WO2021207950A1 - Anti-blackening coating composition - Google Patents

Anti-blackening coating composition Download PDF

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Publication number
WO2021207950A1
WO2021207950A1 PCT/CN2020/084811 CN2020084811W WO2021207950A1 WO 2021207950 A1 WO2021207950 A1 WO 2021207950A1 CN 2020084811 W CN2020084811 W CN 2020084811W WO 2021207950 A1 WO2021207950 A1 WO 2021207950A1
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WO
WIPO (PCT)
Prior art keywords
coating composition
organic
weight
composition according
proceeding
Prior art date
Application number
PCT/CN2020/084811
Other languages
French (fr)
Inventor
Yakun ZHU
Yi Zhang
Xilin ZHANG
Xiaomeng Wu
Original Assignee
Henkel Ag & Co. Kgaa
Henkel (China) Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Ag & Co. Kgaa, Henkel (China) Co., Ltd. filed Critical Henkel Ag & Co. Kgaa
Priority to CN202080099691.9A priority Critical patent/CN115397926B/en
Priority to PCT/CN2020/084811 priority patent/WO2021207950A1/en
Priority to AU2020442769A priority patent/AU2020442769A1/en
Priority to EP20931344.4A priority patent/EP4136174A4/en
Publication of WO2021207950A1 publication Critical patent/WO2021207950A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/086—Organic or non-macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4

Definitions

  • This invention relates to a coating composition
  • a coating composition comprising: (a) at least one water soluble or water dispersible polymer; (b) at least one anti-blackening agent; and (c) water.
  • the anti-blackening agent of the present invention is selected from organic acid, organic acid ester or organic acid salt, organic metal complex, or any combination thereof.
  • the coating composition of the present invention exhibits excellent anti-blackening property after cured.
  • Magnesium containing steel plate has many advantages over other metal plates, such as light weight, impact resistance and anti-corrosion property.
  • one limitation for the use of magnesium containing steel plate is that the surface of the magnesium containing steel plate could easily turn black when composed to oxygen and moisture in the air, because magnesium on the surface is converted into magnesium hydroxide or magnesium oxide.
  • the present invention relates to a coating composition, comprising:
  • anti-blackening agent is selected from organic acid, organic acid ester, organic acid salt, organic metal complex, or any combination thereof.
  • the coating composition of the presentation has excellent anti-blackening property after cured.
  • the present invention also relates to a substrate coated by the coating composition.
  • acrylate refers to both or any one of “acrylate” and “methacrylate” .
  • acrylic refers to both or any one of “acrylic” and “methacrylic” .
  • water soluble means that the relevant component or ingredient of the composition can be dissolved in the aqueous phase on the molecular level.
  • water dispersible means that that the relevant component or ingredient of the composition can be dispersed in the aqueous phase and forms a stable emulsion or suspension.
  • hydrocarbon group refers to an organic group consisting of carbon and hydrogen.
  • Example of hydrocarbon group includes but limited to an alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, tertiary butyl, isobutyl and the groups alike; an o alkenyl group, such as vinyl, allyl, butenyl, pentenyl, hexenyl and the groups alike; an aralkyl group, such as benzyl, phenethyl, 2- (2, 4, 6-trimethylphenyl) propyl and the groups alike; or an aryl group, such as phenyl, tolyl, xyxyl and the groups alike.
  • alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, tertiary butyl, isobutyl and the
  • optionally substituted in the term of “optionally substituted hydrocarbon group” means that one or more hydrogens on the hydrocarbon group may be replaced with a corresponding number of substituents preferably selected from halogen, nitro, azido, amino, carbonyl, ester, cyano, sulfide, sulfate, sulfoxide, sulfone, sulfone groups, and the likes.
  • substantially free means that a material or functional group can be present in an incidental amount or that a particular occurrence or reaction only takes place to an insignificant extent, which does not affect desired properties.
  • the material or functional group is not intentionally added to an indicated composition, but may be present at minor or inconsequential levels, for example, because it was carried over as an impurity as part of an intended composition component.
  • the coating composition of the present invention comprises at least one water soluble or water dispersible polymer.
  • the water soluble or water dispersible polymer may be derived from water soluble or water dispersible monomers and the combinations thereof, and optionally from monomers that are water insoluble. Suitable water soluble or water dispersible monomers include but are not limited to acrylic acid, glacial acrylic acid, methacrylic acid, isooctyl acrylic acid, crotonic acid, cinnamic acid, maleic acid, 2-methylmaleic acid, isocrotonic acid, and fumaric acid.
  • Exemplary water soluble or water dispersible polymers include, but are not limited to, water soluble polyurethane resin, water dispersible polyurethane resin, water soluble polyacrylic resin, water dispersible polyacrylic resin, water soluble silicon resin, water dispersible silicon resin, water soluble epoxy resin, and water dispersible epoxy resin.
  • the water soluble or water dispersible polymer can be used alone or in any combination.
  • Examples of commercially available water soluble or water dispersible polymers are L-3090 from Hauthaway; BAYHYDROL A 2524 and 2846 XP from Covestro.
  • the amount of water soluble or water dispersible polymer in the coating composition of the invention is preferably from 5 to 60%, and more preferably from 10 to 30%by weight based on the total weight of the coating composition.
  • the coating composition of the present invention comprises at least one anti-blackening agent.
  • the anti-blackening agent is believed to prevent a rapid increase in pH value caused by a high oxidation rate of magnesium if moisture permeates into a coating layer of a magnesium-containing steel plate which may lead to the blackening of the magnesium-containing steel plate.
  • the anti-blackening agents of the present invention is selected from organic acid, organic acid ester, organic acid salt, organic metal complex compound, or any combination thereof.
  • the metal complex compound of the present invention preferably contains at least one organic ligand represented by the following general formula (1) which is coordinatively bounded to a metal atom in the metal complex compound,
  • R 1 and R 2 are identical or different, and independently represent optionally substituted univalent hydrocarbon groups.
  • R 1 and R 2 are optionally substituted C 1 to C 20 alkyl groups, alkenyl groups, or alkoxyl groups. More preferably, R 1 and R 2 are optionally substituted C 1 to C 8 alkyl groups, alkenyl groups or alkoxyl groups.
  • organic acid includes, but is not limited to, organic phosphonic acid, ascorbic acid, aminocarboxylic acid, benzoic acid, benzenesulfonic acid and phytic acid.
  • organic acid ester includes, but is not limited to, the ester of organic phosphonic acid, ascorbic acid, aminocarboxylic acid, benzoic acid, benzenesulfonic acid and phytic acid.
  • organic acid salt includes, but is not limited to, the sodium, magnesium or nickel salt of organic phosphonic acid, ascorbic acid, aminocarboxylic acid, benzoic acid, benzenesulfonic acid and phytic acid.
  • organic metal complex compound includes, but is not limited to, organic nickel complex compound, organic vanadium complex compound, organic zirconium complex compound, organic cerium complex compound and organic molybdenum complex compound.
  • the anti-blackening agent preferably comprises at least one ascorbic acid salt, benzenesulfonic acid salt, organic phosphate ester, or any combination thereof.
  • Example of commercially available anti-blackening agent is, for example, HALOX 515 LFG from ICL; benzenesulfonic acid nickel (II) salt hexahydrate from Tokyo Chemical Industry Co., Ltd.; L-ascorbic acid sodium salt from Shanghai Time Chemicals Co., Ltd.; trimethyl phosphate from Jiangsu Victory Chemical Co., Ltd.; phytic acid from Sinopharm Chemical Reagent; and zirconium (IV) acetylacetonate from Sachem Europe.
  • the amount of anti-blackening agent is preferably from 0.005 to 10%, more preferably from 0.01 to 10%, and even more preferably from 0.05 to 5%by weight based on the total weight of the coating composition.
  • the coating composition of the present invention comprises water as a balance to make up the total weight of the coating composition to 100%.
  • the water of the present invention is preferably purified water.
  • the amount of water is preferably from 10 to 95%, and more preferably from 65 to 85%by weight based on the total weight of the coating composition.
  • the coating composition may further comprise optional additives.
  • suitable additives for the coating composition of the invention depends on the specific intended use of the coating composition and can be determined in the individual case by those skilled in the art.
  • the coating composition of the present invention may further comprise at least one crosslinker selected from melamine crosslinker, epoxy crosslinker, polycarbodiimide crosslinker, metal complex crosslinker, blocked isocyanate croslinker, siloxane, the oligomerized or polymerized compound of siloxane, and oxazoline modified polymer.
  • the crosslinker can be used alone or in any combination. Without wishing to be bound by theory, the crosslinker is believed to be able to improve the intactness of the coating layer formed from the coating composition of the present invention so that moisture and oxygen are blocked from penetrating the coating layer.
  • crosslinkers examples include HA-808 from Hauthaway; XL-732 from Stahl; and Z-6040 from Dowcorning.
  • the amount of the crosslinker is from 0 to 5%, and preferably from 0.5 to 4.5%by weight based on the total weight of the coating composition.
  • the coating composition of the present invention may further comprise at least one adhesion promoter selected from an amino functional metal organic adhesion promoter, an acid and hydroxyl functional polymer adhesion promoter, and aminosilane agents.
  • the adhesion promoter can be used alone or in any combination. Without wishing to be bound by theory, adhesion promoter is believed to be able to improve the adhesion of the coating layer formed from the coating composition of the present inventions to the substrate to be coated so that moisture and oxygen are blocked from penetrating the coating layer.
  • adhesion promoters examples include BYK-4510 from BYK; and B-516.71HR from Chartwell.
  • the amount of the adhesion promoter is from 0 to 5%, and preferably from 0.5 to 3%by weight based on the total weight of the coating composition.
  • the crosslinker and adhesion promoter are able to work coordinatively to facilitate the anti-blackening agent to prevent the blackening of a substrate, such as magnesium containing steel plate.
  • the coating composition of the present invention may further comprise at least one lubricant selected from PE wax, PTFE wax, carnauba wax, paraffin wax, elastomer emulsion, HMW silicone emulsion and silicone polyether.
  • the lubricant can be used alone or in any combination.
  • lubricants examples include, for example, AQUASLIP 952 from Lubrizol;
  • the amount of the lubricant is from 0 to 10%, and preferably from 0.5 to 5%by weight based on the total weight of the coating composition.
  • the coating composition of the present invention may further comprise at least one coalescing agent selected from ester alcohol kind of coalescing agent and glycol ether kind coalescing agent, such as texanol, 2-butoxy ethanol, tripropylene glycol n-butyl ether, dipropylene glycol n-butyl ether, 1, 2-propylene glycol-1-monobutyl, and proprylene glycol monomethyl ether.
  • at least one coalescing agent selected from ester alcohol kind of coalescing agent and glycol ether kind coalescing agent, such as texanol, 2-butoxy ethanol, tripropylene glycol n-butyl ether, dipropylene glycol n-butyl ether, 1, 2-propylene glycol-1-monobutyl, and proprylene glycol monomethyl ether.
  • coalescing agents examples include, for example, DB and DPnB from Dow; and DPM from Redox.
  • the amount of the coalescing agent is from 0 to 10%, and preferably from 0.5 to 5%by weight based on the total weight of the coating composition.
  • the coating composition of the present invention may further comprise at least one defoamer.
  • exemplary defoamer includes but is not limited to silicone type defoamer and acrylic type defoamer. The defoamer can be used alone or in combination.
  • defoamer examples include BYK-012, BYK-051, BYK-052, BYK-053, BYK-054, BYK-055 from BYK-Chemie GmbH; DISPARLON 1930N and DISPARLON 1934 from Kusumoto Chemicals, Ltd.; and Foamaster MO NXZ from BASF.
  • the amount of defoamer is from 0 to 2%, and preferably from 0.01 to 1%by weight based on the total weight of the coating composition.
  • the coating composition of the present invention may further comprise at least one leveling agent.
  • exemplary leveling agent includes but is not limited to silicone type leveling agent and acrylic type leveling agent.
  • the leveling agent can be used alone or in combination.
  • leveling agent examples include BYK-302, BYK-307, BYK-325, BYK-331, BYK-333, BYK-342, BYK-346, BYK-347, BYK-348, BYK-349, BYK-378, BYK-3455, BYK-381, BYK-3441 from BYK-Chemie GmbH; and Tego wet KL245, Tego wet 250, Tego wet 260, Tego wet 265, Tego wet 270, and Tego wet 280 from Evonic Tego Chemie GmbH.
  • the amount of leveling agent is from 0 to 2%, and preferably from 0.1 to 1%by weight based on the total weight of the coating composition.
  • the coating composition of the present invention may further comprise other additives, such as at least one anti-corrosion agent, and/or at least one wetting agent, and/or at least one thickening agent, and/or at least one filler.
  • the coating composition is substantially free of chromium.
  • the coating composition comprises:
  • coalescing agent from 0 to 10%by weight of at least one coalescing agent
  • weight percentages of all components add up to 100%by weight
  • the coating composition of the present invention may be prepared by mixing all the components together, and applied to a surface of a substrate, such as magnesium containing steel plate, at room temperature.
  • the coating composition is allowed to be cured at a temperature ranging from room temperature to 130°C to form a coating layer on the surface of the substrate.
  • the coating layer has a dry weight of 600 mg/m 2 to 2000 mg/m 2 .
  • the coating layer formed by the coating composition has good anti-blackening property.
  • the coating layer also has good moisture resistance, and/or alkali resistance, and/or acid resistance, and/or solvent resistance, and/or paintability, and/or fingerprint resistance, and/or UV resistance, and/or corrosion resistance.
  • HA-808 (melamine crosslinking agent from Hauthaway) ;
  • Trimethyl phosphate (from Jiangsu Victory Chemical Co., Ltd. ) ;
  • HALOX 515 aminocarboxylate salt from ICL
  • Ni (NO 3 ) 2 nickel nitrate from SHANGHAI TRUSTIN CHEMICAL CO., LTD
  • AQUASLIP 952 (carnauba wax from Lubrizol) ;
  • DB diethylene glycol monobutyl ether from Dow
  • BYK-348 polyether modified siloxane from BYK
  • BYK-012 mixture of foam-destroying polymers and hydrophobic solids from BYK
  • BYK-4510 solution of a hydroxy-functional copolymer with acidic groups from BYK
  • the coating compositions were formulated according to the components and amounts in Table 1 by mixing well all components.
  • a magnesium containing steel plate containing 0.1 -5 wt%of Mg, 1-60 wt%of Al, 0-10 wt%of Si, and a remainder of Zn was firstly cleaned with a degreasing agent and then rinsed with water. After the magnesium containing steel plate was completely dried, the coating composition prepared according to Table 1 was applied to the magnesium containing steel plate at room temperature via a bar coater. The coating composition was allowed to be dried at 80°C to form a coating layer on the magnesium containing steel plate having a dry weight of 900-1200 mg/m 2 . The coated magnesium containing steel plate was used as the sample plate for various tests described below.
  • a sample plate was placed vertically into a water tank containing boiling water so that half of the sample plate was immersed into the boiling water, and the other half of the sample plate was exposed to the open air.
  • the sample plate was left in the water tank for 2 hours.
  • Degree of discoloration ( ⁇ E) which was obtainable by using the machine of ColorFlex EZ Spectrophotometer from Hunter Lab, was used to evaluate the anti-blackening property of the coating layer of the sample plate.
  • the anti-blackening property of the coating layer was rated as below:
  • the part of the sample plate which was immersed in the boiling water had a ⁇ E value less than 3, and the part of the sample plate which was exposed to the open air had a ⁇ E value less than 3;
  • the part of the sample plate which was immersed in the boiling water had a ⁇ E value greater than or equal to 3; the part of the sample plate which was exposed to the open air had a ⁇ E value less than 3;
  • a sample plate was maintained in a thermo-hygrostat for 120 hours at a temperature of 49°C and a relative humidity (RH) of 98%under a pressure of 10 kgf/cm 2 .
  • RH relative humidity
  • ⁇ E Degree of discoloration
  • the moisture resistance of the coating layer was rated as below:
  • a sample plate was completely submerged in a 0.1%w/w NaOH solution at temperature of 25° C for 60 minutes, and then washed with running water and dried thoroughly.
  • Degree of whiteness change ( ⁇ L) which was obtainable by using the machine of ColorFlex EZ Spectrophotometer from Hunter Lab, was used as one factor to evaluate the alkali resistance of the coating layer of the sample plate.
  • Degree of separation of the coating layer from the magnesium containing steel plate was used as another factor to evaluate the alkali resistance of the coating layer of the sample plate.
  • the alkali resistance of the coating layer was rated as below:
  • the coating layer was completely peeled off from the magnesium containing steel plate, regardless of ⁇ L value.
  • a sample plate was completely submerged in a 0.1%w/w HCl solution at temperature of 25° C for 60 minutes, and then washed with running water and dried thoroughly.
  • Degree of whiteness change ( ⁇ L) which was obtainable by using the machine of ColorFlex EZ Spectrophotometer from Hunter Lab, was used as one factor to evaluate the acid resistance of the coating layer of the sample plate.
  • Degree of separation of the coating layer from the magnesium containing steel plate was used as another factor to evaluate the acid resistance of the coating layer of the sample plate.
  • the acid resistance of the coating layer was rated as below:
  • the coating layer was completely peeled off from the magnesium containing steel plate, regardless of ⁇ L value.
  • Pieces of gauze were prepared by dampening the gauze sufficiently with 80%ethanol, and each sample plate was rubbed back and forth 50 times with a piece of the gauze prepared.
  • Degree of discoloration ( ⁇ E) which was obtainable by using the machine of ColorFlex EZ Spectrophotometer from Hunter Lab, was used as one factor to evaluate the solvent resistance of the coating layer of the sample plate.
  • Degree of separation of the coating layer from the magnesium containing steel plate was used as another factor to evaluate the solvent resistance of the coating layer of the sample plate.
  • the solvent resistance of the coating layer was rate as below:
  • Acrylic melamine-based baking-type paint (Feihu White from Zhenghua Painting Company) was sprayed onto a sample plate and dried to form a painting layer having a thickness of 30 ⁇ m on top of the coating layer of the sample plate.
  • Eleven parallel straight lines were firstly cut on the painting layer at an interval of 1 mm with a knife to expose the magnesium containing steel plate. Another eleven parallel straight lines were cut across the first eleven lines at an interval of 1 mm so that 100 squares (size of each square: 1mm x 1mm) were formed on the magnesium containing steel plate. The area defined by the 100 squares was referred to as the testing area.
  • a cellophane tape 600 from 3M was stick to the surface of the painting layer covering the full testing area, and was peeled off to evaluate the paintability of the coating layer of the sample plate.
  • the paintability of the coating layer was rated as below:
  • a surface of sample plate was treated with Vaseline (from Sinopharm Chemical Reagent) for one hour.
  • Degree of discoloration ( ⁇ E) which was obtainable by using the machine of ColorFlex EZ Spectrophotometer from Hunter Lab, was used to evaluate the Fingerprint resistance of the coating layer of the sample plate.
  • the fingerprint resistance of the coating layer was rated as below:
  • a sample plate was placed in a QUV tester from Q-lab.
  • the sample plate was firstly radiated with UV light for 4 hours under UVB with a wavelength of 313nm and an energy of 0.63W/m 2 at a temperature of 60°C.
  • the sample plate was then exposed to water condensation at a temperature of 50°C for 4 hours.
  • the UV radiation and water condensation treatment were carried out alternatively for 500 hours in total.
  • Degree of discoloration ( ⁇ E) which was obtainable by using the machine of ColorFlex EZ Spectrophotometer from Hunter Lab, was used to evaluate the UV resistance of the coating layer of the sample plate.
  • the UV resistance of the coating layer was rated as below:
  • Corrosion resistance of the sample plate was evaluated by checking the occurrence of white rust on the surface of the sample plate with respect to time by a method according to ASTM B117.
  • the test results are shown in Table 2.
  • the coating layers from Ex. 1 to 8 had good anti-blackening property compared with the coating layer in Ex. 9.
  • trimethyl phosphate, L-ascorbic acid sodium and benzenesulfonic acid nickel (II) salt hexahydrate were used as anti-blackening agents in the coating composition together with crosslinker and adhesion promoter as in Ex. 1 to 3, the sample plates showed almost no blackening and no corrosion on the surfaces.
  • inorganic metal salt such as Ni (NO 3 ) 2
  • was incorporated in the coating composition the surface of the sample plate failed the anti-blackening property test of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

A coating composition comprises: (a) at least one water soluble or water dispersible polymer; (b) at least one anti-blackening agent; and (c) water. The anti-blackening agent is selected from organic acid, organic acid ester or organic acid salt, organic metal complex, or any combination thereof. The coating composition exhibits excellent anti-blackening property after cured.

Description

ANTI-BLACKENING COATING COMPOSITION Technical field
This invention relates to a coating composition comprising: (a) at least one water soluble or water dispersible polymer; (b) at least one anti-blackening agent; and (c) water. The anti-blackening agent of the present invention is selected from organic acid, organic acid ester or organic acid salt, organic metal complex, or any combination thereof. The coating composition of the present invention exhibits excellent anti-blackening property after cured.
Background of the invention
Magnesium containing steel plate has many advantages over other metal plates, such as light weight, impact resistance and anti-corrosion property. However, one limitation for the use of magnesium containing steel plate is that the surface of the magnesium containing steel plate could easily turn black when composed to oxygen and moisture in the air, because magnesium on the surface is converted into magnesium hydroxide or magnesium oxide.
To solve the blackening issue of magnesium containing steel plate, traditional methods such as applying a rust-preventive oil, forming an anodic coating or an organic coating on the surface of a magnesium containing steel plate have been widely used. However, the rust-preventive oil will dry out with time, and therefore is not suitable to prevent the blackening of a magnesium containing steel plate if the magnesium containing steel plate needs to be stored for a long time. The method of forming an anodic coating on the surface of a magnesium containing steel plate needs to utilize large amounts of strong inorganic acids which is hazardous to the environment and endangers workers’ health, and therefore not convenient to be used. Whereas the method of forming an organic coating on the surface of a magnesium containing steel plate requires a high-temperature  coating condition and a long drying time for the organic coating, and therefore not suitable for mass production.
Recently, coatings containing inorganic metal salts are also developed to prevent the blackening of magnesium containing steel plates. However, the coatings are only helpful under modest conditions, such as low environmental temperature.
Therefore, there is a need for developing a coating composition which is easy to be applied to the magnesium containing steel plate and has excellent anti-blackening property after cured.
Summary of the invention
The present invention relates to a coating composition, comprising:
(a) at least one water soluble or water dispersible polymer;
(b) at least one anti-blackening agent; and
(c) water;
wherein the anti-blackening agent is selected from organic acid, organic acid ester, organic acid salt, organic metal complex, or any combination thereof.
The coating composition of the presentation has excellent anti-blackening property after cured.
The present invention also relates to a substrate coated by the coating composition.
Detailed description of the invention
In the following passages the present invention is described in more detail. Each aspect so described may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other  feature or features indicated as being preferred or advantageous.
In the context of the present invention, the terms used are to be construed in accordance with the following definitions, unless a context dictates otherwise.
As used herein, the singular forms “a” , “an” and “the” include both singular and plural referents unless the context clearly dictates otherwise.
The terms “comprising” , “comprises” and “comprised of” as used herein are synonymous with “including” , “includes” or “containing” , “contains” , and are inclusive or open-ended and do not exclude additional, non-recited members, elements or process steps.
The recitation of numerical end points includes all numbers and fractions subsumed within the respective ranges, as well as the recited end points.
All references cited in the present specification are hereby incorporated by reference in their entirety.
Unless otherwise defined, all terms used in the disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of the ordinary skills in the art to which this invention belongs to. By means of further guidance, term definitions are included to better appreciate the teaching of the present invention.
In the context of this disclosure, a number of terms shall be utilized.
The term “acrylate” refers to both or any one of “acrylate” and “methacrylate” .
The term “acrylic” refers to both or any one of “acrylic” and “methacrylic” .
The term “water soluble” means that the relevant component or ingredient of the composition can be dissolved in the aqueous phase on the molecular level.
The term “water dispersible” means that that the relevant component or ingredient of the composition can be dispersed in the aqueous phase and forms a stable emulsion or suspension.
The term “hydrocarbon group” refers to an organic group consisting of carbon and hydrogen. Example of hydrocarbon group includes but limited to an alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, tertiary butyl, isobutyl and the groups alike; an o alkenyl group, such as vinyl, allyl, butenyl, pentenyl, hexenyl and the groups alike; an aralkyl group, such as benzyl, phenethyl, 2- (2, 4, 6-trimethylphenyl) propyl and the groups alike; or an aryl group, such as phenyl, tolyl, xyxyl and the groups alike.
The term "optionally substituted" in the term of “optionally substituted hydrocarbon group” means that one or more hydrogens on the hydrocarbon group may be replaced with a corresponding number of substituents preferably selected from halogen, nitro, azido, amino, carbonyl, ester, cyano, sulfide, sulfate, sulfoxide, sulfone, sulfone groups, and the likes.
The term "substantially free" means that a material or functional group can be present in an incidental amount or that a particular occurrence or reaction only takes place to an insignificant extent, which does not affect desired properties. In other words, the material or functional group is not intentionally added to an indicated composition, but may be present at minor or inconsequential levels, for example, because it was carried over as an impurity as part of an intended composition component.
Water soluble or water dispersible polymer
The coating composition of the present invention comprises at least one water soluble or water dispersible polymer. The water soluble or water dispersible polymer may be derived from water  soluble or water dispersible monomers and the combinations thereof, and optionally from monomers that are water insoluble. Suitable water soluble or water dispersible monomers include but are not limited to acrylic acid, glacial acrylic acid, methacrylic acid, isooctyl acrylic acid, crotonic acid, cinnamic acid, maleic acid, 2-methylmaleic acid, isocrotonic acid, and fumaric acid. Exemplary water soluble or water dispersible polymers include, but are not limited to, water soluble polyurethane resin, water dispersible polyurethane resin, water soluble polyacrylic resin, water dispersible polyacrylic resin, water soluble silicon resin, water dispersible silicon resin, water soluble epoxy resin, and water dispersible epoxy resin. The water soluble or water dispersible polymer can be used alone or in any combination.
Examples of commercially available water soluble or water dispersible polymers, for example, are L-3090 from Hauthaway; BAYHYDROL A 2524 and 2846 XP from Covestro.
In some embodiments of the present invention, the amount of water soluble or water dispersible polymer in the coating composition of the invention is preferably from 5 to 60%, and more preferably from 10 to 30%by weight based on the total weight of the coating composition.
Anti-blackening agent
The coating composition of the present invention comprises at least one anti-blackening agent. Without wishing to be bound by theory, the anti-blackening agent is believed to prevent a rapid increase in pH value caused by a high oxidation rate of magnesium if moisture permeates into a coating layer of a magnesium-containing steel plate which may lead to the blackening of the magnesium-containing steel plate. The anti-blackening agents of the present invention is selected from organic acid, organic acid ester, organic acid salt, organic metal complex compound, or any combination thereof. The metal complex compound of the present invention preferably contains at least one organic ligand represented by the following general formula (1) which is coordinatively bounded to a metal atom in the metal complex compound,
Figure PCTCN2020084811-appb-000001
wherein*represents a coordinating position of the metal atom in the metal complex compound. R 1 and R 2 are identical or different, and independently represent optionally substituted univalent hydrocarbon groups. Preferably, R 1 and R 2 are optionally substituted C 1 to C 20 alkyl groups, alkenyl groups, or alkoxyl groups. More preferably, R 1 and R 2 are optionally substituted C 1 to C 8 alkyl groups, alkenyl groups or alkoxyl groups.
Illustrative example of the organic acid includes, but is not limited to, organic phosphonic acid, ascorbic acid, aminocarboxylic acid, benzoic acid, benzenesulfonic acid and phytic acid. Illustrative example of the organic acid ester includes, but is not limited to, the ester of organic phosphonic acid, ascorbic acid, aminocarboxylic acid, benzoic acid, benzenesulfonic acid and phytic acid. Illustrative example of the organic acid salt includes, but is not limited to, the sodium, magnesium or nickel salt of organic phosphonic acid, ascorbic acid, aminocarboxylic acid, benzoic acid, benzenesulfonic acid and phytic acid. Illustrative example of the organic metal complex compound includes, but is not limited to, organic nickel complex compound, organic vanadium complex compound, organic zirconium complex compound, organic cerium complex compound and organic molybdenum complex compound.
In some embodiments of the present invention, the anti-blackening agent preferably comprises at least one ascorbic acid salt, benzenesulfonic acid salt, organic phosphate ester, or any combination thereof.
Example of commercially available anti-blackening agent is, for example, HALOX 515 LFG from ICL; benzenesulfonic acid nickel (II) salt hexahydrate from Tokyo Chemical Industry Co., Ltd.; L-ascorbic acid sodium salt from Shanghai Time Chemicals Co., Ltd.; trimethyl phosphate from Jiangsu Victory Chemical Co., Ltd.; phytic acid from Sinopharm Chemical Reagent; and zirconium (IV) acetylacetonate from Sachem Europe.
In some embodiments of the present invention, the amount of anti-blackening agent is preferably from 0.005 to 10%, more preferably from 0.01 to 10%, and even more preferably from 0.05 to 5%by weight based on the total weight of the coating composition.
Water
The coating composition of the present invention comprises water as a balance to make up the total weight of the coating composition to 100%. The water of the present invention is preferably purified water.
In some embodiments of the present invention, the amount of water is preferably from 10 to 95%, and more preferably from 65 to 85%by weight based on the total weight of the coating composition.
Optional Additives
The coating composition may further comprise optional additives. The selection of suitable additives for the coating composition of the invention depends on the specific intended use of the coating composition and can be determined in the individual case by those skilled in the art.
<Crosslinker>
The coating composition of the present invention may further comprise at least one crosslinker selected from melamine crosslinker, epoxy crosslinker, polycarbodiimide crosslinker, metal complex crosslinker, blocked isocyanate croslinker, siloxane, the oligomerized or polymerized compound of  siloxane, and oxazoline modified polymer. The crosslinker can be used alone or in any combination. Without wishing to be bound by theory, the crosslinker is believed to be able to improve the intactness of the coating layer formed from the coating composition of the present invention so that moisture and oxygen are blocked from penetrating the coating layer.
Examples of commercially available crosslinkers are, for example, HA-808 from Hauthaway; XL-732 from Stahl; and Z-6040 from Dowcorning.
In some embodiments of the present invention, the amount of the crosslinker is from 0 to 5%, and preferably from 0.5 to 4.5%by weight based on the total weight of the coating composition.
<Adhesion promoter>
The coating composition of the present invention may further comprise at least one adhesion promoter selected from an amino functional metal organic adhesion promoter, an acid and hydroxyl functional polymer adhesion promoter, and aminosilane agents. The adhesion promoter can be used alone or in any combination. Without wishing to be bound by theory, adhesion promoter is believed to be able to improve the adhesion of the coating layer formed from the coating composition of the present inventions to the substrate to be coated so that moisture and oxygen are blocked from penetrating the coating layer.
Examples of commercially available adhesion promoters are, for example, BYK-4510 from BYK; and B-516.71HR from Chartwell.
In some embodiments of the present invention, the amount of the adhesion promoter is from 0 to 5%, and preferably from 0.5 to 3%by weight based on the total weight of the coating composition.
In some embodiments of the present invention, it is surprisingly found that the crosslinker and adhesion promoter are able to work coordinatively to facilitate the anti-blackening agent to prevent the blackening of a substrate, such as magnesium containing steel plate.
<Lubricant>
The coating composition of the present invention may further comprise at least one lubricant selected from PE wax, PTFE wax, carnauba wax, paraffin wax, elastomer emulsion, HMW silicone emulsion and silicone polyether. The lubricant can be used alone or in any combination.
Examples of commercially available lubricants are, for example, AQUASLIP 952 from Lubrizol;
Sasaolwax H1 from Sasol Wax; AC-400 from Honeywell; MC-400 from Marcus Oil Company;
Epolene C-18 from Eastman Chemical; Wax 58#from Sinopharm; and AC-575P from Honeywell.
In some embodiments of the present invention, the amount of the lubricant is from 0 to 10%, and preferably from 0.5 to 5%by weight based on the total weight of the coating composition.
<Coalescing agent>
The coating composition of the present invention may further comprise at least one coalescing agent selected from ester alcohol kind of coalescing agent and glycol ether kind coalescing agent, such as texanol, 2-butoxy ethanol, tripropylene glycol n-butyl ether, dipropylene glycol n-butyl ether, 1, 2-propylene glycol-1-monobutyl, and proprylene glycol monomethyl ether.
Examples of commercially available coalescing agents are, for example, DB and DPnB from Dow; and DPM from Redox.
In some embodiments of the present invention, the amount of the coalescing agent is from 0 to 10%, and preferably from 0.5 to 5%by weight based on the total weight of the coating composition.
<Defoamer>
The coating composition of the present invention may further comprise at least one defoamer. Exemplary defoamer includes but is not limited to silicone type defoamer and acrylic type defoamer. The defoamer can be used alone or in combination.
Examples of commercially available defoamer are, for example, BYK-012, BYK-051, BYK-052, BYK-053, BYK-054, BYK-055 from BYK-Chemie GmbH; DISPARLON 1930N and DISPARLON 1934 from Kusumoto Chemicals, Ltd.; and Foamaster MO NXZ from BASF.
In some embodiments of the present invention, the amount of defoamer is from 0 to 2%, and preferably from 0.01 to 1%by weight based on the total weight of the coating composition.
<Leveling agent>
The coating composition of the present invention may further comprise at least one leveling agent. Exemplary leveling agent includes but is not limited to silicone type leveling agent and acrylic type leveling agent. The leveling agent can be used alone or in combination.
Examples of commercially available leveling agent are, for example, BYK-302, BYK-307, BYK-325, BYK-331, BYK-333, BYK-342, BYK-346, BYK-347, BYK-348, BYK-349, BYK-378, BYK-3455, BYK-381, BYK-3441 from BYK-Chemie GmbH; and Tego wet KL245, Tego wet 250, Tego wet 260, Tego wet 265, Tego wet 270, and Tego wet 280 from Evonic Tego Chemie GmbH.
In some embodiments of the present invention, the amount of leveling agent is from 0 to 2%, and preferably from 0.1 to 1%by weight based on the total weight of the coating composition.
The coating composition of the present invention may further comprise other additives, such as at least one anti-corrosion agent, and/or at least one wetting agent, and/or at least one thickening  agent, and/or at least one filler. Preferably, the coating composition is substantially free of chromium.
In a preferred embodiment, the coating composition comprises:
from 5 to 60%by weight of at least one water soluble or water dispersible polymer;
from 0.005 to 10%by weight of at least one anti-blackening agent;
from 0 to 5%by weight of at least one crosslinker;
from 0 to 5%by weight of at least adhesion promoter;
from 0 to 10%by weight of at least one lubricant;
from 0 to 10%by weight of at least one coalescing agent;
from 0 to 2%by weight of at least one defoamer;
from 0 to 2 %by weight of least one leveling agent; and
from 10 to 95%by weight of water;
wherein the weight percentages of all components add up to 100%by weight;
The coating composition of the present invention may be prepared by mixing all the components together, and applied to a surface of a substrate, such as magnesium containing steel plate, at room temperature. The coating composition is allowed to be cured at a temperature ranging from room temperature to 130℃ to form a coating layer on the surface of the substrate. Preferably, the coating layer has a dry weight of 600 mg/m 2 to 2000 mg/m 2.
The coating layer formed by the coating composition has good anti-blackening property. Preferably, the coating layer also has good moisture resistance, and/or alkali resistance, and/or acid resistance, and/or solvent resistance, and/or paintability, and/or fingerprint resistance, and/or UV resistance, and/or corrosion resistance.
Examples:
The present invention will be further described and illustrated in detail with reference to the following examples. The examples are intended to assist one skilled in the art to better understand and practice the present invention, however, are not intended to restrict the scope of the present invention. All numbers in the examples are based on weight unless otherwise stated.
Example 1-9
The following materials were used in the examples.
L-3090 (waterborne polyurethane resin containing 35%of polyurethane resin and 65%of water from Hauthaway) ;
HA-808 (melamine crosslinking agent from Hauthaway) ;
Z-6040 (siloxane from Dowcorning) ;
XL-732 (poly-carbodiimide crosslinker from Stahl) ;
Trimethyl phosphate (from Jiangsu Victory Chemical Co., Ltd. ) ;
L-ascorbic acid sodium (from Shanghai Time Chemicals CO., Ltd. ) ;
Benzenesulfonic acid nickel (II) salt hexahydrate (from Tokyo Chemical Industry Co., Ltd) ;
HALOX 515 (aminocarboxylate salt from ICL) ;
Phytic acid (from Sinopharm Chemical Reagent) ;
Zirconium (IV) acety-lacetonate (from Sachem Europe) ;
Ni (NO 3)  2 (nickel nitrate from SHANGHAI TRUSTIN CHEMICAL CO., LTD) ;
AQUASLIP 952 (carnauba wax from Lubrizol) ;
DB (diethylene glycol monobutyl ether from Dow) ;
BYK-348 (polyether modified siloxane from BYK) ;
BYK-012 (mixture of foam-destroying polymers and hydrophobic solids from BYK) ;
BYK-4510 (solution of a hydroxy-functional copolymer with acidic groups from BYK) ; and
B-516.71HR (an amino functional metal organic adhesion promoter from Chartwell) .
The coating compositions were formulated according to the components and amounts in Table 1 by mixing well all components.
A magnesium containing steel plate containing 0.1 -5 wt%of Mg, 1-60 wt%of Al, 0-10 wt%of Si, and a remainder of Zn was firstly cleaned with a degreasing agent and then rinsed with water. After the magnesium containing steel plate was completely dried, the coating composition prepared according to Table 1 was applied to the magnesium containing steel plate at room temperature via a bar coater. The coating composition was allowed to be dried at 80℃ to form a coating layer on the magnesium containing steel plate having a dry weight of 900-1200 mg/m 2. The coated magnesium containing steel plate was used as the sample plate for various tests described below.
Table 1. Coating composition
Figure PCTCN2020084811-appb-000002
Figure PCTCN2020084811-appb-000003
Test Methods
<Anti-blackening Property>
A sample plate was placed vertically into a water tank containing boiling water so that half of the sample plate was immersed into the boiling water, and the other half of the sample plate was exposed to the open air. The sample plate was left in the water tank for 2 hours. Degree of discoloration (△E) , which was obtainable by using the machine of ColorFlex EZ Spectrophotometer from Hunter Lab, was used to evaluate the anti-blackening property of the coating layer of the sample plate.
The anti-blackening property of the coating layer was rated as below:
◎:the part of the sample plate which was immersed in the boiling water had a △E value less than 3, and the part of the sample plate which was exposed to the open air had a △E value less than 3;
O:the part of the sample plate which was immersed in the boiling water had a △E value greater than or equal to 3; the part of the sample plate which was exposed to the open air had a △E value less than 3;
X:the part of the sample plate which was immersed in the boiling water had a △E value greater than or equal to 3; the part of the sample plate which was exposed to the open air had a △E value greater than or equal to 3.
<Moisture Resistance>
A sample plate was maintained in a thermo-hygrostat for 120 hours at a temperature of 49℃ and a relative humidity (RH) of 98%under a pressure of 10 kgf/cm 2. Degree of discoloration (△E) , which was obtainable by using the machine of ColorFlex EZ Spectrophotometer from Hunter Lab, was used to evaluate the moisture resistance of the coating layer of the sample plate.
The moisture resistance of the coating layer was rated as below:
◎:△E<1
O:1≤△E<3
X:△E≥3
<Alkali Resistance>
A sample plate was completely submerged in a 0.1%w/w NaOH solution at temperature of 25° C for 60 minutes, and then washed with running water and dried thoroughly. Degree of whiteness change (△L) , which was obtainable by using the machine of ColorFlex EZ Spectrophotometer from Hunter Lab, was used as one factor to evaluate the alkali resistance of the coating layer of the sample plate. Degree of separation of the coating layer from the magnesium containing steel plate was used as another factor to evaluate the alkali resistance of the coating layer of the sample plate.
The alkali resistance of the coating layer was rated as below:
◎:△L ≤ 2 and no separation of the coating layer from the magnesium containing steel plate;
O:2<△L ≤ 3, but no separation of the coating layer from the magnesium containing steel plate;
X:the coating layer was completely peeled off from the magnesium containing steel plate, regardless of △L value.
<Acid Resistance>
A sample plate was completely submerged in a 0.1%w/w HCl solution at temperature of 25° C for 60 minutes, and then washed with running water and dried thoroughly. Degree of whiteness change (△L) , which was obtainable by using the machine of ColorFlex EZ Spectrophotometer from Hunter Lab, was used as one factor to evaluate the acid resistance of the coating layer of the sample plate. Degree of separation of the coating layer from the magnesium containing steel plate was used as another factor to evaluate the acid resistance of the coating layer of the sample plate.
The acid resistance of the coating layer was rated as below:
◎:△L ≤ 1 and no separation of the coating layer from the magnesium containing steel plate;
O:1<△L ≤ 2, but no separation of the coating layer from the magnesium containing steel plate;
X:the coating layer was completely peeled off from the magnesium containing steel plate, regardless of △L value.
<Solvent Resistance>
Pieces of gauze were prepared by dampening the gauze sufficiently with 80%ethanol, and each sample plate was rubbed back and forth 50 times with a piece of the gauze prepared. Degree of discoloration (△E) , which was obtainable by using the machine of ColorFlex EZ Spectrophotometer from Hunter Lab, was used as one factor to evaluate the solvent resistance of the coating layer of the sample plate. Degree of separation of the coating layer from the magnesium containing steel plate was used as another factor to evaluate the solvent resistance of the coating layer of the sample plate.
The solvent resistance of the coating layer was rate as below:
◎:△E<3 and no separation of the coating layer from the magnesium containing steel plate;
O:The coating layer was completely peeled off from the magnesium containing steel plate after twenty or more rounds of rubbing regardless of △E value; and
X:The coating layer was completely peeled off from the magnesium containing steel plate before twenty rounds of rubbing regardless of △E value.
<Paintability>
Acrylic melamine-based baking-type paint (Feihu White from Zhenghua Painting Company) was sprayed onto a sample plate and dried to form a painting layer having a thickness of 30 μm on top of the coating layer of the sample plate.
Eleven parallel straight lines were firstly cut on the painting layer at an interval of 1 mm with a knife to expose the magnesium containing steel plate. Another eleven parallel straight lines were cut across the first eleven lines at an interval of 1 mm so that 100 squares (size of each square: 1mm x 1mm) were formed on the magnesium containing steel plate. The area defined by the 100 squares was referred to as the testing area. A cellophane tape (600 from 3M) was stick to the surface of the painting layer covering the full testing area, and was peeled off to evaluate the paintability of the coating layer of the sample plate.
The paintability of the coating layer was rated as below:
◎:Less than 1%of testing area was peeled off
O:1%of testing area was peeled off
X:More than 1%of testing area was peeled off
<Fingerprint Resistance>
A surface of sample plate was treated with Vaseline (from Sinopharm Chemical Reagent) for one hour. Degree of discoloration (△E) , which was obtainable by using the machine of ColorFlex EZ Spectrophotometer from Hunter Lab, was used to evaluate the Fingerprint resistance of the coating layer of the sample plate.
The fingerprint resistance of the coating layer was rated as below:
◎:△E<1
O:1≤△E<2
X:△E≥2
<UV Resistance>
A sample plate was placed in a QUV tester from Q-lab. The sample plate was firstly radiated with UV light for 4 hours under UVB with a wavelength of 313nm and an energy of 0.63W/m 2 at a temperature of 60℃. The sample plate was then exposed to water condensation at a temperature  of 50℃ for 4 hours. The UV radiation and water condensation treatment were carried out alternatively for 500 hours in total. Degree of discoloration (△E) , which was obtainable by using the machine of ColorFlex EZ Spectrophotometer from Hunter Lab, was used to evaluate the UV resistance of the coating layer of the sample plate.
The UV resistance of the coating layer was rated as below:
◎:△E≤2
O:1＜△E≤3
X:△E＞3
<Corrosion Resistance>
Corrosion resistance of the sample plate was evaluated by checking the occurrence of white rust on the surface of the sample plate with respect to time by a method according to ASTM B117.
◎:No white rust
O:5%or less white rust
X:5%or more white rust
The test results are shown in Table 2. The coating layers from Ex. 1 to 8 had good anti-blackening property compared with the coating layer in Ex. 9. Especially when trimethyl phosphate, L-ascorbic acid sodium and benzenesulfonic acid nickel (II) salt hexahydrate were used as anti-blackening agents in the coating composition together with crosslinker and adhesion promoter as in Ex. 1 to 3, the sample plates showed almost no blackening and no corrosion on the surfaces. On the contrary, when inorganic metal salt, such as Ni (NO 3)  2, was incorporated in the coating composition, the surface of the sample plate failed the anti-blackening property test of the present invention.
Table 2. Properties of the coating composition
Figure PCTCN2020084811-appb-000004
Figure PCTCN2020084811-appb-000005

Claims (14)

  1. A coating composition comprising:
    (a) at least one water soluble or water dispersible polymer;
    (b) at least one anti-blackening agent; and
    (c) water;
    wherein the anti-blackening agent is selected from organic acid, organic acid ester, organic acid salt, organic metal complex compound, or any combination thereof.
  2. The coating composition according to claim 1, wherein the water soluble or water dispersible polymer comprises at least one selected from the group consisting of water soluble polyurethane resin, water dispersible polyurethane resin, water soluble polyacrylic resin, water dispersible polyacrylic resin, water soluble silicon resin, water dispersible silicon resin, water soluble epoxy resin, and water dispersible epoxy resin.
  3. The coating composition according to claim 1 or 2, the amount of water soluble or water dispersible polymer is preferably from 5 to 60%, and more preferably from 10 to 30%by weight based on the total weight of the coating composition.
  4. The coating composition according to any one of the proceeding claims, wherein the organic acid comprises at least one selected from the group consisting of organic phosphonic acid, ascorbic acid, aminocarboxylic acid, benzoic acid, benzenesulfonic acid and phytic acid.
  5. The coating composition according to any one of the proceeding claims, wherein the organic metal complex compound preferably contains at least one organic ligand represented by the following general formula (1) which is coordinatively bounded to a metal atom in the metal complex compound,
    Figure PCTCN2020084811-appb-100001
    wherein *represents a coordinating position of the metal atom in the metal complex compound; R 1 and R 2 are identical or different, and independently represent optionally substituted univalent hydrocarbon groups; preferably, R 1 and R 2 are optionally substituted C 1 to C 20 alkyl groups, alkenyl groups, or alkoxyl groups; and more preferably, R 1 and R 2 are optionally substituted C 1 to C 8 alkyl groups, alkenyl groups or alkoxyl groups.
  6. The coating composition according to any one of the proceeding claims, wherein the organic metal complex compound preferably comprises at least one selected from the group consisting of organic nickel complex compound, organic vanadium complex compound, organic zirconium complex compound, organic cerium complex compound and organic molybdenum complex compound.
  7. The coating composition according to any one of the proceeding claims, wherein the anti-blackening agent preferably comprises at least one selected from ascorbic acid salt, benzenesulfonic acid salt and organic phosphate ester.
  8. The coating composition according to any one of the proceeding claims, wherein the amount of anti-blackening agent is preferably from 0.005 to 10%, more preferably from 0.01 to 5%, and even more preferably from 0.05 to 4.5%by weight based on the total weight of the coating composition.
  9. The coating composition according to any one of the proceeding claims, is substantially free of chromium.
  10. The coating composition according to any one of the proceeding claims, further comprises at least one crosslinker, and/or at least one adhesion promoter.
  11. The coating composition according to any one of the proceeding claims, comprising:
    from 5 to 60%by weight of at least one water soluble or water dispersible polymer;
    from 0.005 to 10%by weight of at least one anti-blackening agent;
    from 0 to 5%by weight of at least one crosslinker;
    from 0 to 5%by weight of at least adhesion promoter;
    from 0 to 10%by weight of at least one lubricant;
    from 0.1to 10%by weight of at least one coalescing agent;
    from 0 to 2%by weight of at least one defoamer;
    from 0 to 2 %by weight of least one leveling agent; and
    from 10 to 95%by weight of water;
    wherein the weight percentages of all components add up to 100%by weight.
  12. The coating composition according to any one of the proceeding claims for use as an anti-blackening coating composition for magnesium containing steel plate.
  13. A substrate coated by the coating composition according to any one of the proceeding claims.
  14. Use of the coating composition according to any one of the proceeding claims.
PCT/CN2020/084811 2020-04-15 2020-04-15 Anti-blackening coating composition WO2021207950A1 (en)

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