Two-component coating composition, process for preparing the same and coated article
Patent Information
- Application Number
- EP2024778206
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-03-30
- Filing Date
- 2024-03-29
- Publication Date
- 2025-12-24
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Figure PCTCN2024084709-FTAPPB-I100001 
Figure PCTCN2024084709-FTAPPB-I100002 
Figure PCTCN2024084709-FTAPPB-I100003
Abstract
Description
TWO-COMPONENT COATING COMPOSITION, PROCESS FOR PREPARING THE SAME AND COATED ARTICLE
[0001] CROSS REFERENCE TO RELATED APPLICATION
[0002] This application is an international patent application which claims priority to Chinese Patent Application No. 202310334627. X, filed on March 30, 2023, which is incorporated here by reference in its entirety.TECHNICAL FIELD
[0003] The application relates to the technical field of anticorrosion of metal surfaces or substrates. In particular, the present application relates to a two-component coating composition, a process for preparing the same and a coated article.BACKGROUND
[0004] With the rapid development of the economy, coatings on metal surfaces or substrates are facing more and more problems, and the performance requirements are becoming more stringent and demanding.
[0005] For example, in most of the existing anticorrosive coating systems, a primer, an intermediate paint, a topcoat or a composite anticorrosive coating system of primer and topcoat is adopted. Due to the complex application processes, such systems have several drawbacks including long construction periods and high cost.
[0006] Moreover, a large amount of organic solvents are used in most traditional anticorrosive coating systems. As environmental problems attract more and more attention, the laws and regulations for environmental protection in various countries and regions are becoming stricter, so it is increasingly important to reduce the amount of organic solvents in the coating systems. The waterborne anticorrosive systems proposed by some researchers involve a modified hydrophilic curing agent. However, this modified hydrophilic curing agent usually involves complex synthesis processes and raw materials, which greatly increases the cost of coatings and affects the popularization and application of waterborne coatings. Moreover, coating layers formed from the existing waterborne anticorrosive coatings usually show relatively poor coating performance properties, such as reduced gloss, insufficient resistance to salt spray, etc.SUMMARY
[0007] In view of this, there is need for an anticorrosive coating system which not only has good workability and satisfactory environmental protection performance, but also can provide excellent coating performance. More specifically, there is a need for a coating system that is simple to apply, green and environmentally friendly, and capable of providing an anticorrosive coating having excellent resistance to salt spray, weather resistance, mechanical properties, adhesion and chemical resistance.
[0008] The above object can be achieved by using the two-component coating composition described herein.
[0009] A first aspect of the present application provides a two-component coating composition, comprising: a component A comprising at least one hydroxyl functional polyurethane dispersion and an antirust pigment, and a component B comprising a non-hydrophilic isocyanate curing agent, and the component A has a change rate of grind fineness after 14 days at 40℃ of 10%or less relative to the initial fineness of the component A, and the fineness is measured with a fineness plate according to GB / T 1724-2019.
[0010] A second aspect of the present application provides a process for preparing a two-component coating composition comprising mixing a component A and a component B, characterized in that, the component A comprises at least one hydroxyl functional polyurethane dispersion and an antirust pigment, the component B comprises a non-hydrophilic isocyanate curing agent, and the component A has a change rate of grind fineness after 14 days at 40℃ of 10%or less relative to an initial fineness of the component A, and the fineness is measured with a fineness plate according to GB / T 1724-2019.
[0011] A third aspect of the present application provides a coated article, characterized in that the coated article comprises: a metal substrate having at least one major surface; and the two-component coating composition as described herein or a cured coating formed therefrom, applied on the at least one major surface of the metal substrate.
[0012] The inventors have surprisingly found that the two-component coating composition described in the present application has the advantages including simple construction, green and environmental protection, and capability of providing an anticorrosive coating having excellent performance (such as resistance to salt spray, weather resistance, mechanical properties, adhesion and chemical resistance) . In particular, the coating or the cured coating film of the present application has one or more of the following properties: no blistering at 35℃ for at least 1000 hours in neutral salt spray test on aluminum plate, phosphated plate or both, no blistering at 20℃ for at least 120 hours in 5%sulfuric acid solution, no blistering at 20℃ for at least 120 hours in 5%sodium hydroxide solution, ΔE of 1.0 or lower and a light retention at 60℃ of greater than 80%after exposure to a xenon lamp for 1000 hours.
[0013] Moreover, the coating and two-component coating composition of the present application have the advantages including low VOC (the amount of organic solvent being 15%or lower relative to the total weight of the composition, or even no solvent) and low cost, thus are healthy and environment-friendly products, and are easier to be accepted and popularized by consumers.
[0014] The above summary of present application is not intended to describe each disclosed embodiment or every implementation in this application. Illustrative embodiments are exemplified in more detail in the detailed description as follows.DETAILED DESCRIPTION
[0015] Selected Definitions
[0016] As used herein, "a” , "an” , "such" , "at least one" and "one or more" may be used interchangeably unless otherwise stated. Thus, for example, a coating composition comprising "an" additive may be interpreted as indicating that the coating composition comprises "one or more" additives. Unless otherwise stated herein, the use of singular forms herein is intended to include plural forms.
[0017] Unless otherwise expressly stated, the use of the terms "comprising" , "including" , "containing" and "having” and variations thereof should generally be construed to be open-ended and non-limiting. For example, when a composition is described as comprising, including, containing, or having certain components, it is intended that the composition may include other optional components than the certain components expressly listed, and that the composition may consist of or be composed of the certain components; when a method is described as comprising, including, containing, or having certain steps, it is intended that the method may include other optional steps than the certain steps expressly listed, and that the method may consist of or be composed of the certain steps.
[0018] For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form a range that is not explicitly described; and any lower limit may be combined with other lower limit to form an unspecified range; and any upper limit may be combined with any other upper limit to form an unspecified range. Further, although not explicitly specified, each point or single value between the endpoints of a range is included in the range. Thus, each point or single value can be combined with any other point or single value or combined with other lower or upper limits to form a range that is not explicitly specified.
[0019] Unless otherwise noted, the term "substantially consist of" means that the subject (e.g. a composition, method, or structure) may include additional elements (e.g. components, steps, and / or portions) in addition to those described elements, provided that the additional elements (e.g. components, steps, and / or portions) do not substantially alter the essential and novel characteristics of the subject (e.g. A composition, method, or structure) . Thus, depending on the particular case, the term "substantially consist of" preferably means that the vast majority (e.g. 90%or more, such as 95%or more, particularly 99%or more, and even more particularly 99.5%or more) of the subject is composed of the described elements, including entirely (i.e. 100%) consisting of the described elements.
[0020] Unless otherwise noted, each point or individual value between the endpoints of a range is included in the range. For example, a range from 1 to 5 includes the values 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, and so on. Further, disclosure of a range includes disclosure of all subranges included within the broader range. For example, a range of from 1 to 5 includes the subranges of from 1 to 4, from 1.5 to 4.5, from 1 to 2, etc. Thus, each point or individual value may serve as lower or upper limit for combining with any other point or individual value or any other lower or upper limit, and the resulting range is explicitly disclosed in the present application.
[0021] As used herein, the term "or" is inclusive. That is, the phrase "A or B" means "A, B, or both A and B" , which may also be abbreviated as "A and / or B" . More specifically, any of the following conditions satisfy the condition "A or B" : A is true (or exists) and B is false (or does not exist) ; A is false (or does not exist) and B is true (or exists) ; or both A and B are true (or exist) . In contrast, the exclusive "or" is represented herein, for example, by the terms such as "either A or B" and "one of A or B. "
[0022] When used in the context of "acoating applied on a surface or substrate" , the term "on" includes coatings that are directly or indirectly applied on the surface or substrate. Thus, for example, a coating applied on a primer coating on a substrate is regarded as a coating applied on the substrate.
[0023] The term “anticorrosive" coating composition refers to a coating composition that, when applied on a metal substrate in one or more layers, a coating formed from the coating composition can be exposed to corrosive conditions (e.g. salt spray exposure for three, five or more weeks) for a considerable period of time without unpleasant visible deterioration or corrosion or expansion.
[0024] As used herein, the term "hydroxyl functional" means the presence of at least one unreacted hydroxyl functional group.
[0025] As used herein, the meanings of the terms “hydrophilic curing agent" and "non-hydrophilic curing agent" are well known in the art. Generally, non-hydrophilic curing agents (also referred to as hydrophobic curing agents or oily curing agents) are difficult to mix with water or aqueous A components uniformly, and are prone to phase separation. For example, non-hydrophilic curing agents include most of unmodified polyisocyanates. Hydrophilic curing agent is usually obtained by hydrophilic modification of curing agent. The hydrophilic curing agent may be, for example, nonionic hydrophilic modified (e.g. Bayhydur series from Covestro) , ionic modified, nonionic and ionic composite modified.
[0026] The terms “preferred” , “preferably” , and any other variation thereof are used to refer to the embodiments of the present application that may provide certain advantages under certain circumstances. Under the same or other circumstances, however, other embodiments may be preferred. In additional, the description of one or more preferred embodiments in no way indicates that other embodiments should be unusable, and it is not intended to exclude other embodiments from the scope of the invention.
[0027] Unless otherwise noted, the methods or processes described herein are performed under standard environmental conditions well known in the art. For example, they may be carried out at 25℃, 101, 325 Pa and a relative humidity (RH) of 40%to 80% (e.g. 50%or 60%) .
[0028] Two-component coating composition
[0029] The two-component coating composition according to the first aspect of the present application comprises a component A comprising at least one hydroxyl functional polyurethane dispersion and an antirust pigment, and a component B comprising a non-hydrophilic isocyanate curing agent, and the component A has a change rate of fineness after 14 days at 40℃ of 10%or less relative to an initial fineness of the component A, and the fineness is measured with a fineness plate according to GB / T 1724-2019.
[0030] After in-depth study and screening, the inventors have surprisingly found that the change rate of fineness of the A component comprising an antirust pigment has a significant effect on the performance of the coating composition. In this disclosure, by measuring the change rate of fineness using suitable conditions, the measuring conditions described herein can not only accurately characterize the change rate of fineness, but also ensure no consumption of too much time while keeping the coating system substantially stable, so that the measuring process can be conveniently and easily performed in practical industrial applications. The ionic stability of antirust pigments can be determined by the change rate of fineness after 14 days at 40℃ relative to the initial fineness. A relatively low change rate of fineness is desirable. In some embodiments, the change rate of fineness may be about 9%or less, preferably about 8%or less, more preferably about 7%or less, and even more preferably about 6%or less. For example, the change rate of fineness may be about 5%or less, about 4%or less, about 3%or less, about 2%or less, or about 1%or less.
[0031] Hydroxyl functional polyurethane dispersion preferably has a higher hydroxyl value. In some embodiments, the hydroxyl functional polyurethane dispersion may have a hydroxyl value of from about 40 to about 200 mg KOH / g, preferably from about 60 to about 150 mg KOH / g, more preferably from about 80 to about 120 mg KOH / g. For example, the hydroxyl functional polyurethane dispersion may have a hydroxyl value of about 60 mg KOH / g, about 70 mg KOH / g, about 80 mg KOH / g, about 90 mg KOH / g, about 100 mg KOH / g, about 110 mg KOH / g, about 120 mg KOH / g, about 130 mg KOH / g, about 140 mg KOH / g, about 150 mg KOH / g, or about 180 mg KOH / g.
[0032] The hydroxyl functional polyurethane dispersion has a minimum film-forming temperature of preferably greater than or equal to 16℃, and more preferably from 18 to 60℃ and even more preferably from 25 to 50℃. For example, the hydroxyl functional polyurethane dispersion has a minimum film-forming temperature of about 20℃, about 30℃, about 35℃, about 40℃, or about 45℃.
[0033] In some embodiments, the hydroxyl functional polyurethane dispersion has a Brookfield viscosity at 25℃ of from 500 to 5000 mPa·s. Preferably, the hydroxyl functional polyurethane dispersion has a Brookfield viscosity at 25℃ of 800 mPa·sor higher, or 4800 mPa·sor lower. For example, the hydroxyl functional polyurethane dispersion may have a Brookfield viscosity at 25 ℃of 1000 mPa·s, 1500 mPa·s, 2000 mPa·s, 2500 mPa·s, 3000 mPa·s, 3500 mPa·s, 4000 mPa·sor 4500 mPa·s. The Brookfield viscosity can be measured by a method known in the art using known instruments. For example, the Brookfield viscosity may be measured at 25 ℃ using Brookfield LV, 61 #at 30 rpm according to GB / T2794-2013 or DIN 53019.
[0034] In some embodiments, the hydroxyl functional polyurethane dispersion has an average particle size of from 10 to 80 nm. Preferably, the hydroxyl functional polyurethane dispersion has an average particle size of about 20 nm to 70 nm, more preferably about 25 nm to 60 nm. For example, the hydroxyl functional polyurethane dispersion has an average particle size of about 20 nm, about 30 nm, about 40 nm, about 50 nm, about 60 nm, or about 70 nm. The average particle size may be measured by a method known in the art using known instruments. For example, a laser correlation spectroscopy (LKS) may be used to determine the average particle size.
[0035] In some embodiments, the hydroxyl functional polyurethane dispersion used to formulate component A has a non-volatile content of from about 20 to 60%, preferably from about 30 to 50%. For example, the hydroxyl functional polyurethane dispersion used to formulate component A may have a non-volatile content of about 25%, 30%, 35%, 40%, 45%or 50%.
[0036] In some embodiments, based on the total weight of the component A, the hydroxyl functional polyurethane dispersion is present in an amount of from 40 wt. %to 80 wt. %, preferably from 45 wt. %to 75 wt. %, more preferably from 50 wt. %70 wt. %. For example, based on the total weight of the component A, the hydroxyl functional polyurethane dispersion may be present in an amount of 50 wt. %, 55 wt. %, 60 wt. %, 65 wt. %, or 70 wt. %.
[0037] Preferably, the hydroxyl functional polyurethane dispersion in the present application is obtained by reacting a compound having a hydroxyl functional group with a compound having an NCO functional group. Suitable hydroxyl functional polyurethane resins that may be used are prepared, for example, by the reaction of compounds reactive to isocyanate groups with polyisocyanates having at least 2 free isocyanate groups per molecule. High molecular weight polyols may be used as compounds reactive to isocyanate groups. Examples of polyols may include polyester polyols, polyether polyols, polycarbonate polyols, and polyurethane polyols. Preferably, polyester polyols, polyether polyols, polycarbonate polyols or any combination thereof having a molecular weight of, for example, from 500 g / mol to 6000 g / mol are used. Examples of useful polyisocyanates include teraphenyl diisocyanate, xylylene diisocyanate, diphenyl methane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethyl hexamethylene diisocyanate. In the reaction mixture, a molar equivalent ratio of NCO / OH functional groups may be from 0.2: 1 to 5: 1.
[0038] Preferably, the hydroxyl functional polyurethane dispersion in the present application has a relatively narrow molecular weight distribution. In some embodiments, the hydroxyl functional polyurethane dispersion may have an average particle size of from about 10 nm to 80 nm, preferably from about 15 nm to 70 nm, and more preferably from 20 nm to 50 nm. For example, the hydroxyl functional polyurethane dispersion may have an average particle size of about 25 nm, 30 nm, 35 nm, 40 nm, or 45 nm.
[0039] For ease of understanding only, some of the preferred hydroxyl functional polyurethane dispersions in this application may be briefly represented by formula (a) below. As can be seen from formula (a) , in these preferred hydroxyl functional polyurethane dispersions, the hydroxyl groups are substantially located at the end of the segment. This is different from other hydroxyl functional resins in the art in which some hydroxyl groups are located in the side chains of the segments (e.g. represented by the following formula (b) ) .
[0040] Furthermore, in the hydroxyl functional polyurethane dispersions described herein, the hydroxyl groups preferably comprise primary hydroxyl groups and more preferably substantially consist of primary hydroxyl groups. In some exemplary embodiments, 90%or more of the hydroxyl groups in the hydroxyl functional polyurethane dispersion are primary hydroxyl groups.
[0041] The inventors have found that hydroxyl-terminated polyurethane aqueous dispersions have the advantages including for example adjustable ratio of soft and hard segments, easy design of molecular structure and good compatibility with non-hydrophilic isocyanate curing agents, and excellent appearance and mechanical properties of coating film. In particular, the inventors have found that by combining the hydroxyl-terminated polyurethane aqueous dispersion described herein with an antirust pigment (in particular the antirust pigments described herein) , the obtained component A has a very low change rate of fineness. The inventors have also surprisingly found that the A component with very low change rate of fineness described herein enables the resulting cured coating to have improved resistance to salt spray, weather resistance and chemical resistance while maintaining excellent mechanical properties and adhesion.
[0042] In some embodiments, the hydroxyl functional polyurethane dispersion may be a polyester type polyurethane dispersion. Examples of a hydroxyl functional polyurethane dispersion include, but are not limited to, Bayhydrol U XP 2755 from Covestro. The hydroxyl functional polyester polyurethane dispersion described herein has an improved hydrolysis resistance, good mechanical properties and placement stability, and may be applied in complex outdoor environments (humidity, high temperature, salt spray, etc. ) .
[0043] In some embodiments, based on the total weight of the component A, the antirust pigment is present in an amount of from 2 wt. %to -20 wt. %, preferably from 5 wt. %to 15 wt. %, more preferably from 5 wt. %to 10 wt. %. For example, based on the total weight of the component A, the antirust pigment is present in an amount of 3 wt. %, 4 wt. %, 6 wt. %, 8 wt. %, 10 wt. %, 12 wt.%, 14 wt. %, 16 wt. %, 18 wt. %, or 20 wt. %.
[0044] In some embodiments, the antirust pigment is or contains calcium ion-exchanged silica. The antirust pigment may have a calcium content of from 0.5 wt. %to 15 wt. %, preferably from 1 wt.%to 12 wt. %, and more preferably from 3 wt. %to 10 wt. %, on dry basis. For example, the calcium content in the antirust pigment is 2 wt. %, 4 wt. %, 6 wt. %or 8 wt. %on dry basis.
[0045] In some embodiments, the antirust pigment itself (preferably, the calcium ion-exchanged silica itself) releases little or no Zn during acid washing or water washing for 1 hour. No Zn element can be detected by ICP-OES in the liquid obtained after acid washing or water washing antirust pigment for 1 hour. For example, after acid washing and / or water washing antirust pigment for 1 hour, the Zn concentration in the obtained liquid does not exceed 10.0 mg / kg. Preferably, after water washing the antirust pigment for 1 hour, no Zn element is detected by ICP-OES in the obtained liquid. Preferably, after acid washing the antirust pigment for 1 hour, no Zn element is detected by ICP-OES in the obtained liquid.
[0046] In some embodiments, after water washing the antirust pigment itself (preferably, calcium ion-exchanged silica itself) for 1 hour, the obtained liquid has a concentration of Ca element of not exceeding about 1600 mg / kg, more preferably not exceeding about 1000 mg / kg, and even more preferably not exceeding about 800 mg / kg. Preferably, after water washing the antirust pigment itself (preferably, calcium ion-exchanged silica itself) for 1 hour, the obtained liquid has a concentration of Ca element of from about 50 mg / kg to 700 mg / kg. For example, after water washing the antirust pigment itself (preferably, calcium ion-exchanged silica itself) for 1 hour, the obtained liquid has a concentration of Ca element of about 700 mg / kg, about 600 mg / kg, about 500 mg / kg, about 400 mg / kg, about 300 mg / kg, about 200 mg / kg, about 100 mg / kg or about 50 mg / kg.
[0047] GB / T 23991-2009 "Determination of soluble harmful elements content of coatings” may be referred to, wherein the sample is extracted with 0.07 mol / L hydrochloric acid solution and DI water (deionized water) for 1 hour in a constant temperature water bath oscillating tank at 37℃, and then a clear solution is obtained after filtration, and the elements (such as Zn and Ca) in the clear solution are analyzed by ICP-OES.
[0048] In some embodiments, the antirust pigment (preferably, calcium ion-exchanged silica itself) has an oil absorption value of from 20 g / 100 g to 100 g / 100 g. Preferably, the antirust pigment has an oil absorption value of 90 g / 100 g or less, more preferably 80 g / 100 g or less. For example, the antirust pigment (preferably, calcium ion-exchanged silica itself) has an oil absorption value of 20 g / 100 g, 30 g / 100 g, 40 g / 100 g, 50 g / 100 g, 60 g / 100 g, 70 g / 100 g, 80 g / 100 g or 90 g / 100 g. The oil absorption value of the antirust pigment may be determined by methods known in the art, for example according to DIN ISO 787-5.
[0049] In some embodiments, the antirust pigment (preferably, calcium ion-exchanged silica itself) has a particle size of from 1.8 μm to 20 μm. Preferably, from 2.5 to 6 μm, and more preferably 2.7-5 μm. For example, the antirust pigment has a particle size of about 2.3 μm, 2.6 μm, 3.0 μm, 3.5 μm, 4 μm or 4.5 μm. The particle size of antirust pigment may be measured by using Malvern 3000E laser particle size analyzer.
[0050] In some embodiments, the antirust pigment (preferably, calcium ion-exchanged silica itself) has a pH of from 7 to 10, preferably from 8.0 to 10, more preferably from 8.5 to 10.0. For example, the antirust pigment has a pH of about 8.5, 8.8, 9, 9.3, 9.5 or 9.8. The pH of the antirust pigment may be determined in a 10 wt. %aqueous suspension. The pH of the antirust pigment may be determined by methods known in the art, for example according to DIN EN ISO 787-9.
[0051] The inventors have found that traditional antirust pigments generally involve highly toxic substances (such as red lead, lead powder, chromate, etc. ) , which not only pollutes the environment, but also harms human health. Some antirust products use zinc-rich primer, phosphate antirust pigment, chromate antirust pigment, borate antirust pigment, etc. However, zinc-rich primer usually has high amount of zinc powder, which may be up to 85%or 95%. As a result, when the paint film of zinc-rich primer is undergoing the operation of electric welding and cutting and flame, a large amount of zinc will be released and overflow, and the steam generated will bring serious harm to the health of operators who may easily develop hot zinc disease. Most of phosphate, chromate and borate antirust pigments are insoluble and have poor dispersion in waterborne coatings, which leads to poor antirust performance when these antirust pigments are used alone. The inventors have found that calcium ion-exchanged silica has the advantages including no heavy metals, no toxicity, no pollution, good stability and so on. Without wishing to being bound by theory, calcium ion-exchanged silica may promote the formation of insoluble silicates with stable chemical properties in coating systems, and these insoluble silicates may migrate to the metal surface to form a passivation layer, thereby preventing the electrochemical reaction on the metal surface and inhibiting the corrosion process of metals.
[0052] In addition to calcium ion-exchanged silica, component A may further comprise other antirust pigments. In some embodiments, component A comprises one or more of wollastonite, strontium phosphate, zinc phosphate, and zinc oxide. The inventors have surprisingly found that the resistance to salt spray, acid resistance and weather resistance of the coating can be significantly improved by employing a combination of specific antirust pigments. The combination of one or more of wollastonite, strontium phosphate, zinc phosphate and zinc oxide with calcium ion-exchanged silica produces synergistic effect, and the resulting coating performance is apparently much better than that of using a certain antirust pigment alone. Without wishing to being bound by theory, calcium ion-exchanged silica can not only promote the formation of insoluble silicate with stable chemical properties, but also can combine with metal oxide film to form a composite protective layer, which can quickly solve the problem related to salt spray, avoid foaming, have high weather resistance and improve the hardness of coating film. In particular, the inventors have found that the combination of wollastonite with calcium ion-exchanged silica can significantly enhance the synergistic effect. In some preferred embodiments, component A comprises from 2 wt. %to 20 wt.%of calcium ion-exchanged silica and from 3 wt. %to 20 wt. %of wollastonite. More preferably, component A comprises from 4 wt. %to 10 wt. %of calcium ion-exchanged silica and from 4 wt. %to 8 wt. %of wollastonite.
[0053] The two-component coating composition, preferably component A, may further comprise a silane coupling agent. In some embodiments, the coupling agent comprises a silane compound having Formula I:
[0054] where each X1 is independently selected from a group consisting of -Cl, -OCH3, -OCH2CH3, -OC2H4OCH3, -OSi (CH3) 3 and -OCOCH3; and
[0055] Y1 is an alkyl group terminated by -Cl, -NH2, -SH, -OH, epoxy group, -N3γ-methacryloxypropyl or isocyanate.
[0056] In some embodiments, the silane coupling agent has a molecular weight of from 100 Dalton to 800 Dalton, preferably from 200 Dalton to 400 Dalton, e.g. about 150 Dalton, about 250 Dalton, 300 Dalton.
[0057] Preferably, the silane coupling agent is an epoxy silane coupling agent. For example, in Formula I, Y1 is an alkyl group terminated by epoxy group.
[0058] The inventors have found that on the one hand, the silane coupling agent has the active group that can react with metal oxide on the metal surface or water on the surface to form hydrogen bonds, which improves the adhesion of the coating to the metal substrate; On the other hand, the silane coupling agent can further promote the function of antirust pigment in coating composition and improve the resistance to salt spray and acid resistance of coating. Especially, when an epoxy silane coupling agent is used, the benefits of these two aspects are more prominent.
[0059] More importantly, in some embodiments, the beneficial effects described above can be observed by adding a smaller amount of the silane coupling agent. Based on the total weight of the component A, the silane coupling agent is present in an amount of from 0.2 wt. %to 2 wt. %, preferably from 0.3 wt. %to 1.8 wt. %, more preferably from 0.5 wt. %1.5 wt. %. For example, the amount of the silane coupling agent may be about 0.4 wt. %, about 0.5 wt. %, about 0.6 wt. %, about 0.8 wt. %, about 1.0 wt. %, about 1.2 wt. %.
[0060] In the two-component coating composition according to the present application, component A may further comprise an additive. These additives do not adversely affect the two-component coating composition or the cured coating obtained therefrom. Suitable additives include, for example, those that improve the processability or manufacturing properties of the composition, enhance the aesthetic feeling of the composition, improve the specific functional properties or characteristics (such as adhesion to the substrate) of the coating composition or the cured composition obtained therefrom, or reduce the cost. Additives that may be included are, for example, pigments, lubricants, film forming aids, wetting agents, plasticizers, defoamers, colorants, antioxidants, flow control agents, thixotropic agents, matte powders, dispersants, adhesion promoters, thickeners, pH regulators, light stabilizers, anti-flash rust agents, curing promoters or combinations thereof. The amount of each optional ingredient is sufficient for its intended purpose but preferably such amount does not adversely affect the two-component coating composition or the cured coating obtained therefrom. In some preferred embodiments, component A may comprise as a conventional additives a defoamer, a dispersant, a leveling agent, a light stabilizer, an anti-flash rust agent, a thickener, or any combination thereof. According to the present application, the total amount of the conventional additives is from 0.3 wt. %to 20 wt. %, preferably from 0.5 wt. %to 18 wt.%, for example about 10 wt. %, relative to the total weight of component A. In some embodiments, the amount of dispersant may be from 0.1 wt. %to 2 wt. %, the amount of defoamer may be from 0.1 wt.%to 0.8 wt. %, the amount of leveling agent may be from 0.1 wt. %to 2 wt. %, the amount of light stabilizer may be from 0.5 wt. %to 3 wt. %, and / or the amount of anti-flash rust agent may be from 0.1 wt. %to 1 wt. %.
[0061] Examples of light stabilizers may include, but not limited to, hindered amine compounds, hindered phenolic compounds; CHIMAS0RB 944, TINUVIN 144, TINUVIN 292, TINUVIN 770, IRGANOX 1010, IRGANOX 1098 (trade names, available from Ciba Specialty Chemicals K. K. respectively) , etc.
[0062] In some embodiments, component A may further comprise pigments other than the antirust pigments as described above. Pigments may be of spherical, fibrous, flaky, or other regular or irregular shape with micron or even nanometer sizes. Examples of pigments include metal oxides such as titanium dioxide, iron oxide, zirconia, alumina; hybrid metal oxides of two or more metals including manganese, nickel, titanium, chromium, antimony, magnesium, cobalt, iron or aluminum; oxymetallic compound, such as bismuth vanadate, cobalt aluminate, cobalt zincate; pigments with metallic effects, such as aluminum sheets, copper and copper-zinc alloys; pearlescent pigments, such as lead carbonate and bismuth oxychloride; talc; and any combination thereof. Preferably, the pigment is titanium dioxide and / or iron oxide.
[0063] Based on the total weight of the component A, the total amount of pigments other than the antirust pigment as described above may be from 0 wt. %to 40 wt. %, such as from 1 wt. %to 35 wt.%, from 2 wt. %to 30 wt. %, from 3 wt. %to 25 wt. %, from 4 wt. %to 20 wt. %, or from 5 wt. %to 15 wt. %. Further preferably, based on the total weight of the component A, the amount of each pigment is independently from 0 wt. %to 40 wt. %, from 1 wt. %to 30 wt. %, from 2 wt. %to 20 wt. %, from 3 wt. %to 15 wt. %, or from 4 wt. %to 10 wt. %.
[0064] In some embodiments, the dispersion medium (solvent or carrier fluid) in component A mainly or primarily comprises water. For example, in some embodiments, the dispersion medium in component A comprises at least about 50 wt. %, preferably at least about 60 wt. %, more preferably at least 70 wt. %, and at most about 99 wt. %, at most about 100 wt. %of water, based on the total weight of the dispersion medium. For example, based on the total weight of the dispersion medium, the dispersion medium contains about 80 wt. %, about 85 wt. %or about 95 wt. %of water.
[0065] The two-component coating compositions of the present application may have relatively fewer volatile components. In some embodiments, based on the total weight of the component A, the component A comprises from 0 wt. %to 15 wt. %, preferably from 0 wt. %to 12 wt. %of a solvent (in particular an organic solvent) . For example, based on the total weight of the component A, the component A comprises about 2 wt. %, 5 wt. %, 7 wt. %, 10 wt. %of a solvent (in particular an organic solvent) . Examples of an organic solvent include monohydric or polyhydric alcohols such as propanol, butanol, hexanol, benzyl alcohol; diol ethers or esters, such as diethylene glycol dialkyl ethers, dipropylene glycol dialkyl ethers, ethoxypropanol, and butyl ethylene glycol, each having a C1-C6 alkyl group; diols, such as ethylene glycol and propylene glycol; and ketones, such as methyl ethyl ketone, acetone, cyclohexanone; N-methylpyrrolidone, N-ethylpyrrolidone; aromatic or aliphatic hydrocarbons, such as toluene, xylene, or linear or branched aliphatic C6-C12 hydrocarbons. In some embodiments, the organic solvent comprises dipropylene glycol butyl ether, propylene glycol diacetate, propylene glycol methyl ether acetate, or any combination thereof.
[0066] In some embodiments, based on the total weight of the component A, the component A comprises:
[0067] from 40 wt. %to 80 wt. %of the hydroxyl functional polyurethane dispersion, from 2 wt. %to 20 wt. %of antirust pigment,
[0068] from 0.2 wt. %to 2 wt. %of silane coupling agent,
[0069] from 0.3 wt. %to 20 wt. %of an additive,
[0070] from 0 wt. %to 15 wt. %of a solvent.
[0071] In the two-component coating composition described herein, component B comprises a non-hydrophilic isocyanate curing agent. In some embodiments, the non-hydrophilic isocyanate curing agent comprises aliphatic diisocyanate, aromatic diisocyanate, cycloaliphatic diisocyanate, or any combination thereof. Preferably, the non-hydrophilic isocyanate curing agent comprises aliphatic diisocyanate.
[0072] Preferably, the non-hydrophilic isocyanate curing agent has a NCO content in the range of from 10 wt. %to 30 wt. %. Preferably, the NCO content is in the range of from 15 wt. %to 25 wt.%. For example, the NCO content may be 18 wt. %, 21 wt. %, 22 wt. %, 23 wt. %, or 24 wt. %. The NCO content may be determined according to DIN EN ISO 11 909.
[0073] Preferably, a non-hydrophilic isocyanate curing agent with low viscosity is used. For example, the non-hydrophilic isocyanate curing agent has a viscosity at 23℃ of less than 4000 mPa·s. More preferably, the non-hydrophilic isocyanate curing agent has a viscosity at 23℃ of from 600 mPa·sto lower than 3800 mPa·s. For example, a non-hydrophilic isocyanate curing agent may have a viscosity at 23℃ be 730 mPa·s, 1000 mPa·s, 1500 mPa·s, 2000 mPa·sor 3000 mPa·s. The viscosity as described above may be measured according to DIN EN ISO 3219 / A. 3.
[0074] The non-hydrophilic isocyanate curing agent may be in the form of oligomer or homopolymer. The oligomer or homopolymer may be an oligomer or homopolymer containing 2 to 8 monomer units. For example, the non-hydrophilic isocyanate curing agent may be a trimer.
[0075] Examples of the non-hydrophilic isocyanate curing agent include isocyanate curing agents based on hexamethylene diisocyanate (HDI) , dicyclohexylmethane-4, 4'-diisocyanate (HMDI) , xylylene diisocyanate (XDI) , or tetramethyl m-xylylene diisocyanate (TMXDI) .
[0076] In some preferred embodiments, the aliphatic diisocyanate is an aliphatic diisocyanate based on hexamethylene diisocyanate (HDI) , particularly preferably an HDI trimer. Preferably, the aliphatic diisocyanate may comprise one or more of an asymmetric trimer, a symmetric trimer and homopolymer that are based on HDI. Commercially available isocyanate curing agents, such as DESMODUR N 3300, 3600 and 3900, may be used.
[0077] The non-hydrophilic isocyanate curing agent may be used alone or in combination. In some embodiments, the non-hydrophilic isocyanate curing agent may further comprise a combination of two or more of the curing agents described above. For example, in an exemplary embodiment, DESMODUR N 3300, 3600, and 3900 in a 1: 1: 1 weight ratio may be used as non-hydrophilic isocyanate curing agents.
[0078] Component B may or may not contain a hydrophilic isocyanate curing agent.
[0079] In some embodiments, the component B comprises a hydrophilic isocyanate curing agent. The hydrophilic isocyanate curing agent may be prepared by modification in a manner known in the art. Examples of the hydrophilic isocyanate include, but not limited to, isophorone diisocyanate (IPDI) based hydrophilic isocyanates and HDI types isocyanates.
[0080] In some embodiments, the weight ratio of the non-hydrophilic isocyanate curing agent to the hydrophilic isocyanate curing agent is in the range of from 99: 1 to 5: 95. Preferably, the weight ratio of the non-hydrophilic isocyanate curing agent to the hydrophilic isocyanate curing agent is in the range of from 90: 10 to 10: 90, more preferably from 80: 20 to 20: 80. For example, the weight ratio of the non-hydrophilic isocyanate curing agent to the hydrophilic isocyanate curing agent is 90:10, 70: 30, 50: 50, 30: 70 or 10: 90.
[0081] In the two-component polyurethane coating composition described herein, component B comprises a diluent. The diluent may comprise at least one solvent with low boiling point. In this context, boiling point has a general meaning as understood by those of ordinary skill in the art. "Boiling point" is understood as the temperature at which a liquid boils at atmospheric pressure (i.e. 1 bar) , i.e. the temperature at which the saturated vapor pressure of the liquid is equal to the external pressure. The boiling point value of compounds can be obtained from scientific and technological literature or reference books.
[0082] Preferably, the solvent with low boiling point has a boiling point of 160℃ or less. For example, the solvent with low boiling point includes one or more of propylene glycol monomethyl ether acetate (PMA) , dipropylene glycol dimethyl ether (DMM) , methyl ethyl ketone (MEK) , acetone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, trimethylbenzene, 100 #solvent naphtha, 2-methylpropanol acetate (MPA) , and n-butyl acetate (BAC) . More preferably, the solvent with low boiling point is PMA, MEK, or a combination of both.
[0083] In some preferred embodiments, the weight ratio of the diluent to the non-hydrophilic curing agent is from 30: 70 to 90: 10. More preferably, the weight ratio of the diluent to the non-hydrophilic curing agent is from 40: 60 to 85: 15. For example, the weight ratio of the diluent to the non-hydrophilic curing agent may be 45: 65, 50: 50, 55: 45, 60: 40, 70: 30, or 80: 20.
[0084] In the two-component polyurethane coating composition described herein, the relative amount of component A and component B may be adjusted as desired. In some embodiments, the mass ratio of component A to component B is from 1: 1 to 10: 1, preferably from 1: 1 to 10: 1, more preferably 2: 1 to 8: 1, such as 3: 1, 4: 1, 5: 1, 6: 1, 7: 1.
[0085] According to the present application, a two-component coating composition may be prepared by simply mixing component A and component B in a predetermined ratio in a mixing device before application. The resulting coating composition may be applied using a variety of methods familiar to those skilled in the art, including spraying (e.g. air-assisted, airless, or electrostatic spraying) , brush coating, roll coating, overflow coating, and impregnation. In one embodiment of the present application, the mixed coating composition is applied by spraying. The coating composition may be applied in various wet film thicknesses. In embodiments of the present application, the wet film thickness preferably provides a dry film thickness of from about 40 μm to about 260 μm, and more preferably about 50 μm to about 150 μm. The applied coating may be cured by air drying or by accelerating curing using various drying devices (e.g. ovens) familiar to those skilled in the art.
[0086] Process for preparing two-component coating composition
[0087] A second aspect of the present application provides a process for preparing a two-component coating composition comprising mixing a component A and a component B, characterized in that, the component A comprises at least one hydroxyl functional polyurethane dispersion and an antirust pigment, the component B comprises a non-hydrophilic isocyanate curing agent, and the component A has a change rate of fineness after 14 days at 40℃ of 10%or less relative to an initial fineness of the component A, and the fineness is measured with a fineness plate according to GB / T 1724-2019.
[0088] The content described in the context of a two-component coating composition also applies to a process for preparing a two-component coating composition.
[0089] Coated article
[0090] A third aspect of the present application provides a coated article, characterized in that the coated article comprises: a metal substrate having at least one major surface; and the two-component coating composition as described herein or a cured coating formed therefrom, applied on the at least one major surface of the metal substrate.
[0091] The two-component coating composition of the present application may be applied directly on a substrate or on a coating on a substrate. In some embodiments, the two-component coating composition of the present application may be used in conjunction with a primer. In this case, the article of the present application includes a substrate, a primer coating, and a coating formed from the two-component coating composition of the present application. In other embodiments of the present application, the two-component coating composition of the present application may be applied without a primer and applied directly on a major surface of a substrate. Preferably, the two-component coating composition of the present application has the two-in-one advantage of primer and topcoat, can greatly reduce the construction complexity, reduce the equipment and personnel investment, and also has excellent coating properties (including resistance to salt spray, acid resistance, adhesion, etc. ) .
[0092] Any suitable metal substrate known in the art may be used as a metal substrate for manufacturing the article of this application. As an exemplary illustration, the metal substrate may include one or more of an iron substrate, an aluminum substrate, a copper substrate, a carbon steel, a stainless steel, an aluminum zinc alloy, a zinc-coated steel substrate, a tin-coated steel substrate, and a phosphated plate.
[0093] Advantageously, the cured coating in the coated article described herein has one or more of the following properties: no blistering at 35℃ for at least 500 hours in neutral salt spray test on aluminum plate, phosphated plate or both, no blistering at 20℃ for at least 120 hours in 5%sulfuric acid solution, no blistering at 20℃ for at least 120 hours in 5%sodium hydroxide solution, has a ΔE of 1.0 or lower and a light retention at 60℃ of greater than 80%after exposure to a xenon lamp for 1000 hours. In particular, the cured coating in the coated article described herein has a very excellent combination of properties, such as two or more properties: no blistering at 35℃ for at least 1000 hours in neutral salt spray test on aluminum plate, phosphated plate or both, no blistering at 20℃for at least 120 hours in 5%sulfuric acid solution, no blistering at 20℃ for at least 120 hours in 5%sodium hydroxide solution, has a ΔE of 1.0 or lower and a light retention at 60℃ of greater than 80%after exposure to a xenon lamp for 1000 hours. Preferably, the cured coating in the coated article described herein does not blister at 35℃ for at least 1000 hours in neutral salt spray test on aluminum plate, phosphated plate or both, does not blister at 20℃ for at least 120 hours in 5%sulfuric acid solution, does not blister at 20℃ for at least 120 hours in 5%sodium hydroxide solution, has a ΔE of 1.0 or lower and a light retention at 60℃ of greater than 80%after exposure to a xenon lamp for 1000 hours. More preferably, the cured coating in the coated article described herein does not blister at 35℃ for at least 1000 hours, or even more preferably at least 1100 hours, in a neutral salt spray test on an aluminum plate, a phosphated plate, or both. For example, the cured coating in the coated article described herein does not blister at 35℃ for at least 1200 hours in a neutral salt spray test on an aluminum plate, a phosphated plate, or both. The inventors believe that such an excellent combination of performance as described herein could not have been achieved prior to the present application and goes beyond the knowledge and ability of those of ordinary skill in the art.
[0094] According to the present application, the coated article may be prepared, for example, by the following steps: (1) providing a polished metal substrate; (2) employing a applying process, sequentially applying and forming one or more layers of the coating composition described herein on the metal substrate, and curing to obtain a cured coating.
[0095] The metal articles of this application may be used for the following end applications, including, but not limited to, refrigerated containers and non-refrigerated transport containers (e.g. dry cargo containers) from suppliers or manufacturers including China International Marine Containers (CIMC) , Graaff Transportsystem Gmbh, Maersk Line, and other suppliers or manufacturers well known to those of ordinary skill in the art; chassis, trailers (including semi-trailers) , rail vehicles, truck bodies, ships, bridges, petrochemical tank walls, building skeletons and prefabricated or existing metal parts requiring temporary indoor or outdoor anticorrosion during manufacture. Additional uses include metal corners, passages, beams (e.g. I-beams) , conduits, pipes, plates, or other components that can be welded into these or other metal pieces.
[0096] Examples
[0097] The following examples are intended to describe the present application more specifically, merely for the purpose of illustration. Various modifications and variations within the scope of the present application are apparent to those skilled in the related art. Unless otherwise stated, all portions, percentages, and ratios reported in the following examples are based on weight. Furthermore, all of the reagents used in the examples are commercially available and can be used directly without further treatment.
[0098] Test Methods
[0099] Glossiness: 60° glossiness was evaluated according to ASTM D523 using Sheen Hole Gloss Meter.
[0100] Change rate of grind fineness: The initial fineness before storage and the fineness after storage were measured after 14 days of storage at 40℃. The change rate of fineness after 14 days at 40℃ relative to the initial fineness was calculated. Fineness was measured using a fineness plate according to GB / T 1724-2019.
[0101] Pencil hardness: Pencil hardness was evaluated by ASTM D3363. Data were reported as pencil hardness for the last successful test before the coating breaks. Thus, for example, if the coating does not break when tested with a 2H pencil, but breaks when tested with a 3H pencil, the coating is reported to have a pencil hardness of 2H.
[0102] Impact resistance: The impact resistance of coating film was determined according to GB / T 1732-2020.
[0103] Adhesion: Adhesion was measured according to GB / T3324-2017 (grid method) . 10 groups of cross grids were drawn with a spacing of about 2 mm by using a carving knife, then transparent tape was used to stick on the notch surface, compacted, and peeled off. The pigment exfoliation in grids was evaluated in a scale of from 0 to 5 grades. Grade 0 represented the best and grade 5 represented the worst.
[0104] Moisture and heat resistance: The moisture and heat resistance of coating films was measured according to GB / T 1740-2007.
[0105] Resistance to salt spray: The resistance to salt spray of coating film was determined according to GB / T 1771-2007. Peeling width was required to be lower than 2.5 mm.
[0106] Chemical resistance: Sample was soaked in 5%sulfuric acid, 5%sodium hydroxide, gasoline or light oil according to GB 9274-1988 at 20±1℃, then observed whether the sample blistered, cracked, peeled off and had other bad states. The latest time when no adverse state was observed was recorded.
[0107] Weather resistance: was measured by using artificial aging machine with xenon lamp 1000 h, having light loss and color difference within grade 1, refer to national standard GB / T 1865-2009 "Paints and varnishes -Artificial weathering and exposure to artificial radiation -Exposure to filtered xenon-arc radiation" .
[0108] Concentration of elements in the clear solution after water washing or acid washing pigments: was measured in accordance with GB / T 23991-2009 "Determination of soluble harmful elements content of coatings” , by extracting a sample with 0.07 mol / L hydrochloric acid solution and DI water (deionized water) , respectively, for 1 hour in a constant temperature water bath oscillating tank at 37℃, and then filtering to obtain a clear solution, followed by analyzing elements (such as Zn and Ca) in the clear solution by ICP-OES.
[0109] Examples 1-8
[0110] The two-component coating compositions of Examples 1-8 and Comparative Examples 1 were prepared. Unless otherwise indicated, Bayhydrol U XP 2755 from Covestro was used as an aqueous hydroxyl polyurethane dispersion, and Bayhydrol A 2770 was used as an aqueous hydroxyl polyacrylate dispersion.
[0111] The used calcium ion-exchanged silica did not release Zn during acid washing (or water washing) for 1 hour (no Zn element detected using ICP-OES) . After water washing the used calcium ion-exchanged silica for 1 hour, the obtained clear liquid had a concentration of Ca element of about 565 mg / kg. Moreover, the used calcium ion-exchanged silica had an oil absorption value of about 80 g / 100 g, an average particle size of about 3 ± 0.5 μm, and a pH of 9.3 ± 0.5 in an aqueous suspension (10 wt. %) .
[0112] Component A and component B were separately prepared in accordance with the components and amounts shown in Table 1 below, and mixed to obtain the two-component coating compositions.
[0113] The obtained coating compositions were applied on an aluminum plate and then cured. The properties of coating compositions and coatings were tested, and the results were shown in Table 2 below.
[0114] From the experimental results, it can be seen that the two-component coating composition of this application can provide a coating with excellent resistance to salt spray, weather resistance, mechanical properties, adhesion, and chemical resistance. Moreover, the two-component coating composition of the application has the characteristics of two-in-one primer and topcoat, simple construction and environmental protection.
[0115] While the present application is described with reference to numerous embodiments and Examples, one of ordinary skill in the art would recognize from the disclosure of the present application that other embodiments may be designed. It will be readily apparent to those skilled in the art that modification may be made to embodiments of the present application without departing from the principles disclosed in the foregoing specification. For example, without departing from the principles disclosed in the foregoing description, the technical solutions obtained by combining multiple features or preferred implementations described herein shall be understood as belonging to the contents described herein. Such modifications are to be considered as being included within the claims unless otherwise expressly stated in the claims. Accordingly, the embodiments described in detail herein are exemplary only and are not intended to limit the scope of the application which is the complete scope of the appended claims and any and all of their equivalents..
Claims
1.A two-component coating composition, comprising:a component A comprising at least one hydroxyl functional polyurethane dispersion and an antirust pigment, anda component B comprising a non-hydrophilic isocyanate curing agent, andwherein the component A has a change rate of grind fineness after 14 days at 40℃ of 10%or less relative to an initial fineness of the component A, and the fineness is measured with a fineness plate according to GB / T 1724-2019.2.The two-component coating composition according to claim 1, wherein the hydroxyl functional polyurethane dispersion has a hydroxyl value of from 40 mg KOH / g to 200 mg KOH / g.3.The two-component coating composition according to claim 1 or 2, wherein the hydroxyl functional polyurethane dispersion has an average particle size of from 10 nm to 80 nm.4.The two-component coating composition according to any one of claims 1 to 3, wherein based on the total weight of the A component, the antirust pigment is present in an amount of from 2 wt. %to 20 wt. %, and the hydroxyl functional polyurethane dispersion is present in an amount of from 40 wt. %to 80 wt. %.5.The two-component coating composition according to any one of claims 1 to 4, wherein the antirust pigment comprises calcium ion-exchanged silica, and the antirust pigment has a calcium content of from 0.5 wt. %to 15 wt. %, on dry basis.6.The two-component coating composition according to any one of claims 1 to 5, wherein the antirust pigment has an oil absorption value of from 20 g / 100 g to 100 g / 100 g.7.The two-component coating composition according to any one of claims 1 to 6, wherein the antirust pigment has a particle size of from 1.8 μm to 20 μm.8.The two-component coating composition according to any one of claims 1 to 7, wherein the antirust pigment has a pH value of from 7 to 10.9.The two-component coating composition according to any one of claims 1 to 8, wherein the component A comprises one or more of wollastonite, strontium phosphate, zinc phosphate, and zinc oxide.10.The two-component coating composition according to any one of claims 1 to 9, wherein the component A comprises a silane coupling agent, and preferably, the silane coupling agent is an epoxy silane coupling agent.11.The two-component coating composition according to any one of claims 1 to 10, wherein a weight ratio of component A to component B is in a range of from 1: 1 to 10: 1.12.The two-component coating composition according to any one of claims 1 to 11, wherein based on the total weight of component A, the component A comprises:from 40 wt. %to 80 wt. %of the hydroxyl functional polyurethane dispersion,from 2 wt. %to 20 wt. %of antirust pigment,from 0.2 wt. %to 2 wt. %of silane coupling agent,from 0.3 wt. %to 20 wt. %of an additive,from 0 wt. %to 15 wt. %of a solvent.13.A process for preparing the two-component coating composition according to any one of claims 1 to 12, comprising:mixing component A and component B,wherein the component A comprises at least one hydroxyl functional polyurethane dispersion and an antirust pigment, and the component B comprises a non-hydrophilic isocyanate curing agent, and the component A has a change rate of grind fineness after 14 days at 40℃ of 10%or less relative to an initial fineness of the component A, and the fineness is measured with a fineness plate according to GB / T 1724-2019.14.A coated article, comprising:a metal substrate having at least one major surface; andthe two-component coating composition according to any one of claims 1 to 12 or a cured coating formed therefrom, applied on the at least one major surface of the metal substrate.15.The coated article according to claim 14, wherein the metal substrate comprises one or more of an iron substrate, an aluminum substrate, a copper substrate, a carbon steel, a stainless steel, an aluminum zinc alloy, a zinc-coated steel substrate, a tin-coated steel substrate, and a phosphated plate.16.The coated article according to claim 14 or 15, wherein the coated article has a cured coating that does not blister at 35℃ for at least 1000 hours in neutral salt spray test, does not blister at 20℃for at least 120 hours in 5%sulfuric acid solution, does not blister at 20℃ for at least 120 hours in 5%sodium hydroxide solution, has a ΔE of 1.0 or lower and a light retention at 60℃ of greater than 80%after exposure to a xenon lamp for 1000 hours.