CN113265189B - Water-based acrylic polyurethane finish paint and preparation method and application thereof - Google Patents
Water-based acrylic polyurethane finish paint and preparation method and application thereof Download PDFInfo
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- CN113265189B CN113265189B CN202110420202.1A CN202110420202A CN113265189B CN 113265189 B CN113265189 B CN 113265189B CN 202110420202 A CN202110420202 A CN 202110420202A CN 113265189 B CN113265189 B CN 113265189B
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T30/00—Transportation of goods or passengers via railways, e.g. energy recovery or reducing air resistance
Abstract
The invention discloses a water-based acrylic polyurethane finish paint, which comprises a paint and a curing agent, wherein the paint comprises: the coating comprises a hydroxyl polyacrylate water dispersion, a hydroxyl styrene acrylic copolymer, a pigment filler, saturated polyester resin and an auxiliary agent; the auxiliary agent comprises a polyurethane associative thickener; the curing agent comprises HDI trimer and IPDI. The invention is mainly used for coating the dry film with a thickness of more than 60 mu m once in the construction process of the outer wall of the locomotive, the maximum film thickness reaches 120 mu m, the paint film does not bubble, does not sag and has good leveling property, the coating interval is 1 hour and is shortened to 1 coating by coating the finish paint of the original locomotive for 2 times, and the construction time of each locomotive is shortened by 1.5 hours. In addition, the product has better leveling property, stone impact resistance, chemical solvent resistance, water (40 ℃) resistance and aging resistance.
Description
Technical Field
The invention relates to a water-based acrylic polyurethane finish paint, in particular to a thick-coating water-based acrylic polyurethane finish paint for rolling stocks and a preparation method and application thereof.
Background
The water-based paint does not contain organic solvent in the construction process, and water is used as diluent, so that the VOC emission in coating construction is greatly reduced, and the working environment of coating workers is improved. In recent years, the coating in the rail transportation field is also changed into water-based coating, but in the rail transportation field, particularly in the field of rolling stocks, the coating process requirements are high, the requirements on the appearance, thickness, water resistance and chemical resistance of a paint film are high, and the quality problem of the water-based coating process is more. The film thickness of the finish paint is required to be more than 60 mu m in rail transit, the appearance is required to be smooth, and the defects of heavy orange marks, bubbling, sagging and other paint films are avoided. The thickness of a common water-based paint in construction is generally 30-50 mu m of the thickness of a dry film sprayed in one step, and if the thickness is too thick in one-step spraying, the problems of paint film sagging, foaming, pin holes and the like are easy to occur.
CN 110885616A is a thick coating type waterborne epoxy finish paint for rail transit vehicles, which comprises a paint vehicle and a curing agent, wherein the paint vehicle comprises the following raw materials in parts by weight: 45-55 parts of water-based acrylic hybrid epoxy resin, 15-20 parts of barium sulfate, 0.2-0.4 part of fumed silica, 2-2.5 parts of high molecular weight block copolymer dispersant, 19-22 parts of pigment, 0.5-0.6 part of polysiloxane defoamer, 3-0.5 part of flatting agent, 2.0-3.0 parts of thickener and the balance of deionized water, wherein the thickness of the one-time spraying paint film can reach more than 100 mu m, and the coating film has excellent adhesion, good impact resistance and thick coating performance.
However, the thick-coating water-based epoxy finish paint is mainly used for vehicle bogie and underframe parts needing thick coating, the product mainly improves the elasticity of the thick coating and the paint film, the appearance requirement is not high, the main resin is epoxy resin emulsion, and the weather resistance of the paint film is poor.
CN 102977760A discloses a thick film type polyurethane finish paint, belongs to the technical field of new materials, and relates to the field of heavy-duty anticorrosion engineering. The thick film type polyurethane finish paint is prepared from the following raw materials, including alkyd resin, hydroxy acrylic resin, 25% -30% of aliphatic polyisocyanate content of the sum of the weight of the alkyd resin and the weight of the hydroxy acrylic resin, titanium dioxide, a defoaming agent, a dispersing agent, a flatting agent, a rheological additive, organic bentonite and a diluting agent. The dry film range is 50-60 mu m during spraying, so that the traditional 3-4 coating procedures can be simplified into 2-3 coating procedures, the coating system is simplified, the construction time is shortened, the coating speed is accelerated, and the steel structure manufacturing efficiency is improved.
However, the thick-coating polyurethane finish paint is a low-solvent resin paint, belongs to a special solvent-based paint, and is mainly characterized in that the product viscosity is low, the solid content is high, the drying is fast, an organic solvent is added during construction, the VOC content is lower than that of other solvent-based paints, but the VOC content is still too high when the thick-coating polyurethane finish paint is used compared with a water-based paint. And the construction film thickness of the paint film of the outer wall of the vehicle body is higher than the requirement of 50-60 mu m, the requirement on the appearance is strict, and the performance requirement of the paint film of the outer wall of the vehicle body cannot be met.
CN101104765 discloses a water-based acrylic finish, which comprises 10-60 wt% of water-based acrylic emulsion, 3-25 wt% of coloring pigment, 5-20 wt% of filler, 2-15 wt% of film-forming additive, 0.5-1.5 wt% of leveling thickener, 9-23 wt% of softened water and 0.5-2.6 wt% of other additives; the other auxiliary agents comprise a dispersing agent, a wetting agent, a defoaming agent, a preservative, a mildew preventive and a neutralizing agent; the coating effect of the oily acrylic finish paint can be achieved, and the gloss can reach 40%; the initial water resistance is good, and the water sealing test can be passed; in addition, the water-based acrylic finish paint has no pollution to the environment, is harmless to the health of constructors, and is safe and convenient to use; the paint is suitable for high-pressure airless spraying, has high construction efficiency, can finish paint construction in one step, and can ensure that the thickness of a single-pass coating layer can reach 30-100 microns without sagging or cracking.
However, the invention is a water-based finish paint for the header tank, the requirements on the appearance, the gloss and the chemical resistance of a paint film can not reach the requirements of finish paint for rolling stocks, and the product focuses more on water resistance, corrosion resistance, quick drying and thick coating in construction.
Disclosure of Invention
The invention aims to provide a thick-coating water-based acrylic polyurethane finish paint for the outer wall of a vehicle body, which has excellent paint film appearance, good weather resistance, water resistance and chemical resistance, and can be sprayed to form a film in the product coating process, thereby meeting the requirements of the coating construction process of rolling stocks.
In order to achieve the purpose, the technical scheme of the invention is as follows:
an aqueous acrylic polyurethane topcoat comprising a vehicle and a curing agent, the vehicle comprising: the coating comprises a hydroxyl polyacrylate water dispersion, a hydroxyl styrene acrylic copolymer, a pigment filler, saturated polyester resin and an auxiliary agent; the auxiliary agent comprises a polyurethane associative thickener; the curing agent comprises HDI trimer and IPDI.
Preferably, the auxiliaries include fumed silica, dispersants, surfactants, defoamers, wetting agents, ultraviolet light absorbers, light stabilizers, pH adjusters, co-solvents, and solvents.
Preferably, the aqueous hydroxy polyacrylate dispersion comprises an aqueous hydroxy polyacrylate dispersion No. 1 and an aqueous hydroxy polyacrylate dispersion No. 2, wherein the aqueous hydroxy polyacrylate dispersion No. 1 and the aqueous hydroxy polyacrylate dispersion No. 2 are both aqueous hydroxy polyacrylate dispersions. However, the solid content and the hydroxyl group content of the two are different.
The solid content of the No. 1 hydroxyl polyacrylate aqueous dispersion is low and is 40-43 percent; the hydroxyl content is high and is 4 to 4.5 percent; the paint film has better leveling property and higher glossiness, and the solid content of the No. 2 hydroxyl polyacrylate water dispersion is higher and is 44-50%; the hydroxyl content is low, and is 3.5 to 3.9 percent; the paint film has better chemical resistance and longer activation period. The two are used in a matching way, and the whole formula is adjusted, so that the coating film has the advantages of two types of water-based resin emulsion, and a paint film with better performance is obtained.
Preferably, the hydroxystyrene acrylic copolymer is copolymerized from a polyacrylate monomer and a styrene monomer.
The hydroxy styrene acrylic copolymer resin has low hydroxy content, and the hydroxy content is 1.0-1.5%; CO generated by the crosslinking reaction2Can be released without generating bubbles. Meanwhile, the glass transition temperature of the resin is as high as 56 ℃, and a paint film is not easy to sag and is suitable for thick coating.
Preferably, the water-based acrylic polyurethane finish paint comprises, by weight, 20-25 parts of No. 1 hydroxyl polyacrylate water dispersion, 8-10 parts of hydroxystyrene acrylic copolymer, 8-10 parts of No. 2 hydroxyl polyacrylic acid dispersion, 0.8-1.0 part of fumed silica, 2.0-2.5 parts of dispersing agent, 0.8-1.0 part of surfactant, 0.2-0.3 part of defoaming agent, 0.3-0.5 part of wetting agent, 0.4-0.6 part of ultraviolet light absorbent, 0.4-0.6 part of light stabilizer, 25-30 parts of pigment and filler, 3-5 parts of saturated polyester resin, 0.3-0.5 part of polyurethane associative thickener, 0.8-1 part of cosolvent, 13-16 parts of solvent and 0.3-0.5 part of pH regulator.
Preferably, the cosolvent is a glycol ether ester high-boiling point solvent.
The glycol ether ester high-boiling point solvent has excellent dissolving capacity, and the leveling property of a paint film can be effectively improved by adding a small amount of the glycol ether ester high-boiling point solvent.
Preferably, the dispersant is an anionic polymeric dispersant.
The anionic polymer dispersant has uniform and better dispersion effect and storage stability on the coating system concentrated slurry.
The anionic polymer dispersant has great steric hindrance effect, charged radicals and pigment ions generate anchoring effect, so that the pigment ions are more stable and cannot flocculate when colliding with each other, meanwhile, the polymer dispersant is high-molecular, high-molecular chain segments are well dissolved and unfolded, the effect of reducing the system viscosity is achieved, a small amount of water is added, the construction state can be achieved, and the coating film can have thicker film thickness after being sprayed.
Preferably, the surfactant is a nonionic surfactant.
Preferably, the surfactant is an acetylenic diol nonionic surfactant.
Due to the special alkyne diol structure, the product has multiple functions of wetting, defoaming, improving dispersibility, improving flowing and leveling property and the like, can effectively reduce surface tension, control foam and stabilize consistency and viscosity. Compared with the traditional surfactant, the water-based surfactant has lower water sensitivity and is suitable for an aqueous system. The surfactant has the characteristics that the surfactant has low dynamic/static surface tension, can quickly reduce the dynamic/static surface tension of a system and quickly migrate to the surface, ensures good wetting of a base material, and simultaneously has small variation between the dynamic surface tension and static state, so that the system can still well wet the base material during violent movement, and the interface rapid formation processes such as spraying, rolling, brushing and the like can be realized. Some of the paint film defects caused by thick coating can be avoided.
Preferably, the defoamer is a polysiloxane defoamer.
The defoaming agent is a siloxane defoaming agent, and has a good defoaming effect.
The siloxane defoaming agent can be paved on the surface of a paint film, the surface tension is reduced, the bubble film is thinned and broken, the defoaming capability is strong, the paint film is thick and coated with a plurality of bubbles which are difficult to eliminate, the defoaming agent is used, no bubbles are generated when the paint film is thick and coated, and the appearance of the paint film is ensured to meet the requirement.
Preferably, the wetting agent is a polyether siloxane based wetting agent.
The polyether siloxane wetting agent has good compatibility and recoatability, is strong in shrinkage prevention, can reduce the surface tension of a substrate and the surface energy of water, can prevent a water-based paint film from being better spread on the surface of the substrate, can avoid the defects of shrinkage cavities, pinholes and the like of the paint film, enhances the leveling property, is good in compatibility with water and an organic solvent, reduces surface orange marks when the paint film is thickly coated, and has better appearance.
Preferably, the pH adjusting agent is dimethylethanolamine.
The dimethyl ethanolamine has strong alkalinity, can adjust the system PH value of the water-based paint, and has slow volatilization and stable performance compared with ammonia water. The water-based paint has the most stable system performance only in a weakly alkaline environment, and the construction performance including thick paint performance is guaranteed.
Preferably, the curing agent comprises the following components in parts by weight: 50-60 parts of HDI tripolymer, 15-20 parts of IPDI and 25-30 parts of ethylene glycol butyl ether acetate.
Preferably, the solvent is water.
The invention is a water-based acrylic polyurethane finish paint, which only uses water as a solvent except a small amount of cosolvent to reduce VOC. Meanwhile, in order to meet the requirements of the water-based finish paint, a plurality of optimized choices are made on the selection of raw materials, and the overall formula needs to be in a coordinated balance among water solubility, paint film appearance, weather resistance, water resistance and chemical resistance.
The invention also aims to provide a preparation method of the water-based acrylic polyurethane finish paint, which comprises the following steps:
s1, mixing the No. 1 hydroxyl polyacrylate water dispersion, a dispersing agent, fumed silica, a surfactant, a defoaming agent, a partial solvent and a pigment and filler to obtain pre-dispersed slurry; grinding the pre-dispersed slurry, adding hydroxystyrene acrylic acid copolymer, No. 2 hydroxyl polyacrylate aqueous dispersion, wetting agent, ultraviolet absorbent, light stabilizer and thickening agent, uniformly dispersing, adding pH regulator to regulate the pH to 8.0-8.2, finally adding saturated polyester resin, cosolvent and residual solvent, stirring for 10-15 minutes, adding pH regulator to regulate the pH to 8.2-8.5, and finally filtering for later use;
s2, mixing the HDI tripolymer, the IPDI and the ethylene glycol monobutyl ether acetate, and uniformly dispersing for later use;
s3, mixing the paint and the curing agent according to the weight ratio of 100:30 when in use.
In the step S1, the No. 1 hydroxyl polyacrylate water dispersion, the dispersant, the fumed silica, the surfactant, the defoamer, the partial solvent, and the pigment and filler are dispersed in advance, so that the pigment and filler reach a sufficiently small grinding fineness, and the paint film surface performance is better by virtue of the huge shearing force between the ground particles. While some aqueous emulsions or adjuvants do not undergo high shear and can degrade their properties, they are prepared in steps by preparing a predispersed slurry from a raw material that can be ground.
The solvent is water, and the purpose of adding water in batches for multiple times is to ensure that the product has proper viscosity, and the viscosity cannot be too high or too low.
The performance of the water-based paint is stable only in a weak alkaline environment, and the addition of the pH regulator in step S1 is to ensure the stability of the system and to increase the viscosity of the system to a suitable degree. The pH value is adjusted to 8.0-8.2 for the first time, so that the system is kept stable in a weak alkali environment, and meanwhile, the viscosity is not too high, so that the system is not suitable for adding subsequent raw materials and the dispersing effect is influenced. After all the raw materials are added finally, the pH is adjusted in order to keep the system stable. The best tested alkaline environment state of the system is that the pH value is 8.2-8.5.
The invention also aims to provide application of the water-based acrylic polyurethane finish paint, wherein the water-based acrylic polyurethane finish paint can be applied to thick coating of outer walls of locomotive bodies, and the thickness of a paint film is more than 60 mu m.
The invention is further explained below:
(1) functional hydroxyl (-OH) in the hydroxyl polyacrylic acid dispersoid reacts with isocyanate (-N ═ C ═ O) in HDI trimer and IPDI to form a film through crosslinking and curing, and various chemical resistance and weather resistance are excellent.
(2) The hydroxy styrene acrylic copolymer resin has low hydroxy content, and CO2 generated by crosslinking reaction can be released without generating bubbles. Meanwhile, the glass transition temperature of the resin is as high as 56 ℃, and a paint film is not easy to sag and is suitable for thick coating.
(3) The saturated polyester resin does not contain organic solvent and has 100 percent of solid content, and can effectively improve the glossiness, the film thickness, the elastic property, the surface hardness and the chemical resistance of a coating product.
(4) The associative polyurethane thickener is hydrophobic associative water soluble polymer with little hydrophobic group in hydrophilic macromolecular chain. In the aqueous solution of the polymer, hydrophobic groups are aggregated due to hydrophobic effect, so that intramolecular and intermolecular association is generated in macromolecular chains, and the rheological property of the aqueous solution is greatly influenced. Above the critical association concentration, a supermolecular structure mainly based on intermolecular association is formed, the hydrodynamic volume is increased, and therefore the super-molecular-weight-adjustable water-soluble polymer has better thickening property. However, the two lipophilic groups in the molecule are not necessarily in the same micelle, and are linked to form a structure. The oleophilic groups in the associative thickener may adsorb the emulsion particles and the pigment particles, which in turn enhances the structure. Furthermore, the particles bridged by the macromolecules of the thickener form a physical network (cross-linked) structure which can be gradually destroyed in a shear field, so that the flow properties of the system can be controlled. Such associations are broken down at high shear rates, reducing the viscosity, and re-forming after the shear is removed, restoring the viscosity. However, the formation of association takes time, so that the recovery of viscosity is not as fast as cellulose, thereby giving a certain flow time, facilitating leveling and improving gloss.
(5) IPDI curing agent, excellent optical stability, and chemical resistance. Its isocyanate group has low reactivity and can prolong the service life of the paint. Is suitable for long-time coating construction of large workpieces. Because of having a cycloparaffin structure in the molecule, the strength of the cured network structure is superior to that of other aliphatic isocyanates, and the yellowing resistance of a paint film is excellent.
The various raw materials have respective functions, so that the product performances are ensured: the hydroxy polyacrylic acid dispersoid and the hydroxy styrene acrylic copolymer resin are subjected to crosslinking reaction with the isocyanate curing agent to generate a paint film, so that the mechanical property, chemical resistance and weather resistance of the paint film are ensured. The saturated polyester and the isocyanate curing agent are subjected to crosslinking reaction, so that the glossiness, the film thickness, the elastic property, the surface hardness and the anti-ageing property of a paint film are improved, the thickening agent forms a net structure, emulsion particles and pigment particles are adsorbed, the viscosity of the paint is improved, and the anti-sagging property of the paint film is improved. The components also react with each other and affect each other, so that the balance of the performances is achieved.
The technical points of the invention are as follows: the functional hydroxyl (-OH) in the hydroxyl polyacrylate aqueous dispersion reacts with isocyanate (-N ═ C ═ O) to crosslink and cure to form a film with excellent chemical resistance and weather resistance.
The invention uses hydroxystyrene acrylic acid copolymer resin, the hydroxyl content of the resin is low, CO2 generated by alternating current reaction can be released, and no air bubble is generated. Meanwhile, the glass transition temperature of the resin is as high as 56 ℃, a paint film is not easy to sag, and the resin is suitable for thick coating and has good leveling property.
The invention uses saturated polyester resin with high solid content (more than or equal to 96 percent) and can effectively improve the glossiness, the film thickness, the elastic property, the surface hardness and the chemical resistance of a coating product.
The curing agent used in the invention is HDI tripolymer and IPDI, the HDI tripolymer can ensure good flexibility and dryness under the condition that a paint film is not yellowed and has high hardness, the reactivity of the IPDI curing agent and cyanate ester group is low, and the service life of the paint can be prolonged. Is suitable for long-time coating construction of large workpieces. Because the molecule of the organic silicon resin has a cycloparaffin structure, the strength of a cured network structure is superior to that of other aliphatic isocyanates, so that a paint film has excellent optical stability and chemical resistance.
The gas phase silicon dioxide has excellent anti-settling performance, and the storage stability of the product is improved.
The invention relates to an associative polyurethane thickener, a hydrophobic associative water-soluble polymer, a water-soluble polymer with a small amount of hydrophobic groups on a hydrophilic macromolecular chain. In the aqueous solution of the polymer, hydrophobic groups are aggregated due to hydrophobic effect, so that intramolecular and intermolecular association is generated between macromolecular chains, the association is released at a high shear rate, the viscosity is reduced, and the macromolecular chains are reformed after being sheared off, so that the viscosity is recovered. But the formation of association takes time, so the recovery of viscosity is not as fast as cellulose, thereby giving a certain flow time, being beneficial to leveling and improving the gloss of a paint film.
The polyether siloxane wetting agent used in the invention has good compatibility, good recoatability and strong shrinkage prevention, and the anionic polymer dispersant has uniform and better dispersion effect and storage stability on the coating system concentrated slurry. The defoaming agent is a siloxane defoaming agent, and has a good defoaming effect; the ultraviolet light absorber and the light stabilizer can improve the aging resistance of the paint film.
The cosolvent used in the invention is an environment-friendly glycol ether ester high-boiling point solvent, has excellent dissolving capacity, and can effectively improve the leveling property of a paint film by adding a small amount of the cosolvent.
The water-based acrylic polyurethane finish paint has the following advantages:
(1) the paint film has good thick coating performance. CO generated by crosslinking reaction by using low-hydroxyl hydroxystyrene acrylic acid copolymer resin2Can be released without generating bubbles. Meanwhile, the glass transition temperature of the resin is as high as 56 ℃, and a paint film is not easy to sag and is suitable for thick coating. The paint has the advantages of no sagging in one-step coating, no foaming of paint film, and good leveling property, and the maximum foaming film thickness reaches 120 mu m.
(2) The paint film has good weather resistance, light and color retention. The crosslinking reaction of the hydroxyl polyacrylate water dispersion and HDI and IPDI curing agents is adopted, so that a paint film has good chemical resistance, weather resistance, light retention and color retention.
(3) The paint film has high luster and good toughness. Paint film gloss (20 °): 82-85. The saturated polyester resin is adopted, so that the glossiness, the film thickness, the elastic property, the surface hardness and the chemical resistance of a coating product are effectively improved.
(4) The paint film has good storage stability and anti-sagging performance. The fumed silica and the associative polyurethane thickener are selected, so that the paint is not precipitated and agglomerated after being stored for a long time, a wet film is not easy to flow and fall during spraying, and a certain flowing time is provided, so that the paint film is favorably leveled, and the orange peel on the surface is reduced.
(5) Has extremely low VOC content and no solvent odor. The resin is water emulsion and high solid polyester resin, the dosage of the cosolvent is not more than 1 percent, and all solvents are deionized water, so the environment-friendly water-based paint is real.
(6) The finish paint of the original locomotive is coated for 2 times, the coating interval is 1 hour, the coating is shortened to 1 time, the construction time of each locomotive is shortened by 1.5 hours, the comprehensive performance is good, the comprehensive performance is excellent, and the performance can meet the requirement of the Q/CR546.1-2016 standard of the Chinese railway general company.
Drawings
FIG. 1 is a flow chart of the preparation of a waterborne acrylic polyurethane topcoat.
Detailed Description
Example 1
The water-based acrylic polyurethane finish paint comprises paint and a curing agent, and the raw materials are shown in the table 1 in parts by weight;
table 1 three formulations of the invention
The preparation method of the water-based acrylic polyurethane finish paint comprises the following steps:
A. preparation of paint vehicle: the 16 raw materials for forming the paint are mixed according to the weight ratio, the No. 1 hydroxyl polyacrylate aqueous dispersion is poured into a container cylinder, the container cylinder is placed under a dispersion machine for dispersion, the rotating speed is adjusted to be 500 plus 800 r/min, and then the dispersing agent, the fumed silica, the surfactant, the defoaming agent, the deionized water and the pigment (filling) are sequentially added under the stirring state. After the feeding is finished, the rotating speed of the dispersion machine is adjusted to 1000-; then grinding a pre-dispersion slurry pump such as a sand mill by using a diaphragm pump until the fineness is less than or equal to 10 mu m, discharging, adding hydroxystyrene acrylic acid copolymer resin, No. 2 hydroxyl polyacrylate aqueous dispersion, a wetting agent, an ultraviolet light absorber, a light stabilizer and a thickening agent, adjusting the rotating speed of a dispersion machine to 1000-1200 turns/min after the feeding is finished, stirring for 10-15 min, adding a DMEA solution to adjust the PH to 8.0-8.2, stirring for 10-15 min, finally adding a saturated polyester resin, a cosolvent and the rest deionized water, stirring for 10-15 min, adding a DMEA solution to adjust the PH to 8.2-8.5, adding deionized water to adjust the viscosity, filtering by using a 120-mesh filter screen, removing mechanical impurities, and packaging by using a plastic barrel for later use;
B. preparation of the curing agent: firstly, HDI trimer and IPDI in the curing agent raw materials are added into a container cylinder according to the weight ratio, the container cylinder is placed under a dispersion machine for dispersion, the rotation speed is adjusted to be 500 plus 800 r/min, then ethylene glycol monobutyl ether acetate is added under the stirring state, after the addition is finished, the rotation speed of the dispersion machine is adjusted to be 1000 plus 1200 r/min, and the stirring is carried out for 5-10 min. Packaging for later use;
C. preparing thick coating type water-based finish paint for rolling stock: when in use, the paint and the curing agent are stirred and mixed according to the weight ratio of 100:30, and the construction viscosity can be adjusted by using a proper amount of deionized water during construction.
Note: the above No. 1 hydroxyl polyacrylic acid dispersoid is NeocrylTMXK-542 polyacrylic hydroxy acid dispersion, produced by Disman China Co., Ltd; the hydroxystyrene acrylic copolymer resin is
XK-110 hydroxystyrene acrylic acid copolymer resin, produced by Dismann China Co., Ltd; the 2 nd hydroxyl polyacrylic acid dispersoid is
A2470 Hydroxypolyacrylic acid DispersionManufactured by scientific creative polymer, china ltd; fumed silica manufactured by Germany winning, Chungdousai, Inc.; anionic polymeric dispersants are manufactured by TEGO, Germany; the nonionic surfactant is produced by German winning and creating Special chemical company; silicone antifoam agent, BYK Germany; polyether siloxane type wetting agents manufactured by TEGO, Germany; ultraviolet light absorbers manufactured by BASF corporation of Germany; light stabilizers manufactured by BASF corporation, Germany; the saturated polyester resin is
SY944 saturated polyester resin, manufactured by Disman China Co., Ltd; the polyurethane associative thickener is
U905 polyurethane associative thickener, produced by Wanhua chemical group, Inc., China; cosolvent Shanghai Kamm practice Co., Ltd; DMEA is produced in Shanghai; self-made deionized water; HDI trimer is TLA-100, produced by Asahi Kasei corporation; IPDI is Vestanat T1890E, produced by Germany winning and creating company; ethylene glycol monobutyl ether acetate, Shanghai Kamm practice Co., Ltd.
The thick coating type water-based acrylic polyurethane finish paint for the rolling stock is characterized by comprising the following standard: the Q/CR546.1-2016 main performance test requirements and results are as follows:
TABLE 2 Performance results for waterborne acrylic polyurethane topcoats
Example 2
Preparing raw materials according to the formula shown in table 3 in parts by weight;
table 3 comparative six formulations of the invention
The preparation method of the water-based acrylic polyurethane finish paint comprises the following steps:
A. preparation of paint vehicle: the raw materials for forming the paint are mixed according to the weight ratio, the No. 1 hydroxyl polyacrylate aqueous dispersion is poured into a container cylinder, the container cylinder is placed under a dispersion machine for dispersion, the rotating speed is adjusted to 500 plus 800 r/min, and then the dispersing agent, the fumed silica, the surfactant, the defoaming agent, the deionized water and the pigment (filler) are sequentially added in a stirring state. After the feeding is finished, the rotating speed of the dispersion machine is adjusted to 1000-; then grinding a pre-dispersion slurry pump such as a sand mill by using a diaphragm pump until the fineness is less than or equal to 10 mu m, discharging, adding hydroxystyrene acrylic acid copolymer resin, No. 2 hydroxyl polyacrylate aqueous dispersion, a wetting agent, an ultraviolet light absorber, a light stabilizer and a thickening agent, adjusting the rotating speed of a dispersion machine to 1000-1200 turns/min after the feeding is finished, stirring for 10-15 min, adding a DMEA solution to adjust the PH to 8.0-8.2, stirring for 10-15 min, finally adding a saturated polyester resin, a cosolvent and the rest deionized water, stirring for 10-15 min, adding a DMEA solution to adjust the PH to 8.2-8.5, adding deionized water to adjust the viscosity, filtering by using a 120-mesh filter screen, removing mechanical impurities, and packaging by using a plastic barrel for later use;
B. preparation of the curing agent: firstly, HDI trimer and IPDI in the curing agent raw materials are added into a container cylinder according to the weight ratio, the container cylinder is placed under a dispersion machine for dispersion, the rotation speed is adjusted to be 500 plus 800 r/min, then ethylene glycol monobutyl ether acetate is added under the stirring state, after the addition is finished, the rotation speed of the dispersion machine is adjusted to be 1000 plus 1200 r/min, and the stirring is carried out for 5-10 min. Packaging for later use;
C. preparing thick coating type water-based finish paint for rolling stock: when in use, the paint and the curing agent are stirred and mixed according to the weight ratio of 100:30, and the construction viscosity can be adjusted by using a proper amount of deionized water during construction.
Note: the above No. 1 hydroxyl polyacrylic acid dispersoid is NeocrylTMXK-542 polyacrylic hydroxy acid dispersion, produced by Disman China Co., Ltd; the hydroxystyrene acrylic copolymer resin is
XK-110 hydroxystyrene acrylic acid copolymer resin, produced by Dismann China Co., Ltd; the 2 nd hydroxyl polyacrylic acid dispersoid is
A2470 Hydroxypolyacrylic acid Dispersion, produced by Kostew Polymer, China Co., Ltd; fumed silica manufactured by Woundplast GmbH of Germany; anionic polymeric dispersants are manufactured by TEGO, Germany; the nonionic surfactant is produced by German winning and creating Special chemical company; silicone antifoam agent, BYK Germany; polyether siloxane type wetting agents manufactured by TEGO, Germany; ultraviolet light absorbers manufactured by BASF corporation of Germany; light stabilizers manufactured by BASF corporation, Germany; the saturated polyester resin is
SY944 saturated polyester resin, produced by Dismann China Co., Ltd; the polyurethane associative thickener is
U905 polyurethane associative thickener, produced by Wanhua chemical group, Inc., China; cosolvent Shanghai Kamm practice Co., Ltd; DMEA is produced in Shanghai; self-made deionized water; the HDI trimer is TLA-100, produced by Asahi Kasei corporation; IPDI is Vestanat T1890E, produced by Germany winning and creating company; ethylene glycol monobutyl ether acetate, Shanghai Kamm practice Co., Ltd.
The thick coating type water-based acrylic polyurethane finish paint for the rolling stock is characterized by comprising the following standard: the Q/CR546.1-2016 main performance test requirements and results are as follows:
table 4 performance results for the waterborne acrylic polyurethane topcoat of example 2
It can be seen that the thick coating sagging properties of the coating material are reduced if the hydroxystyrene acrylic copolymer resin is not used. If no No. 1 hydroxyl polyacrylic acid dispersoid is used, the leveling property is poor, the gloss of a paint film is reduced, and if No. 2 hydroxyl polyacrylic acid dispersoid is used, the fullness and the weather resistance of the paint film are reduced. Without the use of HDI curing agents, all the mechanical properties of the paint film will be deteriorated, the hardness will be reduced, and the drying time will be prolonged. Without the use of IPDI curing agents, the product's activation period will be shortened and the resistance to yellowing and yellowing of the paint film will be reduced. The associative polyurethane thickener is not used, and the common inorganic thickener fumed silica in the field is used for replacing the associative polyurethane thickener, so that the viscosity of a paint film is increased, the water demand is increased, the anti-sagging performance is reduced, and the leveling property of vertical spraying is poor.
Claims (10)
1. An aqueous acrylic polyurethane finish paint for thick coating of outer walls of locomotive bodies, which comprises a paint body and a curing agent, and is characterized in that the paint body comprises: the coating comprises a hydroxyl polyacrylate water dispersion, a hydroxyl styrene acrylic copolymer, a pigment filler, saturated polyester resin and an auxiliary agent; the auxiliary agent comprises a polyurethane associative thickener; the curing agent comprises HDI trimer and IPDI;
the hydroxyl polyacrylate aqueous dispersion comprises a No. 1 hydroxyl polyacrylate aqueous dispersion and a No. 2 hydroxyl polyacrylate aqueous dispersion, wherein the solid content of the No. 1 hydroxyl polyacrylate aqueous dispersion is 40-43%, and the hydroxyl content is 4% -4.5%; the solid content of the No. 2 hydroxyl polyacrylate water dispersion is 44-50%, and the hydroxyl content is 3.5% -3.9%;
the hydroxystyrene acrylic acid copolymer is formed by copolymerizing a polyacrylate monomer and a styrene monomer; the hydroxyl content of the hydroxystyrene acrylic copolymer resin is 1.0-1.5 percent, and the glass transition temperature is 56 ℃;
wherein the thickness of the paint film is more than 60 mu m.
2. The waterborne acrylic polyurethane topcoat of claim 1, wherein the adjuvants comprise fumed silica, dispersants, surfactants, defoamers, wetting agents, ultraviolet light absorbers, light stabilizers, pH adjusters, cosolvents, and solvents; the solvent is water.
3. The waterborne acrylic polyurethane topcoat of claim 2, wherein the pH adjuster is dimethylethanolamine.
4. The waterborne acrylic polyurethane finish paint of claim 2, wherein the cosolvent is a glycol ether ester high boiling point solvent; the dispersant is an anionic polymer dispersant.
5. The waterborne acrylic polyurethane topcoat of claim 2, wherein the surfactant is a nonionic surfactant.
6. The waterborne acrylic polyurethane topcoat of claim 5, wherein the nonionic surfactant is an acetylenic diol nonionic surfactant.
7. The waterborne acrylic polyurethane topcoat of claim 2, wherein the defoamer is a polysiloxane defoamer; the wetting agent is a polyether siloxane wetting agent.
8. The water-based acrylic polyurethane finish paint according to claim 2, characterized by comprising, by weight, 20-25 parts of No. 1 hydroxyl polyacrylate water dispersion, 8-10 parts of hydroxystyrene acrylic acid copolymer, 8-10 parts of No. 2 hydroxyl polyacrylic acid dispersion, 0.8-1.0 part of fumed silica, 2.0-2.5 parts of dispersing agent, 0.8-1.0 part of surfactant, 0.2-0.3 part of defoaming agent, 0.3-0.5 part of wetting agent, 0.4-0.6 part of ultraviolet absorber, 0.4-0.6 part of light stabilizer, 25-30 parts of pigment and filler, 3-5 parts of saturated polyester resin, 0.3-0.5 part of polyurethane associated thickener, 0.8-1 part of cosolvent, 13-16 parts of solvent and 0.3-0.5 part of pH regulator; the curing agent comprises the following components in parts by weight: 50-60 parts of HDI tripolymer, 15-20 parts of IPDI and 25-30 parts of ethylene glycol butyl ether acetate.
9. The method of preparing the aqueous acrylic polyurethane topcoat of any one of claims 1-8, comprising the steps of:
s1, mixing the No. 1 hydroxyl polyacrylate water dispersion, a dispersing agent, fumed silica, a surfactant, a defoaming agent, a partial solvent and a pigment and filler to obtain pre-dispersed slurry; grinding the pre-dispersed slurry, adding hydroxystyrene acrylic acid copolymer, No. 2 hydroxyl polyacrylate aqueous dispersion, wetting agent, ultraviolet absorbent, light stabilizer and thickening agent, uniformly dispersing, adding pH regulator to regulate the pH to 8.0-8.2, finally adding saturated polyester resin, cosolvent and residual solvent, stirring for 10-15 minutes, adding pH regulator to regulate the pH to 8.2-8.5, and finally filtering for later use;
s2, mixing the HDI tripolymer, the IPDI and the ethylene glycol monobutyl ether acetate, and uniformly dispersing for later use;
s3, mixing the paint and the curing agent according to the weight ratio of 100:30 when in use.
10. The use of the aqueous acrylic polyurethane finish according to any one of claims 1 to 8, wherein the aqueous acrylic polyurethane finish is used for thick wall coating of a motor vehicle body, wherein the paint film thickness is 60 μm or more.
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