Coating compositions, materials, kits and methods of use thereof

Abstract

The present invention relates to the field of coatings and coatings, and discloses a coating composition, a material product, a kit and a method of use thereof, which are characterized by environmental protection and efficient application. The coating composition comprises a main agent A and a curing agent B; wherein the main agent A comprises a silane small molecule containing a silane alkoxy group and / or a silane oligomer containing a silane alkoxy group, and the curing agent B comprises a small molecule containing an isocyanate group and / or a polymer whose monomer contains at least one isocyanate group. The coating composition is cross-linked and cured with the participation of water molecules to form a paint film with excellent physical and chemical properties. In addition, the present invention also discloses a material product, a kit and a method of use based on the coating composition, which are suitable for various industrial and commercial applications.

Description

Technical Field

[0001] The invention relates to the field of coatings, and in particular to a coating composition and a material product, a kit and a use method thereof. Background Art

[0002] Coating composition systems include epoxy resin systems, polyurethane systems, and polyurea systems. Among them, polyurethane coatings show good adhesion, toughness, water resistance, chemical resistance, UV resistance, and weather resistance on many substrates (such as metal, wood, leather, masonry, etc.). However, most polyurethane coatings require the participation of solvents during the synthesis process. Because the organic solvents used in the synthesis of traditional polyurethane coatings are highly volatile, they affect human health and environmental safety. Therefore, some studies focus on the research and application of water-based polyurethane coatings, but not all polymers are completely soluble in water, and the high latent heat of evaporation of water complicates the solidification and drying process of the coating. For this reason, many studies have focused on the realization of high-solid, ultra-high-solid, and even solvent-free polyurethanes.

[0003] However, due to the high viscosity of general solvent-free polyurethane systems, there are problems such as short operation time (<30 minutes) due to rapid heat release and side reactions, coating foaming failure, serious coating surface defects, or even non-curing.

[0004] Therefore, the industry still has a great demand for coating compositions with good comprehensive performance (such as high corrosion resistance and high weather resistance), convenient construction (such as low viscosity and sprayability, controllable operation time), and environmental protection (low VOC emissions). Summary of the invention

[0005] In view of the defects of existing coating compositions, the present invention provides a new type of coating composition, which has the advantages of strong operability (low viscosity for easy spraying, adjustable curing rate, and controllable operation time), environmental friendliness, and can take into account the comprehensive performance of the cured paint film (high corrosion resistance, high weather resistance, high substrate adhesion, etc.). In addition, the present invention also provides a material product, a kit, and a method of use based on the coating composition.

[0006] To achieve the above object, the present invention provides a coating composition comprising the following components:

[0007] A main agent A, wherein the main agent A comprises a silane small molecule containing a silane alkoxy group and / or a silane oligomer containing a silane alkoxy group, and

[0008] Curing agent B, wherein the curing agent B includes a small molecule containing an isocyanate group and / or a polymer whose monomer contains at least one isocyanate group.

[0009] Furthermore, the coating composition of the present invention also satisfies at least one or more of the following conditions:

[0010] The molar ratio of the silane group in the main agent A to the isocyanate group in the curing agent B is 1 to 10, preferably 1 to 5, more preferably 1.2 to 3, 1.5 to 3;

[0011] The coating composition remains liquid in an anhydrous environment;

[0012] At room temperature and pressure in the absence of a catalyst, the silane small molecule containing silanoxy groups and / or the silane oligomer containing silanoxy groups and the small molecule containing isocyanate groups and / or the polymer containing at least one isocyanate group in the monomer do not undergo a one-step addition reaction;

[0013] The silane small molecules containing silane alkoxy groups and / or the silane oligomers containing silane alkoxy groups do not contain active hydrogen;

[0014] The coating composition further comprises a catalyst C, wherein the catalyst C comprises at least one catalyst capable of catalyzing an addition reaction between a hydroxyl group of an alkyl alcohol and an isocyanate group; or

[0015] The coating composition further comprises a functional component D, which comprises a component with toughening, plasticizing or compatibilizing functions, and the component with toughening, plasticizing or compatibilizing functions comprises hydroxyl-terminated polydimethylsiloxane, hydroxyl acrylic resin or bisphenol A epoxy resin.

[0016] Furthermore, in the above-mentioned coating composition of the present invention, the main agent A may additionally satisfy at least one or more of the following conditions:

[0017] It is liquid in the range of -50℃ to 90℃;

[0018] The silane small molecule containing a silane alkoxy group is selected from at least one of alkoxysilanes containing a saturated alkyl group, alkoxysilanes containing an ester group, alkoxysilanes containing an aromatic hydrocarbon group, alkoxysilanes containing an unsaturated hydrocarbon group, or alkoxysilanes containing an epoxy group; preferably, selected from methacryloxypropyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, glycidyl ether propyltrimethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, One or more of methoxysilane, methacryloxypropyl triethoxysilane, vinyl triethoxysilane, phenyl triethoxysilane, glycidyl ether propyl triethoxysilane, methyl triethoxysilane, dimethyl diethoxysilane, diphenyl diethoxysilane, or methyl phenyl diethoxysilane; more preferably, one or more of vinyl trimethoxysilane, dimethyl dimethoxysilane, methacryloxypropyl trimethoxysilane, glycidyl ether propyl trimethoxysilane, or phenyl trimethoxysilane;

[0019] The silane oligomer containing silane alkoxy groups is polymerized from at least one monomer containing silane alkoxy groups, and has a degree of polymerization of 2 to 20;

[0020] The viscosity of the silane oligomer containing silaneoxy groups at 25° C. is in the range of 10 centipoise to 10,000 centipoise; or

[0021] The silane oligomer containing silane alkoxy groups is polymerized from one or more monomers selected from alkoxysilanes containing saturated alkyl groups, alkoxysilanes containing ester groups, alkoxysilanes containing aromatic hydrocarbon groups, alkoxysilanes containing unsaturated hydrocarbon groups, or alkoxysilanes containing epoxy groups. Preferably, it is polymerized from one or more monomers selected from vinyltrimethoxysilane, dimethyldimethoxysilane, methacryloxypropyltrimethoxysilane, glycidyl ether propyltrimethoxysilane, and phenyltrimethoxysilane.

[0022] Furthermore, in the above-mentioned coating composition of the present invention, the curing agent B may additionally satisfy at least one or more of the following conditions:

[0023] It is liquid in the range of -50℃ to 100℃;

[0024] The small molecule containing an isocyanate group is selected from aromatic isocyanate or aliphatic isocyanate;

[0025] The polymer whose monomer contains at least one isocyanate group is selected from aromatic isocyanate polymers or aliphatic isocyanate polymers;

[0026] The polymer having at least one isocyanate group has a viscosity of less than 10,000 centipoise at 40°C; or

[0027] The monomers contain at least one isocyanate group and the molecular weight of the polymer is from 150 to 5000 grams per mole.

[0028] Furthermore, in the above-mentioned coating composition of the present invention, the coating composition further comprises a catalyst C, and the catalyst C may additionally satisfy at least one or more of the following conditions:

[0029] The catalyst C is a polyurethane catalyst, preferably a metal salt polyurethane catalyst or a tertiary amine polyurethane catalyst; or

[0030] The catalyst C is a catalyst with a delay function, and is preferably a composition formed by a metal salt polyurethane catalyst and a complexing agent.

[0031] The present invention also provides another coating composition, which comprises:

[0032] Main agent A, wherein the main agent A includes one or more of methacryloxypropyl trimethoxysilane, phenyl trimethoxysilane, vinyl trimethoxysilane, and glycidyl ether propyl trimethoxysilane,

[0033] Curing agent B, wherein the curing agent B includes one or more of diphenylmethane diisocyanate or a polymer thereof, hexamethylene diisocyanate or a polymer thereof, or toluene diisocyanate or a polymer thereof,

[0034] Catalyst C, wherein the catalyst C includes one or more of dibutyltin dilaurate (DBTL), 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), or 1,8-diazacyclo[5,4,0]undecene-7 (DBU);

[0035] Wherein, the molar amount of silaneoxy groups in the main agent A: the molar amount of isocyanate groups in the curing agent B = 1: (0.1~1);

[0036] The mass ratio of the catalyst C to the coating composition is no more than 5%, preferably no more than 1%, and more preferably no more than 0.2%.

[0037] The present invention also provides another coating composition, which comprises:

[0038] A main agent A, wherein the main agent A comprises a silane small molecule containing a silane alkoxy group and / or a silane oligomer containing a silane alkoxy group, and

[0039] The curing agent B comprises aromatic isocyanate and / or a polymer thereof.

[0040] Furthermore, in the above-mentioned coating composition of the present invention, under normal temperature and pressure and in the absence of a catalyst, the silane small molecules containing silane alkoxy groups and / or silane oligomers containing silane alkoxy groups do not undergo a one-step addition reaction with the aromatic isocyanate and / or its polymer.

[0041] The present invention also provides a coating material product, comprising a substrate and a coating in contact with the surface of the substrate, wherein the coating is prepared in an aqueous environment based on the coating composition provided by the present invention.

[0042] The present invention also provides a coating kit, comprising the components of the coating composition provided by the present invention, wherein the components are physically independent of each other, or a mixture of some components is physically independent of other components. Preferably, the main agent A and the curing agent B are physically independent of each other (e.g., independently packaged).

[0043] The coating kit may further include a substrate; optionally, the coating kit may further include an instruction manual.

[0044] The present invention also provides a method for using the above coating composition, comprising the step of coating the coating composition provided by the present invention on the surface of a substrate in a water environment.

[0045] The present invention also provides a product coated with a coating prepared based on the above method.

[0046] The technical solution provided by the present invention has the following characteristics and beneficial effects:

[0047] (1) One of the substrates that trigger the reaction is water, especially water vapor in the air. Before coating construction, theoretically, the material does not undergo a major reaction in the mother barrel, which prevents the material from cross-linking too quickly in the mother barrel, thereby achieving the advantages of low viscosity, good construction performance, and sprayability;

[0048] (2) The reaction of silane condensation product alkyl alcohol with isocyanate is cleverly utilized to transfer the alkoxy group to the urethane group by exchange, thus solving the problem of alkyl alcohol emission, the main VOC emission in the reaction process of commercially available mature condensation-type silicone polymers; the optimized formula in the present invention can achieve a theoretical VOC of 0;

[0049] (3) Isocyanate curing agents integrate the formula advantages of polyurethane systems, with adjustable operation time and curing speed and a variety of catalyst types;

[0050] (4) Through reasonable component selection, the weather resistance of the paint film can be effectively guaranteed, and the gloss and color can be preserved (≈fluorocarbon or slightly lower>polyurethane);

[0051] (5) Through reasonable component selection, the anti-corrosion performance of the paint film can be effectively guaranteed, and it is resistant to salt spray, water, and chemical media, and meets the standards of the container industry;

[0052] (6) Raw materials are in sufficient supply and at low prices. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 The following is a typical process flow chart for the production and use of a coating composition. DETAILED DESCRIPTION

[0054] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0055] The technical solutions between the various embodiments in the present invention can be combined with each other, but it must be based on the fact that ordinary technicians in the field can implement it. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such combination of technical solutions does not exist and is not within the protection scope required by the present invention.

[0056] The "composition" referred to in the present invention is composed of two or more components and may be a mixture mixed together or a combination of physically independent components.

[0057] The "kit" referred to in the present invention consists of two or more parts, each part being a physically independent combination, or a mixture of some components and a physically independent combination of other components.

[0058] The term "coating" as used herein includes any method of applying the coating composition to the surface of the substrate, such as spraying, brushing, rolling, casting, etc. Those skilled in the art can make the decision based on the properties of the coating composition, the desired coating properties, the application environment, and cost-effectiveness.

[0059] The "silanol alkoxy group" referred to in the present invention refers to an alkoxy functional group covalently bonded directly to a silicon atom.

[0060] The “normal temperature and pressure” referred to in the present invention refers to a temperature of 25 degrees Celsius and a pressure of 101.325 kPa (1 standard atmospheric pressure, 760 mmHg).

[0061] The "active hydrogen" referred to in the present invention refers to hydrogen atoms that can participate in chemical reactions under normal temperature and pressure and in the absence of a catalyst.

[0062] The "operable time" referred to in the present invention refers to the time range during which the coating composition can be operated or processed after construction. Those skilled in the art can determine it as needed according to conventional methods. The specific time range may vary depending on the component types of the coating composition, the test method, the application scenario, and the manufacturer's regulations.

[0063] The "curing rate" referred to in the present invention refers to the speed at which the coating composition cures or hardens after application, and can be used to describe the time required for the coating composition to cure into a paint film after application. Generally speaking, in addition to being related to the inherent characteristics of the coating composition, the curing rate is also affected by environmental factors such as temperature, humidity and ventilation. Generally, higher temperature, higher humidity and sufficient ventilation will accelerate the curing rate of the coating composition.

[0064] The "finger pressure dry time" referred to in the present invention is the time to evaluate the surface dryness by pressing the coating surface with fingers and feeling whether it still has a sticky or tacky feeling and recording it.

[0065] The "complete curing time" referred to in the present invention refers to the time required for the organic volatile components in the coating to have basically evaporated and the cross-linking and curing reaction of the coating components to have been mostly (or completely) completed, and the degree of coating curing has reached the expected use target, that is, the paint film performance has reached or exceeded the expected target value.

[0066] In the present invention, expressions related to numerical ranges are generally understood to include the endpoint values ​​(the actual number), except for those explicitly expressed as "greater than (>)" or "less than (<)". For example, "not more than" referred to in the present invention includes the endpoint value, that is, less than or equal to a certain endpoint value; "A to B" or "A~B" includes the endpoint values ​​A and B.

[0067] In some embodiments, the coating composition provided by the present invention comprises the following components:

[0068] The main agent A includes silane small molecules containing silaneoxy groups and / or silane oligomers containing silaneoxy groups, and the curing agent B includes small molecules containing isocyanate groups and / or polymers whose monomers contain at least one isocyanate group; wherein the molar ratio of the silaneoxy groups in the main agent A to the isocyanate groups in the curing agent B is 1 to 10.

[0069] In some specific embodiments, the above coating composition provided by the present invention further comprises:

[0070] Catalyst C comprises at least one catalyst capable of catalyzing the addition reaction between the hydroxyl group of alkyl alcohol and the isocyanate group.

[0071] In some specific embodiments, the curing agent B includes aromatic isocyanate and / or a polymer thereof.

[0072] In some embodiments, the coating composition provided by the present invention comprises the following components:

[0073] The main agent A includes a silane small molecule containing a silane group and / or a silane oligomer containing a silane group, and the curing agent B includes a small molecule containing an isocyanate group and / or a polymer whose monomer contains at least one isocyanate group; wherein the silane small molecule containing a silane group and / or the silane oligomer containing a silane group of the main agent A does not contain active hydrogen that can undergo a one-step addition reaction with the small molecule containing an isocyanate group and / or the polymer whose monomer contains at least one isocyanate group of the curing agent B.

[0074] In some specific embodiments, the above coating composition provided by the present invention further comprises:

[0075] Catalyst C comprises at least one catalyst capable of catalyzing the addition reaction between the hydroxyl group of alkyl alcohol and the isocyanate group.

[0076] In some specific embodiments, curing agent B includes aromatic isocyanate and / or a polymer thereof.

[0077] In some embodiments, under normal temperature and pressure and in the absence of a catalyst, the silane small molecules containing silane alkoxy groups and / or silane oligomers containing silane alkoxy groups in the main agent A and the small molecules containing isocyanate groups and / or the polymer containing at least one isocyanate group in the curing agent B do not undergo a one-step addition reaction;

[0078] In some embodiments, the silane small molecules containing silane alkoxy groups and / or the silane oligomers containing silane alkoxy groups of the main agent A do not contain active hydrogen;

[0079] In some embodiments, the solvent-free composition remains liquid in a water-free environment. Specifically, when the coating composition is in a single mixed form, it remains liquid in a water-free environment.

[0080] According to some embodiments of the technical solution provided by the present invention, the main agent A mainly includes silane small molecules containing silaneoxy groups and / or silane oligomers containing silaneoxy groups, which are the main raw material components for forming the paint film after cross-linking and curing.

[0081] In some embodiments, the main agent A is in liquid form within a temperature range of -50°C to 90°C.

[0082] In some embodiments, the silane small molecule containing a silane alkoxy group is selected from at least one of an alkoxysilane having a saturated alkyl group, an alkoxysilane having an ester group, an alkoxysilane having an aromatic hydrocarbon group, an alkoxysilane having an unsaturated hydrocarbon group, or an alkoxysilane having an epoxy group; preferably, selected from methacryloxypropyltrimethoxysilane (KH570), phenyltrimethoxysilane (KH631), vinyltrimethoxysilane (A171), glycidyl ether propyltrimethoxy (KH560), methyltrimethoxysilane (MTMS), dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, polyalkyl (C n H 2n+1 , n≤16) one or more of trimethoxysilane, methacryloxypropyl triethoxysilane, vinyl triethoxysilane, phenyl triethoxysilane, glycidyl ether propyl triethoxysilane, methyl triethoxysilane, dimethyl diethoxysilane, diphenyl diethoxysilane or methyl phenyl diethoxysilane; more preferably, one or more of vinyl trimethoxysilane (A171), dimethyl dimethoxysilane, methacryloxypropyl trimethoxysilane (KH570), glycidyl ether propyl trimethoxysilane (KH560), and phenyl trimethoxysilane (KH631).

[0083] In some embodiments, the silane oligomer containing a silane alkoxy group is selected from a polymer formed by polymerizing one or more monomers of alkoxysilane having a saturated alkyl group, alkoxysilane having an ester group, alkoxysilane having an aromatic hydrocarbon group, alkoxysilane having an unsaturated hydrocarbon group, or alkoxysilane having an epoxy group; preferably, it is a polymer formed by polymerizing one or more monomers of vinyltrimethoxysilane (A171), dimethyldimethoxysilane, methacryloxypropyltrimethoxysilane (KH570), glycidyl ether propyltrimethoxysilane (KH560), and phenyltrimethoxysilane (KH631).

[0084] In some embodiments, the silane oligomer containing silaneoxy groups is selected from polymers having a degree of polymerization of 2 to 20 and a viscosity of 10 to 10,000 centipoise at 25°C, preferably a polymer having a viscosity of 10 to 5000 centipoise at 25°C.

[0085] In some embodiments, the silane oligomer containing a silaneoxy group may be selected from compounds formed and defined by the following structural formula (the product of further condensation between A1, A2, or A1 and A2 molecules):

[0086] A1

[0087] A2

[0088] Wherein, 2≤n≤20, M may be methyl or ethyl, and Ra may independently be at least one of methacryloyloxypropyl, phenyl, vinyl, (2,3-epoxypropyloxy)propyl, alkyl, ester, ether, urea, epoxy, or hydrocarbon.

[0089] According to the technical solution provided by the present invention, wherein, curing agent B mainly includes small molecules containing isocyanate groups and / or polymers containing at least one isocyanate group in monomers. Curing agent, also known as hardener, curing agent or curing agent, is a type of substance or mixture that promotes or controls the curing reaction. Resin curing is a process in which thermosetting resin undergoes irreversible changes through chemical reactions such as condensation, ring closure, addition or catalysis, and curing is accomplished by adding a curing (cross-linking) agent. Curing agent is an indispensable additive, and curing agent must be added whether it is used as an adhesive, coating, or casting material. The type of curing agent has a great influence on the mechanical properties, heat resistance, water resistance, corrosion resistance, etc. of the cured product.

[0090] In some embodiments, curing agent B is liquid in the range of -50°C to 100°C.

[0091] In some embodiments, the small molecule containing an isocyanate group may be selected from aromatic isocyanates or aliphatic isocyanates; the polymer having at least one isocyanate group in the monomer may be selected from aromatic isocyanate polymers or aliphatic isocyanate polymers;

[0092] In some embodiments, the small molecule containing an isocyanate group is preferably selected from aromatic isocyanates, and the polymer having at least one isocyanate group in the monomer is preferably selected from aromatic isocyanate polymers;

[0093] In some embodiments, the polymer containing at least one isocyanate group has a viscosity at 25° C. of less than 10,000 centipoise, preferably less than 3000 centipoise;

[0094] In some embodiments, the molecular weight of the polymer containing at least one isocyanate group is selected from 150 to 5000 grams per mole, preferably from 150 to 2000 grams per mole.

[0095] In some embodiments, the amount of the main agent A and the curing agent B is determined according to the relative content of the key reactive groups therein. For example, the molar ratio of the silane group in the main agent A to the isocyanate group in the curing agent B in the composition can be in the range of 1 to 10, preferably 1 to 5, more preferably 1.5 to 3, or 1.2 to 3.

[0096] According to the technical solution provided by the present invention, the catalyst C is mainly used to catalyze the addition reaction between the hydroxyl group of the alkyl alcohol and the isocyanate group, and regulate the rate of the curing process. For the type or amount of the catalyst, technicians in this field can freely choose according to the needs of the actual use scenario in combination with their professional knowledge. For example, in some scenes that require slow curing, you can choose not to add catalyst C, add a relatively small amount of catalyst C, or choose to add a catalyst C with a low catalytic efficiency; and in some scenes that require rapid curing, you can choose to add a relatively large amount of catalyst C or choose to add a catalyst C with a relatively high catalytic efficiency.

[0097] In some embodiments, the catalyst C can be selected from a polyurethane catalyst, preferably a metal salt polyurethane catalyst (such as organic tin, organic bismuth, organic zirconium, organic cobalt, etc.) or a tertiary amine polyurethane catalyst (such as 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), or 1,8-diazacyclo[5,4,0]undecene-7 (DBU)).

[0098] In some embodiments, the catalyst C is selected from a catalyst having a delay function, preferably a composition formed by a metal salt polyurethane catalyst and a complexing agent thereof;

[0099] In some embodiments, the complexing agent is a component having a complexing effect with the metal salt polyurethane catalyst, preferably some volatile, low-toxic and environmentally friendly components, such as acetylacetone, methyl acetoacetate or ethyl acetoacetate;

[0100] In some specific embodiments, the mass ratio of the metal salt polyurethane catalyst to the complexing agent is 1: (1-1000), preferably 1: (10-1000), and more preferably 1: (50-500). For example, the metal salt polyurethane catalyst is dibutyltin dilaurate (DBTL), and the complexing agent is acetylacetone, and the mass ratio of the metal salt polyurethane catalyst to the complexing agent is dibutyltin dilaurate: acetylacetone = 1: (10-1000), preferably 1: (50-500).

[0101] In some embodiments, the amount of catalyst C can be determined according to the amount of main agent A or curing agent B. For example, the mass ratio of catalyst C to the coating composition can be no more than 5%, preferably no more than 1%, and more preferably no more than 0.2%.

[0102] In some specific embodiments, the coating composition provided by the present invention comprises the following composition:

[0103] Main agent A includes one or more of methacryloxypropyl trimethoxysilane (KH570), phenyl trimethoxysilane (KH631), vinyl trimethoxysilane (A171), and glycidyl ether propyl trimethoxysilane (KH560).

[0104] The curing agent B includes one or more of diphenylmethane diisocyanate (MDI) or a polymer thereof, hexamethylene diisocyanate (HDI) or a polymer thereof, or toluene diisocyanate or a polymer thereof,

[0105] Catalyst C, comprising one or more of dibutyltin dilaurate (DBTL), 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), or 1,8-diazacyclo[5,4,0]undecene-7 (DBU);

[0106] Among them, the molar amount of silaneoxy in the main agent A: the molar amount of isocyanate in the curing agent B = 1: (0.1~1);

[0107] The mass ratio of the catalyst C to the coating composition is not more than 5%, preferably not more than 1%, and more preferably not more than 0.2%.

[0108] It can be understood that, in some embodiments, the main agent A, the curing agent B or the catalyst C can be independently composed of a single substance, or can be a mixture of two or more substances.

[0109] It is understandable that in some embodiments, the "coating composition" referred to in the present invention can be used to prepare a high-solid coating composition, an ultra-high-solid coating composition and / or a solvent-free coating composition, and is particularly suitable for preparing an ultra-high-solid coating composition or a solvent-free coating composition. For example, in one embodiment, the main agent A is selected from low-volatile silanes (such as methacryloxypropyl triethoxysilane, epoxypropyl triethoxysilane) or silane oligomers with extremely low VOC emissions, and the ratio of the silane group of the main agent A to the isocyanate group of the curing agent B is close to 1. By appropriately adjusting the ratio of the VOC-free component, a solvent-free coating composition can be prepared.

[0110] It should be noted that the selection or addition of specific components in the coating composition has different effects on the curing process (such as finger-drying time, curing temperature, etc.) and the properties of the paint film finally formed by curing (such as weather resistance, corrosion resistance, plasticization and volume expansion properties, etc.). Therefore, those skilled in the art can select or adjust the specific components of the coating composition according to the specific actual usage scenarios or usage requirements.

[0111] In some embodiments, for the weathering or anti-corrosion scenario of the paint film, the main agent A can be selected from methacryloxypropyl trimethoxysilane (KH570); for the room temperature curing scenario, the main agent A can be selected from phenyl trimethoxysilane (KH631); for the low viscosity + low temperature curing scenario, the main agent A can be selected from silanes with a high silaneoxy content, preferably vinyl trimethoxysilane (A171); for the difficult-to-attach substrate (such as a nylon substrate) scenario, the main agent A can be selected from a silane component rich in epoxy groups, preferably a mixture of methacryloxypropyl trimethoxysilane (KH570) and glycidyl ether propyl trimethoxysilane (KH560), and the usage ratio is KH570: KH560 = 75~100%: 0~25%. For the scene of room temperature / low temperature curing + difficult-to-attach substrate, the main agent A can be selected from a mixture of methacryloxypropyl trimethoxysilane (KH570), phenyl trimethoxysilane (KH631), and glycidyl ether propyl trimethoxysilane (KH560), and the dosage ratio is KH570: KH631: KH560 = 50~100%: 0~25%: 0~25%, and the preferred dosage ratio is KH570: KH631: KH560 = 80~100%: 0~10%: 0~10%; for the scene of low temperature curing + no methanol emission, the main agent A can be selected from a mixture of methacryloxypropyl triethoxysilane, phenyl triethoxysilane, and glycidyl ether propyl triethoxysilane, and the dosage ratio is methacryloxypropyl triethoxysilane: phenyl triethoxysilane: glycidyl ether propyl triethoxysilane = 0~50%: 50~100%: 0~50%, preferably the dosage ratio is methacryloxypropyl triethoxysilane: phenyl triethoxysilane: glycidyl ether propyl triethoxysilane = 0~25%: 50~100%: 0~25%; for high temperature curing + no methanol emission (for example, > 80°C) scenario, the main agent A can be selected from a silane component with low volatility, preferably a mixture of methacryloxypropyl triethoxysilane and glycidyl ether propyl triethoxysilane, and the dosage ratio is methacryloxypropyl triethoxysilane: glycidyl ether propyl triethoxysilane = 0~50%: 50~100%, preferably the dosage ratio is methacryloxypropyl triethoxysilane: glycidyl ether propyl triethoxysilane = 0~30%: 70~100%. The dosage ratio of each component in the main agent A is determined based on the molar amount of the silaneoxy group in each component molecule.

[0112] In some embodiments, for the paint film weathering scenario, curing agent B can be selected from aliphatic isocyanates and / or polymers thereof, such as HDI trimer or HDI uretdione curing agent, such as 1,6-hexane diisocyanate and its prepolymers (such as Covestro N3300, N3600, N3400), isophorone diisocyanate (IPDI) and its prepolymers, dicyclohexylmethane diisocyanate (HMDI) and its prepolymers, or toluene diisocyanate TDI and its prepolymers (such as Covestro E14, E15); for the paint film corrosion protection scenario, curing agent B can be selected from aromatic isocyanates and / or polymers thereof, such as MDI polymers or modified MDI prepolymers, such as polymethylene polyphenyl isocyanate (such as Wanhua Chemical PM200), or diphenylmethane diisocyanate or its polymers (such as Covestro E21, or Covestro CDC).

[0113] In some specific embodiments, for high weather resistance scenarios, curing agent B can be a mixture of N3300, N3600, and N3400, and the usage ratio is N3300: N3600: N3400 = 50~100%: 0~50%: 0~25%, and the preferred usage ratio is N3300: N3600: N3400 = 50~100%: 0~25%: 0~10%; for high corrosion protection scenarios, curing agent B can be a mixture of PM200, E21, and N3300, and the usage ratio is PM200: E21: N3300 = 50~100%: 0~50%: 0~50%, and the preferred usage ratio is PM200: E21: N3300 = 80~100%: 0~20%: 0~20%. The usage ratio of each component in the above curing agent B is determined based on the molar amount of isocyanate groups in each component molecule.

[0114] In some embodiments, especially for scenarios where slow curing is required, for example, the coating composition needs to be naturally and slowly cured within a required time after coating, wherein the curing agent B is preferably an aromatic isocyanate and / or its polymer, more preferably an MDI polymer or a modified MDI prepolymer, such as polymethylene polyphenyl isocyanate (such as Wanhua Chemical PM200), or diphenylmethane diisocyanate or its polymer (such as Covestro E21). Generally, in this scenario, the catalyst C component can be selected as needed.

[0115] In some embodiments, for operation-friendly (e.g., long operation time) scenarios, catalyst C can be selected from a mixture of dibutyltin dilaurate (DBTL) and acetylacetone; and for scenarios with fast curing requirements, catalyst C can be selected from tertiary amine polyurethane catalysts, such as 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) or 1,8-diazacyclo[5,4,0]undecene-7 (DBU).

[0116] In some specific embodiments, when the catalyst C is selected from dibutyltin dilaurate (DBTL), the mass ratio of its usage to the coating composition is in the range of 0.01‰ to 10‰, preferably in the range of 0.1‰ to 1‰; when the catalyst C is selected from a mixture of dibutyltin dilaurate (DBTL) and acetylacetone, the mass ratio of dibutyltin dilaurate (DBTL): acetylacetone is 1: (10~1000), preferably 1: (50~500).

[0117] In some embodiments, a functional component D may be added to the coating composition to provide the coating composition with auxiliary functions such as regulating reaction crosslinking, enhancing adhesion to the substrate, improving substrate wetting, plasticization, compatibilization, toughening, leveling, anti-sagging, improving the gloss of the paint film, and satisfying the special functions of the coating.

[0118] In some specific embodiments, the functional component D may be a component having toughening, plasticizing or compatibilizing functions, preferably hydroxyl-terminated polydimethylsiloxane (PDMS) or hydroxyl acrylic resin.

[0119] In other specific embodiments, the functional component D can be various common additives for enhancing / improving coating properties, such as ultraviolet light absorbers and / or antioxidants, etc., wherein the ultraviolet light absorber can be selected from BASF Tinuvin 99-2, Tinuvin 384-2, Tinuvin 928, Tinuvin 1130, Tinuvin CaroProtect, Tinuvin 400, Tinuvin 477, or Tinuvin 479, etc., and the antioxidant can be selected from Antioxidant 264 (BHT), BASF Tinuvin 123, Tinuvin 249, Tinuvin 292, or Tinuvin 5151, etc.

[0120] In some embodiments, for scenarios requiring plasticization and weather resistance, the functional component D can be selected from hydroxyl-terminated polydimethylsiloxane (PDMS) having a molecular weight of 100 to 2000 grams per mole, preferably a molecular weight of 100 to 500 grams per mole; for scenarios requiring plasticization and compatibilization, the functional component D can be selected from hydroxyl acrylic resin; for scenarios requiring cross-linking / assisted film formation, the functional component D can be selected from bisphenol A glycidyl ether type epoxy resin, such as a combination of one or more of E51, E44, E20, or E12.

[0121] In some specific embodiments, when the functional component D is selected from hydroxyl-terminated polydimethylsiloxane (PDMS), the mass ratio of its amount to the coating composition is in the range of 0 to 30%, preferably in the range of 2 to 20%, and more preferably in the range of 1 to 10%; when the functional component D is selected from hydroxyl acrylic resin, the mass ratio of its amount to the coating composition is in the range of 0.1 to 30%, preferably in the range of 1 to 10%.

[0122] In some embodiments, the functional component D may include common coating additives, such as pigments, fillers, dispersants, thickeners, defoamers, and the like.

[0123] It is understandable that the present invention does not limit the type or content of the functional component D in the provided coating composition, and those skilled in the art can freely select it according to the needs of the actual use scenario in combination with their professional knowledge. For example, a certain type of substance with a specific auxiliary function can be added, or a mixture of several types with the same or different auxiliary functions can be added.

[0124] It should be noted that the coating composition of the present invention may be a mixture mixed together, or a combination of some components physically independent. When at least some of the components are physically independent, each different component may be stored in a different container, or two or more components may be mixed and then stored in a different container with other components.

[0125] In some embodiments, the main agent A and the curing agent B in the coating composition provided by the present invention are stored or packaged in different containers, respectively.

[0126] In some embodiments, the three components of the coating composition provided by the present invention, namely, the main agent A, the curing agent B, and the catalyst C, are stored or packaged in different containers, respectively.

[0127] In some embodiments, the three components of the main agent A, curing agent B, and catalyst C in the coating composition provided by the present invention are stored or packaged in different containers respectively, and the functional component D in the solvent-free composition can be stored or packaged in a separate container, or can be mixed and stored or packaged in the container of the main agent A, curing agent B, or catalyst C.

[0128] In a specific embodiment, the three components of the coating composition, namely the main agent A, the curing agent B, and the catalyst C, are packaged separately. When used, the step of mixing the separately packaged components in a certain proportion is included. The mixing step is preferably carried out under conditions that minimize or avoid curing.

[0129] The coating composition provided by the present invention is physically mixed, and after being applied to a substrate, it absorbs water molecules and undergoes a chemical reaction to generate polysiloxane (main structure) and polyurethane (or carbamate) plasticizer components, thereby forming a stable paint film on the surface of the substrate.

[0130] Figure 1 A typical process flow of production and use of coating composition is given. First, the raw materials of each component used to prepare the coating composition are confirmed, and each raw material is produced according to a certain preparation method and / or process, for example, it may include process steps such as dispersion, grinding or coloring; then, the product produced is quality inspected according to the preset standards, and the product that passes the quality inspection can enter the packaging process to form a coating composition product. For example, a possible product form is to form a product including main agent A, curing agent B and catalyst C separately packaged. When the coating composition product is used to coat the surface of the substrate, it is first necessary to mix and / or mature the components separately, and the surface of the substrate can be pre-treated as needed, such as grinding or polishing; after the coating composition and the substrate are ready, the coating composition can be applied to the surface of the substrate according to the set construction parameters (such as temperature or humidity), and the coating composition is completed after it is cured into a film.

[0131] In some specific embodiments, the components can be mixed evenly to form a coating composition, which is then applied to the surface of the substrate to form a paint film with a thickness of 5 μm to 1000 μm, preferably 30 to 150 μm. An example of production conditions may be: the ambient humidity is maintained at 5% RH to 95% RH, at room temperature (e.g., 5 to 40° C.), and the finger-drying time is 10 minutes to 6 hours to form a cured paint film.

[0132] In one embodiment, humidification means can also be used to achieve a suitable ambient humidity in the paint shop, wherein the humidity can be selected to be 5% RH to 100% RH, 10% RH to 95% RH, 20% RH to 95% RH, 30% RH to 95% RH, 40% RH to 95% RH, or 50% RH to 95% RH; preferably, the humidity is 20% RH to 90% RH, more preferably 30% RH to 75% RH, for example, 35% RH, 40% RH, 50% RH, 55% RH, 60% RH, 64% RH, 65% RH, 67% RH, 70% RH, or 75% RH.

[0133] In one embodiment, low temperature heating means can also be used to make the paint shop reach a suitable ambient temperature. The upper temperature limit can be reasonably adjusted according to factors such as silane volatility, coating anti-sagging, curing shrinkage, appearance, etc., and the heating energy consumption and benefits must be weighed in the actual production process. Specifically, the temperature can be 20 to 80°C, preferably 40 to 80°C, such as 45°C, 50°C, 55°C, 60°C, 65°C, 70°C or 75°C.

[0134] Some optional construction parameters are exemplified below.

[0135] In a specific implementation, for a large workpiece and when heating conditions are limited, the following construction parameters may be used:

[0136] (1) Wet film thickness 50 to 100 μm;

[0137] (2) Catalyst content: dibutyltin dilaurate (total weight 0.1‰ to 1‰), DMP-30 or DBU total weight 0.1‰ to 1‰, acetylacetone (total weight 0.5% to 5%);

[0138] (3) Construction temperature: 0°C to 40°C (the temperature is not controlled, so the actual temperature depends on the air temperature in the workshop during construction);

[0139] (4) Construction humidity: 5%RH to 95%RH, preferably 20%RH to 90%RH, more preferably 30%RH to 70%RH.

[0140] In a specific implementation, for a scenario where rapid curing is required but heating conditions are limited, the following construction parameters may be used:

[0141] (1) Wet film thickness 30 to 50 μm;

[0142] (2) Catalyst: DMP-30 or DBU (total weight 0.5% to 1%); dibutyltin dilaurate (total weight 0.5% to 1%);

[0143] (3) Construction temperature: 5°C to 40°C (the temperature is not controlled, so the actual temperature depends on the air temperature in the workshop during construction);

[0144] (4) Construction humidity: 5%RH to 95%RH, preferably 20%RH to 90%RH, more preferably 30%RH to 70%RH.

[0145] In a specific embodiment, for a scenario where rapid curing is required and heating curing is possible, the following construction parameters may be used:

[0146] (1) Wet film thickness 50 to 150 μm;

[0147] (2) Catalyst: dibutyltin dilaurate (total weight 0.1‰ to 1‰): acetylacetone (total weight 0.5% to 5%);

[0148] (3) Construction temperature: heated to 40°C to 80°C;

[0149] (4) Construction humidity: 5%RH to 95%RH, preferably 20%RH to 90%RH, more preferably 30%RH to 70%RH.

[0150] It should be noted that the paint film obtained based on the coating composition provided by the present invention has the following performance advantages compared with typical commercial coating product systems (such as epoxy, polyurea and polyurethane):

[0151] Viscosity Operation time Curing rate Anti-corrosion and weathering The present invention Low long Fast and flexible according to needs Good anti-corrosion and excellent weather resistance Epoxy (bisphenol F + modified fatty amine) medium Medium to short generally Excellent corrosion resistance, poor weather resistance Epoxy (Silane Modified) medium medium quick Excellent anti-corrosion, average weather resistance Polyurea-primary amine Medium to high Very short Very fast excellent Polyurea-Secondary Amine Medium to high Medium to short generally excellent Polyurethane (polyol + isocyanate) medium Medium to short quick generally

[0152] It should be emphasized that the coating composition provided by the present invention has outstanding advantages over general polyurethane (polyol + isocyanate) coating systems. For example, compared with high-solid, ultra-high-solid, or even solvent-free polyurethane systems, the coating composition provided by the present invention has a lower viscosity, can achieve a longer and controllable operable time, and is convenient for construction operations; compared with organic solvent polyurethane systems, the coating composition provided by the present invention has extremely low VOC, overcomes the pollution problem caused by the volatilization of organic solvents, and is more environmentally friendly; compared with water-based polyurethane systems, the coating composition provided by the present invention has an increased single-layer coating thickness, and does not need to be diluted with water, which overcomes the solubility problem of some organic matter in water, and solves the problem that water-based polyurethane cannot be applied thickly.

[0153] In addition, the present invention provides a coated material product, comprising a substrate and a coating in contact with the surface of the substrate, wherein the coating is prepared in an aqueous environment based on the coating composition provided by the present invention.

[0154] In addition, the present invention also provides a coating kit, comprising a substrate, a coating composition provided by the present invention, and optionally, a user manual.

[0155] It should be noted that the technical solution of the present invention has no special restrictions on the material, shape, structure, surface characteristics, etc. of the substrate to which it is applicable.

[0156] In some embodiments, the substrate may include common steel structural materials in the industrial field, composite materials (e.g., epoxy, polyurethane, unsaturated polyester coatings containing pigments and fillers, continuous fiber reinforced epoxy, fiber reinforced polyurethane, or fiber reinforced unsaturated ester, etc.), various engineering plastics, natural organic materials (e.g., wood), and cement or concrete inorganic building materials, etc.

[0157] In some embodiments, the substrate can be of any thickness; the substrate surface can be smooth, substantially smooth, or textured; and the substrate can be regular or irregular in shape.

[0158] It should be noted that the coated material product or solvent coating kit involved in the present invention can be independently applied to a variety of industries without special restrictions, including but not limited to the office supplies industry, the electronic and electrical products industry, and the construction industry.

[0159] In some embodiments, in order to ensure good adhesion between the paint film and the substrate layer, the coating composition may be pre-treated on the substrate surface before coating; for example, after removing impurities and oil stains, the surface may be physically sandblasted, polished or plasma treated.

[0160] In addition, the present invention also provides a method for using the coating composition, comprising the step of coating the coating composition provided by the present invention on the surface of a substrate in a water environment.

[0161] In some embodiments, the method of using the coating composition comprises the following steps:

[0162] S1: uniformly mixing the components of the coating composition;

[0163] S2: uniformly coating the coating composition mixed uniformly in S1 on the substrate;

[0164] S3: Set appropriate humidity to cure the coating;

[0165] S4: Waiting for the coating composition to cure to form a paint film.

[0166] In some embodiments, the method of using the coating composition comprises the following steps:

[0167] S1: uniformly mixing the components of the coating composition;

[0168] S2: uniformly coating the coating composition mixed uniformly in S1 on the substrate;

[0169] S3: waiting for the coating composition to cure to form a paint film;

[0170] As required, before step S3, certain curing parameters (such as temperature and humidity) may be set to meet the environmental requirements for coating curing.

[0171] In addition, the present invention also provides a product coated with a coating prepared based on the above method.

[0172] The reaction mechanism of the curing process of the coating system of the present invention is likely to be the following steps:

[0173] Step 1: The silane or its oligomer having silane alkoxy groups in the main agent A reacts with water molecules in the air to form silanol and alkyl alcohol:

[0174]

[0175] Step 2: Under the catalytic action of catalyst C, the isocyanate group of curing agent B rapidly undergoes addition reaction with the alkyl alcohol product in step 1 to form (poly) alkyl carbamate. Since the alkyl alcohol product in step 1 is consumed, the reaction in step 1 rapidly proceeds in the forward direction, that is, the reaction in step 2 strongly promotes the reaction in step 1:

[0176]

[0177] Step 3: Under the promotion of step 2, a large amount of silanols are formed in step 1. Silanols can condense with themselves, releasing water molecules and forming silicon-oxygen-silicon covalent bonds, i.e., the main chain of polysiloxane:

[0178]

[0179] Alternatively, silanol can undergo addition substitution reaction with the siloxy group of the main agent A to form a silicon-oxygen-silicon covalent bond, i.e., a polysiloxane main chain structure, while releasing new alkyl alcohol:

[0180]

[0181] Step 4: The water molecules and alkyl alcohol generated by the above reaction repeatedly participate in reaction steps 1 to 3 to form more polysiloxane main chain structures. The proportion of the main chain structure increases as the reaction progresses, and finally a paint film with highly cross-linked and cured polysiloxane as the main component is formed.

[0182] Through experimental research, it is believed that water molecules preferentially react with the main agent A in the coating composition of the present invention in step 1, and will not react with the isocyanate groups in the curing agent B in large quantities.

[0183] It can be seen that compared with the existing solutions (for example, using the main agent A alone as a coating raw material is one of the typical applications of commercial one-component silicone coatings), the alkyl alcohol produced in the technical solution of the present invention will further react with the isocyanate group in the curing agent B to form an alkyl urethane component that remains in the paint film (step 2), thereby avoiding the environmental pollution problem caused by VOC emissions and meeting the solvent-free / ultra-high solid content / high solid content standards. At the same time, the alkyl urethane component helps to increase the adhesion between the coating and the substrate, so that the applicability of the technical solution of the present invention to various substrates has reached the same level as that of ordinary polyurethane systems, and is superior to common one-component silicone commercial product systems.

[0184] It is understandable that the above description is only an explanation of the technical solution and technical effect of the present invention from the perspective of mechanism, and does not limit the protection scope of the present invention.

[0185] The technical scheme and technical effects of the present invention will be further described below in conjunction with specific embodiments and comparative examples.

[0186] Example 1: Preparation of coating compositions 1-1 to 1-18

[0187] Each component was formulated according to the substance and content formula in Table 1 to obtain the corresponding coating composition.

[0188] Among them, the molar content of the substance in the main agent A is calculated based on the molar content of the siloxy groups therein, the molar content of the substance in the curing agent B is calculated based on the molar content of the isocyanate groups therein, and the content of the catalyst C and the functional component D is calculated based on the mass fraction of the coating composition they occupy.

[0189] Table 1: Formulations of coating compositions (1-1 to 1-18)

[0190] Main agent A substance (molar content) Curing agent B substance (molar content) Catalyst C substance (mass fraction) Functional component D substance (mass fraction) Molar ratio of main agent A to curing agent B 1-1 KH570 (3) Wanhua Chemical PM200 (2) / / 1.5 1-2 KH570 (3) Covestro CDC (2) / / 1.5 1-3 KH570 (3) Covestro N3300 (1.5) DBTL (1‰) / 2 1-4 KH631 (3) Covestro N3300 (1.5) DBTL (1‰) / 2 1-5 KH560 (3) Covestro N3300 (1.5) DBTL (1‰) / 2 1-6 LA2388 (3) Covestro N3300 (1.5) DBTL (1‰) / 2 1-7 SH3047 (3) Covestro N3300 (1.5) DBTL (1‰) / 2 1-8 KH570 (3) Wanhua Chemical PM200 (2) DBTL (0.1‰) Acetylacetone (1%) / 1.5 1-9 KH570 (3) Covestro E21 (2) DBTL (0.1‰) Acetylacetone (1%) / 1.5 1-10 KH570 (3) Covestro CDC (2) DBTL (0.1‰) Acetylacetone (1%) / 1.5 1-11 KH570 (3) Dicyclohexylmethane diisocyanate (2) DBTL (0.1‰) Acetylacetone (1%) / 1.5 1-12 KH570 (3) Covestro N3300 (3) DBTL (0.1‰) Acetylacetone (1%) / 1 1-13 KH570 (3) Covestro N3300 (2) DBTL (0.1‰) Acetylacetone (1%) / 1.5 1-14 KH570 (3) Covestro N3300 (1) DBTL (0.1‰) Acetylacetone (1%) / 3 1-15 KH570 (3) Covestro N3300 (0.6) DBTL (0.1‰) Acetylacetone (1%) / 5 1-16 KH570 (3) Covestro N3300 (0.3) DBTL (0.1‰) Acetylacetone (1%) / 10 1-17 KH570 (3) Covestro N3300 (1.5) DMP-30 (1‰) / 2 1-18 KH570 (3) Covestro N3300 (1.5) DBTL (1‰) PDMS (10%) 2

[0191] Example 2: Use of coating compositions 1-1 to 1-18

[0192] Coating compositions 1-1 to 1-18 were prepared according to the formula in Table 1 to obtain uniform mixed coatings, which were applied to the surface of the substrate, and then dried and cured to form a paint film, and the finger-press dry time of each was recorded, as shown in the following Table 2. The test method of the finger-press dry time refers to the description of ASTM D 1640.

[0193] Table 2: Curing of coating compositions 1-1 to 1-18

[0194] Substrate Temperature and humidity of coating environment Temperature and humidity of the curing environment Finger press drying time 1-1 Tinplate 22℃,67%RH 60℃,50%RH 70 minutes 1-2 Tinplate 22℃,67%RH 60℃,50%RH 80 minutes 1-3 Tinplate 22℃,75%RH 60℃,50%RH 20 minutes 1-4 Tinplate 21℃,64%RH 60℃,50%RH 25 minutes 1-5 Tinplate 21℃,64%RH 60℃,50%RH 25 minutes 1-6 Tinplate 21℃,64%RH 60℃,50%RH 30 minutes 1-7 Tinplate 21℃,64%RH 60℃,50%RH 240 minutes 1-8 Tinplate 22℃,67%RH 60℃,50%RH 30 minutes 1-9 Tinplate 22℃,67%RH 60℃,50%RH 20 minutes 1-10 Tinplate 22℃,67%RH 60℃,50%RH 25 minutes 1-11 Tinplate 21℃,64%RH 60℃,50%RH 195 minutes 1-12 Tinplate 21℃,64%RH 60℃,50%RH 35 minutes 1-13 Tinplate 21℃,64%RH 60℃,50%RH 30 minutes 1-14 Tinplate 21℃,64%RH 60℃,50%RH 20 minutes 1-15 Tinplate 21℃,64%RH 60℃,50%RH 30 minutes 1-16 Tinplate 21℃,64%RH 60℃,50%RH 30 minutes 1-17 Tinplate 21℃,64%RH 60℃,50%RH 240 minutes 1-18 Tinplate 22℃,75%RH 60℃,50%RH 30 minutes 1-3 (low humidity) Tinplate 22℃,75%RH 60℃,10%RH 45 minutes

[0195] According to the data in Table 2, within the scope of the technical solution disclosed in the present invention, by changing the type and ratio of the main agent A and the curing agent B, the formed coating compositions 1-1 to 1-19 can be successfully cured to form a paint film under certain temperature and humidity environment settings. Among them, by comparing the data of coating compositions 1-1 and 1-8, and coating compositions 1-2 and 1-10, it can be found that by adding an appropriate amount of catalyst to the formula of the coating composition, the efficiency of curing the coating composition to form a paint film can be significantly promoted. By comparing the data of coating compositions 1-3 to 1-7, it can be found that selecting different types of main agents A can adjust the finger-pressing dry time for forming a paint film to a certain extent, among which KH570, KH631 and KH560 are used as the main agent A. The finger-pressing dry time is shorter. By comparing the data of coating compositions 1-8 to 1-11, it can be found that selecting different types of curing agents B also has a certain effect on adjusting the finger-pressing dry time for forming a paint film, among which dicyclohexylmethane diisocyanate is used as the curing agent B. The finger-pressing dry time is longer (suitable for slow curing scenarios). By comparing the data of coating compositions 1-12 to 1-16, it can be seen that when the ratio of the main agent A and the curing agent B varies in the range of 1 to 10, they can all be cured to form a paint film. By comparing the data of coating compositions 1-3 and 1-17, it can be seen that the type of catalyst selected has a greater influence on the adjustment of the finger-drying time for forming the paint film. By comparing the data of coating compositions 1-3 and 1-18, it can be seen that adding an appropriate amount of functional component D to the coating composition, while bringing additional performance to the paint film, has little effect on its finger-drying time. By comparing the data of coating compositions 1-3 and 1-3 (low humidity), it can be seen that the coating composition disclosed in the present invention can still be successfully cured to form a paint film at an ambient humidity as low as 10% RH, and changing the humidity of the environment has a certain regulating effect on the finger-drying time of the paint film. Generally speaking, the higher the humidity, the faster the curing rate.

[0196] Example 3: Preparation of coating compositions 1-19 to 1-22

[0197] The coating compositions 1-19 to 1-22 were prepared according to the materials and content formulas in Table 3, wherein "parts" refers to parts by mass.

[0198] Table 3: Formulations of coating compositions (1-19 to 1-22)

[0199] Main agent A Curing agent B Catalyst C Functional component D 1-19 KH570 (248 copies) Covestro N3300 (280 copies) DBTL (0.5 parts) Acetylacetone (11 parts) Titanium dioxide (83 parts) 4A molecular sieve (22 parts) dispersant (5 parts) thickener (5 parts) hydroxy 9% PDMS (55 parts) 1-20 KH570 (248 copies) Covestro N3300 (248 copies) DBTL (0.5 copies) Carbon black (5 parts) Dispersant (5 parts) Allnex 1198 (15 parts) UV absorber (1.5 parts) Antioxidant (1.5 parts) 1-21 KH570 (248 copies) Wanhua Chemical PM200 (270 copies) DBTL (0.01 parts) Acetylacetone (5 parts) Titanium dioxide (158 parts) 4A molecular sieve (15 parts) dispersant (5 parts) thickener (1.5 parts) E20 epoxy resin (104 parts) 1-22 KH570 (248 copies) Wanhua Chemical PM200 (420 copies) DBTL (0.5 copies) Hydroxyl 9% PDMS (82 parts)

[0200] Comparative Example 1: Preparation of commonly used coating compositions (D1, D2 and D3) on the market

[0201] The components were formulated according to the substances and contents in Table 4 to obtain the corresponding coating compositions D1, D2 and D3, wherein the numbers in brackets are the mass fractions of the components in the coating composition.

[0202] Table 4: Formulations of common coating compositions (D1, D2 and D3)

[0203] Main agent Curing agent other D1 (two-component epoxy) Bisphenol F epoxy resin (20%), reactive diluent (5.6%), petroleum hydrocarbon resin (2.4%), silane coupling agent (4%) Fatty amine adduct (20%) Cardanol aldehyde amine (4%) Barium sulfate (36%) Titanium dioxide (6.4%) Dispersant (0.4%) Defoamer (0.4%) Catalyst (0.2%) D2 (two-component polyurea) Covestro NH1420 (50%) Covestro N3600 (35%) Titanium dioxide (15%), dipropylene glycol dimethyl ether (5%), dispersant (0.3%), defoamer (0.3%) D3 (two-component fluorocarbon polyurethane) Changxing Chemical 3320 (40%) Covestro BAYHYDOL A 2846 (40%) Covestro BAYHYDOL A2846 (10%) Carbon black (1%), dipropylene glycol dimethyl ether (2.5%), dispersant (0.5%), defoamer (0.3%)

[0204] Example 4: Use of coating compositions 1-19 to 1-22, D1 to D3

[0205] The components of the coating composition in Example 3 and Comparative Example 1 are dispersed, ground, and uniformly mixed, and then "ripened", that is, after being mixed uniformly, wait for a period of time before construction, which is conducive to obtaining better component miscibility, thereby bringing better film-forming performance. After aging, coating can be carried out. Among them, D3 is a water-based two-component fluorocarbon polyurethane coating. Before coating, it is necessary to add an appropriate amount of deionized water to the coating composition to reach the construction viscosity. In this embodiment, the volume mixing ratio of D3 coating composition and deionized water is 100: (40~50).

[0206] In the coating workshop, the coating compositions obtained above were uniformly sprayed on the surface of a specific substrate according to the construction parameters in Table 5. The selection and treatment of the substrate are as described in Table 5.

[0207] The operating instruments involved in the coating process are as follows:

[0208] Spraying: Compressed air small-caliber paint spray gun;

[0209] Brush coating: Use a small brush to apply to the corresponding substrate; D1 and D2 are brush-coated.

[0210] Oven: Electric heating blast drying oven.

[0211] Among them, finger-press dry time: after spraying is completed, the corresponding finger-press dry time is recorded in an oven environment with a certain temperature and humidity. The test method of the finger-press dry time refers to the record of ASTM D 1640.

[0212] Table 5: Construction parameters

[0213] Substrate Coating environment temperature Coating environment humidity Coating thickness Finger press drying time Full curing time 1-19 Epoxy fiberglass material, surface polished to no gloss 18℃ 40%RH 125±25 microns About 45 minutes (60°C, 10%RH oven) 1 hour in oven (60°C) + 7 days natural drying (25°C) 1-19 Epoxy fiberglass material, surface polished to no gloss 18℃ 40%RH 125±25 microns About 10 minutes (60°C, 50%RH oven) 1 hour in oven (60°C) + 7 days natural drying (25°C) D1 Epoxy fiberglass material, surface polished to no gloss 20℃ 45%RH 125±25 microns About 60 minutes (60°C, 10%RH oven) 1 hour in oven (60°C) + 7 days in natural drying (25°C) D2 Epoxy fiberglass material, surface polished to no gloss 20℃ 40%RH 125±25 microns About 12 minutes (60°C, 10%RH oven) 1 hour in oven (60°C) + 7 days in natural drying (25°C) 1-20 Phosphorus iron plate material, surface polished to no gloss 17℃ 35%RH 90±25 microns About 50 minutes (60°C oven, 10% RH) 1 hour in oven (60°C) + 7 days natural drying (25°C) D3 Phosphorus iron plate material, surface polished to no gloss 20℃ 50%RH 60±10 microns About 30 minutes (60°C oven) 1 hour in oven (60°C) + 7 days in natural drying (25°C) 1-21 Carbon steel Q235 material, surface sandblasted SA2.5 and sprayed with 20 micron thick M116-9080 water-based zinc-rich primer 25℃ 45%RH 80±20 microns About 50 minutes (60°C oven, 10% RH) 1 hour in oven (60°C) + 7 days in natural drying (25°C) D1 Carbon steel Q235 material, surface sandblasted SA2.5 and sprayed with 20 micron thick M116-9080 water-based zinc-rich primer 25℃ 45%RH 80±20 microns About 60 minutes (60°C, 10%RH oven) 1 hour in oven (60°C) + 7 days in natural drying (25°C) 1-22 Carbon steel Q235 material, no surface treatment 17℃ 40%RH 75±15 microns About 30 minutes (80°C, 10%RH oven) 50 minutes in oven (80°C) + 7 days in natural drying (25°C) D1 Carbon steel Q235 material, no surface treatment 17℃ 40%RH 90±25 microns About 60 minutes (60°C, 10%RH oven) 1 hour in oven (60°C) + 7 days in natural drying (25°C)

[0214] According to the construction parameter data in Table 5, each coating composition can be cured to form a paint film under certain construction parameters. By comparing the two sets of data 1-19, the technical solution disclosed in the present invention can also flexibly adjust the finger-pressing drying time required to form a paint film by changing the environmental conditions. For example, under the same conditions, by adjusting the humidity of the oven from 10% RH to 50% RH, the finger-pressing drying time can be greatly reduced.

[0215] Example 5: Determination of the construction performance of coating compositions 1-19 to 1-22, D1 to D3

[0216] Through experimental measurement, the construction performance parameters of the coating compositions 1-19 to 1-22 and D1 to D3 were obtained and are shown in Table 6 below.

[0217] Table 6: Construction performance of each coating composition

[0218] Substrate Initial mixed viscosity (KU) Single sprayable thickness (micrometer) Operating time (35℃) Solid content 1-19 Epoxy fiberglass material, surface polished to no gloss Approx. 50 ＞200 1.5~2 hours About 94% 1-20 Phosphorus iron plate material, surface polished to no gloss Approx. 45 ＞200 >1 hour / 1-21 Carbon steel Q235 material, surface sandblasted SA2.5 and sprayed with 20 micron thick M116-9080 water-based zinc-rich primer Approx. 50 ＞200 45 minutes to 1.5 hours About 93% 1-22 Carbon steel Q235 material, no surface treatment Approx. 50 ＞200 / About 92% D1 Epoxy fiberglass material, surface polished to no gloss Approx. 80 ＞200 ≤40 mins About 96% D1 Carbon steel Q235 material, surface sandblasted SA2.5 and sprayed with 20 micron thick M116-9080 water-based zinc-rich primer Approx. 80 ＞200 ≤40 mins About 96% D1 Carbon steel Q235 material, no surface treatment Approx. 80 ＞200 ≤40 mins About 96% D2 Epoxy fiberglass material, surface polished to no gloss Approx. 80 ＞200 ≤ 8 mins About 94% D3 Phosphorus iron plate material, surface polished to no gloss About 80 (with deionized water) 60 / About 50%

[0219] Among them, each construction performance parameter is obtained through the following measurement steps or calculation methods:

[0220] Initial mixed viscosity: The viscosity of the system is measured within 5 to 10 minutes after the components are mixed into the coating composition, thereby obtaining the initial mixed viscosity. The viscosity is measured using the Stormer viscometer method (reference GB-T 9269-2009), and the unit of the measured viscosity is Krebs unit (KU).

[0221] Single sprayable thickness: Under the premise that the appearance and performance of the paint film meet the standards, the paint film is as thick as possible in a single coating, and the corresponding dry film thickness is the single sprayable thickness. Among them, when the single spraying thickness reaches 200 microns, it is found that the appearance and performance of the paint film can still meet the standards, then the test is stopped, and it is considered that the single sprayable thickness of the coating composition is greater than 200 microns.

[0222] Operable time: Place the paint mixture container in a 35°C constant temperature water bath and stir slowly (30-120 rpm), and count from the time the paint is mixed to the time when the rotational viscosity is greater than 85KU. (Due to the high initial mixed viscosity (close to or greater than 80KU), the operable time of D1 and D2 is counted from the time the paint is mixed to the time when film formation is impossible)

[0223] Solid content: Under the condition of natural drying at room temperature for 7 days, the mass change of the coating composition before and after curing was measured, and the mass fraction after curing to that before curing was calculated.

[0224] According to the data in Table 6 above, the technical solution disclosed in the present invention has a lower initial mixing viscosity (less than 70KU) than the prior art, which is convenient for construction and coating operations; correspondingly, the operable time of coating compositions 1-19 and 1-21 can reach more than 1 hour, while the operable time of coating compositions D1 and D2 is less than 1 hour, and even the operable time of D2 is less than 10 minutes. At the same time, the single sprayable thickness of the technical solution disclosed in the present invention can reach a level comparable to that of the two-component epoxy system (D1) and the two-component polyurea system (D2) of the prior art, and is much higher than the water-based two-component fluorocarbon polyurethane system (D3). In addition, the technical solution disclosed in the present invention can reach the level of ultra-high solid content coating compositions, and the solid content of coating compositions 1-19, 1-21 and 1-22 is above 90%.

[0225] Example 6: Determination of coating film properties of coating compositions 1-19 to 1-22

[0226] Through experimental measurement, the performance measurement data of the above coating compositions after curing to form paint films on different substrate surfaces are shown in Table 7 below.

[0227] Table 7: Properties of the paint films formed by various coating compositions

[0228] Substrate Pull-off Adhesion Cross-cut Adhesion Shock resistance Watertight Salt spray resistant UVB aging resistance Humidity UV resistant 1-19 Epoxy fiberglass material, surface polished to no gloss ~15Mpa Level 0 / / / 3000 hours color difference ΔE*<4; light loss rate about 50% / D1 Epoxy fiberglass material, surface polished to no gloss ~20Mpa Level 0 / / / 168 hours color difference ΔE*>4; / D2 Epoxy fiberglass material, surface polished to no gloss ~15Mpa Level 0 / / / 1500 hours light loss rate is about 50% / 1-20 Phosphorus iron plate material, surface polished to no gloss / Level 0 / / / / When the irradiation amount is 250kwh / m2, it starts to powderize, and the color difference ΔE*≈2~3; when the irradiation amount is 300kwh / m2, it reaches the second level of powderization, and the color difference ΔE*≈2~3 D3 Phosphorus iron plate material, surface polished to no gloss / Level 0 / / / / Irradiation: 250kwh / m2, no powdering; color difference ΔE*≈5~6 1-21 Carbon steel Q235 material, surface sandblasted SA2.5 and sprayed with 20 micron thick M116-9080 water-based zinc-rich primer / Level 0 >50kgcm / >240 hours / / D1 Carbon steel Q235 material, surface sandblasted SA2.5 and sprayed with 20 micron thick M116-9080 water-based zinc-rich primer / Level 0 >50kgcm / >240 hours / / 1-22 Carbon steel Q235 material, no surface treatment / Level 0~1 >50kgcm >480 hours / / / D1 Carbon steel Q235 material, no surface treatment / Level 0~1 >50kgcm >480 hours / / /

[0229] Among them, the cross-hatch adhesion, pull-off adhesion or impact resistance test is mainly used to evaluate the substrate adhesion and flexibility of the paint film, the watertightness and salt spray resistance are mainly used to evaluate the corrosion resistance of the paint film, and the UVB aging resistance and humidity resistance are mainly used to evaluate the weather resistance of the paint film. Each paint film performance parameter is obtained through the following measurement steps or calculation methods:

[0230] The test method for cross-cut adhesion refers to GB / T 9286; the test method for pull-off adhesion refers to GB / T 5210; the test method for impact resistance refers to GB / T 1732; the test method for watertightness resistance refers to ISO 6270-2, where the test temperature is 60°C; the test method for salt spray resistance refers to ISO9227; the test method for UVB aging resistance refers to Type 1 of GB / T 23981 (4 hours of light exposure at 60°C and 4 hours of spraying at 50°C); the moisture and UV resistance is tested using a 3KW halogen lamp, where the sample temperature is 85~130°C, the sample test box environment humidity is 75%RH~95%RH, and the sample UV exposure irradiation intensity is 1000~1300W / m 2 (UVB radiation intensity accounts for UVB / (UVA+UVB)≈3~5%), the radiation amount is calculated as total radiation intensity*test time, the unit is kwh / m 2 .

[0231] According to the data in Table 7, the paint film obtained by the technical solution disclosed in the present invention after construction through conventional formula adjustment can reach standards comparable to or even better than the prior art in terms of substrate adhesion performance, corrosion resistance, and weather resistance. Specifically, by comparing the performance test data of coating compositions 1-19, D1 and D2 on epoxy glass fiber reinforced plastic materials, the surface of which is polished to a substrate without gloss, it can be seen that the pull-out adhesion and cross-cut adhesion levels of coating composition 1-19 are comparable to the prior art, and the UVB aging resistance is better than the prior art. By comparing the performance test data of coating compositions 1-20 and D3 on phosphorus iron plate materials, the surface of which is polished to a substrate without gloss, it can be seen that the cross-cut adhesion of coating composition 1-20 is comparable to the prior art, and the wet UV resistance is excellent, and the color difference change is smaller under the same irradiation amount. By comparing the performance test data of coating compositions 1-21 and D1 on carbon steel Q235 material, surface sandblasted SA2.5 and sprayed with 20 micron thick M116-9080 water-based zinc-rich primer, it can be seen that the cross-cut adhesion, impact resistance and salt spray resistance can reach the level comparable to the prior art. By comparing the performance test data of coating compositions 1-22 and D1 on carbon steel Q235 material, substrates without surface treatment, it can be seen that the cross-cut adhesion, impact resistance and watertightness resistance can also reach the level comparable to the prior art. It can be seen that the paint film obtained according to the technical solution disclosed in the present invention has excellent performance and high industrial and commercial application value.

[0232] The above description is only a preferred embodiment of the present invention, and does not limit the patent scope of the present invention. All equivalent transformations made by using the contents of the present specification and drawings under the inventive concept of the present invention, or direct / indirect application in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A coating composition, characterized in that The components include: A main agent A, wherein the main agent A comprises a silane small molecule containing a silane alkoxy group and / or a silane oligomer containing a silane alkoxy group, and Curing agent B, wherein the curing agent B includes a small molecule containing an isocyanate group and / or a polymer whose monomer contains at least one isocyanate group; The molar ratio of the silanol group in the main agent A to the isocyanate group in the curing agent B is 1 to 10; the main agent A contains at least one silanol group that can undergo a hydrolysis reaction with water molecules to form silanol and alkyl alcohol, and compared with the isocyanate group in the curing agent B, the water molecule preferentially undergoes a hydrolysis reaction with the silanol group; Wherein, under normal temperature and pressure and in the absence of a catalyst, the silane small molecule containing silanoxy groups and / or the silane oligomer containing silanoxy groups and the small molecule containing isocyanate groups and / or the polymer containing at least one isocyanate group in the monomer do not undergo a one-step addition reaction, or the silane small molecule containing silanoxy groups and / or the silane oligomer containing silanoxy groups do not contain active hydrogen, or The coating composition remains liquid in an anhydrous environment.

2. The coating composition according to claim 1, further comprising the following components: Catalyst C, wherein the catalyst C comprises at least one catalyst capable of catalyzing the addition reaction between the hydroxyl group of the alkyl alcohol and the isocyanate group.

3. The coating composition according to claim 2, wherein: The silane small molecule containing a silicon alkoxy group includes at least one of an alkoxysilane having a saturated alkyl group, an alkoxysilane having an ester group, an alkoxysilane having an unsaturated hydrocarbon group, or an alkoxysilane having an epoxy group; and / or The silane oligomer containing silane alkoxy groups is polymerized from at least one monomer containing silane alkoxy groups, has a degree of polymerization of 2 to 20, and has a viscosity at 25° C. in the range of 10 centipoise to 10,000 centipoise; and / or The silane oligomer containing silane alkoxy groups is polymerized from one or more monomers selected from alkoxysilane containing saturated alkyl groups, alkoxysilane containing ester groups, alkoxysilane containing unsaturated hydrocarbon groups, or alkoxysilane containing epoxy groups.

4. The coating composition according to claim 3, wherein: The silane small molecule containing silane alkoxy groups is selected from one or more of methacryloxypropyl trimethoxysilane, phenyl trimethoxysilane, vinyl trimethoxysilane, glycidyl ether propyl trimethoxysilane, methyl trimethoxysilane, dimethyl dimethoxysilane, methyl phenyl dimethoxysilane, diphenyl dimethoxysilane, methacryloxypropyl triethoxysilane, vinyl triethoxysilane, phenyl triethoxysilane, glycidyl ether propyl triethoxysilane, methyl triethoxysilane, dimethyl diethoxysilane, diphenyl diethoxysilane, or methyl phenyl diethoxysilane.

5. The coating composition according to claim 3, wherein: The silane small molecule containing silaneoxy groups is selected from one or more of vinyl trimethoxy silane, dimethyl dimethoxy silane, methacryloxy propyl trimethoxy silane, glycidyl ether propyl trimethoxy silane, and phenyl trimethoxy silane; and / or The silane oligomer containing silane alkoxy groups is polymerized from one or more monomers selected from vinyl trimethoxy silane, dimethyl dimethoxy silane, methacryloxy propyl trimethoxy silane, glycidyl ether propyl trimethoxy silane, and phenyl trimethoxy silane.

6. The coating composition according to claim 2, wherein: The small molecule containing an isocyanate group is selected from aromatic isocyanates or aliphatic isocyanates; and / or The polymer containing at least one isocyanate group is selected from aromatic isocyanate polymers or aliphatic isocyanate polymers; and / or The polymer having at least one isocyanate group has a viscosity of less than 10,000 centipoise at 40°C; and / or, The molecular weight of the polymer containing at least one isocyanate group is selected from 150 to 5000 grams per mole.

7. The coating composition according to claim 1, wherein: The small molecule containing an isocyanate group is selected from aromatic isocyanates; and / or The polymer whose monomer contains at least one isocyanate group is selected from aromatic isocyanate polymers.

8. The coating composition according to claim 2, wherein: The catalyst C is selected from polyurethane catalysts.

9. The coating composition according to claim 2, wherein: The catalyst C is selected from catalysts having a delay function.

10. The coating composition according to claim 8, wherein: The catalyst C is selected from a metal salt polyurethane catalyst, a tertiary amine polyurethane catalyst or a combination of a metal salt polyurethane catalyst and a complexing agent.

11. The coating composition according to claim 2, wherein: The main agent A includes one or more of methacryloxypropyl trimethoxysilane, phenyl trimethoxysilane, vinyl trimethoxysilane, or glycidyl ether propyl trimethoxysilane. The curing agent B includes one or more of diphenylmethane diisocyanate or a polymer thereof, hexamethylene diisocyanate or a polymer thereof, or toluene diisocyanate or a polymer thereof, and the catalyst C includes one or more of dibutyltin dilaurate, 2,4,6-tris(dimethylaminomethyl)phenol, or 1,8-diazacyclo[5,4,0]undecene-7; The mass ratio of the catalyst C to the coating composition is no more than 5%.

12. The coating composition according to claim 2, wherein: The coating composition further comprises a functional component D.

13. The coating composition according to claim 12, wherein: The functional component D comprises a component with toughening, plasticizing or compatibilizing functions, wherein the component with toughening, plasticizing or compatibilizing functions is selected from hydroxyl-terminated polydimethylsiloxane, hydroxyl acrylic resin or bisphenol A epoxy resin.

14. A material product having a coating, characterized in that: The invention comprises a substrate and a coating applied on the surface of the substrate, wherein the coating is prepared from the coating composition described in any one of claims 1 to 13.

15. A coating kit, characterized in that: It comprises a coating composition according to any one of claims 1 to 13, wherein the main agent A and the curing agent B of the coating composition are packaged separately.

16. A method for using a coating composition, characterized in that: The steps include: In a water environment, the coating composition according to any one of claims 1 to 13 is applied to the surface of a substrate.

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