WO2021237404A1 - 一种水性环氧防腐涂料及其制备方法 - Google Patents
一种水性环氧防腐涂料及其制备方法 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- the invention relates to the technical field of chemical materials, in particular to a waterborne epoxy anticorrosive paint and a preparation method thereof.
- Water-based anticorrosive coatings with water as dispersion and resin as film-forming base material have the advantages of low VOC emissions, performance equivalent to solvent-based anticorrosive coatings, and low cost. It has become one of the development trends of environmentally friendly coatings in the future.
- the preparation process is generally: pre-grind the pigment and filler solution, and then disperse and mix with the emulsion at high speed; at the same time, the emulsion type waterborne epoxy also needs to add the film-forming auxiliary, which has a high boiling point. Solvent, assist the resin to cure into a film.
- the A component includes the following mass percentages Component: 22%-25% bisphenol A type epoxy resin water-based dispersion, 8%-10% o-cresol novolac epoxy resin water-based dispersion, 0.8%-1% solvent, 1.5%-1.8% Dispersant, 0.1%-0.2% anti-settling agent, 0.8%-1% wetting and leveling agent, 0.4%-0.6% thickener, 0.6%-0.7% defoamer, 2%-20 % Titanium dioxide, 20%-40% filler and the balance of deionized water, which contains 0.8%-1% volatile solvent, the pigment in this scheme needs to be pre-grinded with a fineness of less than 20 ⁇ m.
- Water-based epoxy resin A water-based epoxy resin B, dispersant, defoamer, wetting agent, thixotropic agent, anti-flash agent, pigment, filler, deionized water;
- the water-based epoxy resin A is a self-emulsifying water-based epoxy resin
- the water-based epoxy resin B is a glycidyl ester epoxy resin
- the second component includes: curing agent and deionized water
- the curing agent is an amine curing agent.
- the mass parts of each raw material in the first component are:
- the mass parts of the raw materials in the second component are: 60 parts of curing agent and 40 parts of deionized water.
- the solid content of the water-based epoxy resin A is 100%, which is selected from Foshan Tongde Chemical 3EE107B self-emulsifying water-based epoxy resin.
- the solid content of the water-based epoxy resin B is 100%, and is selected from the group consisting of diglycidyl hexahydrophthalate, diglycidyl isophthalate, and diglycidyl adipic acid.
- diglycidyl hexahydrophthalate diglycidyl isophthalate
- diglycidyl adipic acid diglycidyl adipic acid.
- diglycidyl esters One or two or more of glycidyl esters.
- the thixotropic agent is at least one of water-based bentonite, water-based silicate, and organically modified hectorite clay.
- the pigments and fillers are at least one of mica dust, composite iron titanium powder, mica powder, iron oxide red, talc powder, zinc phosphate, aluminum tripolyphosphate, feldspar powder, and titanium dioxide Three combinations.
- the defoaming agent is selected from at least one of 180W, 182W, 280W, 282W, 285W, 290W, and 291W.
- the dispersant is at least one of modified polyurethane, high molecular polymer, unsaturated carboxylic acid, and high molecular block polymer.
- the dispersant is selected from at least one of Eucalyptus 520S, 560S, 650U, 685U, 690W, and 765S.
- the wetting agent is at least one of organically modified polysiloxane, fluorocarbon modified silicone, functional acrylate, and fluorocarbon polymer.
- the wetting agent is selected from at least one of Eucalyptus 430S, 470U, 375S, 360S, 361S, and 385S.
- the present invention also provides a preparation method according to any of the above-mentioned water-based epoxy anticorrosive coatings, including:
- the water-based epoxy resin A has a hydrophilic group in the resin molecular chain, which can self-emulsify in contact with water
- the water-based epoxy resin B has one end hydrophilic and one end containing a highly active epoxy It has good compatibility with resin A and has self-emulsification function. Its viscosity is low, and its activity is high. It is easy to react with the curing agent; and after the water-based epoxy resin A and the water-based epoxy resin B are mixed, the water-based epoxy resin B ring
- the oxygen group preferentially reacts with the curing agent amine group. The progress of this reaction can promote the reaction between the curing agent and A resin, and the final system will form a film on its own without the application of cosolvents, which greatly reduces the VOC emission.
- the principle of the existing cosolvent in the emulsion system is that in the process of water volatilization, the concentration of the solvent inside and outside the emulsion particles changes, and more solvent enters the emulsion particles to have a swelling effect.
- the resin contacts the curing agent and solidifies to form a film.
- the cosolvent Slowly volatilize into the environment.
- the present invention utilizes single-end hydrophilic low-viscosity and high-activity water-based epoxy resin B, which is easy to contact and react with the curing agent.
- the molecular weight of the reaction resin increases, and the self-emulsified emulsion particles swell, which drives the contact between the water-based epoxy resin A and the curing agent.
- the final film is formed and cured without any solvent volatilization.
- Self-emulsifying resins have the advantage of high-speed dispersion or grinding with pigments and fillers.
- Emulsion resins are oil-in-water. If they are ground or high-speed dispersion with pigments and fillers for a long time, they will easily break the emulsion, and the coating system will lose its application value. Or, if the high-speed dispersion time is short, the fineness of the pigments and fillers will not meet the requirements, and the performance of the coating will decrease and the application value will be lost.
- the self-emulsifying resin has a hydrophilic group in the molecular chain, which is a chemical bonding method, so it will not affect its structure if it is ground with pigments and fillers and high-speed dispersion.
- the water-based epoxy resin B is also an epoxy resin.
- the water-based epoxy resin A has good compatibility and hydrophilic groups, which is more conducive to improving the dispersion effect of the water-based epoxy resin A and pigments and fillers. It solves the process of separate pre-high-speed dispersion or grinding of pigments and fillers, saving production costs.
- the water-based epoxy anticorrosive coating provided by the present invention does not require additional pre-grinding of pigments and fillers to prepare the slurry process.
- the water-based epoxy resin A and the water-based epoxy resin B are combined without adding additional film-forming additives.
- the VOC content is low; it has the characteristics of high storage stability, strong adhesion, high mechanical strength, excellent anti-corrosion performance, good construction process performance, energy saving, environmental protection, and low cost.
- the present invention provides the following examples (parts per unit mass):
- Waterborne epoxy resin B uses diglycidyl isophthalate
- the dispersing agent is 650U; the defoaming agent is 285W; the wetting agent is 470U; the thixotropic agent is water-based bentonite and the anti-flash agent is general F5100;
- the water-based curing agent adopts modified polyamide
- Waterborne epoxy resin B uses diglycidyl hexahydrophthalate
- the dispersant adopts 690W defoamer, 280W wetting agent, 360S thixotropic agent, and water-based silicate;
- the anti-flash agent adopts general F5100
- the water-based curing agent adopts modified alicyclic amine
- Waterborne epoxy resin B uses diglycidyl adipate
- the dispersant adopts 520S
- the thixotropic agent adopts organically modified hectorite clay
- the anti-flash agent is generally F5100;
- the water-based curing agent adopts modified polyamidoamine
- Comparative Example 1 and Comparative Example 2 except for the water-based epoxy resins A and B, the other specific raw materials and ratios used are the same as those in Example 3.
- Example 1 component A and component B were used according to 6.5:1, 7:1 and 7.3:1, and tested according to the indicators shown in the following table:
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Abstract
水性环氧防腐涂料,包括:甲组分和乙组分,甲组分包括水性环氧树脂A、水性环氧树脂B、分散剂、消泡剂、润湿剂、触变剂、防闪剂、颜料、填料、去离子水,其中,水性环氧树脂A为自乳化水性环氧树脂,水性环氧树脂B为缩水甘油酯环氧树脂;乙组分包括固化剂和去离子水,其中,固化剂为胺类固化剂。并且提供了水性环氧防腐涂料的制备方法,包括具体的混合顺序和工艺参数。
Description
本发明涉及化工材料技术领域,特别涉及一种水性环氧防腐涂料及其制备方法。
以水为分散体,树脂为成膜基料的水性防腐涂料具有低VOC排放,性能与溶剂型防腐涂料相当,成本低等优点,成为未来环保涂料的发展趋势之一。
目前市面上水性环氧防腐树脂多为乳液型,制备工艺一般为:预先研磨好颜填料溶液,然后再与乳液高速分散混合;同时,乳液型水性环氧还需加入成膜助剂既高沸点溶剂,辅助树脂固化成膜。
上述方法存在如下缺点:(1)颜填料预先研磨,非搅拌下极易沉淀,存储不稳定,使用极不方便,增添生产工艺流程,增加成本;(2)添加成膜助剂,体系VOC含量增加,导致有机挥发物增多,不利环保。
中国专利申请CN 110183932 A《一种含有复合活性盐的水性环氧防腐涂料及其制备方法》,公开日为2020年08月30日,该技术方案中,公开A组份制备方法:先将各种助剂与去离子水搅拌混合均匀,然后加入颜填料和制备的复合活性亚磷酸盐/偏铝酸盐,研磨至需求细度,制得无树脂乳液浆料,然后与水性环氧树脂乳液和触变剂,搅拌均匀,制得A组分。
中国专利申请CN 110643265 A《一种可淋涂和浸涂的水性环氧涂料及其制备方法》,公开日为2020年01月03日,该技术方案中,所述A组分包括如下质量百分比的组分:22%-25%的双酚A型环氧树脂水性分散体,8%-10%的邻甲酚醛环氧树脂水性分散体,0.8%-1%的溶剂,1.5%-1.8%的分散剂, 0.1%-0.2%的防沉剂,0.8%-1%的润湿流平剂,0.4%-0.6%的增稠剂,0.6%-0.7%的消泡剂,2%-20%的钛白粉,20%-40%的填料和余量的去离子水,其中含0.8%-1%的挥发性溶剂,该方案中的颜料需要预先研磨细度小于20μm。
发明内容
为解决现有技术中存在的需要先对颜填料预研磨以及需要添加成膜助剂的问题;本发明提供一种水性环氧防腐涂料,包括甲组分和乙组分,其中,甲组分包括了:
水性环氧树脂A、水性环氧树脂B、分散剂、消泡剂、润湿剂、触变剂、防闪剂、颜料、填料、去离子水;
其中,所述水性环氧树脂A为自乳化水性环氧树脂;
所述水性环氧树脂B为缩水甘油酯环氧树脂;
乙组分包括了:固化剂和去离子水;
所述固化剂为胺类固化剂。
在上述方案的基础上,进一步地,所述甲组分中各原料的质量份数为:
在上述方案的基础上,进一步地,所述乙组分中各原料的质量份数为:固化剂60份,去离子水40份。
在上述方案的基础上,进一步地,所述水性环氧树脂A的固含量为100%,选自佛山同德化工3EE107B自乳化水性环氧树脂。
在上述方案的基础上,进一步地,所述水性环氧树脂B的固含量为100%,选自六氢邻苯二甲酸二缩水甘油酯、间苯二甲酸二缩水甘油酯、已二酸二缩水甘油酯中一种或两种以上。
在上述方案的基础上,进一步地,所述触变剂为水性膨润土、水性硅酸盐和有机改性锂蒙脱石粘土中的至少一种。
在上述方案的基础上,进一步地,所述颜填料为云铁灰、复合铁钛粉、云母粉、氧化铁红、滑石粉、磷酸锌、三聚磷酸铝、长石粉、钛白粉中的至少三种组合。
在上述方案的基础上,进一步地,所述消泡剂选自卡180W、182W、280W、282W、285W、290W、291W中的至少一种。
在上述方案的基础上,进一步地,所述分散剂为改性聚氨酯、高分子聚合物、不饱和羧酸、高分子嵌段聚合物中的至少一种。
在上述方案的基础上,进一步地,所述分散剂选用优卡520S、560S、650U、685U、690W、765S中的至少一种。
在上述方案的基础上,进一步地,所述润湿剂为有机改性聚硅氧烷、氟碳改性有机硅、功能丙烯酸酯、氟碳聚合物中的至少一种。
在上述方案的基础上,进一步地,所述润湿剂选自优卡430S、470U、375S、360S、361S、385S中的至少一种。
本发明还提供一种根据上述任意所述水性环氧防腐涂料的制备方法,包 括:
甲组份的制备方法:
S110、将去离子水加入拉缸中,分别加入消泡剂、分散剂、润湿剂,分散5~10min,转速500~1000r/min,获得均匀溶液L1;
S120、在上述均匀溶液L1中加入水性环氧树脂A,分散15~20min,转速500~1000r/min,得到混合物L2;
S130、在混合溶液L2中加入水性环氧树脂B,分散15~20min,转速500~1000r/min,得到混合物L3;
S140、在混合溶液L3中,投入颜料,填料,分散至细度85um以下,转速800~1000r/min,得到混合物L4;
S150、在混合物L4中,投入触变剂,分散15~20min,转速500~1000r/min,得到混合物L5;
S160、冷却后,过滤,包装,即得到甲组份;
乙组分的制备方法:
S210、在拉缸中投入去离子水,边搅拌,边缓慢加入水性固化剂,分散10~15min,转速500~800r/min;
S220、分散后,进行过滤,包装,即得到乙组分。
本发明提供的水性环氧防腐涂料中,水性环氧树脂A的树脂分子链内具有亲水基团,遇水可自乳化,而水性环氧树脂B中一端亲水,一端含高活性环氧基,与树脂A相容性良好,具有自乳化功能,其粘度低,活性高,易与固化剂反应;而水性环氧树脂A和水性环氧树脂B进行混合后,水性环氧树脂B环氧基优先与固化剂胺基反应,该反应的进行能够促进固化剂与A树脂反应,最终体系自行成膜,无需助溶剂的应用,极大降低VOC释放量。
现有的助溶剂在乳液体系中作用原理是,水挥发过程,溶剂在乳液粒子 里外浓度发生变化,溶剂更多进入乳液粒子起溶胀作用,树脂与固化剂接触,固化成膜,最终助溶剂缓慢挥发进入环境。本发明是利用单端亲水的低粘度高活性水性环氧树脂B,与固化剂易接触反应,反应树脂分子量增加,自乳化乳液粒子发生溶胀,带动水性环氧树脂A与固化剂的接触,最终成膜固化,无任何溶剂挥发。
自乳化型树脂具有与颜填料同时高速分散或研磨的优势,乳液型树脂则是水包油方式,如果与颜填料研磨或高速分散长时间接触容易破乳,则涂料体系失去应用价值,如果研磨或高速分散时间短,则颜填料细度达不到要求,涂层性能下降也失去应用价值。而自乳化型树脂是分子链内含亲水性基团,属于化学键结合方式,所以和颜填料研磨,高速分散都不会影响其结构;此外,水性环氧树脂B也为环氧树脂,与水性环氧树脂A相容性好,又带有亲水基团,更有利于提高水性环氧树脂A与颜填料的分散效果。解决了颜填料单独预高速分散或研磨的工艺,节约生产成本。
本发明提供的水性环氧防腐涂料无需额外的颜填料预研磨制备浆料工艺,通过上述发明构思,将水性环氧树脂A和水性环氧树脂B进行结合,无需添加额外的成膜助剂,VOC含量低;其具有存储稳定高,附着力强,机械强度高,防腐性能优异,施工工艺性能好,节能,环保,低成本等特性。
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明提供如下实施例(单位质量份数):
表1
上述实施例1中:
水性环氧树脂B采用间苯二甲酸二缩水甘油酯;
分散剂采用650U;消泡剂采用285W;润湿剂采用470U;触变剂采用水性膨润土防闪剂采用普为F5100;
水性固化剂采用改性聚酰胺;
实施例2中:
水性环氧树脂B采用六氢邻苯二甲酸二缩水甘油酯;
分散剂采用690W消泡剂采用280W润湿剂采用360S触变剂采用水性硅酸盐;
防闪剂采用普为F5100
水性固化剂采用改性脂环胺;
实施例3中:
水性环氧树脂B采用已二酸二缩水甘油酯;
分散剂采用520S;
消泡剂采用290W、润湿剂采用385S;
触变剂采用有机改性锂蒙脱石粘土;
防闪剂采用普为F5100;
水性固化剂采用改性聚酰胺基胺;
对比例1和对比例2中,除水性环氧树脂A、B外,其余采用的具体原料及比例和实施例3一致。
其中,实施例1、2、3中,甲组分和乙组分按照6.5:1、7:1和7.3:1进行使用,并按照下表所示指标进行测试:
表2
实施例1、2、3的测试结果如下表所示:
表3
由上表比较可以看出,若单独采用水性环氧树脂A或水性环氧树脂B,和实施例3相比,其附着力、抗冲击、耐水性、盐雾试验、耐酸性和耐碱性方面均有所降低,这是由于单独使用A树脂,与固化剂反应慢,涂层固化不完全,耐酸碱性能差;另外,单独使用B树脂,与固化剂反应快,对基材润湿铺张性能差,力学性能和耐性都下降,无法满足要求。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改, 或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (13)
- 一种水性环氧防腐涂料,其特征在于,包括甲组分和乙组分,其中,甲组分包括了:水性环氧树脂A、水性环氧树脂B、分散剂、消泡剂、润湿剂、触变剂、防闪剂、颜料、填料、去离子水;其中,所述水性环氧树脂A为自乳化水性环氧树脂;所述水性环氧树脂B为缩水甘油酯环氧树脂;乙组分包括了:固化剂和去离子水;所述固化剂为胺类固化剂。
- 根据权利要求1所述的水性环氧防腐涂料,其特征在于:所述乙组分中各原料的质量份数为:固化剂60份,去离子水40份。
- 根据权利要求1所述的水性环氧防腐涂料,其特征在于:所述水性环氧树脂A的固含量为100%,选自佛山同德化工3EE107B自乳化水性环氧树脂。
- 根据权利要求1所述的水性环氧防腐涂料,其特征在于:所述水性环氧树脂B的固含量为100%,选自六氢邻苯二甲酸二缩水甘油酯、间苯二甲酸二缩水甘油酯、已二酸二缩水甘油酯中一种或两种以上。
- 根据权利要求1所述的水性环氧防腐涂料,其特征在于:所述触变剂为水性膨润土、水性硅酸盐和有机改性锂蒙脱石粘土中的至少一种。
- 根据权利要求1所述的水性环氧防腐涂料,其特征在于:所述颜填料为云铁灰、复合铁钛粉、云母粉、氧化铁红、滑石粉、磷酸锌、三聚磷酸铝、长石粉、钛白粉中的至少三种组合。
- 根据权利要求1所述的水性环氧防腐涂料,其特征在于:所述消泡剂选自卡180W、182W、280W、282W、285W、290W、291W中的至少一种。
- 根据权利要求1所述的水性环氧防腐涂料,其特征在于:所述分散剂为改性聚氨酯、高分子聚合物、不饱和羧酸、高分子嵌段聚合物中的至少一种。
- 根据权利要求9所述的水性环氧防腐涂料,其特征在于:所述分散剂选用优卡520S、560S、650U、685U、690W、765S中的至少一种。
- 根据权利要求1所述的水性环氧防腐涂料,其特征在于:所述润湿剂为有机改性聚硅氧烷、氟碳改性有机硅、功能丙烯酸酯、氟碳聚合物中的至少一种。
- 根据权利要求1所述的水性环氧防腐涂料,其特征在于:所述润湿剂选自优卡430S、470U、375S、360S、361S、385S中的至少一种。
- 一种根据权利要求1-10任一项所述水性环氧防腐涂料的制备方法,包括:甲组份的制备方法:S110、将去离子水加入拉缸中,分别加入消泡剂、分散剂、润湿剂,分散 5~10min,转速500~1000r/min,获得均匀溶液L1;S120、在上述均匀溶液L1中加入水性环氧树脂A,分散15~20min,转速500~1000r/min,得到混合物L2;S130、在混合溶液L2中加入水性环氧树脂B,分散15~20min,转速500~1000r/min,得到混合物L3;S140、在混合溶液L3中,投入颜料,填料,分散至细度85um以下,转速800~1000r/min,得到混合物L4;S150、在混合物L4中,投入触变剂,分散15~20min,转速500~1000r/min,得到混合物L5;S160、冷却后,过滤,包装,即得到甲组份;乙组分的制备方法:S210、在拉缸中投入去离子水,边搅拌,边缓慢加入水性固化剂,分散10~15min,转速500~800r/min;S220、分散后,进行过滤,包装,即得到乙组分。
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