CN111892864A - High-performance environment-friendly industrial decorative anticorrosive finish paint - Google Patents
High-performance environment-friendly industrial decorative anticorrosive finish paint Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- 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
- C09D5/084—Inorganic compounds
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C08K3/20—Oxides; Hydroxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C08K2003/327—Aluminium phosphate
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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Abstract
The invention relates to a high-performance environment-friendly industrial decorative anticorrosive finish paint which is prepared from a component A and a component B according to the weight ratio of 4:1 are mixed. The component A comprises, by weight, 50-65 parts of versatic acid glycidyl ester modified hydroxy acrylic resin (mass solid 75%), 10-20 parts of pigment and filler, 10-20 parts of chromium-free anti-rust pigment and 5-10 parts of solvent. The component B comprises the following components in parts by weight: 50-70 parts of aliphatic diisocyanate and 30-50 parts of butyl acetate. The invention has higher comprehensive performance requirements on weather resistance, fullness, salt spray resistance, adhesive force, fullness, chemical resistance and the like.
Description
The technical field is as follows:
the invention belongs to coatings, and particularly relates to a high-performance environment-friendly industrial decorative anticorrosive finish paint.
Background
The common acrylic polyurethane finish paint can meet the requirements of general industrial decoration corrosion resistance, namely better physical and chemical properties, and the salt spray resistance can reach 200-500 hours. However, in the fields of anticorrosive equipment, metal surfaces, large bridges, heavy anticorrosive engineering and the like which have higher comprehensive performance requirements on weather resistance, fullness, salt spray resistance, adhesive force, fullness, chemical resistance and the like of acrylic polyurethane (such as artificial aging property 1000h light loss rate less than 2 level, salt spray resistance for more than 600 hours, and one-time spraying dry film thickness of 60 micrometers), the common acrylic polyurethane finish paint cannot meet the requirements.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a high-solid chromium-free acrylic polyurethane finish paint with high requirements on comprehensive properties such as weather resistance, fullness, salt spray resistance, adhesive force, fullness, chemical resistance and the like.
As conceived above, the technical scheme of the invention is as follows: an anticorrosive finish paint for high-performance environment-friendly industrial decoration is prepared by mixing a component A and a component B according to a ratio of 4: 1.
Wherein, the component A comprises the following components in parts by weight:
tertiary carbonic acid glycidyl ester modified high solid
The component B comprises the following components in parts by weight: 50-70 parts of aliphatic diisocyanate and 30-50 parts of butyl acetate;
the high-solid hydroxy acrylic resin modified by the tertiary carbonic acid glycidyl ester (mass solid is 75%) comprises the following components in parts by weight,
further, the component A also comprises the following raw materials in parts by weight:
further, the self-made glycidyl versatate modified high-solid hydroxy acrylic resin (75% of mass solid) also comprises the following raw materials in parts by weight:
99% acrylic acid 0.5-1.5
Azobisisobutyronitrile 1.0-3.0
Mercaptoethanol molecular weight regulator 0.5-3.0.
Further, the preparation method of the self-made modified high-solid hydroxyl acrylic resin (75% of mass solid) of the tertiary carbonic acid glycidyl ester is carried out according to the following steps,
adding methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, butyl acrylate and acrylic acid into a dripping tank according to a formula amount, uniformly stirring, adding azobisisobutyronitrile with the formula amount of 70%, and starting stirring to dissolve the azobisisobutyronitrile for later use;
adding mercaptoethanol molecular weight regulator, butyl acetate and dehydrated petroleum xylene which account for 5 percent of the formula amount into a dripping tank, and uniformly stirring for later use;
thirdly, adding the tertiary carbonic acid glycidyl ester in the formula amount, butyl acetate and dehydrated petroleum xylene which account for 85% of the formula amount respectively into the reaction kettle, stirring and heating;
fourthly, when the temperature in the kettle rises to the reflux temperature of the mixed solvent, namely 140-145 ℃, respectively dripping the product in the step (1) and the product in the step (2) in the step b for 3-4 hours;
fifthly, carrying out copolymerization for 1h at the reflux temperature after dripping, adding 15% of azodiisobutyronitrile and 5% of butyl acetate and dehydrated petroleum xylene, continuing to carry out copolymerization for 1h, adding 15% of azodiisobutyronitrile and 5% of butyl acetate and dehydrated petroleum xylene, carrying out copolymerization for 3h at the reflux temperature, sampling, measuring the viscosity and the solid content, and calculating the conversion rate; when the conversion rate reaches more than 95 percent, stopping heating the reaction, introducing cooling water to reduce the temperature to below 50 ℃, filtering and packaging.
Further, the preparation method of the component A comprises the following steps: adding 70% of tertiary carbonic acid glycidyl ester modified high-solid hydroxyl acrylic resin (75% of mass solid) into a mixing tank, adding 50% of solvent into the mixing tank under stirring, uniformly stirring, then adding an adhesion promoter, dispersing at high speed for 8-12 minutes, then adding a dispersing agent, an antifoaming agent, a pigment filler, a chromium-free anti-rust pigment, dispersing at high speed for 15-30 minutes, grinding the slurry after high-speed dispersion in a sand mill until the fineness reaches 30 micrometers, pumping the slurry into a paint preparation tank, adding the rest 30% of self-made tertiary carbonic acid glycidyl ester modified high-solid hydroxyl acrylic resin, uniformly stirring, then adding a rheological additive, digao 450 and the rest 50% of solvent, controlling and detecting viscosity, fineness, solid content and gloss in stirring at 600 plus 800 rpm, filtering and packaging after qualification.
Further, the pigment and filler is one or more of rutile titanium white, precipitated barium sulfate, talcum powder and calcium carbonate.
Further, the chromium-free antirust pigment is one or more of ZAPP chromium-free aluminum zinc polyphosphate hydrate, low lead zinc phosphate and aluminum tripolyphosphate.
Further, the dispersant is one or more of BYK161, DA-325, and D.E. 903.
Further, the rheological additive is one or more of X-8800, A630-20X and 4200-10X.
Further, the solvent is one or more of dimethylbenzene, butyl acetate and butyl acetate.
The invention relates to a specially designed pure acrylic acid high-solid hydroxyl acrylic resin modified by tertiary carbonic acid glycidyl ester (mass solid is 75%), which does not contain styrene, has good weatherability, good gloss and color retention, has a hydroxyl value of 140%, and forms an insoluble and infusible network structure by crosslinking reaction with component B aliphatic diisocyanate (the hydroxyl value is low, the crosslinking density of the component B is not enough, and a paint film has poor solvent resistance, various medium resistance and physical and chemical properties).
The invention adopts a new polymerization process to synthesize high-performance high-solid hydroxy acrylic resin, and utilizes the super-weather resistance of the tertiary carbonic acid glycidyl ester to modify the hydroxy acrylic resin, so that the developed tertiary carbonic acid glycidyl ester modified hydroxy acrylic resin has the characteristics of light color, high decoration, excellent physical and mechanical properties, high solid and low viscosity.
According to the invention, two hydroxy monomers of hydroxyethyl acrylate and hydroxypropyl acrylate are compounded, so that uniform drying of a film formed by crosslinking with the component B is facilitated; the azo diisobutyronitrile initiator has high initiation efficiency and high resin conversion rate because the azo diisobutyronitrile initiator can be decomposed into 2 free radicals at the same time, and the generated free radicals have no oxidation effect and rarely generate branching, so the relative molecular mass distribution is narrow. The adoption of the mercaptoethanol molecular weight regulator not only regulates the molecular weight of the resin, but also overcomes the odor of the commonly used mercaptan molecular weight regulator.
The developed tertiary carbonic acid glycidyl ester modified high-solid hydroxyl acrylic resin is used as main body resin, the developed tertiary carbonic acid glycidyl ester modified high-solid hydroxyl acrylic resin and component B aliphatic diisocyanate are subjected to cross-linking reaction to form an insoluble and infusible net-shaped structure, and simultaneously, weather-resistant pigment, chromium-free anti-rust pigment, anti-sagging agent, leveling agent and anti-settling agent are preferably selected to prepare the high-solid chromium-free acrylic polyurethane finish paint, so that the comprehensive performances of the paint film, such as fullness, weather resistance, adhesive force, salt mist resistance, gloss retention and color retention, are more excellent, and particularly, the weather resistance is doubled compared with that of the commercially available hydroxyl acrylic resin (the self-made high-solid hydroxyl acrylic resin has a 1000h light loss rate of less than 1 level, and the commercially available hydroxyl. Meanwhile, the product has high solid content, low Volatile Organic Compound (VOC), no heavy metal chromium, and little environmental pollution, and meets the coating requirement of long-acting heavy corrosion resistance.
The specific implementation mode is as follows:
an anticorrosive finish paint for high-performance environment-friendly industrial decoration is prepared by mixing a component A and a component B according to a ratio of 4: 1.
Wherein, the component A comprises the following components in parts by weight:
tertiary carbonic acid glycidyl ester modified high solid
The component B comprises the following components in parts by weight: 50Kg of aliphatic diisocyanate and 30Kg of butyl acetate.
The self-made glycidyl versatate modified high-solid hydroxy acrylic resin (75% by mass and solid) consists of the following components in parts by weight,
the preparation method of the tertiary carbonic acid glycidyl ester modified high-solid hydroxy acrylic resin (75% of mass solid) is carried out according to the following steps,
adding methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, butyl acrylate and acrylic acid into a dripping tank according to a formula amount, uniformly stirring, adding azobisisobutyronitrile with the formula amount of 70%, and starting stirring to dissolve the azobisisobutyronitrile for later use;
adding mercaptoethanol molecular weight regulator, butyl acetate and dehydrated petroleum xylene which account for 5 percent of the formula amount into a dripping tank, and uniformly stirring for later use;
thirdly, adding the tertiary carbonic acid glycidyl ester in the formula amount, butyl acetate and dehydrated petroleum xylene which account for 85% of the formula amount respectively into the reaction kettle, stirring and heating;
fourthly, when the temperature in the kettle rises to the reflux temperature of the mixed solvent, namely 140-145 ℃, respectively dripping the product in the step (1) and the product in the step (2) in the step b for 3-4 hours;
fifthly, carrying out copolymerization for 1h at the reflux temperature after dripping, adding 15% of azodiisobutyronitrile and 5% of butyl acetate and dehydrated petroleum xylene, continuing to carry out copolymerization for 1h, adding 15% of azodiisobutyronitrile and 5% of butyl acetate and dehydrated petroleum xylene, carrying out copolymerization for 3h at the reflux temperature, sampling, measuring the viscosity and the solid content, and calculating the conversion rate; (conversion ═ actual solids content/theoretical solids content × 100%),
when the conversion rate reaches more than 95 percent, stopping heating the reaction, introducing cooling water to reduce the temperature to below 50 ℃, filtering and packaging.
The preparation method of the component A comprises the following steps: adding 70% of tertiary carbonic acid glycidyl ester modified high-solid hydroxyl acrylic resin (75% of mass solid) into a mixing tank, adding 50% of solvent into the mixing tank under stirring, uniformly stirring, then adding an adhesion promoter, dispersing at high speed for 8-12 minutes, then adding a dispersing agent, an antifoaming agent, a pigment filler, a chromium-free anti-rust pigment, dispersing at high speed for 15-30 minutes, grinding the slurry after high-speed dispersion in a sand mill until the fineness reaches 30 micrometers, pumping the slurry into a paint preparation tank, adding the rest 30% of self-made tertiary carbonic acid glycidyl ester modified high-solid hydroxyl acrylic resin, uniformly stirring, then adding a rheological additive, digao 450 and the rest 50% of solvent, controlling and detecting viscosity, fineness, solid content and gloss in stirring at 600 plus 800 rpm, filtering and packaging after qualification.
The pigment and filler is one or more of rutile titanium dioxide, precipitated barium sulfate, talcum powder and calcium carbonate.
The chromium-free antirust pigment is one or more of ZAPP chromium-free aluminum zinc polyphosphate hydrate, low lead zinc phosphate and aluminum tripolyphosphate.
The dispersant is one or more of BYK161, DA-325, and D.E. 903.
The rheological additive is one or more selected from X-8800, A630-20X and 4200-10X.
The solvent is one or more of xylene, butyl acetate and butyl acetate.
The self-made high-solid hydroxyl acrylic resin is modified by adopting a pure acrylic monomer and introducing the glycidyl versatate, so that the self-made high-solid hydroxyl acrylic resin has good weather resistance, light and color retention and chemical and water resistance.
According to the invention, through developing the high-solid hydroxyl acrylic resin modified by the tertiary carbonic acid glycidyl ester, designing a proper hydroxyl content to enable the hydroxyl content to be subjected to a crosslinking reaction with the component B aliphatic diisocyanate to form an insoluble and infusible net-shaped structure, and preferably selecting a weather-resistant pigment, a chromium-free anti-rust pigment and various auxiliaries, the comprehensive performances of a paint film, such as fullness, weather resistance, adhesive force, salt mist resistance, light and color retention, are more excellent, and particularly the weather resistance is doubled compared with that of the commercially available hydroxyl acrylic resin (the 1000h light loss rate of the high-solid hydroxyl acrylic resin modified by the self-made tertiary carbonic acid glycidyl ester is less than 1 level, and the 1000h light loss rate of the commercially available hydroxyl acrylic resin is more than 2 level).
The invention has high solid content, low Volatile Organic Compound (VOC) and no heavy metal chromium, and can meet the coating requirements of small environmental pollution and long-acting heavy corrosion resistance. The finishing coat is used as a finishing coat product in coating systems of bridges, steel structures and large-scale heavy-duty anticorrosion projects, and has the advantages of excellent fullness and weather resistance, long service life, low maintenance cost and remarkable economic and social benefits.
Claims (10)
1. A high-performance environment-friendly industrial decorative anticorrosion finish paint is characterized in that: is prepared by mixing the component A and the component B according to the proportion of 4:1,
wherein, the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight: 50-70 parts of aliphatic diisocyanate and 30-50 parts of butyl acetate;
the high-solid hydroxy acrylic resin modified by the tertiary carbonic acid glycidyl ester (mass solid is 75%) comprises the following components in parts by weight,
2. the high-performance environment-friendly industrial decorative anticorrosion finish paint as claimed in claim 1, wherein: the component A also comprises the following raw materials in parts by weight:
3. the high-performance environment-friendly industrial decorative anticorrosion finish paint as claimed in claim 1, wherein: the self-made glycidyl versatate modified high-solid hydroxy acrylic resin (75% of mass solid) also comprises the following raw materials in parts by weight:
99% acrylic acid 0.5-1.5
Azobisisobutyronitrile 1.0-3.0
Mercaptoethanol molecular weight regulator 0.5-3.0.
4. The high solids, chromium-free acrylic polyurethane topcoat of claims 1-3, wherein: the preparation method of the self-made glycidyl versatate modified high-solid hydroxy acrylic resin (mass solid is 75%) is characterized by comprising the following steps of: the method comprises the following steps:
adding methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, butyl acrylate and acrylic acid into a dripping tank according to a formula amount, uniformly stirring, adding azobisisobutyronitrile with the formula amount of 70%, and starting stirring to dissolve the azobisisobutyronitrile for later use;
secondly, adding the mercaptoethanol molecular weight regulator with the formula amount, and 5 percent of propylene glycol monomethyl ether acetate and dehydrated petroleum xylene with the formula amount into a dripping tank, and uniformly stirring for later use;
thirdly, adding the tertiary carbonic acid glycidyl ester in the formula amount, propylene glycol monomethyl ether acetate and dehydrated petroleum xylene which account for 85 percent of the formula amount respectively into the reaction kettle, stirring and heating;
fourthly, when the temperature in the kettle rises to the reflux temperature of the mixed solvent, namely 140-145 ℃, respectively dripping the product in the step (1) and the product in the step (2) in the step b for 3-4 hours;
fifthly, after dripping is finished, keeping copolymerization for 1h at the reflux temperature, adding 15% of azodiisobutyronitrile, 5% of propylene glycol monomethyl ether acetate and 5% of dehydrated petroleum xylene, continuing copolymerization for 1h, adding 15% of azodiisobutyronitrile, 5% of propylene glycol monomethyl ether acetate and 5% of dehydrated petroleum xylene, keeping copolymerization for 3h at the reflux temperature, sampling, measuring viscosity and solid content, and calculating conversion rate; when the conversion rate reaches more than 95 percent, stopping heating the reaction, introducing cooling water to reduce the temperature to below 50 ℃, filtering and packaging.
5. The high solids, chromium-free acrylic polyurethane topcoat of claims 1-3, wherein: the preparation method of the component A comprises the following steps: adding 70% of tertiary carbonic acid glycidyl ester modified high-solid hydroxyl acrylic resin (75% of mass solid) into a mixing tank, adding 50% of solvent into the mixing tank under stirring, uniformly stirring, then adding an adhesion promoter, dispersing at high speed for 8-12 minutes, then adding a dispersing agent, an antifoaming agent, a pigment filler, a chromium-free anti-rust pigment, dispersing at high speed for 15-30 minutes, grinding the slurry after high-speed dispersion in a sand mill until the fineness reaches 30 micrometers, pumping the slurry into a paint preparation tank, adding the rest 30% of self-made tertiary carbonic acid glycidyl ester modified high-solid hydroxyl acrylic resin, uniformly stirring, then adding a rheological additive, digao 450 and the rest 50% of solvent, controlling and detecting viscosity, fineness, solid content and gloss in stirring at 600 plus 800 rpm, filtering and packaging after qualification.
6. The high solids, chromium-free acrylic polyurethane topcoat of claim 1, wherein: the pigment and filler is one or more of rutile titanium dioxide, precipitated barium sulfate, talcum powder and calcium carbonate.
7. The high solids, chromium-free acrylic polyurethane topcoat of claim 1, wherein: the chromium-free antirust pigment is one or more of ZAPP chromium-free aluminum zinc polyphosphate hydrate, low lead zinc phosphate and aluminum tripolyphosphate.
8. The high solids, chromium-free acrylic polyurethane topcoat of claim 1, wherein: the solvent is one or more of dimethylbenzene, butyl acetate and propylene glycol methyl ether acetate.
9. The high solids, chromium-free acrylic polyurethane topcoat of claim 2, wherein: the dispersant is one or more of BYK161, DA-325 and D.E. 903.
10. The high solids, chromium-free acrylic polyurethane topcoat of claim 2, wherein: the rheological additive is one or more of X-8800, A630-20X and 4200-10X.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010585593.8A CN111892864A (en) | 2020-06-24 | 2020-06-24 | High-performance environment-friendly industrial decorative anticorrosive finish paint |
| CN202210733086.3A CN115232541A (en) | 2020-06-24 | 2020-06-24 | Anti-corrosion finish paint |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010585593.8A CN111892864A (en) | 2020-06-24 | 2020-06-24 | High-performance environment-friendly industrial decorative anticorrosive finish paint |
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| CN202210733086.3A Division CN115232541A (en) | 2020-06-24 | 2020-06-24 | Anti-corrosion finish paint |
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| CN202210733086.3A Pending CN115232541A (en) | 2020-06-24 | 2020-06-24 | Anti-corrosion finish paint |
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| CN116855160A (en) * | 2023-05-30 | 2023-10-10 | 江苏海耀化工有限公司 | Preparation method of aliphatic polyurethane coating with high weather resistance, high performance and high cost performance |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555178A (en) * | 2013-11-07 | 2014-02-05 | 天津五一天立油漆有限公司 | High-solid chrome-free acrylic polyurethane finish paint |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555178A (en) * | 2013-11-07 | 2014-02-05 | 天津五一天立油漆有限公司 | High-solid chrome-free acrylic polyurethane finish paint |
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Application publication date: 20201106 |