CN1876731A - Aqueous coating containing three layer nuclear shell structure rubber particle latex and its preparation method - Google Patents

Aqueous coating containing three layer nuclear shell structure rubber particle latex and its preparation method Download PDF

Info

Publication number
CN1876731A
CN1876731A CN 200510075254 CN200510075254A CN1876731A CN 1876731 A CN1876731 A CN 1876731A CN 200510075254 CN200510075254 CN 200510075254 CN 200510075254 A CN200510075254 A CN 200510075254A CN 1876731 A CN1876731 A CN 1876731A
Authority
CN
Grant status
Application
Patent type
Prior art keywords
monomer
layer
emulsion
core
group
Prior art date
Application number
CN 200510075254
Other languages
Chinese (zh)
Other versions
CN100389156C (en )
Inventor
李效玉
刘月文
Original Assignee
北京化工大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Abstract

The invention relates the water paint with three-layer shell sandwich rubber latex emulsion and preparing method. The method has the advantages of low cost, simple technology and improving fire-resisting property, water resistance and hardness of water paint film.

Description

一种含有三层核壳结构胶乳粒子乳液的水性涂料及其制备方法 An aqueous coating and preparation method of a three-layer core-shell emulsion containing latex particles

技术领域 FIELD

:本发明涉及一种含有三层核壳结构胶乳粒子乳液的水性涂料及其制备方法。 : The present invention relates to a method for preparing aqueous coating and three-layer core-shell emulsion containing latex particles.

背景技术 Background technique

:丙烯酸酯类水性涂料是以水为分散稀释剂的涂料,在涂装中无有机溶剂的挥发,在使用时无有机溶剂的残存,属于环境友好型涂料,比较多的用于建筑内外墙涂装。 : Acrylic water-based paint is a water dispersible coating diluent, volatile organic solvent-free coating, the organic solvent remaining in the non-use, is environmentally friendly coatings, more coating for external walls of buildings installed. 当用于木器以及金属表面的涂装时,要求涂料表面硬度高、耐热性好、耐水性好。 When used for coating wood and metal surfaces, the coating requires high surface hardness, heat resistance, water resistance. 但是丙烯酸酯类水性涂料涂装在木器、金属表面的时候,水性涂料耐水性差、耐热性差,清漆硬度低的问题就会突显出来,限制了水性丙烯酸系水性涂料的应用。 However, water-based acrylic paint coating when wood, metal surfaces, water-based coatings has poor water resistance, poor heat resistance, low hardness varnish highlighted problems will limit the use of aqueous acrylic water-based paint.

为了提高涂膜的机械强度,耐水性等性能,通常要在涂膜的同时使大分子链相互交联,因此人们对能够室温成膜的乳液进行了大量的研究,如US4772680通过乙酰乙酸基与肼反应生成酮亚胺结构获得室温交联乳液;EP567128,CN1144242通过带有端羧基的聚合物和含氮杂环丙烯基团的聚合物可以在室温下进行稳定的反应,CN1537895为两种组分涂料,将伯胺基团/环氧基团按1∶1的摩尔比混合,实现交联反应。 In order to improve the mechanical strength, water resistance performance of the coating, usually at the same time that the coating film macromolecular chains crosslinked to each other, so it is capable of forming an emulsion at room temperature a lot of research, such as acetoacetate groups and by US4772680 hydrazine at room temperature obtained ketimine structure crosslinked latex; EP567128, CN1144242 stable reaction can be carried out at room temperature by a nitrogen-containing heterocyclic polymer and a propylene polymer with a terminal carboxyl group is, CN1537895 for the two components coatings, a primary amine group / epoxy group by mole ratio of 1:1 achieve crosslinking reaction. 上述的室温交联体系不足之处是原料毒性大,价格昂贵,且双组分施工时,混合后在施工期内容易固化,使体系黏度增大,影响施工,人为因素对涂膜的影响较大。 The above-described deficiencies crosslinking system at room temperature is large feed toxic, expensive, and construction, easily mixed two-component curing during the construction period, so that the viscosity of the system increases, the impact of construction, human factors in the coating film more Big.

发明内容 SUMMARY

:本发明试图以含有三层核壳结构胶乳粒子乳液为成膜物质,提供一种环境友好型室温固化交联的单组分水性涂料及其制备方法,使原料价格低廉,制备及施工工艺简单,且提高水性涂料涂膜的耐水性、耐热性、硬度等性能。 : The present invention seeks in a three-layer core-shell structure comprising latex emulsion particles film-forming material, to provide a single-component aqueous coating environment and preparation method friendly crosslinking room temperature curing the low price of raw materials and preparation process is simple construction and coating the aqueous coating to improve water resistance, heat resistance, hardness and other properties.

本发明的一种含有三层核壳结构胶乳粒子乳液的水性涂料,由聚合物乳液、多种助剂、颜填料配制而成的水性涂料,其特征是所说的聚合物乳液为一种具有三层核壳结构胶乳粒子的乳液,固含量为25~55%,胶乳粒子的核层为烯类硬单体、烯类软单体和多烯类交联单体的共聚物,次外层为烯类硬单体、烯类软单体和含有环氧基团、酸酐基团或活性卤素基团的烯类单体的共聚物,最外层为烯类硬单体、烯类软单体及含有羧基、羟基、胺基或酰胺基的烯类单体的共聚物。 The present invention contains one kind three-layer core-shell structure particle latex aqueous coating emulsion, a polymer emulsion, a variety of additives, pigments and fillers prepared from aqueous coating, wherein said polymer emulsion having a three-layer core-shell emulsion latex particles have a solids content of 25 to 55%, the latex particle nucleation layer is hard ethylenic monomers, ethylenic monomers and copolymers soft polyenes crosslinking monomer, once the outer layer hard monomer is a diene, diene soft monomer and the epoxy group-containing copolymer, an acid anhydride-based monomer groups or active halogen groups, the outermost layer is hard diene monomer, diene soft single and copolymers thereof containing a carboxyl group, a hydroxyl group, amine or amide group of the vinyl monomer.

三层核壳结构胶乳粒子的核层占聚合物总质量的25~50%,次外层占25~50%,最外层占25~50%。 Nuclear three layer core-shell latex particles of from 25 to 50% of the total mass of the polymer, times of from 25 to 50% of the outer layer, the outermost layer of from 25 to 50%.

胶乳粒子的平均粒径最好小于100纳米。 The average particle diameter of the latex particles is preferably less than 100 nanometers.

所说的烯类硬单体为下列物质中的任何一种或它们的组合:苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸异冰片酯、丙烯酸异冰片酯、叔九碳酸乙烯酯、叔十碳酸乙烯酯、叔十一碳酸乙烯酯、丙烯腈单体。 He said hard monomer is ethylenically any of the following materials or a combination thereof: styrene, methyl methacrylate, isobornyl methacrylate, isobornyl acrylate, t-nine ethylene carbonate, t-ten ethylene carbonate, t-undecanoate, vinyl monomer acrylonitrile.

烯类软单体为下列物质中的任何一种或它们的组合:丙烯酸乙酯、丙烯酸丁酯、丙烯酸异戊酯、丙烯酸2-乙基己酯。 Diene soft monomer is any one of the following materials or a combination thereof: ethyl acrylate, butyl acrylate, isoamyl acrylate, 2-ethylhexyl acrylate.

多烯类交联单体为下列物质中的任何一种或它们的组合:二乙烯基苯、双丙烯酰胺、乙二醇二甲基丙烯酸酯、二缩乙二醇二甲基丙烯酸酯、三缩乙二醇二甲基丙烯酸酯、三缩丙二醇二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇四甲基丙烯酸酯。 Polyenes crosslinking monomer is any of the following materials or a combination thereof: divinylbenzene, bis acrylamide, ethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, triethylene diethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetra methacrylate.

含有环氧基团、酸酐基团或活性卤素基团的烯类单体为下列物质组中的一种或它们的组合:甲基丙烯酸缩水甘油酯、烯丙基缩水甘油醚、马来酸酐、氯乙烯乙烯基醚、氯乙酸乙烯酯、对氯甲基苯乙烯。 Containing epoxy groups, acid anhydride-based monomer groups or active halogen group is one of the following group of substances or a combination thereof: glycidyl methacrylate, allyl glycidyl ether, maleic anhydride, vinyl ether, vinyl chloroacetate, chloromethylstyrene.

带有羧基、磷酸基、羟基、胺基或酰胺基烯类单体为下列物质组中的一种或它们的组合:丙烯酸、甲基丙烯酸、丙烯酰胺、甲基丙烯酰胺、羟甲基丙烯酰胺、丙烯酸胺乙酯、甲基丙烯酸胺乙酯、甲基丙烯酸N,N二甲胺基乙酯、丙烯酸羟乙酯、丙烯酸羟丙酯。 Having a carboxyl group, a phosphoric acid group, a hydroxyl group, an amine group or an amide group as a vinyl monomer of the following group of substances or a combination thereof: acrylic acid, methacrylic acid, acrylamide, methacrylamide, methylol acrylamide , amine, ethyl acrylate, ethyl methacrylate, amine, methacrylate, N, N dimethylaminoethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate.

三层核壳结构胶乳粒子乳液采用如下的方法制备:在惰性气体保护的反应釜中,搅拌条件下,依次加入去离子水、乳化剂、核层单体进行乳化,加热至40~88℃,加入引发剂的水溶液引发聚合,1~2小时完成核层粒子合成反应,其中所用烯类硬单体、烯类软单体和多烯类交联单体的质量比:40~80∶20~60∶0.1~1。 A three-layer core-shell latex particles of emulsion prepared as follows: In the reaction vessel in an inert atmosphere, under stirring, followed by adding deionized water, emulsifier, the core layer monomer emulsion was heated to 40 ~ 88 ℃, aqueous solution was added to initiate the polymerization initiator, 1 to 2 hours to complete the core particle synthesis reaction layer, wherein the hard monomer with a diene, diene soft monomer and the crosslinking monomer polyenes mass ratio: 80:20 to 40 ~ 60:0.1 to 1.

然后将次外层烯烃单体混合,与引发剂水溶液同时滴加入反应釜中,滴加完毕后,反应0.5~2小时,完成次外层粒子的合成,其中所用烯类硬单体、烯类软单体和含有环氧基团、酸酐基团或活性卤素基团的烯类单体的质量比:25~60∶35~60∶5~40。 The secondary layer is then mixed olefin monomers with aqueous initiator solution was dropwise added to the kettle, after the addition was complete, the reaction for 0.5 to 2 hours to complete the synthesis of secondary particles of the outer layer, wherein the hard monomer with a diene, diene soft monomer containing epoxy groups and quality, acid anhydride-based monomer groups or active halogen groups ratio: 25 ~ 60:35 ~ 40 ~ 60:5.

再将最外层烯类单体混合逐渐滴加到反应釜中,同时滴加引发剂水溶液,滴加完毕后,反应0.5~2小时,完成最外层粒子的合成,其中所用烯类硬单体、烯类软单体及含有羧基、羟基、胺基或酰胺基的烯类单体的质量比为:25~60∶35~90∶5~40。 Then the outermost-based monomer mixture is gradually added dropwise to the reaction vessel, while the initiator aqueous solution was added dropwise. After the addition was complete, the reaction for 0.5 to 2 hours to complete the synthesis of the outermost layer of the particles, wherein a single hardware-based body mass ratio, the soft monomer and diene-based monomer having a carboxyl, hydroxyl, amine or amide group of: 25 ~ 60:35 ~ 40 ~ 90:5.

向反应釜中加入后消除引发剂水溶液,保温1~2小时,经降温,过滤出料,得到三层核壳结构胶乳粒子乳液。 After the addition to the kettle eliminate initiator aqueous solution, incubated for 1 to 2 hours, after cooling, the material was filtered, to obtain three-layer core-shell structure latex emulsion particles. 总体上胶乳粒子乳液制备所用单体中核层单体占单体总质量的25~50%,次外层单体占单体总质量的25~50%,最外层单体占单体总质量的25~50%。 Preparing an emulsion latex particles generally used in the core layer monomer comprises a monomer 25 to 50% of the total mass of the monomers, the outer secondary monomer comprises 25 to 50% of the total mass of monomers, the monomers outermost total monomer mass 25 to 50%.

三层核壳结构胶乳粒子乳液制备中所用的引发剂及用量与一般乳液聚合类似,为过硫酸钾、过硫酸铵、过硫酸钾-亚硫酸氢钠或过硫酸铵-亚硫酸氢钠,用量通常为乳液聚合所用单体质量的0.005~1%。 A three-layer core-shell particles prepared latex emulsion used in the general emulsion polymerization initiator and an amount similar to, potassium persulfate, ammonium persulfate, potassium persulfate - sodium bisulfite or ammonium persulfate - sodium bisulfite, an amount typically 0.005 to 1% by mass of the monomers used for the emulsion polymerization.

所用的乳化剂为乳液聚合常用的阴离子型、非离子型或阴离子和非离子复合型,或者反应性乳化剂。 Emulsifiers commonly used for emulsion polymerization of anionic, nonionic, or anionic and non-ionic compound, or a reactive emulsifier. 用量与一般乳液聚合类似,通常为单体质量的0.5~2%。 The amount of the emulsion is generally similar, usually from 0.5 to 2% by mass of the monomer.

本发明还提供了一种含有三层核壳结构胶乳粒子乳液的水性涂料的制备方法,由三层核壳结构胶乳粒子乳液、多种助剂、颜填料配制而成,具体的配制方法为:以三层核壳结构胶乳粒子乳液为成膜物质,复配以成膜助剂、流平剂、消泡剂、增稠剂、流变改性剂、防霉剂、防腐剂、润湿剂、抗划花剂、消光剂、以及无机颜填料制成水性涂料,其中三层核壳结构胶乳粒子乳液的重量百分含量为35~95%。 The present invention further provides a method of preparing a three-layer core-shell structure comprising latex particles of the aqueous coating emulsion, a three-layer core-shell latex particles are an emulsion, a variety of additives, pigments and fillers prepared from, as the specific method of preparation: in a three-layer core-shell latex particles as an emulsion forming substance, together with complex coalescents, leveling agents, defoamers, thickeners, rheology modifiers, mildewcides, preservatives, wetting agents weight percentage of an anti-scratching agent, a matting agent, and an inorganic pigment is made water-based paint, wherein the emulsion is a three-layer core-shell latex particles is 35 to 95%.

本发明的关键是设计和合成了一种含有三层核壳结构胶乳粒子乳液,以这种粒子乳液作为成膜物质,实现水性涂料的室温交联、高耐热性和高硬度。 The key of the present invention is the design and synthesis of a three-layer core-shell structure comprising latex emulsion particles, the particles in this emulsion as a film-forming substance, to achieve room temperature crosslinking of waterborne coatings, high heat resistance and high hardness.

本发明是通过多层核壳的粒子结构设计将参与交联反应的两类官能团(一类为环氧基团、酸酐基团、活性卤素,另一类为能与它们反应的羧基、羟基、胺基、酰胺基)分别分布在不同的壳层,亲水性官能团(羧基、羟基、胺基、酰胺基)设计在最外层,由于有水作为分散剂,在乳液和水性涂料状态时,亲水基团始终朝向水相,限制了次外层和最外层共聚物间的容合,因此避免了在聚合和水分散乳液体系存放时二者的反应,使乳液和涂料有很好的存放稳定性能;而在涂料涂装成膜时,随着水分的挥发,朝向水相的亲水基团就会失去水的环境,在适宜的温度以及成膜助剂的作用下,聚合物分子链运动,粒子间相互融合、内外层渗透,实现交联反应,另外核聚合物设计为微交联的较硬聚合物,玻璃化温度较高,带给膜较高的硬度,壳聚合物设计为较软聚合物, The present invention is a crosslinking reaction by the design of the multilayer core-shell particle structure of the two participating functional groups (a class of epoxy groups, anhydride groups, active halogen, and the other is capable of reacting with a carboxyl group thereof, a hydroxyl group, amine, amide) are distributed in different shell, a hydrophilic functional group (carboxyl, hydroxyl, amine, amide) designed in the outermost layer, since water as a dispersant, and an aqueous coating emulsion state, hydrophilic group always face the aqueous phase, it limits the capacity of the engagement between the outer layer and the outermost copolymers times, thus avoiding both the polymerization reaction and during storage of the aqueous dispersion of the emulsion system, the emulsion and coatings have good storage stability; and in the paint coating film formation, with the evaporation of water, the aqueous phase towards the hydrophilic group will lose the environment of water, at a suitable temperature and the effect of film-forming aid, a polymer molecule chain motion, fusion between particles to each other, the inner and outer layers permeable to achieve the crosslinking reaction, additional hard core polymer is designed to lightly crosslinked polymers, high glass transition temperature, gives higher film hardness, designed shell polymer as the softer polymer, 利于室温成膜。 Conducive to the deposition temperature. 由此方法得到的水性涂料贮存稳定性好、且涂装操作工艺简单,得到的涂膜性能优良。 Good storage stability of the aqueous coating obtained by this method, the coating operation and simple process to obtain good film properties.

具体实施方式 Detailed ways

:实施例1:(1)三层核壳乳液的制备:A.核层聚合物的制备:在带有冷凝水,搅拌,温度计,滴加装置的100升搪瓷反应釜中加入34公斤去离子水,0.15公斤烷基二苯磺酸二钠,0.30公斤的反应性乳化剂烯丙基聚乙氧基磺酸盐(SEN-10),9.1公斤苯乙烯,2.8公斤丙烯酸丁酯,0.1公斤二乙烯基苯,搅拌乳化,通氮气20min,升温至40℃引发聚合,加入0.012公斤过硫酸钾和0.012公斤亚硫酸氢钠水液(水量为400克),引发反应1小时后,体系的反应温度逐渐保持在60±2℃。 : Example 1: Preparation of (1) a three-layer core-shell emulsion General: A preparation of the core polymer layer: In the condensation with water, stirred, 34 kg of deionized 100 liters a thermometer, a dropping device, enamel reactor was added water, 0.15 kg disodium alkyl diphenyl sulfonate, 0.30 kg of a reactive emulsifier polyethoxylated allyl sulfonate (SEN-10), 9.1 kilograms of styrene, 2.8 kg of butyl acrylate, 0.1 kg two after divinylbenzene, emulsifying stirring, nitrogen 20min, warmed to 40 ℃ polymerization initiator, was added 0.012 kg 0.012 kg of potassium persulfate and sodium hydrogen sulfite aqueous solution (400 g of water) to initiate the reaction one hour, the reaction temperature of the system gradually maintained at 60 ± 2 ℃.

B:次外层聚合物的制备:将混合好的2.5公斤甲基丙烯酸甲酯,5.0公斤丙烯酸丁酯,1.5公斤甲基丙烯酸缩水甘油酯,与0.009g过硫酸钾和0.009公斤亚硫酸氢钠水溶液同时滴加(水量为900克),1小时内滴加完成。 Preparation of the secondary layer polymer:: B the mixed 2.5 kg of methyl methacrylate, 5.0 kg of butyl acrylate, 1.5 kg of glycidyl methacrylate, and 0.009g of potassium persulfate and 0.009 kg of sodium bisulfite added dropwise aqueous (water 900 g) was added dropwise over 1 hour to complete.

C:最外层聚合物的制备:将混合好的3.3公斤甲基丙烯酸甲酯,5.0公斤丙烯酸丁酯,0.7公斤甲基丙烯酸与0.009公斤过硫酸钾和0.009公斤亚硫酸氢钠(配成水溶液,水量为900克)同时滴加,滴加完毕后反应1小时。 C: Preparation of the outermost layer polymer: the mixed 3.3 kg of methyl methacrylate, 5.0 kg of butyl acrylate, 0.7 kg of methacrylic acid and 0.009 kg 0.009 kg of potassium persulfate and sodium bisulfite (aq dubbed , water 900 g) was added dropwise, after the addition was complete the reaction for 1 hour.

升温至72±2℃,加入后消除引发剂0.015公斤的雕白块和0.015公斤的叔丁基过氧化氢(配成水溶液,水量为400克),反应1~2小时,冷却至40℃以下过滤出料,得到固含量为45%的三层核壳结构乳液,聚合过程中反应稳定,未发现凝胶。 Warmed to 72 ± 2 ℃, after elimination of the initiator was added 0.015 kg of carved white block and 0.015 kg of t-butyl hydroperoxide (formulated as an aqueous solution, 400 g of water), for 1 to 2 hours, cooled to 40 ℃ the material was filtered to give a solid content of 45% by a three-layer core-shell structure of the emulsion, stability during the polymerization reaction, the gel was found.

(2)清漆型水性涂料的复配(以下所说份数均指质量份数)将本发明的三层核壳结构乳液100份加入搅拌釜内,开启搅拌,逐渐滴加0.2份的pH值调节剂AMP95,5份的成膜助剂795,2份助成膜助剂(丙二醇),0.5份润湿剂,0.8份流平剂2020,0.2份消泡剂681F,0.1份增稠剂5230,0.01份防霉剂1138,0.01份防腐剂MV,5份抗划花剂(防刮擦810),充分搅拌,制成清漆型水性涂料。 (2) an aqueous coating compound novolak (hereinafter, refer to parts by mass of said parts) The structure of a three-layer core-shell emulsion of the present invention is added to 100 parts of the autoclave was stirred, open stirring, gradually added dropwise 0.2 parts of a pH value AMP95,5 parts modulators 795,2 parts coalescent coalescent aid (propylene glycol), 0.5 parts of a wetting agent, 0.8 parts of a leveling agent 2020,0.2 parts of a defoamer 681F, 0.1 parts of a thickener 5230, 0.01 parts preservative fungicide 1138,0.01 parts MV, 5 parts of an anti-scratching agent (anti-scratch 810), sufficiently stirred to prepare a novolak type aqueous coating.

(3)性能测定及其测定方法:(具体数据见表2)交联度的测定:称取一定量在烘箱中烘至恒重的膜,装入预先称量好的滤纸中,在索氏提取器中用丙酮抽提48小时,抽提后的膜于烘箱中干燥至恒重,按照下式计算膜的交联度:膜交联度=抽提后膜的重量(g)/抽提前膜的质量(g)×100%。 (3) Determination and method for measuring the performance of specific data in Table :( 2) Measurement of the degree of crosslinking: weighed amount of baking in an oven to constant weight film charged pre-weighed filter paper in a Soxhlet extraction with acetone for 48 hours extraction, the film after extraction in an oven dried to constant weight according to the degree of crosslinking of the film is calculated by the following formula: degree of crosslinking of the film after extraction = film weight (g) / evacuated in advance quality of the film (g) × 100%.

涂层耐水杯压痕性能测定:往烧杯中灌400ml水,煮开。 Water cup indentation coating properties measured: 400ml irrigation water to the beaker, boil. 在被测基材上倒一些沸水,然后将还有沸水的烧杯放置于涂膜上。 Pour some boiling water on a test substrate, and then the beaker was placed in boiling water as well as on the coating film. 烧杯在被测基材上放置15min。 15min beaker was placed on a test substrate. 15min之后,取走烧杯,立即对涂膜进行评级;待涂膜恢复6小时后进行评级。 After 15min, the beaker is removed, the coating film immediately rate; Recovery rate After the coating film for 6 hours. 无发白,无压痕为优级,无压痕,有微发白,但干后恢复为良级,有压痕或发白后不能恢复为失败。 No white, no indentation is superior grade, non-marking, micro white, but the recovery is good dry stage, is not restored after the failure has indentations or white.

膜的耐水性测试:按照国标GB/T1733-93进行测试。 Water resistance test film: tested in accordance with the national standard GB / T1733-93.

膜硬度的测试:用漆膜铅笔划痕硬度仪按照国标GB/T6739-1966。 Film hardness test: pencil scratch hardness tester with a film according to the national standard GB / T6739-1966.

实施例2-12:合成胶乳粒子所用单体及用量见表1,其它制备条件同实施例1。 Example 2-12: Synthesis of the latex particles and the amount of the monomers shown in Table 1, other conditions were the same as in Example 1.

表1:实施例2-12合成胶乳粒子所用单体及用量单位:公斤 Table 1: Synthesis of the latex particles used in Example 2-12 and the amount of monomeric units: kg 表中St为苯乙烯,MMA为甲基丙烯酸甲酯,BA为丙烯酸丁酯,DVB为二乙烯基苯,GMA为甲基丙烯酸缩水甘油酯,AN为丙烯腈,AA为丙烯酸;TEGDA三缩乙二醇二甲基丙烯酸酯,MALl马来酸酐,IBOMA甲基丙烯酸异冰片酯,AM为丙烯酰胺;IPA丙烯酸异戊酯,IBOA为丙烯酸异冰片酯,HEA丙烯酸羟乙酯,MAL2为顺丁烯二酸酐,HAM为羟甲基丙烯酰胺,TPGDA三缩丙二醇二甲基丙烯酸酯,EA丙烯酸乙酯,VCA氯乙酸乙烯酯,VeoVa-10叔十碳酸乙烯酯,DMEA甲基丙烯酸N,N二甲胺基乙酯。 Table St is styrene, MMA is methyl methacrylate, BA is butyl acrylate, DVB divinylbenzene, GMA is glycidyl methacrylate, AN is acrylonitrile, AA is acrylic acid; TEGDA tripropylene B glycol dimethacrylate, MALl maleic anhydride, IBOMA methacrylate, isobornyl methacrylate, AM is acrylamide; of IPA isoamyl acrylate, IBOA is isobornyl acrylate, HEA hydroxyethyl acrylate, MAL2 as maleic dianhydride, HAM as methylol acrylamide, TPGDA tripropylene glycol dimethacrylate, EA ethyl acrylate, VCA vinyl chloroacetate, VeoVa-10-t ten ethylene carbonate, DMEA methacrylate, N, N-dimethyl amino ethyl.

表2:实施例1-12的清漆型水性涂料各项性能指标测试结果 Table 2: Examples 1-12 novolak type aqueous coating Test results of the performance index 实施例13-18:色漆型涂料的配置在高速分散机的200升分散缸中加入去离子水100份、分散剂DP-270用量5份,消泡剂681F 1.5份,1200转/分搅拌10分钟,缓慢依次加入市售的金红石型二氧化钛50份,高岭土10份、滑石粉5份,继续搅拌分散20分钟,用砂磨机研磨两遍,细度达到30微米以下形成颜料浆液,待用。 Examples 13-18: Configuration paint type coating was added in 200 l speed dispersing machine dispersion tank 100 parts of deionized water, the amount of dispersing agent 5 parts by DP-270, 681F 1.5 parts defoamer, 1200 rev / min stirring 10 minutes, a commercially available were added 50 parts of rutile titanium dioxide, 10 parts of kaolin, 5 parts of talc, dispersed stirring continued for 20 minutes, twice in a sand mill, fineness of less than 30 microns to form a pigment slurry, stand .

在调漆釜内将本发明实施例2、4、6、8、10或12中步骤(1)的三层核壳结构乳液100份加入搅拌釜内,开启搅拌,100-300转/分搅拌,滴加0.2份的pH值调节剂AMP95,5份的成膜助剂795,2份助成膜助剂(丙二醇),0.5份润湿剂,0.2份消泡剂681F。 The three-layer core-shell emulsion was added to 100 parts of the paint in a stirred tank or autoclave step 12 cases 2,4,6,8,10 the embodiment (1) of the present invention, open stirring, 100-300 rpm / min with stirring , AMP95,5 added dropwise 0.2 parts of a pH modifier parts 795,2 parts coalescent coalescent aid (propylene glycol), 0.5 parts of a wetting agent, 0.2 parts of a defoamer 681F.

将研磨好的颜料浆液缓慢加入调漆釜内的乳液中,然后缓慢依次加入2.0份流平剂,0.5份增稠剂5230,0.02份防霉剂1138,0.02份防腐剂MV,视颜色要求加入各种色浆调色,充分搅拌,制成色漆型水性涂料。 The milled pigment slurry was slowly added to the emulsion good in paint pot and then slowly added successively 2.0 parts of a leveling agent, 0.5 parts of a thickener 5230,0.02 parts preservative fungicide 1138,0.02 parts MV, depending on the color requirements added various color paste, sufficiently stirred to prepare a paint-type water-based paint.

表3:实施例13-18的色漆型水性涂料各项性能指标测试结果 Table 3: Examples 13-18 The aqueous coating paint-type test results of the performance index

Claims (6)

  1. 1.一种含有三层核壳结构胶乳粒子乳液的水性涂料,由聚合物乳液及其他助剂配制而成,其特征是所说的聚合物乳液为一种具有三层核壳结构胶乳粒子的乳液,固含量为25~55%,胶乳粒子的核层为烯类硬单体、烯类软单体和多烯类交联单体的共聚物,次外层为烯类硬单体、烯类软单体和含有环氧基团、酸酐基团或活性卤素基团的烯类单体的共聚物,最外层为烯类硬单体、烯类软单体及含有羧基、羟基、胺基或酰胺基的烯类单体的共聚物;所说的三层核壳结构胶乳粒子的核层占聚合物总质量的25~50%,次外层占25~50%,最外层占25~50%。 A three-layer core-shell structure comprising latex particles of the aqueous coating emulsion, formulated with other additives and the polymer emulsion is made, wherein said polymer emulsion is a core-shell structure having a three-layer latex particles emulsion, solid content of 25 to 55%, the core layer of the latex particles ethylenically hard monomer, diene monomer copolymer and the polyene soft crosslinking monomer, once the outer layer is hard diene monomer, ethylenically soft monomer based copolymer containing an epoxy group, an acid anhydride-based monomer groups or active halogen groups, the outermost layer is hard ethylenic monomers, ethylenic monomers and carboxyl group-containing soft, hydroxyl, amine copolymers of vinyl monomers or amide group; a core layer of a three-layer core-shell structure of said latex particles of from 25 to 50% of the total mass of the polymer, times of from 25 to 50% of the outer layer, the outermost layer accounts 25 to 50%.
  2. 2.根据权利要求1的含有三层核壳结构胶乳粒子乳液的水性涂料,其特征是:所说的烯类硬单体为下列物质中的一种或它们的组合:苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸异冰片酯、丙烯酸异冰片酯、叔九碳酸乙烯酯、叔十碳酸乙烯酯、叔十一碳酸乙烯酯、丙烯腈单体;烯类软单体为下列物质中的一种或它们的组合:丙烯酸乙酯、丙烯酸丁酯、丙烯酸异戊酯、丙烯酸2-乙基己酯;多烯类交联单体为下列物质中的一种或它们的组合:二乙烯基苯、双丙烯酰胺、乙二醇二甲基丙烯酸酯、二缩乙二醇二甲基丙烯酸酯、三缩乙二醇二甲基丙烯酸酯、三缩丙二醇二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇四甲基丙烯酸酯;含有环氧基团、酸酐基团或活性卤素基团的烯类单体为下列物质组中的一种或它们的组合:甲基丙烯酸缩水甘油酯、烯丙基缩 2. The aqueous coating containing a three-layer core-shell structure of the emulsion of latex particles according to claim 1, wherein: said hard monomer is ethylenically the following materials or a combination thereof: styrene, methyl methacrylate methyl methacrylate, isobornyl methacrylate, isobornyl acrylate, t-nine ethylene carbonate, ethylene carbonate ten t, t-undecanoate, vinyl cyanide monomer; soft ethylenic monomer is a substance of the following species, or a combination thereof: ethyl acrylate, butyl acrylate, isoamyl acrylate, 2-ethylhexyl acrylate; polyene crosslinking monomer is one of the following materials or a combination thereof: divinylbenzene , bisacrylamide, ethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate; containing epoxy groups, acid anhydride-based monomer groups or active halogen group is one of the following group of substances or a combination thereof: glycerol glycidyl methacrylate ester, allyl reduction 甘油醚、马来酸酐、氯乙烯乙烯基醚、氯乙酸乙烯酯、对氯甲基苯乙烯;带有羧基、羟基、胺基或酰胺基烯类单体为下列物质组中的一种或它们的组合:丙烯酸、甲基丙烯酸、丙烯酰胺、甲基丙烯酰胺、羟甲基丙烯酰胺、丙烯酸胺乙酯、甲基丙烯酸胺乙酯、甲基丙烯酸N,N二甲胺基乙酯、丙烯酸羟乙酯、丙烯酸羟丙酯。 Glycerol ethers, maleic anhydride, vinyl ether, vinyl chloride, vinyl chloroacetate, chloromethylstyrene; having a carboxyl group, a hydroxyl group, an amine group or an amide group as a vinyl monomer of the following materials or groups thereof a combination of: acrylic acid, methacrylic acid, acrylamide, methacrylamide, methylol acrylamide, ethyl acrylamide, methyl acrylamide, ethyl methacrylate, N, N-dimethylamino acrylate, hydroxypropyl acrylate, hydroxypropyl acrylate.
  3. 3.根据权利要求1或2的含有三层核壳结构胶乳粒子乳液的水性涂料,其特征是,三层核壳结构胶乳粒子乳液采用如下的方法制备:在惰性气体保护的反应釜中,搅拌条件下,依次加入去离子水、乳化剂、核层单体进行乳化,加热至40~88℃,加入引发剂的水溶液引发聚合,反应1~2小时完成核层粒子合成反应,其中所用烯类硬单体、烯类软单体和多烯类交联单体的质量比:40~80∶20~60∶0.1~1;然后将次外层烯烃单体混合,与引发剂水溶液同时滴加入反应釜中,滴加完毕后,反应0.5~2小时,完成次外层粒子的合成,其中所用烯类硬单体、烯类软单体和含有环氧基团、酸酐基团或活性卤素基团的烯类单体的质量比:25~60∶35~60∶5~40;再将最外层烯类单体混合逐渐滴加到反应釜中,同时滴加引发剂水溶液,滴加完毕后,反应0.5~2小时,完成最外层粒 The aqueous coating containing a three-layer core-shell structure particle latex emulsion as claimed in claim 1 or 2, characterized in that the method of preparing a three-layer core-shell structure particle latex emulsion employed: inert gas in an autoclave and stirred conditions, were successively added deionized water, emulsifier, the core layer monomer emulsion was heated to 40 ~ 88 ℃, an aqueous solution of initiator is added to initiate the polymerization reaction for 1 to 2 hours to complete the core layer particle synthesis reaction, wherein an olefin type hard monomer, diene monomer and a soft mass polyenes crosslinking monomer ratio: 80:20 ~ 40 ~ 1 ~ 60:0.1; olefin monomer was then sub-layer mixing, with the aqueous initiator solution were added dropwise simultaneously autoclave, after the addition was complete, the reaction for 0.5 to 2 hours to complete the synthesis of secondary particles of the outer layer, wherein the hard olefinic monomers, diene soft monomer and epoxy groups, acid anhydride groups or active halogen-containing group with mass ratio of hydrophilic monomer groups: 25 ~ 60:35 ~ 40 ~ 60:5; then the outermost-based monomer mixture is gradually added dropwise to the reaction vessel, while the initiator aqueous solution was added dropwise, the addition was complete after reacting for 0.5 to 2 hours to complete the outermost layer tablets 的合成,其中所用烯类硬单体、烯类软单体及含有羧基、羟基、胺基或酰胺基的烯类单体的质量比:25~60∶35~90∶5~40;向反应釜中加入后消除引发剂水溶液,保温1~2小时,经降温,过滤出料,得到三层核壳结构胶乳粒子乳液,其中胶乳粒子乳液制备所用单体中核层单体占单体总质量的25~50%,次外层单体占单体总质量的25~50%,最外层单体占单体总质量的25~50%。 Synthesis, wherein the hard mass of diene monomers, vinyl monomers and soft vinyl monomer containing a carboxyl group, a hydroxyl group, amine or amide group with a ratio: 25 ~ 60:35 ~ 40 ~ 90:5; reaction after elimination of the kettle initiator aqueous solution was added, incubated for 1 to 2 hours, after cooling, the material was filtered, to obtain three-layer core-shell structure latex emulsion particles, the core layer monomer mass of monomers of total monomers wherein the latex particles are prepared using emulsion 25 to 50%, the outer secondary monomer comprises 25 to 50% of the total mass of the monomers, the outermost layer of monomer comprises 25 to 50% of the total mass of the monomers.
  4. 4.根据权利要求3的水性涂料,其特征是:制备胶乳粒子乳液所用的引发剂为过硫酸钾、过硫酸钠、过硫酸铵、过硫酸钾-亚硫酸氢钠、过硫酸钠-亚硫酸氢钠、或过硫酸铵-亚硫酸氢钠,后消除引发剂为叔丁基过氧化氢-甲醛化亚硫酸氢钠。 The aqueous coating according to claim 3, characterized in that: preparing an emulsion latex particles used in the initiator is potassium persulfate, sodium persulfate, ammonium persulfate, potassium persulfate - sodium bisulfite, sodium persulfate - sulfite sodium bicarbonate, or ammonium persulfate - sodium bisulfite, after elimination of the initiator is t-butyl hydroperoxide - formaldehyde sodium bisulfite.
  5. 5.根据权利要求3的水性涂料,其特征是:制备胶乳粒子乳液所用的乳化剂为乳液聚合常用的阴离子型、非离子型或阴离子和非离子复合型,或者反应性乳化剂。 The aqueous coating according to claim 3, characterized in that: the emulsifier used in the emulsion of latex particles used for the emulsion polymerization of anionic, nonionic, or anionic and non-ionic compound, or a reactive emulsifier.
  6. 6.一种含有三层核壳结构胶乳粒子乳液的水性涂料的制备方法,由三层核壳结构胶乳粒子乳液、多种助剂、颜填料配制而成,具体的配制方法为:以三层核壳结构胶乳粒子乳液为成膜物质,复配以成膜助剂、流平剂、消泡剂、增稠剂、流变改性剂、防霉剂、防腐剂、润湿剂、抗划花剂、消光剂、以及颜填料制成水性涂料,其中三层核壳结构胶乳粒子乳液的重量百分含量为35~95%。 A method for preparing a three-layer core-shell structure particle latex emulsion containing water-based paint, a three-layer core-shell latex particles are an emulsion, a variety of additives, pigments and fillers prepared from the specific preparation method were as follows: Layer core-shell latex particles of emulsion forming substance, together with complex coalescents, leveling agents, defoamers, thickeners, rheology modifiers, mildewcides, preservatives, wetting agents, anti-scratch flower agents, matting agents, and the weight percentage of the pigment is made water-based paint, wherein the emulsion is a three-layer core-shell latex particles is 35 to 95%.
CN 200510075254 2005-06-09 2005-06-09 Aqueous coating containing three layer nuclear shell structure rubber particle latex and its preparation method CN100389156C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 200510075254 CN100389156C (en) 2005-06-09 2005-06-09 Aqueous coating containing three layer nuclear shell structure rubber particle latex and its preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 200510075254 CN100389156C (en) 2005-06-09 2005-06-09 Aqueous coating containing three layer nuclear shell structure rubber particle latex and its preparation method

Publications (2)

Publication Number Publication Date
CN1876731A true true CN1876731A (en) 2006-12-13
CN100389156C CN100389156C (en) 2008-05-21

Family

ID=37509296

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200510075254 CN100389156C (en) 2005-06-09 2005-06-09 Aqueous coating containing three layer nuclear shell structure rubber particle latex and its preparation method

Country Status (1)

Country Link
CN (1) CN100389156C (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885889A (en) * 2010-07-16 2010-11-17 上海富臣化工有限公司 Acrylic ester elastic emulsion and preparation method thereof
CN101649153B (en) 2009-09-07 2011-12-21 大连工业大学 Silicone-modified acrylic emulsion and water-based wood synthesis
CN102311604A (en) * 2011-06-07 2012-01-11 三棵树涂料股份有限公司 Polymer hollow microspheres, preparation method thereof and preparation method for coating inorganic mineral matters by utilizing polymer hollow microspheres
CN102516446A (en) * 2011-12-02 2012-06-27 佛山市南海高拓包装材料有限公司 Aqueous acrylic resin, and preparation method and application thereof
CN102619135A (en) * 2012-03-28 2012-08-01 广州荣域实业有限公司 Novel aluminum-free lining paper coating for cigarette package and preparation method thereof
CN102942698A (en) * 2012-12-14 2013-02-27 北京化工大学 Preparation method of core-shell polymer nanoparticles with controllable shell thickness
CN103450390A (en) * 2013-08-15 2013-12-18 江苏华夏制漆科技有限公司 Preparation method of water-based hollow nano heat-insulating/warm-keeping resin
CN104311721A (en) * 2014-09-28 2015-01-28 合肥工业大学 Preparation method of polymer hollow double-layer microsphere and prepared polymer hollow double-layer microsphere
CN104448087A (en) * 2013-09-18 2015-03-25 中国石油天然气集团公司 Core-shell type polymer microspheres, preparation and applications thereof
CN105777980A (en) * 2016-05-16 2016-07-20 北京化工大学 Epoxy/carboxyl-containing acrylate copolymer core-shell emulsion and preparation method and application thereof
CN105367703B (en) * 2014-08-27 2017-11-14 齐鲁工业大学 A three-layer core-shell structure of the epoxy-modified acrylic emulsion

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1159357C (en) 2000-03-02 2004-07-28 潍坊永力化工有限公司 Nuclear-shell graft copolymer chemical bond connected between nuclear and shell and its preparing method
CN1537895A (en) 2003-10-24 2004-10-20 天津大学 Emulsion paint resin of aminol epoxy solidified at room-temperature and its synthesis method
CN1554721A (en) 2003-12-22 2004-12-15 天津大学 Double component amido/epoxy type room temperature solidifying emulsion paint resin and synthetic method

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101649153B (en) 2009-09-07 2011-12-21 大连工业大学 Silicone-modified acrylic emulsion and water-based wood synthesis
CN101885889B (en) 2010-07-16 2013-07-17 上海富臣化工有限公司 Acrylic ester elastic emulsion and preparation method thereof
CN101885889A (en) * 2010-07-16 2010-11-17 上海富臣化工有限公司 Acrylic ester elastic emulsion and preparation method thereof
CN102311604A (en) * 2011-06-07 2012-01-11 三棵树涂料股份有限公司 Polymer hollow microspheres, preparation method thereof and preparation method for coating inorganic mineral matters by utilizing polymer hollow microspheres
CN102311604B (en) 2011-06-07 2014-09-03 三棵树涂料股份有限公司 Polymer hollow microspheres, preparation method thereof and preparation method for coating inorganic mineral matters by utilizing polymer hollow microspheres
CN102516446A (en) * 2011-12-02 2012-06-27 佛山市南海高拓包装材料有限公司 Aqueous acrylic resin, and preparation method and application thereof
CN102619135A (en) * 2012-03-28 2012-08-01 广州荣域实业有限公司 Novel aluminum-free lining paper coating for cigarette package and preparation method thereof
CN102942698A (en) * 2012-12-14 2013-02-27 北京化工大学 Preparation method of core-shell polymer nanoparticles with controllable shell thickness
CN102942698B (en) * 2012-12-14 2015-07-08 北京化工大学 Preparation method of core-shell polymer nanoparticles with controllable shell thickness
CN103450390A (en) * 2013-08-15 2013-12-18 江苏华夏制漆科技有限公司 Preparation method of water-based hollow nano heat-insulating/warm-keeping resin
CN103450390B (en) * 2013-08-15 2016-03-30 江苏华夏制漆科技有限公司 An aqueous hollow nano insulation resin preparation
CN104448087B (en) * 2013-09-18 2017-08-04 中国石油天然气集团公司 Core-shell type polymeric microspheres and their preparation and use
CN104448087A (en) * 2013-09-18 2015-03-25 中国石油天然气集团公司 Core-shell type polymer microspheres, preparation and applications thereof
CN105367703B (en) * 2014-08-27 2017-11-14 齐鲁工业大学 A three-layer core-shell structure of the epoxy-modified acrylic emulsion
CN104311721B (en) * 2014-09-28 2016-03-23 合肥工业大学 And a method for preparing a polymer prepared bilayer hollow microspheres obtained bilayer polymeric hollow microspheres
CN104311721A (en) * 2014-09-28 2015-01-28 合肥工业大学 Preparation method of polymer hollow double-layer microsphere and prepared polymer hollow double-layer microsphere
CN105777980A (en) * 2016-05-16 2016-07-20 北京化工大学 Epoxy/carboxyl-containing acrylate copolymer core-shell emulsion and preparation method and application thereof

Also Published As

Publication number Publication date Type
CN100389156C (en) 2008-05-21 grant

Similar Documents

Publication Publication Date Title
US3862071A (en) Aqueous Thermosetting Acrylic Enamel Containing Metallic Flake Pigment
US20030144399A1 (en) Polymeric stabilizer for pigment dispersions
US6242531B1 (en) Acrylic aqueous miniemulsion copolymer thickeners and latex paints containing said thickeners
US6005042A (en) Aqueous polymer dispersions as binders for elastic, nonblocking and scratch-resistant coatings
EP0073529A2 (en) Preparation of sequential polymers and use thereof in coating compositions and as thickening agents
WO2011073417A1 (en) Aqueous emulsion
US5684078A (en) Polymer and use of the polymer as grinding and dispersing resin and binder for paint
US5621058A (en) Hydrophilic crosslinked polymer fine particles and process for production thereof
CN101812260A (en) Multifunctional water-based white primer and preparation method thereof
CN1306050A (en) Organosilicon modified acrylic paint for external wall and its preparing process
US20020103283A1 (en) High solar reflectance coating composition
CN101775101A (en) Organic silicon / hydroxyl phosphate composite modified water emulsion acrylic resin and preparation method and application thereof
CN1456577A (en) Organic siloxane modified phenylethylene-acrylic ester nano-emulsion and preparing method thereof
CN103193924A (en) Phase-control film-formation styrene-acrylate painting emulsion and preparation method thereof
JP2000290464A (en) Aqueous dispersion and its production and paint composition
CN101429267A (en) Preparation and uses of epoxy/acrylic acid hybridisation emulsion
JP2008150401A (en) Back sealer for inorganic ceramic building material and inorganic ceramic building material
CN101029110A (en) Fluoride core-shell acrylic-resin emulsion, its production and use
JP2000109703A (en) Aqueous dispersion
Khan et al. Preparation of core-shell emulsion polymer and optimization of shell composition with respect to opacity of paint film
CN101033360A (en) Method of preparing organic/inorganic hybridization reactivity semi-interpenetrating network structure emulsion
US20070049697A1 (en) Emulsion for vibration damping materials
US5877253A (en) Method of preparing inorganic pigment dispersions
JPH11343449A (en) Coating resin composition
CN102827322A (en) Preparation method and application of internal-external dual cross-linked core-shell structured acrylic acid emulsion

Legal Events

Date Code Title Description
C06 Publication
C10 Request of examination as to substance
C14 Granted
C41 Transfer of the right of patent application or the patent right
ASS Succession or assignment of patent right

Owner name: WUHAN AETNA CHEMICAL INDUSTRIAL CO., LTD.

Effective date: 20081205

Free format text: FORMER OWNER: BEIJING CHEMICAL ENGINEERING UNIV.