CN104789084A - Rust-proof primer of surface tolerant coatings painted on rusty surfaces for ships - Google Patents
Rust-proof primer of surface tolerant coatings painted on rusty surfaces for ships Download PDFInfo
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Abstract
本发明公开了一种船用带锈涂装低表面处理防锈底漆。它包括甲、乙两组份,一份甲组份包括:环氧树脂30~55重量份,纳米复合防锈颜填料1~20重量份,偶联剂0.5~5重量份,触变剂0.5~3重量份,分散剂0.5~5重量份,消泡剂0.5~2重量份,增韧剂1.5~3重量份,成膜助剂1~5重量份,溶剂20~30重量份。一份乙组份包括:聚酰胺固化剂30~55重量份,溶剂40~50重量份。甲组份和乙组份按照一定比例混合充分搅匀得到防锈底漆。本发明将纳米复合防锈颜填料按比例掺杂后制备得到的防锈底漆可涂覆在有一定腐蚀产物堆积的钢铁结构表面,有效减轻繁琐的前处理工艺以及处理过程中带来的粉尘和水污染,施工简便。The invention discloses an anti-rust primer with low surface treatment for marine rusty coating. It includes two components, A and B. One component of A includes: 30-55 parts by weight of epoxy resin, 1-20 parts by weight of nano-composite antirust pigments and fillers, 0.5-5 parts by weight of coupling agent, and 0.5 parts by weight of thixotropic agent. ~3 parts by weight, 0.5-5 parts by weight of dispersant, 0.5-2 parts by weight of defoamer, 1.5-3 parts by weight of toughening agent, 1-5 parts by weight of film-forming aid, and 20-30 parts by weight of solvent. One part of component B includes: 30-55 parts by weight of polyamide curing agent, and 40-50 parts by weight of solvent. Mix components A and B according to a certain ratio and stir well to obtain an antirust primer. The anti-rust primer prepared by doping the nano-composite anti-rust pigments and fillers in proportion can be coated on the surface of the steel structure with certain corrosion products accumulated, effectively reducing the cumbersome pre-treatment process and the dust brought during the treatment process And water pollution, easy construction.
Description
技术领域 technical field
本发明涉及一种防腐涂料,尤其涉及一种船用带锈涂装低表面处理防锈底漆。 The invention relates to an anti-corrosion coating, in particular to an anti-rust primer with low surface treatment for marine rust coating.
背景技术 Background technique
在海洋环境中,海洋工程设备、海上石油天然气平台及船舶在使用过程中不可避免发生各种腐蚀破坏,严重影响其安全和使用寿命。腐蚀主要是材料接触腐蚀因子(水、氧气、离子、微生物等),并与之发生反应,使材料的形态、结构发生改变的过程。为了减缓钢铁材料腐蚀过程,延长产品的使用寿命,保证服役期间使用安全,人们运用了各种防腐蚀方法,如开发各种耐腐蚀钢材;利用表面热镀锌法对钢铁进行防护;利用阴极保护法对腐蚀介质里构件进行防护;利用表面涂覆防腐涂料法对钢结构保护等,综合现有技术和成本因素考虑,采用涂料涂装防护是最广泛、有效和经济的方法。为了获得良好的效果,在涂装前往往需要对底材进行打磨清洗等表面处理。据研究,表面处理的好坏对涂膜寿命影响较大,约有一半涂层失效是由表面处理造成的。普通的重防腐涂料在涂装时为了达到高性能的防护效果,船体和钢件表面必须采取喷砂等处理手段来除去铁锈,以增强涂料与钢铁表面的结合力。但该法不但会增加成本,喷砂过程中的粉尘和噪声还会严重危害施工人员身体健康,对于某些复杂结构的作业面难以做到完全清除干净。为了解决上述问题,能够满足带锈涂装的低表面处理涂料( Surface Tolerant Coating)成为国内外相关领域研究热点。 In the marine environment, various corrosion damages inevitably occur in marine engineering equipment, offshore oil and gas platforms and ships during use, seriously affecting their safety and service life. Corrosion is mainly a process in which materials come into contact with corrosion factors (water, oxygen, ions, microorganisms, etc.) and react with them to change the shape and structure of materials. In order to slow down the corrosion process of steel materials, prolong the service life of products, and ensure the safety of use during service, people have used various anti-corrosion methods, such as developing various corrosion-resistant steel materials; using surface hot-dip galvanizing to protect steel; using cathodic protection The protection of components in corrosive media by means of methods; the protection of steel structures by surface coating with anti-corrosion coatings, etc., considering the existing technology and cost factors, the use of coating protection is the most extensive, effective and economical method. In order to obtain good results, surface treatment such as grinding and cleaning of the substrate is often required before painting. According to research, the quality of surface treatment has a greater impact on the life of the coating film, and about half of the coating failure is caused by surface treatment. In order to achieve a high-performance protective effect when ordinary heavy-duty anti-corrosion coatings are painted, the surface of the hull and steel parts must be treated by means of sandblasting to remove rust, so as to enhance the bonding force between the coating and the steel surface. But this method will not only increase the cost, but also the dust and noise in the sandblasting process will seriously endanger the health of construction workers, and it is difficult to completely clean up the working surface of some complex structures. In order to solve the above problems, the low surface treatment coating (Surface Tolerant Coating) that can meet the rust coating has become a research hotspot in related fields at home and abroad.
为了实现带锈涂装,通常是在涂料制造过程中添加渗透剂、极性溶剂及活性保护物质使残锈稳定钝化或转化,将活泼的锈蚀产物转化为稳定无害的物质,从而实现增加保护效果和降低繁琐处理工序的目的。虽然上述带锈涂料已经得到了广泛应用,但是仍然存在很多不足,如一般带锈涂装涂料在使用过程中受钢结构物表面腐蚀产物堆积量多少影响,很多涂料以铬盐或磷酸盐作为活性物质以起到转锈和稳锈目的,容易造成重金属污染和富营养化,效果仍然不足以令人满意。 In order to achieve rusty coating, penetrating agents, polar solvents and active protective substances are usually added during the coating manufacturing process to stably passivate or transform residual rust, and convert active rust products into stable and harmless substances, thereby achieving increased The purpose of protecting the effect and reducing cumbersome processing procedures. Although the above-mentioned rusty coatings have been widely used, there are still many deficiencies, such as how much rusty coatings are affected by the accumulation of corrosion products on the surface of steel structures during use, and many coatings use chromium salts or phosphates as active substances. For the purpose of turning rust and stabilizing rust, it is easy to cause heavy metal pollution and eutrophication, and the effect is still not satisfactory.
近几年来纳米技术的引入为涂料工业的发展开辟新的思路和方向,利用纳米颗粒的掺杂,实现有机/无机组分在小尺度上的复合改性,从而将有机聚合物优良的成膜性、可延展性、施工性能和无机材料杰出的刚性、稳定性结合起来,大大提高涂料的性能。研究结果显示,将纳米ZnO、CaCO3、TiO2等纳米颗粒作为填料采取合适的比例在制备过程中添加到涂料中,可以有效地改善涂层的性能。特别是纳米ZnO颗粒的掺杂,可以有效地保护金属基体,大大减缓其腐蚀过程,延长使用寿命。 In recent years, the introduction of nanotechnology has opened up new ideas and directions for the development of the coatings industry. The doping of nanoparticles is used to realize the compound modification of organic/inorganic components on a small scale, so that the excellent film-forming properties of organic polymers can be improved. The combination of flexibility, ductility, construction performance and the outstanding rigidity and stability of inorganic materials greatly improves the performance of coatings. The research results show that nano-ZnO, CaCO 3 , TiO 2 and other nano-particles as fillers are added to the coating in an appropriate proportion during the preparation process, which can effectively improve the performance of the coating. In particular, the doping of nano-ZnO particles can effectively protect the metal substrate, greatly slow down its corrosion process, and prolong its service life.
以纳米氧化锌和钙钛矿为基础进行复配改性后的纳米复合防锈颜填料体系,在有机添加剂改性下,有序沉积形成多重微层结构,可以有效阻挡腐蚀介质的渗透,起到良好的屏蔽作用,实现良好的防腐效果。同时,经过有机复合改性后的纳米复合防锈颜填料体系与环氧树脂乳液亲和性好,易于分散,制备的防锈涂料可长期稳定保存。 The nano-composite anti-rust pigment and filler system based on nano-zinc oxide and perovskite is compounded and modified. Under the modification of organic additives, the orderly deposition forms a multiple micro-layer structure, which can effectively block the penetration of corrosive media and play a role in anti-corrosion. To a good shielding effect, to achieve a good anti-corrosion effect. At the same time, the nano-composite anti-rust pigment and filler system modified by organic compound has good affinity with epoxy resin emulsion and is easy to disperse, and the prepared anti-rust coating can be stored stably for a long time.
制得的纳米复合防锈底漆一方面可以将其接触的活性铁锈钝化,抑制锈蚀的进一步发生;另一方面漆膜的吸收作用将铁锈从表面拉起,并通过底漆内经过转化的晶粒加以包裹,隔绝氧气和水分,防止进一步锈蚀。该防腐涂料将有机树脂的韧性、粘结性与无机粉体的刚性充分结合,形成的涂膜具有附着力大、耐蚀、涂膜收缩率低、渗透性好、硬度大的优点。 On the one hand, the prepared nanocomposite anti-rust primer can passivate the active rust it contacts and inhibit the further occurrence of rust; on the other hand, the absorption of the paint film pulls the rust from the surface and passes through the converted The grains are wrapped to isolate oxygen and moisture, preventing further corrosion. The anti-corrosion coating fully combines the toughness and cohesiveness of organic resin with the rigidity of inorganic powder, and the formed coating film has the advantages of high adhesion, corrosion resistance, low shrinkage rate of coating film, good permeability and high hardness.
发明内容 Contents of the invention
本发明的目的是克服现有技术的不足,提供一种船用带锈涂装低表面处理防锈底漆。 The purpose of the invention is to overcome the deficiencies of the prior art and provide a low surface treatment antirust primer for marine rust coating.
一种船用带锈涂装低表面处理防锈底漆,它的组成如下:包括甲、乙两组份,一份甲组份包括:环氧树脂30~55重量份,纳米复合防锈颜填料1~20重量份,偶联剂0.5~5重量份,触变剂0.5~3重量份,分散剂0.5~5重量份,消泡剂0.5~2重量份,增韧剂1.5~3重量份,成膜助剂1~5重量份,溶剂20~40重量份。一份乙组份包括:聚酰胺固化剂30~55重量份,溶剂40~50重量份。所述的船用带锈涂装低表面处理防锈底漆由甲组份和乙组份按所需比例混合搅匀而得。 A kind of antirust primer with low surface treatment for marine rust coating, its composition is as follows: including A and B two components, a part of A component includes: 30~55 parts by weight of epoxy resin, nano composite antirust pigments and fillers 1-20 parts by weight, 0.5-5 parts by weight of coupling agent, 0.5-3 parts by weight of thixotropic agent, 0.5-5 parts by weight of dispersant, 0.5-2 parts by weight of defoamer, 1.5-3 parts by weight of toughening agent, 1-5 parts by weight of film-forming auxiliary agent, and 20-40 parts by weight of solvent. One part of component B includes: 30-55 parts by weight of polyamide curing agent, and 40-50 parts by weight of solvent. The low surface treatment antirust primer for marine rust coating is obtained by mixing and stirring components A and B according to the required ratio.
所述的防腐组分由纳米复合防锈颜填料复配而成。 The anti-corrosion component is compounded by nano-composite anti-rust pigments and fillers.
所述的溶剂由二甲苯和丁醇混合组成,二甲苯与丁醇的重量比为7:3。 The solvent is composed of a mixture of xylene and butanol, and the weight ratio of xylene to butanol is 7:3.
所述的触变剂为膨土粉、二氧化硅、聚酰胺蜡中的一种。所述的增韧剂为邻苯二甲酸二辛酯。 The thixotropic agent is one of bentonite powder, silicon dioxide and polyamide wax. The toughening agent is dioctyl phthalate.
所述的偶联剂为硬脂酸、硬脂酸钙、γ-(2,3-环氧丙氧)丙基三甲氧基硅烷、异丙基三油酸酰氧基钛酸酯、焦磷酸酯钛酸酯、乙撑钛酸酯中的一种。 The coupling agent is stearic acid, calcium stearate, γ-(2,3-epoxypropoxy)propyl trimethoxysilane, isopropyl trioleate acyloxy titanate, pyrophosphoric acid One of ester titanate and ethylene titanate.
所述的纳米复合防锈颜填料其组成主要包括纳米ZnO 2~5重量份,钙钛矿粉体 40~60重量份,碳酸镁3~6重量份,纳米二氧化钛10~20重量份,亚氧化钛5~12重量份。 The composition of the nanocomposite antirust pigment and filler mainly includes 2-5 parts by weight of nano ZnO, 40-60 parts by weight of perovskite powder, 3-6 parts by weight of magnesium carbonate, 10-20 parts by weight of nano-titanium dioxide, suboxide 5-12 parts by weight of titanium.
本发明采用纳米复合防锈颜填料作为防锈颜料代替传统的磷酸盐防锈颜料用于带锈涂装防腐涂料中。制备得到的带锈涂料将有机树脂的韧性、粘结性与无机粉体的刚性充分结合,形成的涂膜具有附着力大、耐蚀、涂膜收缩率低、渗透性好、硬度大的优点,实验室模拟实验表明在带锈钢板表面也具备良好的耐腐蚀性能。 The invention adopts the nanocomposite antirust pigment and filler as the antirust pigment to replace the traditional phosphate antirust pigment for the rust-coated anticorrosion paint. The prepared rust coating fully combines the toughness and cohesiveness of organic resin with the rigidity of inorganic powder, and the formed coating film has the advantages of strong adhesion, corrosion resistance, low shrinkage rate of coating film, good permeability and high hardness , laboratory simulation experiments show that it also has good corrosion resistance on the surface of the rusted steel plate.
具体实施方式 Detailed ways
一种船用带锈涂装低表面处理防锈底漆,它的组成如下:包括甲、乙两组份,一份甲组份包括:环氧树脂30~55重量份,纳米复合防锈颜填料1~20重量份,偶联剂0.5~5重量份,触变剂0.5~3重量份,分散剂0.5~5重量份,消泡剂0.5~2重量份,增韧剂1.5~3重量份,成膜助剂1~5重量份,溶剂20~40重量份。一份乙组份包括:聚酰胺固化剂30~55重量份,溶剂40~50重量份。所述的船用带锈涂装低表面处理防锈底漆由甲组份和乙组份按所需比例混合搅匀而得。 A kind of antirust primer with low surface treatment for marine rust coating, its composition is as follows: including A and B two components, a part of A component includes: 30~55 parts by weight of epoxy resin, nano composite antirust pigments and fillers 1-20 parts by weight, 0.5-5 parts by weight of coupling agent, 0.5-3 parts by weight of thixotropic agent, 0.5-5 parts by weight of dispersant, 0.5-2 parts by weight of defoamer, 1.5-3 parts by weight of toughening agent, 1-5 parts by weight of film-forming auxiliary agent, and 20-40 parts by weight of solvent. One part of component B includes: 30-55 parts by weight of polyamide curing agent, and 40-50 parts by weight of solvent. The low surface treatment antirust primer for marine rust coating is obtained by mixing and stirring components A and B according to the required ratio.
所述的防腐组分由纳米复合防锈颜填料复配而成。所述的溶剂为二甲苯和丁醇混合组成。所述的触变剂为膨土粉、二氧化硅、聚酰胺蜡中的一种。所述的增韧剂为邻苯二甲酸二辛酯。所述的偶联剂为硬脂酸、硬脂酸钙、γ-(2,3-环氧丙氧)丙基三甲氧基硅烷、异丙基三油酸酰氧基钛酸酯、焦磷酸酯钛酸酯、乙撑钛酸酯中的一种。 The anti-corrosion component is compounded by nano-composite anti-rust pigments and fillers. The solvent is a mixture of xylene and butanol. The thixotropic agent is one of bentonite powder, silicon dioxide and polyamide wax. The toughening agent is dioctyl phthalate. The coupling agent is stearic acid, calcium stearate, γ-(2,3-epoxypropoxy)propyl trimethoxysilane, isopropyl trioleate acyloxy titanate, pyrophosphoric acid One of ester titanate and ethylene titanate.
实施例1:一份甲组份包括:环氧树脂30重量份,纳米复合防锈颜填料1重量份,偶联剂0.5重量份,触变剂0.5重量份,分散剂0.5重量份,消泡剂0.5重量份,增韧剂1.5重量份,成膜助剂1重量份,溶剂20重量份。一份乙组份包括:聚酰胺固化剂30重量份,溶剂40重量份。一份甲组份和一份乙组份混合搅匀得到船用带锈涂装低表面处理防锈底漆。防腐组分由纳米复合防锈颜填料复配而成,溶剂为二甲苯和丁醇混合组成,触变剂为二氧化硅,增韧剂为邻苯二甲酸二辛酯,偶联剂为硬脂酸。 Embodiment 1: One part of group A includes: 30 parts by weight of epoxy resin, 1 part by weight of nanocomposite antirust pigment and filler, 0.5 part by weight of coupling agent, 0.5 part by weight of thixotropic agent, 0.5 part by weight of dispersant, defoaming agent 0.5 parts by weight of agent, 1.5 parts by weight of toughening agent, 1 part by weight of film-forming aid, and 20 parts by weight of solvent. One part of component B includes: 30 parts by weight of polyamide curing agent and 40 parts by weight of solvent. One part of component A and one part of component B are mixed well to obtain a low surface treatment anti-rust primer for marine rust coating. The anti-corrosion component is composed of nano-composite anti-rust pigments and fillers, the solvent is a mixture of xylene and butanol, the thixotropic agent is silicon dioxide, the toughening agent is dioctyl phthalate, and the coupling agent is hard Fatty acid.
实施例2:一份甲组份包括:环氧树脂55重量份,纳米复合防锈颜填料20重量份,偶联剂5重量份,触变剂3重量份,分散剂5重量份,消泡剂2重量份,增韧剂3重量份,成膜助剂5重量份,溶剂40重量份。一份乙组份包括:聚酰胺固化剂55重量份,溶剂50重量份。二份甲组份和一份乙组份混合搅匀得到船用带锈涂装低表面处理防锈底漆。防腐组分由纳米复合防锈颜填料复配而成,溶剂为二甲苯和丁醇混合组成,触变剂为二氧化硅,增韧剂为邻苯二甲酸二辛酯,偶联剂为硬脂酸钙。 Embodiment 2: One part of group A includes: 55 parts by weight of epoxy resin, 20 parts by weight of nanocomposite antirust pigments and fillers, 5 parts by weight of coupling agent, 3 parts by weight of thixotropic agent, 5 parts by weight of dispersant, defoaming agent 2 parts by weight of agent, 3 parts by weight of toughening agent, 5 parts by weight of film-forming aid, and 40 parts by weight of solvent. One part of component B includes: 55 parts by weight of polyamide curing agent and 50 parts by weight of solvent. Two parts of component A and one part of component B are mixed and evenly mixed to obtain a low surface treatment anti-rust primer for marine rust coating. The anti-corrosion component is composed of nano-composite anti-rust pigments and fillers, the solvent is a mixture of xylene and butanol, the thixotropic agent is silicon dioxide, the toughening agent is dioctyl phthalate, and the coupling agent is hard Calcium fatty acid.
实施例3:一份甲组份包括:环氧树脂50重量份,纳米复合防锈颜填料5重量份,抗偶联剂1重量份,触变剂3重量份,分散剂1重量份,消泡剂2重量份,增韧剂3重量份,成膜助剂5重量份,溶剂45重量份。一份乙组份包括:聚酰胺50重量份,溶剂45重量份。一点五份甲组份和一份乙组份混合搅匀得到船用带锈涂装低表面处理防锈底漆。防腐组分由纳米复合防锈颜填料复配而成,溶剂为二甲苯和丁醇混合组成,触变剂为二氧化硅,增韧剂为邻苯二甲酸二辛酯,偶联剂为异丙基三油酸酰氧基钛酸酯。 Embodiment 3: One part of group A includes: 50 parts by weight of epoxy resin, 5 parts by weight of nanocomposite antirust pigments and fillers, 1 part by weight of anti-coupling agent, 3 parts by weight of thixotropic agent, 1 part by weight of dispersant, disinfectant 2 parts by weight of foaming agent, 3 parts by weight of toughening agent, 5 parts by weight of film-forming aid, and 45 parts by weight of solvent. One part of component B includes: 50 parts by weight of polyamide and 45 parts by weight of solvent. 1.5 parts of component A and one part of component B are mixed and evenly mixed to obtain a low surface treatment anti-rust primer for marine rust coating. The anti-corrosion component is composed of nano-composite anti-rust pigments and fillers, the solvent is a mixture of xylene and butanol, the thixotropic agent is silicon dioxide, the toughening agent is dioctyl phthalate, and the coupling agent is isophthalic acid Propyl trioleate titanate.
实施例4:一份甲组份包括:环氧树脂45重量份,纳米复合防锈颜填料10重量份,抗偶联剂2重量份,触变剂3重量份,分散剂2重量份,消泡剂2重量份,增韧剂3重量份,成膜助剂5重量份,溶剂43重量份。一份乙组份包括:聚酰胺45重量份,溶剂45重量份。一点七五份甲组份和一份乙组份混合搅匀得到船用带锈涂装低表面处理防锈底漆。防腐组分由纳米复合防锈颜填料复配而成,溶剂为二甲苯和丁醇混合组成,触变剂为二氧化硅,增韧剂为邻苯二甲酸二辛酯,偶联剂为焦磷酸酯钛酸酯。 Embodiment 4: One part of group A includes: 45 parts by weight of epoxy resin, 10 parts by weight of nanocomposite anti-rust pigments and fillers, 2 parts by weight of anti-coupling agent, 3 parts by weight of thixotropic agent, 2 parts by weight of dispersant, disinfectant 2 parts by weight of foaming agent, 3 parts by weight of toughening agent, 5 parts by weight of film-forming aid, and 43 parts by weight of solvent. One part of component B includes: 45 parts by weight of polyamide and 45 parts by weight of solvent. 1.75 parts of component A and one part of component B are mixed and evenly stirred to obtain a low surface treatment antirust primer for marine rust coating. The anti-corrosion component is composed of nano-composite anti-rust pigments and fillers, the solvent is a mixture of xylene and butanol, the thixotropic agent is silicon dioxide, the toughening agent is dioctyl phthalate, and the coupling agent is coke Phosphate titanate.
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US5413628A (en) * | 1993-09-22 | 1995-05-09 | Savin; Ronald R. | Stable inorganic zinc-powder rich coating composition |
CN1876742A (en) * | 2006-04-28 | 2006-12-13 | 彭志伟 | Nanometer modified rust-proof top-coat for metal |
CN103013276A (en) * | 2012-11-30 | 2013-04-03 | 无锡市虎皇漆业有限公司 | Epoxy universal primer for ships and preparation method thereof |
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US5413628A (en) * | 1993-09-22 | 1995-05-09 | Savin; Ronald R. | Stable inorganic zinc-powder rich coating composition |
CN1876742A (en) * | 2006-04-28 | 2006-12-13 | 彭志伟 | Nanometer modified rust-proof top-coat for metal |
CN103013276A (en) * | 2012-11-30 | 2013-04-03 | 无锡市虎皇漆业有限公司 | Epoxy universal primer for ships and preparation method thereof |
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