxybutane-1-carboxylic acid, 1,2-dihydroxybutane-1- Sulfonic acid, 1,3-dihydroxybutyl-trimethylammonium chloride and One or two or more of them, wherein m and n are independently natural numbers of 1-20; more preferably Wherein m, n are mutually independent natural numbers of 1-6; further preferably the sodium salt of N-(2-aminoethyl)-2-aminoethanesulfonic acid and/or N-(2-aminoethyl)-2-amino Sodium salt of propanesulfonic acid.

所述水性聚氨酯分散体的制备工艺包括以下步骤：按照比例，将多元醇、多异氰酸酯单体、低分子多元醇扩链剂及非离子亲水单体在丙酮中在60～100℃进行反应，过程中监控反应体系的异氰酸酯根含量，以判断反应终点；之后降低反应温度至30～50℃，补加丙酮和低分子多元胺扩链剂及离子型亲水单体进行反应至结束。反应完成后，在快速搅拌条件下向体系中逐渐加入水，相反转形成分散体，进行分散，脱除丙酮，形成粒径在50～1000nm的水性聚氨酯分散体。The preparation process of the aqueous polyurethane dispersion comprises the following steps: reacting polyols, polyisocyanate monomers, low-molecular polyol chain extenders and nonionic hydrophilic monomers in acetone at 60-100°C according to the proportion, During the process, monitor the isocyanate content of the reaction system to determine the end point of the reaction; then lower the reaction temperature to 30-50°C, add acetone, low-molecular polyamine chain extender and ionic hydrophilic monomer to complete the reaction. After the reaction is completed, water is gradually added to the system under rapid stirring conditions, the phase is reversed to form a dispersion, and the dispersion is carried out to remove acetone to form a water-based polyurethane dispersion with a particle size of 50-1000nm.

水性聚氨酯分散体合成过程中需要使用丙酮作为溶剂，在生产的最后脱除丙酮获得水性聚氨酯分散体。对于传统的产品，其中的丙酮残留量在几千ppm或者更高的含量。为有效控制乳胶漆中的VOC含量，要求水性聚氨酯分散体中的丙酮含量≤200ppm。Acetone needs to be used as a solvent during the synthesis of water-based polyurethane dispersions, and acetone is removed at the end of production to obtain water-based polyurethane dispersions. For traditional products, the residual amount of acetone is several thousand ppm or higher. In order to effectively control the VOC content in latex paint, the acetone content in the waterborne polyurethane dispersion is required to be ≤200ppm.

本发明所述的颜料为钛白粉。The pigment described in the present invention is titanium dioxide.

本发明所述的填料选自滑石粉、重钙、轻钙、云母粉、硅藻土和高岭土中的一种或两种或多种。The filler described in the present invention is selected from one or two or more of talcum powder, heavy calcium, light calcium, mica powder, diatomaceous earth and kaolin.

本发明所述乳胶漆还可以含有0-10wt％，优选1-8wt％的遮盖聚合物；所述遮盖聚合物优选自粒径200-600nm聚苯乙烯空心微球，更优选DOW化学的优创E空心聚合物微球。The latex paint of the present invention can also contain 0-10wt%, preferably 1-8wt% covering polymer; The covering polymer is preferably selected from polystyrene hollow microspheres with a particle diameter of 200-600nm, more preferably DOW Chemical's excellent E Hollow polymer microspheres.

本发明所述的助剂,包括以下成分：基于乳胶漆总重计，分散剂0.1wt％-3wt％、润湿剂0.1wt％-0.5％、增稠剂0.1wt％-2.0wt％、防腐剂0-0.5wt％、消泡剂0.1wt％-1.5wt％、pH调节剂0-0.5wt％。The auxiliary agent of the present invention includes the following components: based on the total weight of the latex paint, dispersant 0.1wt%-3wt%, wetting agent 0.1wt%-0.5%, thickener 0.1wt%-2.0wt%, anti-corrosion Agent 0-0.5wt%, defoamer 0.1wt%-1.5wt%, pH regulator 0-0.5wt%.

本发明所述分散剂选自聚丙烯酰胺、均聚羧酸盐、共聚羧酸盐中的一种或两种或多种，优选丙烯酸与其它单体共聚物、马来酸酐与其它单体共聚物的钠盐、钾盐，可赋予涂层更好的耐性及环保特性。实例包含但不限于：诺普科SN5040、SN5027，DOW化学的Orotan 1124、Orotan快易、Orotan 731A，万华化学的Vesmody C20,BYK公司DISPERBYK-182等。The dispersant of the present invention is selected from one or two or more of polyacrylamide, homopolycarboxylate, and copolycarboxylate, preferably acrylic acid and other monomer copolymers, maleic anhydride and other monomer copolymers The sodium salt and potassium salt of the substance can give the coating better resistance and environmental protection characteristics. Examples include but are not limited to: Nopco SN5040, SN5027, DOW Chemical’s Orotan 1124, Orotan Quick and Easy, Orotan 731A, Wanhua Chemical’s Vesmody C20, BYK’s DISPERBYK-182, etc.

本发明所述的润湿剂可以是多聚磷酸盐或者非离子表面活性剂一种或两种或多种。所述非离子表面活性剂优选疏水端碳数在8-20，亲水端为聚环氧乙烷或者环氧乙烷与环氧丙烷的共聚物。实例包含但不限于：六偏磷酸钠，DOW化学的Triton CF10、Triton CF-405、Triton BD-109；克莱恩LCN407，诺普科SN-WET990、SN-WET991，润湿剂PE100等。The wetting agent of the present invention may be one or two or more of polyphosphate or nonionic surfactant. The nonionic surfactant preferably has 8-20 carbon atoms at the hydrophobic end, and polyethylene oxide or a copolymer of ethylene oxide and propylene oxide at the hydrophilic end. Examples include but are not limited to: sodium hexametaphosphate, Triton CF10, Triton CF-405, Triton BD-109 of DOW Chemical; Klein LCN407, Nopco SN-WET990, SN-WET991, wetting agent PE100, etc.

本发明所述增稠剂选自纤维素醚类增稠剂、碱溶胀型增稠剂和聚氨酯型增稠剂中的一种或两种或多种。所述碱溶涨型增稠剂可以选择单纯的碱溶涨型增稠剂或者疏水改性碱溶涨型增稠剂，所述纤维素醚类增稠剂可以选择不同分子量大小或者疏水改性的产品。实例包含但不限于：纤维素醚类增稠剂如压跨龙的羟乙基纤维素250HBR，DOW化学的HEC类纤维素醚类增稠剂；碱溶涨性增稠剂如DOW化学的万华化学的等；聚氨酯型增稠剂如万华化学的DOW化学的等。The thickener in the present invention is selected from one or two or more of cellulose ether thickeners, alkali-swellable thickeners and polyurethane thickeners. The alkali-swellable thickener can be selected from a simple alkali-swellable thickener or a hydrophobically modified alkali-swellable thickener, and the cellulose ether thickener can be selected from different molecular weights or hydrophobically modified The product. Examples include but are not limited to: cellulose ether thickeners such as hydroxyethyl cellulose 250HBR of Yasuolong, HEC cellulose ether thickeners of DOW Chemical; alkali-swellable thickeners such as DOW Chemical’s Wanhua Chemical etc.; polyurethane thickener such as Wanhua Chemical DOW chemical wait.

本发明中所述防腐剂没有具体限制，只要不对本发明的发明目的产生限制即可，实例包含但不限于1,2-苯并异噻唑-3-酮、甲基异噻唑啉酮、5-氯-2-甲基-4-异噻唑啉-3-酮、罗门哈斯的KATHON LXE等。The preservatives described in the present invention are not specifically limited, as long as they do not limit the purpose of the present invention, examples include but are not limited to 1,2-benzisothiazol-3-one, methylisothiazolinone, 5- Chloro-2-methyl-4-isothiazolin-3-one, KATHON LXE of Rohm and Haas, etc.

本发明所述的消泡剂选自矿物油类消泡剂、有机硅消泡剂和聚醚改性有机硅消泡剂等中的一种或两种或多种，优选自聚硅氧烷-聚醚共聚物乳液类、聚丙二醇-憎水固体-聚硅氧烷混合物类、聚乙二醇-憎水固体-聚硅氧烷混合物类和矿物油基类中的一种或两种或多种。实例包含但不限于：诺普科NXZ，迪高的Tego1488、825，BYK的BYK-028，道康宁的DC-65等。The defoamer of the present invention is selected from one or two or more of mineral oil defoamers, silicone defoamers and polyether modified silicone defoamers, preferably from polysiloxane - one or both of polyether copolymer emulsions, polypropylene glycol-hydrophobic solid-polysiloxane mixtures, polyethylene glycol-hydrophobic solid-polysiloxane mixtures, and mineral oil-based Various. Examples include but are not limited to: Nopco NXZ, Tego 1488, 825, BYK BYK-028, Dow Corning DC-65, etc.

本发明所述pH调节剂优选为氢氧化钠和/或氢氧化钾。The pH regulator of the present invention is preferably sodium hydroxide and/or potassium hydroxide.

本发明还提供一种环保水性聚氨酯内墙乳胶漆的制备方法，包含以下步骤：The present invention also provides a kind of preparation method of environment-friendly waterborne polyurethane interior wall latex paint, comprises the following steps:

(1)浆料的制备(1) Preparation of slurry

按比例称取水、分散剂、润湿剂、增稠剂、防腐剂、消泡剂、pH调节剂、颜料、填料、遮盖聚合物，搅拌均匀，制成浆料备用；Weigh water, dispersant, wetting agent, thickener, preservative, defoamer, pH regulator, pigment, filler, covering polymer in proportion, stir evenly, and make a slurry for later use;

(2)乳胶漆的制备(2) Preparation of latex paint

按比例称取步骤(1)制得的浆料、水性聚氨酯分散体、增稠剂、消泡剂，搅拌均匀后出料得到环保水性聚氨酯内墙乳胶漆。Weigh the slurry, water-based polyurethane dispersion, thickener, and defoamer prepared in step (1) in proportion, stir evenly, and discharge to obtain an environmentally friendly water-based polyurethane interior wall latex paint.

本发明所述乳胶漆不需加入成膜助剂即可在5℃及以上温度良好成膜，漆膜干爽不粘，手感佳，并且耐擦洗性能优异、耐污渍性能及耐沾污性能优异，低温稳定性良好，绝对有机挥发气体(包括沸点小于、等于250℃及高于250℃的小分子有机挥发物)含量低于500ppm，优选低于300ppm，无气味，属于绿色环保产品装饰性能佳，施工方便。The latex paint of the present invention can form a good film at a temperature of 5°C or above without adding a film-forming aid, the paint film is dry and non-sticky, has a good hand feeling, and has excellent scrub resistance, stain resistance and stain resistance. Good low temperature stability, absolute organic volatile gas (including small molecule organic volatiles with boiling point less than or equal to 250°C and higher than 250°C) content is less than 500ppm, preferably less than 300ppm, odorless, and belongs to green environmental protection products. Construction is convenient.

具体实施方式Detailed ways

以下是本发明的实施例，但不限于所述实施例。The following are examples of the invention, but are not limited to the examples.

(1)水性聚氨酯分散体的合成(1) Synthesis of waterborne polyurethane dispersion

实施例1Example 1

在干燥N2的保护下，向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入400g聚酯多元醇PNHA1500(华大化学，Mn＝1500，新戊二醇：1,6-己二醇质量比＝1:2)，16.06g新戊二醇，8.8g YmerTMN120(非离子型亲水单体)，在60℃条件下搅拌30min，加入86g和56g56g丙酮80℃条件下反应。当NCO含量达到理论值3.12wt％时，将预聚物冷却到40℃，溶解在800g丙酮中，混合10分钟后加入9.6g乙二胺,14gA95(氨基磺酸钠盐，50wt％水溶液)，继续搅拌30min后，在剪切分散机下加入575g去离子水进行分散；将以上乳液在50℃下减压旋蒸1小时除去丙酮，可得到乳白色的1#水性聚氨酯分散体乳液；该乳液粒径280nm，固含量50wt％。Under the protection of dry N2, add 400g polyester polyol PNHA1500 (Hua Da Chemical, Mn=1500, neopentyl glycol: 1,6-hexanedi Alcohol mass ratio=1:2), 16.06g neopentyl glycol, 8.8g Ymer TM N120 (non-ionic hydrophilic monomer), stirred at 60°C for 30min, added 86g and 56g 56g of acetone was reacted at 80°C. When the NCO content reaches the theoretical value of 3.12wt%, the prepolymer is cooled to 40°C, dissolved in 800g of acetone, mixed for 10 minutes and then added with 9.6g of ethylenediamine, 14g A95 (sulfamic acid sodium salt, 50wt% aqueous solution), after continuing to stir for 30min, add 575g of deionized water under the shear disperser to disperse; the above emulsion is decompressed and rotary evaporated at 50°C for 1 hour to remove acetone, and it can be obtained Milky white 1# aqueous polyurethane dispersion emulsion; the particle size of the emulsion is 280nm, and the solid content is 50wt%.

实施例2Example 2

在干燥N2的保护下，向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入357g聚酯多元醇PNHA2000(华大化学，Mn＝2000，新戊二醇：1,6-己二醇质量比＝1:2)，45g PTMEG2000,14g1,4-丁二醇，6g YmerTMN120(非离子型亲水单体)，在60℃条件下搅拌30min，加入72g和46g49g丙酮80℃条件下反应。当NCO含量达到理论值2.65wt％时，将预聚物冷却到40℃，溶解在692g丙酮中，混合10分钟后加入6g乙二胺,14g(氨基磺酸钠盐，50wt％水溶液)，继续搅拌30min后，在剪切分散机下加入501g去离子水进行分散；将以上乳液在50℃下减压旋蒸1小时除去丙酮，可得到乳白色的2#水性聚氨酯分散体乳液；该乳液粒径332nm，固含量50wt％。Under the protection of dry N 2 , add 357g polyester polyol PNHA2000 (Hua Da Chemical, Mn=2000, neopentyl glycol: 1,6-hexane Diol mass ratio = 1:2), 45g PTMEG2000, 14g 1,4-butanediol, 6g Ymer TM N120 (non-ionic hydrophilic monomer), stirred at 60°C for 30min, added 72g and 46g 49g of acetone was reacted at 80°C. When the NCO content reaches the theoretical value of 2.65wt%, the prepolymer is cooled to 40°C, dissolved in 692g of acetone, mixed for 10 minutes and then added with 6g of ethylenediamine, 14g (Sulphamic acid sodium salt, 50wt% aqueous solution), after continuing to stir for 30min, add 501g of deionized water under the shear disperser to disperse; the above emulsion is decompressed and rotary steamed at 50°C for 1 hour to remove acetone, and milky white 2# aqueous polyurethane dispersion emulsion; the particle size of the emulsion is 332nm, and the solid content is 50wt%.

实施例3Example 3

在干燥N2的保护下，向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入397g聚碳酸酯二元醇NPU-964(Mn＝2000)，98g PTMEG2000,8g新戊二醇，6g YmerTMN120(非离子型亲水单体)，在60℃条件下搅拌30min，加入68.3g和43.8g52g丙酮80℃条件下反应。当NCO含量达到理论值2.38wt％时，将预聚物冷却到40℃，溶解在732g丙酮中，混合10分钟后加入17.5g异佛二酮二胺,16g(氨基磺酸钠盐，50wt％水溶液)，继续搅拌30min后，在剪切分散机下加入541g去离子水进行分散；将以上乳液在50℃下减压旋蒸1小时除去丙酮，可得到乳白色的3#水性聚氨酯分散体乳液；该乳液粒径307nm，固含量50wt％。Under the protection of dry N , add 397g polycarbonate dibasic alcohol NPU-964 (Mn=2000), 98g PTMEG2000,8g neopentyl glycol in the four-necked flask that reflux condenser, thermometer and mechanical stirring are housed, 6g Ymer TM N120 (non-ionic hydrophilic monomer), stirred at 60°C for 30min, added 68.3g and 43.8g 52g of acetone was reacted at 80°C. When the NCO content reaches the theoretical value of 2.38wt%, the prepolymer is cooled to 40°C, dissolved in 732g of acetone, mixed for 10 minutes and then added with 17.5g of isophordione diamine, 16g (sulfamic acid sodium salt, 50wt% aqueous solution), after continuing to stir for 30min, add 541g of deionized water under the shear disperser to disperse; the above emulsion is decompressed and rotary steamed at 50°C for 1 hour to remove acetone, and milky white 3# water-based polyurethane dispersion emulsion; the particle size of the emulsion is 307nm, and the solid content is 50wt%.

实施例4Example 4

在干燥N2的保护下，向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入280g聚酯多元醇PNHA1500(华大化学，Mn＝1500，新戊二醇：1,6-己二醇质量比＝1:2)，120g PTMEG2000,30g1,6-己二醇，11g YmerTMN120(非离子型亲水单体)，在60℃条件下搅拌30min，加入107.6g和69.2g50g丙酮80℃条件下反应。当NCO含量达到理论值3.91wt％时，将预聚物冷却到40℃，溶解在697g丙酮中，混合10分钟后加入12g乙二胺,13.5g(氨基磺酸钠盐)，继续搅拌30min后，在剪切分散机下加入510g去离子水进行分散；将以上乳液在50℃下减压旋蒸1小时除去丙酮，可得到乳白色的4#水性聚氨酯分散体乳液；该乳液粒径250nm，固含量50wt％。Under the protection of dry N 2 , add 280g polyester polyol PNHA1500 (Hua Da Chemical, Mn=1500, neopentyl glycol: 1,6-hexane Diol mass ratio = 1:2), 120g PTMEG2000, 30g 1,6-hexanediol, 11g Ymer TM N120 (non-ionic hydrophilic monomer), stirred at 60°C for 30min, added 107.6g and 69.2g 50g of acetone was reacted at 80°C. When the NCO content reaches the theoretical value of 3.91wt%, the prepolymer is cooled to 40°C, dissolved in 697g of acetone, mixed for 10 minutes and then added with 12g of ethylenediamine, 13.5g (Sulphamic acid sodium salt), after continuing to stir for 30 minutes, add 510 g of deionized water to disperse under the shear disperser; rotate the above emulsion at 50 °C for 1 hour to remove acetone, and milky white 4# water-based Polyurethane dispersion emulsion; the particle size of the emulsion is 250nm, and the solid content is 50wt%.

实施例5Example 5

在干燥N2的保护下，向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入400g聚酯多元醇PNHA1500(华大化学，Mn＝1500，新戊二醇：1,6-己二醇质量比＝1:2)，16.6g新戊二醇，6gMPEG1200，在60℃条件下搅拌30min，加入86g和56g6g丙酮80℃条件下反应。当NCO含量达到理论值3.15wt％时，将预聚物冷却到40℃，溶解在790g丙酮中，混合10分钟后加入8.3g乙二胺,14g(氨基磺酸钠盐，50wt％水溶液)，继续搅拌30min后，在剪切分散机下加入573g去离子水进行分散；将以上乳液在50℃下减压旋蒸1小时除去丙酮，可得到乳白色的5#水性聚氨酯分散体乳液；该乳液粒径230nm，固含量50wt％。Under the protection of dry N2, add 400g polyester polyol PNHA1500 (Hua Da Chemical, Mn=1500, neopentyl glycol: 1,6-hexanedi Alcohol mass ratio=1:2), 16.6g neopentyl glycol, 6g MPEG1200, stirred at 60°C for 30min, added 86g and 56g 6g of acetone was reacted at 80°C. When the NCO content reaches the theoretical value of 3.15wt%, the prepolymer is cooled to 40°C, dissolved in 790g of acetone, mixed for 10 minutes and then added with 8.3g of ethylenediamine, 14g (sulfamic acid sodium salt, 50wt% aqueous solution), after continuing to stir for 30min, add 573g of deionized water under the shear disperser to disperse; the above emulsion is decompressed and rotary steamed at 50°C for 1 hour to remove acetone, and milky white 5# aqueous polyurethane dispersion emulsion; the particle size of the emulsion is 230nm, and the solid content is 50wt%.

实施例6Example 6

在干燥N2的保护下，向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入413g聚酯多元醇PNHA2000(华大化学，Mn＝2000，新戊二醇：1,6-己二醇质量比＝1:2)，15g新戊二醇，3gMPEG1200,在60℃条件下搅拌30min，加入70.3g和45.2g54g丙酮80℃条件下反应。当-NCO含量达到理论值2.59wt％时，将预聚物冷却到40℃，溶解在765g丙酮中，混合10分钟后加入5.6g乙二胺,17g(氨基磺酸钠盐，50wt％水溶液)，继续搅拌30min后，在剪切分散机下加入552g去离子水进行分散；将以上乳液在50℃下减压旋蒸1小时除去丙酮，，可得到乳白色的6#水性聚氨酯树脂分散体乳液；该乳液粒径260nm，固含量50wt％。Under the protection of dry N 2 , add 413g polyester polyol PNHA2000 (Hua Da Chemical, Mn=2000, neopentyl glycol: 1,6-hexane Glycol mass ratio=1:2), 15g neopentyl glycol, 3g MPEG1200, stirred at 60°C for 30min, added 70.3g and 45.2g 54g of acetone was reacted at 80°C. When the -NCO content reaches the theoretical value of 2.59wt%, the prepolymer is cooled to 40°C, dissolved in 765g of acetone, mixed for 10 minutes and then added with 5.6g of ethylenediamine, 17g (Sulphamic acid sodium salt, 50wt% aqueous solution), after continuing to stir for 30min, add 552g of deionized water under the shear disperser to disperse; the above emulsion is decompressed and rotary steamed at 50°C for 1 hour to remove acetone, to obtain Milky white 6# aqueous polyurethane resin dispersion emulsion; the emulsion has a particle size of 260nm and a solid content of 50wt%.

实施例7Example 7

在干燥N2的保护下，向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入280g聚酯多元醇PNHA1500(Mn＝1500，新戊二醇：1,6-己二醇质量比＝1:9)，120g PTMEG2000,30g1,6-己二醇，11g YmerTMN120(非离子型亲水单体)，在60℃条件下搅拌30min，加入107.6g和69.2g50g丙酮80℃条件下反应。当NCO含量达到理论值3.91wt％时，将预聚物冷却到40℃，溶解在697g丙酮中，混合10分钟后加入12g乙二胺,13.5g(氨基磺酸钠盐)，继续搅拌30min后，在剪切分散机下加入510g去离子水进行分散；将以上乳液在50℃下减压旋蒸1小时除去丙酮，可得到乳白色的7#水性聚氨酯分散体乳液；该乳液粒径280nm，固含量50wt％。Under the protection of dry N2 , add 280g polyester polyol PNHA1500 (Mn=1500, neopentyl glycol: 1,6-hexanediol mass ratio =1:9), 120g PTMEG2000, 30g 1,6-hexanediol, 11g Ymer TM N120 (non-ionic hydrophilic monomer), stirred at 60°C for 30min, added 107.6g and 69.2g 50g of acetone was reacted at 80°C. When the NCO content reaches the theoretical value of 3.91wt%, the prepolymer is cooled to 40°C, dissolved in 697g of acetone, mixed for 10 minutes and then added with 12g of ethylenediamine, 13.5g (Sulphamic acid sodium salt), after continuing to stir for 30 minutes, add 510g of deionized water under the shear disperser to disperse; the above emulsion is decompressed and rotary steamed at 50°C for 1 hour to remove acetone, and milky white 7# water-based Polyurethane dispersion emulsion; the particle size of the emulsion is 280nm, and the solid content is 50wt%.

实施例8Example 8

在干燥N2的保护下，向装有回流冷凝管、温度计和机械搅拌的四口烧瓶中加入280g聚酯多元醇PNHA1500(Mn＝1500，新戊二醇：1,6-己二醇质量比＝4:1)，120g PTMEG2000,30g1,6-己二醇，11g YmerTMN120(非离子型亲水单体)，在60℃条件下搅拌30min，加入107.6g和69.2g50g丙酮80℃条件下反应。当NCO含量达到理论值3.91wt％时，将预聚物冷却到40℃，溶解在697g丙酮中，混合10分钟后加入12g乙二胺,13.5g(氨基磺酸钠盐)，继续搅拌30min后，在剪切分散机下加入510g去离子水进行分散；将以上乳液在50℃下减压旋蒸1小时除去丙酮，可得到乳白色的8#水性聚氨酯分散体乳液；该乳液粒径230nm，固含量50wt％。Under the protection of dry N2 , add 280g polyester polyol PNHA1500 (Mn=1500, neopentyl glycol: 1,6-hexanediol mass ratio =4:1), 120g PTMEG2000, 30g 1,6-hexanediol, 11g Ymer TM N120 (non-ionic hydrophilic monomer), stirred at 60°C for 30min, added 107.6g and 69.2g 50g of acetone was reacted at 80°C. When the NCO content reaches the theoretical value of 3.91wt%, the prepolymer is cooled to 40°C, dissolved in 697g of acetone, mixed for 10 minutes and then added with 12g of ethylenediamine, 13.5g (Sulphamic acid sodium salt), after continuing to stir for 30 minutes, add 510g of deionized water to disperse under the shear disperser; rotate the above emulsion under reduced pressure at 50°C for 1 hour to remove acetone, and milky white 8# water-based Polyurethane dispersion emulsion; the particle diameter of the emulsion is 230nm, and the solid content is 50wt%.

(2)环保水性聚氨酯内墙乳胶漆的制备(2) Preparation of environmentally friendly water-based polyurethane interior wall latex paint

实施例9Example 9

在1000ml直身瓶中加入138.8g水，开启搅拌800rpm，依次加入1g纤维素醚类增稠剂250HBR，2g pH调节剂10wt％NaOH水溶液，1g润湿剂BD-109，10g分散剂731A，3g消泡剂NXZ，1g防腐剂LXE，220g钛白粉R-902+，60g1000目滑石粉，120g800目重钙，40g遮盖聚合物优创E，提高搅拌速度至1500rpm分散30分钟，将搅拌速度降至800rpm，依次加入1g消泡剂NXZ，400g1#水性聚氨酯分散体，4g增稠剂A401，搅拌20分钟后出料，该乳胶漆的颜料体积浓度(PVC)为45％。Add 138.8g of water into a 1000ml straight bottle, start stirring at 800rpm, add 1g of cellulose ether thickener 250HBR, 2g of pH regulator 10wt% NaOH aqueous solution, 1g of wetting agent BD-109, 10g of dispersant 731A, 3g Defoamer NXZ, 1g preservative LXE, 220g titanium dioxide R-902 + , 60g 1000 mesh talcum powder, 120g 800 mesh heavy calcium, 40g covering polymer Youchuang E, increase the stirring speed to 1500rpm for 30 minutes, reduce the stirring speed to 800rpm, add 1g defoamer NXZ successively, 400g1# aqueous polyurethane dispersion, 4g thickener A401, discharge after stirring for 20 minutes, the pigment volume concentration (PVC) of this latex paint is 45%.

实施例10-16Examples 10-16

所述的环保水性聚氨酯内墙乳胶漆与实施例1的制备区别在于PVC不同，水、颜料、填料、遮盖聚合物和水性聚氨酯分散体及助剂用量不同，实施例10～16依次使用2～8#水性聚氨酯分散体，其它工艺条件与实施例9一致，具体配方见表1和表2。The difference between the described environment-friendly water-based polyurethane interior wall latex paint and the preparation of Example 1 is that PVC is different, and the amount of water, pigment, filler, covering polymer, water-based polyurethane dispersion and auxiliary agent is different. Embodiments 10-16 use 2- 8# waterborne polyurethane dispersion, other processing conditions are consistent with embodiment 9, and concrete formula sees table 1 and table 2.

对比例1Comparative example 1

与实施例9不同的是其成膜物质为净味水性丙烯酸乳液(玻璃化温度为15℃，固含量为45％)，且乳胶漆制备过程中需加入成膜助剂，具体制备过程如下：在1000ml直身瓶中加入113g水，开启搅拌800rpm，依次加入2g纤维素醚类增稠剂250HBR，2g pH调节剂10wt％NaOH水溶液，2g润湿剂BD-109，10g分散剂731A，2g消泡剂NXZ，1g防腐剂LXE，220g钛白粉R-902+，60g1000目滑石粉，120g800目重钙，40g遮盖聚合物优创E，提高搅拌速度至1500rpm分散30分钟，将搅拌速度降至800rpm，依次加入1g消泡剂NXZ，400g水性丙烯酸乳液，10g成膜助剂Texanol，4g增稠剂A401，搅拌20分钟后出料，该乳胶漆的颜料体积浓度(PVC)为45％。The difference from Example 9 is that its film-forming substance is a clean-tasting water-based acrylic emulsion (glass transition temperature is 15° C., solid content is 45%), and film-forming aids need to be added in the latex paint preparation process. The specific preparation process is as follows: Add 113g of water into a 1000ml straight bottle, start stirring at 800rpm, add 2g of cellulose ether thickener 250HBR, 2g of pH regulator 10wt% NaOH aqueous solution, 2g of wetting agent BD-109, 10g of dispersant 731A, 2g of dispersant Foaming agent NXZ, 1g preservative LXE, 220g titanium dioxide R-902 + , 60g 1000 mesh talc powder, 120g 800 mesh heavy calcium, 40g covering polymer Youchuang E, increase the stirring speed to 1500rpm for 30 minutes, reduce the stirring speed to 800rpm , Add 1g defoamer NXZ, 400g aqueous acrylic emulsion, 10g film-forming aid Texanol, 4g thickener A401 successively, discharge after stirring for 20 minutes, the pigment volume concentration (PVC) of this latex paint is 45%.

对比例2Comparative example 2

与实施例9不同的是其成膜物质为水性丙烯酸乳液(玻璃化温度为-22℃，固含量为52％)，具体制备过程如下：在1000ml直身瓶中加入163g水，开启搅拌800rpm，依次加入2g纤维素醚类增稠剂250HBR，2gpH调节剂10％NaOH水溶液，2g润湿剂BD-109，10g分散剂731A，2g消泡剂NXZ，1g防腐剂LXE，220g钛白粉R-902+，60g1000目滑石粉，120g800目重钙，40g遮盖聚合物优创E，提高搅拌速度至1500rpm分散30分钟，将搅拌速度降至800rpm，依次加入1g消泡剂NXZ，350g水性丙烯酸乳液，4g增稠剂A401，搅拌20分钟后出料，该乳胶漆的颜料体积浓度(PVC)为45％。The difference from Example 9 is that its film-forming substance is an aqueous acrylic emulsion (glass transition temperature is -22° C., and the solid content is 52%). The specific preparation process is as follows: add 163 g of water to a 1000 ml straight bottle, start stirring at 800 rpm, Add 2g cellulose ether thickener 250HBR, 2g pH regulator 10% NaOH aqueous solution, 2g wetting agent BD-109, 10g dispersant 731A, 2g defoamer NXZ, 1g preservative LXE, 220g titanium dioxide R-902 + , 60g 1000 mesh talcum powder, 120g 800 mesh heavy calcium, 40g covering polymer Youchuang E, increase the stirring speed to 1500rpm and disperse for 30 minutes, then reduce the stirring speed to 800rpm, add 1g defoamer NXZ, 350g water-based acrylic emulsion, 4g Thickener A401, discharge after stirring for 20 minutes, the pigment volume concentration (PVC) of this latex paint is 45%.

表1：实施例9-16水性聚氨酯乳胶漆的PVC及具体配方Table 1: PVC and specific formula of embodiment 9-16 waterborne polyurethane latex paint

表2：助剂添加明细Table 2: Addition details of additives

性能测试Performance Testing

实施例9-16及对比例1-2的环保水性内墙乳胶漆的性能参数见表2。The performance parameters of the environment-friendly water-based interior wall latex paint of Examples 9-16 and Comparative Examples 1-2 are shown in Table 2.

表2：实施例9-16及对比例1-2性能参数对比Table 2: Comparison of performance parameters of Examples 9-16 and Comparative Examples 1-2

从上述结果可以看到，实施例中的各种PVC的水性聚氨酯内墙乳胶漆其绝对VOC含量远低于目前市场上通用的对比例的乳胶漆；没有明显的气味，远好于对比例丙烯酸酯类乳胶漆；其耐沾污性能也明显好于对比例。在耐擦洗方面，中低PVC实施例的耐擦洗性能等于对比例，只有在很少水性聚氨酯添加量的高PVC体系中(低档乳胶漆)，耐擦洗水平才低于对比例。其耐污渍性能也基本与对比例近似，保持在一个比较好的水平。As can be seen from the above results, the absolute VOC content of the water-based polyurethane interior wall latex paint of various PVCs in the embodiment is far lower than the latex paint of the general comparison example in the market; there is no obvious smell, and it is far better than the comparison example acrylic acid Ester latex paint; its stain resistance is also significantly better than that of the comparative example. In terms of scrub resistance, the scrub resistance of the medium and low PVC examples is equal to the comparative example, only in the high PVC system (low-grade latex paint) with very little water-based polyurethane addition, the scrub resistance level is lower than that of the comparative example. Its stain resistance performance is also basically similar to that of the comparative example, maintaining at a relatively good level.

注：绝对VOC含量按GB18582-2008《室内装饰装修材料-内墙乳胶漆中有害物质限量》方法测试。Note: The absolute VOC content is tested according to the method of GB18582-2008 "Interior Decoration Materials-Limits of Harmful Substances in Interior Wall Emulsion Paint".

耐擦洗性能按GB/T9756-2009《合成树脂乳液内墙乳胶漆》测试。Scrub resistance is tested according to GB/T9756-2009 "Synthetic Resin Emulsion Interior Wall Latex Paint".

耐污渍性能按HG/T4756-2014《内墙耐污渍乳胶乳胶漆》测试。Stain resistance is tested according to HG/T4756-2014 "Stain-resistant latex paint for interior walls".

耐沾污性能按GB/T 9780-2013《建筑涂料涂层耐沾污性试验方法》测试。Stain resistance is tested according to GB/T 9780-2013 "Test method for stain resistance of architectural coatings".

断裂伸长率按GB/T528-2009《硫化橡胶或热塑性橡胶拉伸应力应变性能的测定》测试。The elongation at break is tested according to GB/T528-2009 "Determination of Tensile Stress-Strain Properties of Vulcanized Rubber or Thermoplastic Rubber".

Claims (10)

1. an environment-friendly water-based inner wall polyurethane emulsion paint, it comprises: based on the total restatement of emulsion paint,
2. emulsion paint according to claim 1, is characterized in that, the urethane in described aqueous polyurethane dispersion is comprise the product that following component prepares:
(a1) 10wt%-35wt%, the polyisocynate monomer of preferred 15wt%-35wt%;
(a2) 50wt%-85wt%, the polyvalent alcohol of preferred 60wt%-80wt%, described polyvalent alcohol is selected from the one or two or more in polyester polyol, polyether glycol and polycarbonate polyol; Preferably, described polyvalent alcohol is selected from the one or two or more in polyester diol, polyether Glycols and PCDL;
Described polyester diol is preferably based on one or two or more in hexanodioic acid, phthalic acid, m-phthalic acid and terephthalic acid and Tetra hydro Phthalic anhydride and ethylene glycol, 1,4-butyleneglycol, 1, one or two or more preparation in 3-butyleneglycol, 1,6-hexylene glycol and neopentyl glycol; One or two or more in the preferred polyoxyethylene glycol of described polyether glycol, polypropylene glycol and PTMG;
(a3) 0.1wt%-8wt%, the chainextender of preferred 0.1wt%-6wt%;
(a4) the non-ionic hydrophilic monomer of 0.1wt%-5wt%, preferred 0.1wt%-3wt%;
(a5) the ionic hydrophilic monomer of 0.1wt%-5wt%, preferred 0.5wt%-3wt%;
Each component concentration is all based on the Weight computation of the urethane of described (a) aqueous polyurethane dispersion.
3. emulsion paint according to claim 2, is characterized in that, described polyvalent alcohol is the mixture of polyester diol and the PTMG prepared based on hexanodioic acid, 1,6-hexylene glycol and neopentyl glycol.
4. emulsion paint according to claim 3, is characterized in that, the number-average molecular weight 500-3000 of the described polyester diol prepared based on hexanodioic acid, 1,6-hexylene glycol and neopentyl glycol, preferred 1000-2000; The number-average molecular weight of described PTMG is 500-3000, preferred 1000-2000; The mass ratio of the described polyester diol prepared based on hexanodioic acid, 1,6-hexylene glycol and neopentyl glycol and PTMG is 9:1-1:1, preferred 9:1-7:3.
5. emulsion paint according to claim 4, it is characterized in that, in the described polyester diol prepared based on hexanodioic acid, 1,6-hexylene glycol and neopentyl glycol, neopentyl glycol consumption is 1,5wt% ~ the 100wt% of 6-hexylene glycol and neopentyl glycol total mass, preferred 10wt% ~ 80wt%.
6. emulsion paint according to claim 2, is characterized in that, described non-ionic hydrophilic monomer is selected from simple function polyalkylene oxide and/or the difunctionality compound containing polyalkylene oxide sidechain; The described preferred main chain carbon number of difunctionality compound containing polyalkylene oxide sidechain is 2-20, and side chain contains ethylene oxide unit, and the number-average molecular weight of the difunctionality compound containing polyalkylene oxide sidechain is 200-2000, and preferred number average molecular weight is 500-1500; Described simple function polyalkylene oxide preferred number average molecular weight is terminal hydroxy group polyethylene oxide monomethyl ether and/or the Amino End Group polyethylene oxide monomethyl ether of 200-3000.
7. emulsion paint according to claim 2, it is characterized in that, described ionic hydrophilic monomer is that described hydrophilic stability group is selected from carboxyl, sulfonic group, phosphate groups, tertiary amine group or quaternary ammonium group containing the one or two or more in the dibasic alcohol of hydrophilic stability group, diamine and hydramine; The described preferred dimethylol propionic acid of ionic hydrophilic monomer, 1,3-dihydroxyl butane-1-carboxylic acid, 1,2-dihydroxyl butane-1-sulfonic acid, 1,3-dihydroxyl butyl-trimethylammonium chloride and in one or two or more, the natural number of what wherein m, n were separate is 1-20; More preferably the natural number of what wherein m, n were separate is 1-6; The preferred sodium salt of N-(2 amino-ethyl)-2-aminoethyl sulfonic acid and/or the sodium salt of N-(2-amino-ethyl)-2-aminopropanesulfonic acid further.
8. emulsion paint according to claim 1, is characterized in that, described pigment is titanium dioxide; Described filler is selected from the one or two or more in talcum powder, coarse whiting, fine particle calcium carbonate, mica powder, diatomite and kaolin.
9. emulsion paint according to claim 1, it is characterized in that, described auxiliary agent comprises following composition: based on the total restatement of emulsion paint, dispersion agent 0.1wt%-3wt%, wetting agent 0.1wt%-0.5wt%, thickening material 0.1wt%-2.0wt%, sanitas 0-0.5wt%, defoamer 0.1wt%-1.5wt%, pH adjusting agent 0-0.5wt%.
10. emulsion paint according to claim 1, is characterized in that, described emulsion paint contains 0-10wt%, the opacity polymer of preferred 1-8wt%; Described opacity polymer is selected from polystyrene hollow microballoon.
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105601197A (en) * 2015-12-21 2016-05-25 潍坊市宏源防水材料有限公司 Two-component polyurethane waterproof coating and production technology thereof
CN105885668A (en) * 2016-06-08 2016-08-24 胡军 Zero-VOC waterborne soft-feel coating and preparation method thereof
CN105969158A (en) * 2016-07-13 2016-09-28 李水金 Low-cost environment-friendly internal wall paint
CN106280950A (en) * 2016-08-17 2017-01-04 柳州市亿廷贸易有限责任公司 Waterborne wall surface paint preparation method
CN107216786A (en) * 2017-05-12 2017-09-29 巢湖市荷花渔网有限公司 A kind of natural antifouling paint of fishing net
CN108822711A (en) * 2018-06-26 2018-11-16 深圳市天之科技开发有限公司 A kind of waterborne wall surface paint and preparation method thereof
CN109721717A (en) * 2017-10-31 2019-05-07 万华化学（广东）有限公司 A kind of waterborne epoxy modified saturated polyester resin and its preparation method and application
CN109897523A (en) * 2019-02-20 2019-06-18 张建初 A kind of preparation method of environmental protection scratch-resistant hand-feeling coating
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102690404A (en) * 2011-02-18 2012-09-26 中国石油化工股份有限公司 Nonionic waterborne polyurethane dispersoid and preparation method thereof
CN102746784A (en) * 2012-07-30 2012-10-24 江苏瑞丰科技实业有限公司 Energy-saving insulated flame-retardant water-proof corrosion-proof functional coating and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102690404A (en) * 2011-02-18 2012-09-26 中国石油化工股份有限公司 Nonionic waterborne polyurethane dispersoid and preparation method thereof
CN102746784A (en) * 2012-07-30 2012-10-24 江苏瑞丰科技实业有限公司 Energy-saving insulated flame-retardant water-proof corrosion-proof functional coating and preparation method thereof

Cited By (11)

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CN105601197A (en) * 2015-12-21 2016-05-25 潍坊市宏源防水材料有限公司 Two-component polyurethane waterproof coating and production technology thereof
CN105885668A (en) * 2016-06-08 2016-08-24 胡军 Zero-VOC waterborne soft-feel coating and preparation method thereof
CN105969158A (en) * 2016-07-13 2016-09-28 李水金 Low-cost environment-friendly internal wall paint
CN106280950A (en) * 2016-08-17 2017-01-04 柳州市亿廷贸易有限责任公司 Waterborne wall surface paint preparation method
CN107216786A (en) * 2017-05-12 2017-09-29 巢湖市荷花渔网有限公司 A kind of natural antifouling paint of fishing net
CN109721717A (en) * 2017-10-31 2019-05-07 万华化学（广东）有限公司 A kind of waterborne epoxy modified saturated polyester resin and its preparation method and application
CN108822711A (en) * 2018-06-26 2018-11-16 深圳市天之科技开发有限公司 A kind of waterborne wall surface paint and preparation method thereof
CN109897523A (en) * 2019-02-20 2019-06-18 张建初 A kind of preparation method of environmental protection scratch-resistant hand-feeling coating
CN111500172A (en) * 2020-03-27 2020-08-07 江苏华彩化学科技有限公司 Water-based environment-friendly anti-cracking interior wall coating for building and preparation method thereof
CN115820095A (en) * 2022-12-01 2023-03-21 福建省三棵树新材料有限公司 Skin-feel interior wall finish emulsion paint with high washing resistance and stain resistance and preparation method thereof
CN115820095B (en) * 2022-12-01 2023-12-12 福建省三棵树新材料有限公司 High-brushing-resistance and stain-resistance skin-feel interior wall finish emulsion paint and preparation method thereof

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