CN119192958B - A coating, preparation method and application thereof, and coated product - Google Patents
A coating, preparation method and application thereof, and coated product Download PDFInfo
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- CN119192958B CN119192958B CN202411691158.8A CN202411691158A CN119192958B CN 119192958 B CN119192958 B CN 119192958B CN 202411691158 A CN202411691158 A CN 202411691158A CN 119192958 B CN119192958 B CN 119192958B
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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
- 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
- C09D5/18—Fireproof paints including high temperature resistant paints
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Abstract
本发明属于高分子材料技术领域，具体公开了一种涂料及其制备方法与应用、涂覆制品。本发明涂料的原料组分包括：环氧树脂30~105份、固化剂组合物1~100份和片状填料组合物0.3~100份；其中，所述片状填料组合物包括片状云母粉、片状玻璃鳞片和片状红柱石。本发明通过添加片状填料对涂料进行改性，可以在涂料中形成层叠结构，提高涂料的阻隔和屏蔽能力，进一步优化片状填料组分的配方，可以实现增强环氧树脂涂料耐水性、耐热性、耐腐蚀性以及延长使用寿命的效果；该涂料制备的防腐涂层和涂覆制品，具备涂层致密度高、抗渗透性强、耐热性高的特点，可满足高湿热、酸碱腐蚀等严苛环境下应用需求。The present invention belongs to the technical field of polymer materials, and specifically discloses a coating, a preparation method and application thereof, and a coated product. The raw material components of the coating of the present invention include: 30 to 105 parts of epoxy resin, 1 to 100 parts of a curing agent composition, and 0.3 to 100 parts of a flaky filler composition; wherein the flaky filler composition includes flaky mica powder, flaky glass flakes, and flaky andalusite. The present invention modifies the coating by adding flaky fillers, and a stacked structure can be formed in the coating, thereby improving the barrier and shielding capabilities of the coating, and further optimizing the formula of the flaky filler component, so as to achieve the effect of enhancing the water resistance, heat resistance, corrosion resistance, and extending the service life of the epoxy resin coating; the anti-corrosion coating and coated product prepared by the coating have the characteristics of high coating density, strong anti-permeability, and high heat resistance, and can meet the application requirements in harsh environments such as high humidity and heat, acid and alkali corrosion.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a coating, a preparation method and application thereof, and a coated product.
Background
Epoxy resin is an important thermosetting resin, and has good comprehensive properties including excellent mechanical properties, electrical insulation properties, chemical resistance and adhesive force, so that the epoxy resin is widely applied to the fields of coating, adhesives, electronic device packaging, aerospace, microelectronic materials and the like. The paint using epoxy resin as main film forming matter is called epoxy resin paint, which is one of widely used protective paint, and the formed paint has shielding effect on corrosive medium and can passivate the protected metal to play electrochemical role.
In the related art, bisphenol a epoxy resin is taken as an example, and epoxy resin fused powder based on bisphenol a epoxy resin only contains hydroxyl groups which are easy to absorb water in a crosslinked network structure and has low crosslinking density, so that the problems of poor wet heat stability, poor dielectric property, low high-temperature residual mass fraction and the like exist, and the application of the coating prepared based on the epoxy resin fused powder in extremely severe environments such as high wet heat, acid-base corrosion and the like is greatly limited.
Therefore, the coating material which can be applied in extremely severe environments such as high humidity and heat, acid-base corrosion and the like and has good corrosion resistance, high temperature resistance and strong adhesion is an urgent problem to be solved.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a coating, a preparation method, application and a coated product thereof, and aims to solve the problem that the coating prepared from the conventional epoxy resin is difficult to meet the application requirements in extremely severe environments such as high humidity and heat, acid-base corrosion and the like. According to the invention, the special filler component is added into the epoxy resin coating to improve the barrier and shielding capability of the coating, so that the high temperature resistance, water resistance and corrosion resistance modification of the epoxy resin coating are realized, and the corrosion resistance, the bonding performance and the high temperature resistance of the coating are further improved by combining the action of the curing agent composition, so that the coating and the coated product can meet the application requirements under extremely severe environments such as high humidity and heat, acid-base corrosion and the like.
The embodiment of the first aspect of the invention provides a coating, which comprises, by weight, 30-105 parts of epoxy resin, 1-100 parts of a curing agent composition and 0.3-100 parts of a platy filler composition;
wherein the flaky filler composition comprises flaky mica powder, flaky glass flakes and flaky andalusite.
The coating provided by the embodiment of the invention has at least the following beneficial effects that the coating provided by the invention can form a laminated structure in the coating by adding the flaky filler to modify the coating, so that the blocking and shielding capability of the coating is improved, and further, the formula adjustment of flaky filler components (flaky mica powder, flaky glass flakes and flaky andalusite) is carried out, so that the high-temperature resistance, water resistance and corrosion resistance modification of the epoxy resin coating are realized, wherein the laminated structure of the flaky mica powder can effectively block the permeation of moisture and gas, enhance the corrosion resistance of the coating, improve the water resistance and weather resistance of the coating and the mechanical strength, hardness and impact resistance of the coating, and the flaky glass flakes can slow down the permeation of chemicals and moisture, block corrosive substances, prolong the service life of the coating, and can obviously improve the wear resistance of the coating, and the flaky andalusite can enhance the oxidation resistance of the coating, improve the high-temperature resistance of the coating, prevent oxidative damage at high temperature and improve the wear resistance and the scratch resistance of the coating, and prolong the service life of the coating. Therefore, the invention can realize the effects of enhancing the water resistance, heat resistance and corrosion resistance of the epoxy resin coating and prolonging the service life through the modification of the epoxy resin composition to the coating. Finally, the epoxy resin coating modified by the flaky filler component can obviously improve the corrosion resistance, the adhesive property and the high temperature resistance of the coating, and can meet the application requirements in extremely severe environments such as high humidity and heat, acid-base corrosion and the like.
In some embodiments of the invention, the raw material components of the coating comprise, by weight, 40-90 parts of epoxy resin, 10-40 parts of a curing agent composition and 10-80 parts of a sheet filler composition.
The invention optimizes the formula dosage of main components in the coating, further improves the curing effect of the curing agent composition on the epoxy resin, and realizes better effect improvement effects on the reduction of the processing temperature, the enhancement of heat resistance, the enhancement of permeability resistance or the enhancement of rust resistance of the epoxy resin coating.
In some embodiments of the invention, the flaky filler composition comprises, by weight, 0.1-30 parts of flaky mica powder, 0.1-30 parts of flaky glass flakes and 0.1-50 parts of flaky andalusite.
In some embodiments of the invention, the weight ratio of the flaky mica powder, the flaky glass flakes and the flaky andalusite in the flaky filler composition is 1 (1-5): 1-10.
The invention optimizes the dosage proportion of each component in the flaky filler composition, and when the weight ratio of flaky mica powder to flaky glass flakes to flaky andalusite is in the range, the corrosion resistance and the wet heat stability of the coating prepared by the paint can be further improved.
In some embodiments of the invention, the weight ratio of the flaky mica powder, the flaky glass flakes and the flaky andalusite in the flaky filler composition is 1 (1-2): 2-5. Including any and all ranges and any subranges therein. For example, 1:1:5, 1:2:4, 1:1:3, 1:2:5. Thus, in the above-mentioned range, the coating material of the present invention has excellent mechanical properties, corrosion resistance and wet heat stability.
In some embodiments of the invention, the flake filler composition has a ratio of caliper to thickness in the range of 10 to 25:1.
The invention controls the ratio of the average diameter and the thickness of the flaky filler, and avoids uneven dispersion of the flaky filler in the coating due to agglomeration caused by the excessively high ratio of the flaky filler, thereby influencing the improvement of the coating performance, while the excessively low ratio of the flaky filler is close to the blocky filler, and the high temperature resistance, the water resistance and the corrosion resistance modification of the epoxy resin coating are difficult to realize.
In some embodiments of the invention, the hardener composition includes an organic amine hardener, a phenolic hardener, and a metal salt hardener.
The invention carries out curing modification on the epoxy resin coating by adjusting the formula of components of the curing agent composition (comprising the organic amine curing agent, the phenolic curing agent and the metal salt curing agent), thereby realizing the effects of low processing temperature, enhanced heat resistance, enhanced permeability resistance and enhanced rust resistance of the cured epoxy resin coating. In the combination of the curing agent composition of the coating, the organic amine curing agent contains N-H bonds, can react with epoxy groups of epoxy resin, wherein primary amine groups react with the epoxy groups to generate secondary amine and hydroxyl groups, so that the heat-resistant stability of a crosslinked network is improved, phenolic hydroxyl groups of the phenolic curing agent react with the epoxy groups to generate ether bonds and hydroxyl groups, the ether bonds can improve the overall flexibility of the epoxy resin coating, and the metal salt curing agent is used as an auxiliary curing agent, so that the rust resistance of the epoxy coating can be improved. The curing agent composition is used for curing the epoxy resin composition, and finally, the corrosion resistance, the adhesive property and the high temperature resistance of the coating are obviously improved, so that the application requirements under extremely severe environments such as high humidity and heat, acid-base corrosion and the like can be met.
In some embodiments of the invention, the organic amine curing agent comprises at least one of 4,4'- (1, 4-benzenedioxy) diphenylamine, 4' -bis (4-aminophenoxy) diphenyl sulfone, 4 '-bis (3-aminophenoxy) diphenyl sulfone, 4' -diaminodiphenyl methane.
The organic amine curing agent used in the invention contains N-H bond, and can react with epoxy groups of epoxy resin, for example, primary amine reacts with epoxy groups to generate secondary amine and hydroxyl, and the epoxy resin coating cured by the organic amine curing agent has high heat resistance and high brittleness.
In some embodiments of the present invention, the phenolic curing agent comprises at least one of cardanol, phenolic resin.
The phenolic curing agent used in the invention contains phenol groups, and the phenolic hydroxyl groups react with the epoxy groups to generate ether bonds and hydroxyl groups, so that the epoxy resin coating cured by the phenolic curing agent has low processing temperature, good flexibility and insufficient heat resistance.
In some embodiments of the invention, the metal salt curing agent comprises zinc dithiophosphate-O, O-di-C 1-14 -alkyl ester.
The metal salt curing agent used in the invention is a zinc modified organic curing agent, and can be used as an auxiliary curing agent to enhance the rust resistance of the epoxy coating.
The invention realizes the effects of low processing temperature, enhanced heat resistance, enhanced permeation resistance and enhanced rust resistance of the cured epoxy resin coating by utilizing the combination of the curing agents. In the combination of the curing agent composition of the coating, the organic amine curing agent contains N-H bonds, can react with epoxy groups of epoxy resin, wherein primary amine groups react with the epoxy groups to generate secondary amine and hydroxyl groups, so that the heat-resistant stability of a crosslinked network is improved, phenolic hydroxyl groups of the phenolic curing agent react with the epoxy groups to generate ether bonds and hydroxyl groups, the ether bonds can improve the overall flexibility of the epoxy resin coating, and the metal salt curing agent is used as an auxiliary curing agent, so that the rust resistance of the epoxy coating can be improved. Therefore, the epoxy resin is cured by utilizing the combination of the organic amine curing agent, the phenolic curing agent and the metal salt curing agent, so that the corrosion resistance and the high temperature resistance of the coating can be obviously improved, and further the application requirements of the coating in extremely severe environments such as high humidity and heat, acid-base corrosion and the like can be met.
In some embodiments of the invention, the curing agent composition comprises, by weight, 8-14 parts of an organic amine curing agent, 4-10 parts of a phenolic curing agent, and 1-19 parts of a metal salt curing agent.
In some embodiments of the present invention, the epoxy resin is bisphenol a type epoxy resin, and is at least one selected from the group consisting of E51 epoxy resin, E44 epoxy resin, E20 epoxy resin, and E12 epoxy resin.
The second aspect of the invention provides a preparation method of the paint, which comprises the following steps:
mixing the raw material components according to the weight portions, heating, solidifying and crushing to obtain the coating.
The preparation method provided by the invention has the characteristics of simple process, mild reaction conditions, easiness in operation and high production efficiency, and is suitable for large-scale production and application.
In some embodiments of the invention, the heating and curing process is to raise the temperature to 30-120 ℃ and cure for 10-60 min. The heating and curing process is gradient heating and curing, wherein the gradient heating and curing comprises two stages, namely heating to 30-100 ℃ and curing for 5-30 min, and heating to 80-120 ℃ and curing for 5-30 min.
In some embodiments of the invention, the method of comminution is comminution using a mill.
In some embodiments of the invention, the coating is an epoxy sinter powder.
In some embodiments of the invention, the epoxy resin sintered powder can be directly used as coating powder to carry out electrostatic spraying on a metal substrate, or can be prepared into slurry to carry out coating.
The third aspect of the invention provides an application of the coating or the coating prepared by the preparation method in coating of a metal substrate.
The coating obtained by the invention has the characteristics of high heat resistance, easy processing and high cohesiveness, and can be applied to metal substrate coating to form a coating with high density, high permeation resistance and high heat resistance, thereby meeting the application requirements in extremely severe environments.
The invention provides an anti-corrosion coating, and the preparation raw materials of the anti-corrosion coating comprise the coating or the coating prepared by the preparation method.
The anticorrosive coating provided by the invention is obtained by coating the paint, so that the anticorrosive coating also has the technical effects of the paint. The coating is coated on a metal substrate, so that the formed coating has high density, high permeation resistance and high heat resistance, and can meet the application requirements in extremely severe environments.
In some embodiments of the present invention, the above-mentioned coating may be formulated into a slurry, and then uniformly coated on the surface of the metal substrate by blade coating, spin coating or spray coating, and then cured to obtain the anti-corrosion coating. The coating method may be any method known in the art, and is not limited herein.
In some embodiments of the invention, the thickness of the corrosion-resistant coating is 100-500 μm. Including any and all ranges and any subranges therein. Examples include 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 400 μm and 500 μm. Therefore, when the thickness of the anti-corrosion coating is in the range, the anti-corrosion coating has a good protection effect and is not easy to fall off.
In a fifth aspect, the invention provides a coated article comprising a metal substrate and a coating on the surface of the metal substrate, wherein the coating is the anti-corrosion coating.
In some embodiments of the invention, the metal substrate comprises elemental metal and metal alloys, such as tin, titanium alloys, stainless steel, and the like.
The sixth aspect of the invention provides a home appliance, wherein the preparation raw materials of the home appliance comprise the paint or the anti-corrosion coating.
In some embodiments of the present invention, the home appliances include refrigeration appliances, air conditioners, cleaning appliances, kitchen appliances, electric heating appliances, audio-visual appliances, and water heaters.
The seventh aspect of the invention provides the use of the coating or the corrosion-resistant coating described above in a hot humid environment or an acid-base environment.
According to some embodiments of the invention, the humid and hot environment refers to an environment temperature above 35 ℃ and a relative humidity of the environment above 70%.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
In the description of the present invention, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
In the description of the present invention, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. Unless otherwise indicated, the various reactions or operational steps may or may not be performed sequentially. Preferably, the reaction process in the present invention is carried out sequentially.
The following examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the product specifications. All reagents or equipment were commercially available as conventional products without the manufacturer's knowledge.
The first aspect of the invention provides a coating, which comprises, by weight, 30-105 parts of epoxy resin, 1-100 parts of a curing agent composition and 0.3-100 parts of a sheet filler composition;
wherein the flaky filler composition comprises flaky mica powder, flaky glass flakes and flaky andalusite.
The coating provided by the embodiment of the invention can form a laminated structure in the coating by adding the flaky filler component to modify the coating, so that the blocking and shielding capability of the coating is improved, and further, the formula adjustment and the component optimization of the flaky filler component (flaky mica powder, flaky glass flakes and flaky andalusite) are carried out, so that the high temperature resistance, the water resistance and the corrosion resistance of the epoxy resin coating are better improved, wherein the laminated structure of the flaky mica powder can effectively block the penetration of moisture and gas, enhance the corrosion resistance of the coating, improve the water resistance and the weather resistance of the coating and the mechanical strength, the hardness and the impact resistance of the coating, and the flaky glass flakes can slow down the penetration of chemicals and moisture, block corrosive substances, prolong the service life of the coating, and can obviously improve the wear resistance of the coating, and the flaky andalusite can enhance the oxidation resistance of the coating, improve the high temperature resistance of the coating, prevent oxidative damage at high temperature and improve the wear resistance and the scratch resistance of the coating, and prolong the service life of the coating. Therefore, the modified epoxy resin composition can enhance the effects of water resistance, heat resistance, corrosion resistance and service life of the epoxy resin coating. Finally, the embodiment of the invention utilizes the flaky filler component to modify the epoxy resin coating, can obviously improve the corrosion resistance, the adhesive property and the high temperature resistance of the coating, and can meet the application requirements under extremely severe environments such as high humidity and heat, acid-base corrosion and the like.
In some embodiments of the invention, the raw material components of the coating comprise, by weight, 40-90 parts of epoxy resin, 10-40 parts of a curing agent composition and 10-80 parts of a sheet filler composition.
In some embodiments of the invention, the raw material components of the coating comprise, by weight, 50-80 parts of epoxy resin, 16-40 parts of a curing agent composition and 10-80 parts of a sheet filler composition.
In some embodiments of the invention, the flaky filler composition comprises, by weight, 0.1-30 parts of flaky mica powder, 0.1-30 parts of flaky glass flakes and 0.1-40 parts of flaky andalusite.
In some embodiments of the invention, the flaky filler composition comprises, by weight, 1-20 parts of flaky mica powder, 1-25 parts of flaky glass flakes and 1-40 parts of flaky andalusite.
In some embodiments of the invention, the flaky filler composition comprises, by weight, 3-15 parts of flaky mica powder, 5-20 parts of flaky glass flakes and 10-35 parts of flaky andalusite.
In some embodiments of the invention, the weight ratio of the flaky mica powder, the flaky glass flakes and the flaky andalusite in the flaky filler composition is 1 (1-5): 1-10.
The invention optimizes the dosage proportion of each component in the flaky filler composition, and when the weight ratio of flaky mica powder to flaky glass flakes to flaky andalusite is in the range, the corrosion resistance and the wet heat stability of the coating prepared by the paint can be further improved.
In some embodiments of the invention, the weight ratio of the flaky mica powder, the flaky glass flakes and the flaky andalusite in the flaky filler composition is 1 (1-2): 2-5. Including any and all ranges and any subranges therein. For example, 1:1:5, 1:2:4, 1:1:3, 1:2:5. Thus, in the above-mentioned range, the coating of the embodiment of the invention has excellent mechanical properties, corrosion resistance and wet heat stability.
In some embodiments of the invention, the flake filler composition has a ratio of caliper to thickness in the range of 10 to 25:1.
The ratio of the diameter to the thickness is the ratio of the average diameter to the thickness of the flaky filler, the embodiment of the invention controls the ratio of the diameter to the thickness of the flaky filler composition added into the coating, avoids uneven dispersion of the flaky filler in the coating due to agglomeration caused by the excessively high ratio of the diameter to the thickness, influences the improvement of the coating performance, and the excessively low ratio of the diameter to the thickness of the flaky filler is close to the blocky filler, so that the high temperature resistance, the water resistance and the corrosion resistance modification of the epoxy resin coating are difficult to realize.
In some embodiments of the invention, the flake filler composition has a ratio of caliper in the range of 15 to 20:1.
In some embodiments of the invention, the hardener composition includes an organic amine hardener, a phenolic hardener, and a metal salt hardener.
According to the embodiment of the invention, the epoxy resin coating is cured and modified by adjusting the formula of the components of the curing agent composition (comprising the organic amine curing agent, the phenolic curing agent and the metal salt curing agent), so that the cured epoxy resin coating has the effects of low processing temperature, enhanced heat resistance, enhanced permeability resistance and enhanced rust resistance. In the combination of the curing agent composition of the coating, the organic amine curing agent contains N-H bonds, can react with epoxy groups of epoxy resin, wherein primary amine groups react with the epoxy groups to generate secondary amine and hydroxyl groups, so that the heat-resistant stability of a crosslinked network is improved, phenolic hydroxyl groups of the phenolic curing agent react with the epoxy groups to generate ether bonds and hydroxyl groups, the ether bonds can improve the overall flexibility of the epoxy resin coating, and the metal salt curing agent is used as an auxiliary curing agent, so that the rust resistance of the epoxy coating can be improved. The curing agent composition is used for curing the epoxy resin composition, and finally, the corrosion resistance, the adhesive property and the high temperature resistance of the coating are obviously improved, so that the application requirements under extremely severe environments such as high humidity and heat, acid-base corrosion and the like can be met.
In some embodiments of the invention, the organic amine curing agent comprises at least one of 4,4'- (1, 4-benzenedioxy) diphenylamine, 4' -bis (4-aminophenoxy) diphenyl sulfone, 4 '-bis (3-aminophenoxy) diphenyl sulfone, 4' -diaminodiphenyl methane.
In some embodiments of the present invention, the organic amine curing agent is selected from at least one of 4,4'- (1, 4-benzenedioxy) diphenylamine, 4' -bis (4-aminophenoxy) diphenyl sulfone, 4 '-bis (3-aminophenoxy) diphenyl sulfone, 4' -diaminodiphenyl methane.
The organic amine curing agent used in the embodiment of the invention contains N-H bond, and can react with epoxy groups of epoxy resin, for example, primary amine reacts with epoxy groups to generate secondary amine and hydroxyl, and the epoxy resin coating cured by the organic amine curing agent has high heat resistance and high brittleness.
In some embodiments of the invention, the phenolic curing agent comprises at least one of cardanol, phenolic resin.
In some embodiments of the present invention, the phenolic curing agent is selected from at least one of cardanol, phenolic resin.
The phenolic curing agent used in the embodiment of the invention contains phenol groups, the phenolic hydroxyl groups of the phenolic curing agent react with the epoxy groups to generate ether bonds and hydroxyl groups, and the epoxy resin coating cured by the phenolic curing agent has low processing temperature, good flexibility and insufficient heat resistance.
In some embodiments of the invention, the metal salt curative comprises zinc salts of dithiophosphoric acid-O, O-di-C 1-14 -alkyl esters.
In some embodiments of the invention, the metal salt curative is a zinc salt of a dithiophosphoric acid-O, O-di-C 1-14 -alkyl ester.
The metal salt curing agent used in the embodiment of the invention is a zinc modified organic curing agent, and the zinc modified organic curing agent is used as an auxiliary curing agent, so that the rust resistance of the epoxy coating can be enhanced.
The embodiment of the invention utilizes the combination of the curing agents to realize the effects of low processing temperature, enhanced heat resistance, enhanced permeation resistance and enhanced rust resistance of the cured epoxy resin coating. In the combination of the curing agent composition of the coating, the organic amine curing agent contains N-H bonds, can react with epoxy groups of epoxy resin, wherein primary amine groups react with the epoxy groups to generate secondary amine and hydroxyl groups, so that the heat-resistant stability of a crosslinked network is improved, phenolic hydroxyl groups of the phenolic curing agent react with the epoxy groups to generate ether bonds and hydroxyl groups, the ether bonds can improve the overall flexibility of the epoxy resin coating, and the metal salt curing agent is used as an auxiliary curing agent, so that the rust resistance of the epoxy coating can be improved. Therefore, the epoxy resin is cured by the combination of the organic amine curing agent, the phenolic curing agent and the metal salt curing agent, so that the corrosion resistance and the high temperature resistance of the coating can be obviously improved, and further the application requirements of the coating in extremely severe environments such as high humidity and heat, acid-base corrosion and the like can be met.
In some embodiments of the invention, the curing agent composition comprises, by weight, 8-14 parts of an organic amine curing agent, 4-10 parts of a phenolic curing agent and 1-19 parts of a metal salt curing agent.
In some embodiments of the invention, the curing agent composition comprises 9-13 parts by weight of an organic amine curing agent, 4-9 parts by weight of a phenolic curing agent and 2-15 parts by weight of a metal salt curing agent.
In some embodiments of the present invention, the epoxy resin is bisphenol a type epoxy resin, and is at least one selected from the group consisting of E51 epoxy resin, E44 epoxy resin, E20 epoxy resin, and E12 epoxy resin.
The second aspect of the invention provides a preparation method of the paint, which comprises the following steps:
mixing the raw material components according to the weight portions, heating, solidifying and crushing to obtain the coating.
The preparation method provided by the embodiment of the invention has the characteristics of simple process, mild reaction conditions, easiness in operation and high production efficiency, and is suitable for large-scale production and application.
In some embodiments of the invention, the mixing and the heat curing are performed under an inert atmosphere or an air atmosphere.
In some embodiments of the invention, the mixing and the heat curing are performed under an inert atmosphere.
In some embodiments of the invention, the heating and curing process is to raise the temperature to 30-120 ℃ and cure for 10-60 min. The heating and curing process is gradient heating and curing, wherein the gradient heating and curing comprises two stages, namely heating to 30-100 ℃ and curing for 5-30 min, and heating to 80-120 ℃ and curing for 5-30 min.
In some embodiments of the invention, the heating and curing process is to raise the temperature to 30-100 ℃ and cure for 10-60 min. The heating and curing process is gradient heating and curing, wherein the gradient heating and curing comprises two stages, namely heating to 30-80 ℃ and curing for 5-30 min, and heating to 80-100 ℃ and curing for 5-30 min.
In some embodiments of the invention, the method of comminution is comminution using a mill.
In some embodiments of the invention, the coating is an epoxy sinter powder.
In some embodiments of the invention, the epoxy resin sintered powder can be directly used as coating powder to carry out electrostatic spraying on a metal substrate, or can be prepared into slurry to carry out coating.
The third aspect of the invention provides an application of the coating or the coating prepared by the preparation method in coating of a metal substrate.
The coating obtained by the embodiment of the invention has the characteristics of high heat resistance, easy processing and high cohesiveness, and can be applied to metal substrate coating to form a coating with high density, high permeation resistance and high heat resistance, so that the coating can meet the application requirements in extremely severe environments.
The invention provides an anti-corrosion coating, and the preparation raw materials of the anti-corrosion coating comprise the coating or the coating prepared by the preparation method.
The anti-corrosion coating provided by the embodiment of the invention is obtained by coating the paint, so that the anti-corrosion coating also has the technical effects of the paint. According to the embodiment of the invention, the coating is coated on the metal substrate, so that the formed coating has high density, high permeation resistance and high heat resistance, and can meet the application requirements in extremely severe environments.
In some embodiments of the present invention, the above-mentioned coating may be formulated into a slurry, and then uniformly coated on the surface of the metal substrate by blade coating, spin coating or spray coating, and then cured to obtain the anti-corrosion coating. The coating method may be any method known in the art, and is not limited herein.
In some embodiments of the invention, the thickness of the corrosion-resistant coating is 100-500 μm. Including any and all ranges and any subranges therein. Examples include 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 400 μm and 500 μm. Therefore, when the thickness of the anti-corrosion coating is in the range, the anti-corrosion coating has a good protection effect and is not easy to fall off.
In a fifth aspect, the invention provides a coated article comprising a metal substrate and a coating on the surface of the metal substrate, wherein the coating is the anti-corrosion coating.
In some embodiments of the invention, the metal substrate comprises elemental metal and metal alloys, such as tin, titanium alloys, stainless steel, and the like.
The sixth aspect of the invention provides a home appliance, wherein the preparation raw materials of the home appliance comprise the paint or the anti-corrosion coating.
In some embodiments of the invention, the home appliances include refrigeration appliances (e.g., household refrigerators, cold beverages, etc.), air conditioners (e.g., room air conditioners, fans, ventilators, hot and cold air cleaners, air dehumidifiers, air coolers, humidifiers, etc.), cleaning appliances (e.g., washing machines, dryers, electric irons, cleaners, floor waxers, sweeping robots, etc.), kitchen appliances (e.g., cookers, microwave ovens, induction cookers, electric ovens, rice cookers, dish washers, food processors, etc.), electric heating appliances (e.g., space heaters), acoustic image appliances (e.g., pico projectors, televisions, radios, audio recorders, video recorders, cameras, audio combiners, etc.), water heaters (e.g., air energy water heaters, solar water heaters, electric water heaters, gas fired water heaters, etc.).
The seventh aspect of the invention provides the use of the coating or the corrosion-resistant coating described above in a hot humid environment or an acid-base environment.
According to some embodiments of the invention, the humid and hot environment refers to an environment temperature above 35 ℃ and a relative humidity of the environment above 70%.
Further, the sources of some of the raw materials used in the examples and comparative examples of the present invention are as follows:
Bisphenol A type epoxy resins, E51 epoxy resin, E20 epoxy resin, E44 epoxy resin were all purchased from Shanghai Hua Yi resin Co.
The platy mica powder was purchased from Jiangsu Bosi chemical technology Co.
Sheet glass flakes were purchased from japan plate nitrocellulose products limited.
The flaky andalusite was purchased from xingxin Rong Yilong andalusite limited.
Organic amine curing agents, 4' - (1, 4-benzenedioxy) diphenylamine, 4' -bis (4-aminophenoxy) diphenyl sulfone, and 4,4' -diaminodiphenyl methane were all purchased from Shanghai Ala Biochemical technology Co., ltd.
Phenolic curing agents, cardanol and phenolic resin, are all purchased from Beijing carboline technologies.
The metal salt curing agent is dithiophosphoric acid-O, O-di-C 1-14 -alkyl ester zinc salt, CAS number 68649-42-3, and is commercially available.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims.
Example 1
This example provides a coating and uses the coating to prepare a coating.
The coating comprises, by weight, 75 parts of E51 epoxy resin, 22 parts of a curing agent composition and 40 parts of a platy filler composition, wherein the curing agent composition comprises 10 parts of 4,4' - (1, 4-benzenedioxy) diphenylamine, 5 parts of cardanol and 7 parts of zinc dithiophosphate-O, O-di- 1-14 -alkyl ester, and the platy filler composition comprises 5 parts of platy mica powder, 10 parts of platy glass flakes and 25 parts of platy andalusite. Wherein, the diameter-thickness ratio of the flaky filler composition is 15-20:1.
Mixing the preparation raw materials in parts by weight, and curing for 10min at 80 ℃ and 10min at 100 ℃ under inert atmosphere. And then crushing the cured pre-polymerized resin by using an ACM (alternating current) pulverizer to obtain coating powder, preparing the coating powder into slurry, spraying by taking tin plate as a metal substrate, and performing thermal curing for 15min in an air environment at 230 ℃ to form a final coating.
Wherein the thickness of the coating is 250 μm.
Example 2
The difference between the embodiment and the embodiment 1 is that the formula of the coating is different, in the embodiment, the preparation raw materials comprise, by weight, 60 parts of E20 epoxy resin, 27 parts of a curing agent composition and 45 parts of a platy filler composition, wherein the curing agent composition comprises 12 parts of 4,4' -bis (4-aminophenoxy) diphenyl sulfone, 8 parts of cardanol and 7 parts of zinc dithiophosphate-O, O-di- 1-14 -alkyl ester, and the platy filler composition comprises 10 parts of platy mica powder, 10 parts of platy glass flakes and 25 parts of platy andalusite. The other components are the same as in example 1.
Example 3
The difference between the embodiment and the embodiment 1 is that the formula of the coating is different, in the embodiment, the preparation raw materials comprise 65 parts by weight of E44 epoxy resin, 25 parts by weight of curing agent composition and 45 parts by weight of flaky filler composition, wherein the curing agent composition comprises 10 parts by weight of 4,4' -diaminodiphenyl methane, 5 parts by weight of phenolic resin, 10 parts by weight of zinc dithiophosphate-O, O-di- 1-14 -alkyl ester, 10 parts by weight of flaky mica powder, 10 parts by weight of flaky glass flake and 25 parts by weight of flaky andalusite. The other components are the same as in example 1.
Example 4
This example differs from example 1 only in that the flaky filler composition of this example is 5 parts of flaky mica powder, 5 parts of flaky glass flakes and 5 parts of flaky andalusite. The other components are the same as in example 1.
Example 5
This example differs from example 1 only in that the flaky filler composition of this example is 5 parts of flaky mica powder, 10 parts of flaky glass flakes and 30 parts of flaky andalusite. The other components are the same as in example 1.
Example 6
This example differs from example 1 only in that the flaky filler composition of this example is 5 parts of flaky mica powder, 5 parts of flaky glass flakes and 50 parts of flaky andalusite. The other components are the same as in example 1.
Comparative example 1
The comparative example is different from the example 1 in the formula of the coating, and comprises 75 parts by weight of E44 epoxy resin, 22 parts by weight of a curing agent composition and 40 parts by weight of a flaky filler composition, wherein the curing agent composition comprises 10 parts by weight of 4,4' - (1, 4-dioxy) diphenylamine, 5 parts by weight of cardanol and 7 parts by weight of zinc salt of dithiophosphoric acid-O, O-di- 1-14 -alkyl ester, and the flaky filler composition comprises 10 parts by weight of flaky glass flakes and 30 parts by weight of flaky andalusite and does not contain flaky mica powder. The other components are the same as in example 1.
Comparative example 2
The comparative example is different from the example 1 in the formula of the coating, and in the comparative example, the raw materials for preparation are 75 parts by weight of E44 epoxy resin, 22 parts by weight of curing agent composition and 35 parts by weight of flaky filler composition, wherein the curing agent composition comprises 10 parts by weight of 4,4' - (1, 4-benzene dioxy) diphenylamine, 5 parts by weight of cardanol and 7 parts by weight of zinc salt of dithiophosphoric acid-O, O-di- 1-14 -alkyl ester, and the flaky filler composition comprises 5 parts by weight of flaky mica powder and 30 parts by weight of flaky andalusite and does not contain flaky glass flakes. The other components are the same as in example 1.
Comparative example 3
The comparative example is different from the example 1 in the formula of the coating, and comprises 75 parts by weight of E44 epoxy resin, 22 parts by weight of a curing agent composition and 35 parts by weight of a flaky filler composition, wherein the curing agent composition comprises 10 parts by weight of 4,4' - (1, 4-dioxy) diphenylamine, 5 parts by weight of cardanol and 7 parts by weight of zinc salt of dithiophosphoric acid-O, O-di- 1-14 -alkyl ester, and the flaky filler composition comprises 10 parts by weight of flaky mica powder and 20 parts by weight of flaky glass flakes and does not contain flaky andalusite. The other components are the same as in example 1.
Comparative example 4
The difference between the comparative example and the example 1 is that the curing method is different, in the comparative example, the curing method under the inert atmosphere is to raise the temperature in a gradient way at 120-150 ℃ for 20min. The other components are the same as in example 1.
Comparative example 5
The comparative example differs from example 1 in that a tin plate (iron and steel (tin) limited in shan harbor) was used as a test plate, and the surface was not covered with a protective coating.
Comparative example 6
The difference between this comparative example and example 1 is that a tin plate was used as a test panel, and a Degaku electrostatic powder coating (product number: RAL 1003) was applied to the surface, and the coating was cured at 230℃for 1 hour after the application, with a cured coating thickness of 250. Mu.m.
Test case
1. Drawing strength test (GB/T39289-2020; peel strength after bonding of metal and plastic) the coatings of examples 1-2 of the present invention were tested for drawing strength based on stainless steel substrates.
As a result of the drawing strength test, the drawing strength of the paint based on the stainless steel substrate in example 1 was 3.84MPa, and the drawing strength of the paint based on the stainless steel substrate in example 2 was 5.41MPa. Test results show that the coating formed by the paint has the characteristics of high density and strong adhesion.
2. The corrosion resistance of the coating is evaluated by carrying out a scratching test on the coating in examples 1-6 and comparative examples 1-6, wherein the method comprises the steps of respectively taking prepared coating samples, scratching the surfaces of the prepared coating samples, enabling the scratch sizes of the surfaces of the samples to be consistent, placing the coating samples in a salt spray test box, and detecting the surfaces of the samples after 7 days of salt spray test, wherein the detection standard is GB/T10125-2021. The test results are shown in table 1:
Table 1 results of salt spray test 7 days after coating cross-over of examples and comparative coating samples
The corrosion resistance of the anti-corrosion coating is evaluated through the above cross-cut experiment, no obvious change exists before and after the experiment of the surface coating of examples 1-3, no corrosion condition exists except that the surface coating is exposed to the corrosion of an external substrate, examples 4-6 have the condition that the surface coating is slightly foamed, the addition of three fillers in the coating needs to be adjusted to achieve the best coating surface effect, the partial falling of the surface coating of comparative examples 1-3 shows that the reasonable combination of flaky mica powder, flaky glass flakes and flaky andalusite in flaky fillers in the epoxy resin coating is needed to achieve the improvement of the better corrosion resistance of the coating, the gradient heating method of curing in the preparation process of the coating of comparative example 4 shows that the curing gradient heating method of the coating of the invention needs to be accurately controlled, otherwise uniform coating cannot be formed, the corrosion at the cross-cut of comparative example 5 is serious and the corrosion is outwards derived, the corrosion at the cross-cut of the comparative example 6 is serious and the corrosion at the cross-cut is outwards derived, and the detection results show that the coating prepared by the coating of the invention can be coated on a metal substrate to better corrosion resistance.
3. The high temperature resistance and long-acting corrosion resistance acceleration tests of the examples 1-6 and the comparative examples 1-6 are carried out by taking coating samples respectively, immersing the coating samples in hot water at 170 ℃ for 2 days in a high temperature resistant high pressure kettle under 0.65MPa, and observing the surfaces of the samples and detecting the electrochemical impedance (detection standard GB/T39482.3-2020). The test results are shown in table 2:
TABLE 2 accelerated test results of high temperature resistance, long-lasting Corrosion resistance of examples and comparative examples coating samples
For the coatings prepared in the examples and the comparative examples, the initial electrochemical impedance is 10 12 Ω, after the coatings are soaked in hot water at 170 ℃ and 0.65MPa for 2 days in a high-temperature-resistant autoclave, the electrochemical impedance of the surface coatings in the examples 1-3 is not obviously changed and is only reduced to 10 10 Ω, and examples 4-6 show that the coatings have punctiform hard bubbles and the electrochemical impedance is reduced to 10 8 Ω. The surface coating of comparative examples 1-3 had spot-like bubbling, the electrochemical impedance was reduced to 10 6 Ω, the surface coating of comparative example 4 had severe bubbling, the electrochemical impedance was reduced to 10 6 Ω, and the surface of comparative example 5 had severe corrosion because the test panel was not protected by the coating, the coating of comparative example 6 had poor high temperature and corrosion resistance, and the surface coating had fallen off and had no corrosion protection.
The test results show that the coating prepared by the scheme of the invention has good high-temperature resistance and long-acting corrosion resistance, can play a good role in protecting a base material, and the addition of the flaky filler in the coating can improve the coating structure, effectively block the penetration of moisture, gas and the like, and can also improve the high-temperature resistance of the coating, thereby improving the corrosion resistance of the coating, preventing the damage at high temperature and prolonging the service life. The absence of the platy fillers used in the invention in comparative examples 1-3, namely one of platy mica powder, platy glass flakes and platy andalusite, can affect the high temperature resistance and corrosion resistance of the coating, the gradient temperature rise in the curing process of the coating in comparative example 4 is not precisely controlled, a uniform coating is difficult to form, and the protection performance of the coating is also affected.
In summary, the modification effect of the flaky filler on the epoxy resin coating can enhance the effects of water resistance, heat resistance, corrosion resistance and service life of the epoxy resin coating. Finally, the epoxy resin coating modified by the flaky filler component can obviously improve the corrosion resistance, the adhesive property and the high temperature resistance of the coating, and can meet the application requirements in extremely severe environments such as high humidity and heat, acid-base corrosion and the like.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (12)
1. The coating is characterized by comprising, by weight, 40-90 parts of epoxy resin, 10-40 parts of a curing agent composition and 10-80 parts of a sheet filler composition;
Wherein the flaky filler composition comprises flaky mica powder, flaky glass flakes and flaky andalusite;
the weight ratio of the flaky mica powder to the flaky glass flakes to the flaky andalusite in the flaky filler composition is 1 (1-2) (2-5);
the coating is prepared by a preparation method comprising the following steps:
mixing the raw material components according to the weight parts, heating for curing, and crushing to obtain the coating;
The heating and curing process is gradient heating and curing, wherein the gradient heating and curing comprises two stages, namely heating to 30-100 ℃ and curing for 5-30 min, and heating to 80-120 ℃ and curing for 5-30 min.
2. The coating of claim 1, wherein the platelet filler composition has a ratio of caliper to caliper in the range of 10 to 25:1.
3. The coating of claim 1, wherein the hardener composition comprises an organic amine hardener, a phenolic hardener, and a metal salt hardener.
4. The coating of claim 3, wherein the organic amine curing agent comprises at least one of 4,4'- (1, 4-benzenedioxy) diphenylamine, 4' -bis (4-aminophenoxy) diphenyl sulfone, 4 '-bis (3-aminophenoxy) diphenyl sulfone, 4' -diaminodiphenyl methane;
and/or the phenolic curing agent comprises at least one of cardanol and phenolic resin;
And/or the metal salt curing agent comprises zinc dithiophosphate-O, O-di-C 1-14 -alkyl ester.
5. The coating of claim 1, wherein the epoxy resin is bisphenol a type epoxy resin selected from at least one of E51 epoxy resin, E44 epoxy resin, E20 epoxy resin, E12 epoxy resin.
6. A method for preparing the paint according to any one of claims 1 to 5, comprising the steps of:
mixing the raw material components according to the weight portions, heating, solidifying and crushing to obtain the coating.
7. Use of a coating prepared by the preparation method according to claim 6 for coating a metal substrate.
8. An anticorrosive coating, wherein the anticorrosive coating is prepared from the coating prepared by the preparation method of claim 6.
9. A coated article comprising a metal substrate and a coating applied to the surface of the metal substrate, wherein the coating is the corrosion protection coating of claim 8.
10. An electric home appliance, wherein the raw materials for preparing the electric home appliance comprise the paint as claimed in any one of claims 1 to 5 or the anticorrosive coating as claimed in claim 8.
11. The appliance of claim 10, wherein the appliance comprises a cleaning appliance, a kitchen appliance, an electric heating appliance, a sound-image appliance, an air conditioner, a refrigeration appliance, or a water heater.
12. Use of the coating according to any one of claims 1 to 5 or the corrosion protection coating according to claim 8 in a hot humid environment or an acid-base environment.
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| CN105295482A (en) * | 2015-12-01 | 2016-02-03 | 重庆工商职业学院 | Compound type coating for removing formaldehyde by combining adsorption with chemical reaction |
| CN118791943A (en) * | 2024-08-02 | 2024-10-18 | 芜湖美的厨卫电器制造有限公司 | A coating and its preparation method and application, and coated product |
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| CN101293978A (en) * | 2008-06-12 | 2008-10-29 | 南京工业大学 | A sericite-modified anti-ultraviolet polymer masterbatch and composite material thereof |
| CN104861829A (en) * | 2015-05-05 | 2015-08-26 | 天津翔盛粉末涂料有限公司 | Boiling-resistant epoxy polyester type powder paint and preparation method and application |
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| CN118791943A (en) * | 2024-08-02 | 2024-10-18 | 芜湖美的厨卫电器制造有限公司 | A coating and its preparation method and application, and coated product |
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