CN115074016B - Water-based single-coating UV (ultraviolet) curing aluminum paint and preparation method thereof - Google Patents
Water-based single-coating UV (ultraviolet) curing aluminum paint and preparation method thereof Download PDFInfo
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- CN115074016B CN115074016B CN202110260369.6A CN202110260369A CN115074016B CN 115074016 B CN115074016 B CN 115074016B CN 202110260369 A CN202110260369 A CN 202110260369A CN 115074016 B CN115074016 B CN 115074016B
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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
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
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Abstract
The invention provides a water-based single-coating UV-cured aluminum paint and a preparation method thereof, wherein the water-based single-coating UV-cured aluminum paint comprises the following raw material components in parts by weight: 30-60 parts of aqueous polyurethane acrylate dispersoid; 10 to 30 portions of aqueous acrylic resin secondary fraction; 1-5 parts of a photoinitiator; 1 to 5 portions of cosolvent; 0.5 to 1 percent of water wetting agent; 0.5 to 1.5 percent of aqueous rheological additive; 3-7 parts of aqueous aluminum powder liquid; 10-30 parts of water. The preparation method comprises the following steps: mixing aluminum powder, propylene glycol methyl ether, a dispersing agent and water to prepare aqueous aluminum powder liquid; mixing and dispersing the aqueous polyurethane acrylate dispersion and the aqueous acrylate resin secondary dispersion in water to prepare a dispersion mixed solution; mixing a photoinitiator, a cosolvent, an aqueous wetting agent, aqueous aluminum powder liquid and an aqueous rheological aid with the dispersion mixed liquid to prepare the aqueous single-coating UV-cured aluminum powder paint. The aqueous single-coating UV-cured aluminum paint disclosed by the invention has both resistance and recoating property and good service performance.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a water-based single-coating UV (ultraviolet) curing aluminum paint and a preparation method thereof.
Background
According to the requirements of the industry on environmental protection, the source is controlled in a reinforced way, the original auxiliary materials with low (no) VOCs content are used, the waste gas collection is enhanced, and the high-efficiency treatment facility is installed. This means that in the coatings industry, aqueous low VOC will be a trend.
The traditional water-based aluminum paint is mainly formed by two or more layers, and the coating mode has the defects of high energy consumption, low efficiency and large pollution, and the single coating can well solve the problems.
At present, the water-based single-coating UV-cured aluminum paint on the market cannot well balance the resistance and repainting performance, has good resistance and high abrasion Resistance (RCA), but has poor repainting performance after long-time standing (> 48 h); or the resistance is generally low, RCA is low, and the recoating property is good after long-term placement (> 48 h).
Disclosure of Invention
The invention provides a low-VOCs-content water-based single-coating UV-cured aluminum paint, which solves the contradiction problems of good resistance, high RCA and long-time (more than 48 h) long-time placement of the water-based single-coating UV-cured aluminum paint, or general resistance, lower RCA and better recoating property in the market.
The invention relates to a water-based single-coating UV curing aluminum paint, which comprises the following raw material components in parts by weight:
none of the existing aqueous single-coat UV aluminum paint can well balance resistance and recoating performance, wherein the resistance comprises damp heat resistance, chemical resistance, yellowing resistance and the like; the recoating property means that after the original paint film is damaged, a layer of paint is sprayed on the original paint layer, the paint is consistent with the original paint layer paint, and after solidification, the adhesive force between the original paint layer and the new paint layer is free from problems; the components in the aqueous single-coating UV-curing aluminum paint have synergistic effect, so that the cured paint film has good resistance and recoating property.
The aqueous polyurethane acrylate dispersion is modified by polycarbonate diol and acrylate, so that the aqueous polyurethane acrylate dispersion is a block polymer with a soft segment and a hard segment, wherein the hard segment contains polar groups such as carbamate (-NH-COO), ureido (NH-CO-NH), amido (-NH-CO), and the like, and the more the molecular weight is, the more the polar groups in the molecular structure are, the better the thixotropic property of the resin is, and the better the orientation to aluminum powder is; the soft segment is polycarbonate diol, the polyol has the characteristics of good tolerance and good adhesive force to plastic substrates, and meanwhile, part of polycarbonate diol has certain crystallinity, is helpful for orientation of aluminum powder, and can simultaneously give consideration to adhesive force and tolerance.
The aqueous polyurethane acrylate dispersion comprises the following raw material components in parts by weight:
optionally, the preparation method of the aqueous polyurethane acrylate dispersion comprises the following steps: mixing dimethylolpropionic acid, 4' -dicyclohexylmethane diisocyanate and polycarbonate diol at 80 ℃ for reaction until residual NCO% is less than or equal to 4, and stopping the reaction to obtain aqueous polyurethane resin;
adding 3-functional or 6-functional acrylate monomers to carry out end-capping reaction until NCO% is less than or equal to 2, and stopping the reaction to obtain aqueous polyurethane acrylate resin;
after the water-based polyurethane acrylate resin is neutralized by triethylamine, adding water and a polyamine chain extender to carry out chain extension self-emulsification, thus obtaining the water-based polyurethane acrylate dispersoid.
Optionally, the 3-functional acrylate monomer is pentaerythritol triacrylate (PETA); the 6-functional acrylate monomer is dipentaerythritol hexaacrylate (DPHA).
Optionally, the polycarbonate diol is a product of the company of Asahi Kabushiki Kaisha, including one or more of T6002, T6001, T5652, T5651, T5650J, T4671, T4672, T4692, T4691, 210, 220.
Optionally, the polyamine chain extender is one of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
Optionally, the solids content of the aqueous polyurethane acrylate dispersion is 30 to 50wt%.
Preferably, the solids content of the aqueous polyurethane acrylate dispersion is 40 to 50wt%.
Optionally, the number average molecular weight of the aqueous polyurethane acrylate is 75000-180000; the larger the molecular weight is, the better the thixotropic property of the aqueous polyurethane acrylate is, the better the orientation effect on aluminum powder is, and the higher the Fi value is.
Preferably, the aqueous urethane acrylate has a number average molecular weight of 85000 to 140000.
Optionally, the viscosity of the aqueous polyurethane acrylate is 1000-8000 mPas at 60 ℃.
Preferably, the viscosity of the aqueous urethane acrylate is 3000 to 6500 mPas at 60 ℃.
The aqueous acrylic resin secondary dispersion has good adhesive force to a plastic substrate, and the resin has good aluminum powder orientation effect due to proper molecular weight and glass transition temperature; the paint can be used together with aqueous polyurethane acrylate dispersoid, so that the volume shrinkage of a paint film can be effectively reduced, the adhesive force is ensured, and meanwhile, the paint has better resistance and recoating performance.
Optionally, the aqueous acrylic resin secondary fraction is prepared by copolymerizing acrylic acid ester or methyl acrylic acid ester monomers by a solvent method to obtain aqueous acrylic resin; the aqueous acrylic resin is subjected to solvent removal, amine neutralization and water emulsification to obtain an aqueous acrylic resin secondary fraction.
Optionally, the acrylic ester monomer comprises a plurality of acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, isobornyl acrylate and butyl acrylate; the methacrylate monomer is a plurality of methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, isooctyl methacrylate and cyclohexyl methacrylate.
Optionally, the number average molecular weight of the aqueous acrylic resin is 8000-30000.
Preferably, the aqueous acrylic resin has a number average molecular weight of 12000 to 25000.
The acid value of the aqueous acrylic resin is 45-75 mgKOH/g, and the hydroxyl value is 20-45 mgKOH/g.
The solid content of the aqueous acrylic resin secondary fraction is 20-50wt%;
preferably, the aqueous acrylic resin secondary fraction has a solids content of 25 to 35wt%.
The oligomer with moderate glass transition temperature is selected, which is favorable for the directional arrangement of aluminum powder, reduces the shrinkage of a paint film and improves the recoating performance of the paint film.
Optionally, the glass transition temperature of the aqueous acrylic resin is 50-120 ℃. When the glass transition temperature of the aqueous acrylic resin is lower than 50 ℃, the recoating performance of the aluminum paint is obviously deteriorated, and the recoating time is obviously shortened; when the glass transition temperature is higher than 120 ℃, the film forming property of the dispersion is obviously poor, and the orientation property of the aluminum powder is obviously reduced.
Optionally, the glass transition temperature of the aqueous acrylic resin is 60-100 ℃.
Preferably, the aqueous acrylic resin has a glass transition temperature of 80 to 95 ℃. The aqueous acrylic resin dispersion with the glass transition temperature in the range is used in aluminum powder paint, so that the paint film has high hardness and RCA and good recoating performance.
Optionally, the aqueous aluminum powder liquid comprises the following components in parts by weight: 20:28:2, aluminum powder, propylene glycol methyl ether, water and a dispersing agent.
Optionally, the dispersant is BYK-190.
Optionally, the photoinitiator is selected from one or more of ethyl 2,4, 6-trimethylbenzoyl phosphonate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone or phenyl bis (2.4.6-trimethylbenzoyl) phosphine oxide.
Optionally, the cosolvent is one or more of propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate and propylene glycol butyl ether.
Optionally, the aqueous wetting agent is BYK-333, BYK-380, BYK-346, BYK-307 (product of Pick chemical Co., ltd.); one or more of TEGO 410, TEGO 450, TEGO 260, TEGO 270, and TEGO 500 (TEGO products).
Optionally, the aqueous rheology aid is BYK-420, BYK-425 (BYK products of the pick chemical company); one or more of TEGO viscosus 3000, TEGO viscosus 3010, TEGO viscosus 3030, and TEGO viscosus 3060 (TEGO corporation).
Optionally, the aqueous single-coating UV-curable aluminum paint comprises the following raw material components in parts by weight:
the invention also provides a preparation method of the aqueous single-coating UV-cured aluminum paint, which comprises the following steps:
mixing aluminum powder, propylene glycol methyl ether, a dispersing agent and water to prepare aqueous aluminum powder liquid;
mixing and dispersing the aqueous polyurethane acrylate dispersion and the aqueous acrylate resin secondary dispersion in water to prepare a dispersion mixed solution;
mixing a photoinitiator, a cosolvent, an aqueous wetting agent, aqueous aluminum powder liquid and an aqueous rheological aid with the dispersion mixed liquid to prepare the aqueous single-coating UV-cured aluminum powder paint.
Compared with the prior art, the invention has at least one of the following technical effects:
(1) The coating process of the aqueous single-coating UV-cured aluminum paint is simple, the better metal texture can be achieved by one-time coating, the aluminum powder is well aligned, and the coating cost is effectively reduced;
(2) Meanwhile, the coating has both resistance (damp and heat resistance, chemical resistance, wear resistance and the like) and recoating property, and has better adhesive force and metallic feel after long-time (more than 48 h) recoating.
Detailed Description
The technical scheme of the invention is further described below with reference to the specific embodiments, but the invention is not limited thereto.
Preparation example
1. Preparation of aqueous polyurethane acrylate dispersions
Reacting 4g of dimethylolpropionic acid, 18g of 4,4' -dicyclohexylmethane diisocyanate and 34g of polycarbonate diol at 80 ℃ until the residual NCO% is 3.5, and stopping the reaction to obtain aqueous polyurethane resin; adding 44g of DPHA monomer for end capping reaction until the residual NCO% is 1.25, and stopping the reaction to obtain aqueous polyurethane acrylic resin; after the water-based polyurethane acrylic resin is neutralized by the ethylene triamine, 110g of water and 0.5g of diethylenetriamine chain extender are added for chain extension self-emulsifying process, thus obtaining the water-based polyurethane acrylic dispersion.
2. Preparation of aqueous acrylate resin secondary fraction
Uniformly mixing 6g of acrylic acid, 67g of methyl methacrylate, 19g of butyl methacrylate, 8g of hydroxyethyl methacrylate and 1.2g of benzoyl tert-butyl peroxide, and uniformly dropwise adding the mixture into butyl acetate for reaction for 3-4 hours, wherein the reaction temperature is 125 ℃; obtaining aqueous acrylic resin with an acid value of 47mgKOH/g and a hydroxyl value of 35mgKOH/g through reaction; reflux-removing butyl acetate solvent in the resin, cooling to 60 ℃, neutralizing, adding water, adding triethylamine as neutralizing agent in an amount of 8.4g, adding 235g of water into the resin in batches, and emulsifying and dispersing to obtain the aqueous acrylic resin secondary dispersion.
Examples 1 to 6
The preparation method of the water-based single-coating UV-cured aluminum powder paint comprises the following steps:
dispersing aluminum powder, propylene glycol methyl ether, BYK-190 and water at 400r/min for 30min;
mixing and dispersing the prepared aqueous polyurethane acrylate dispersoid and aqueous acrylic resin secondary dispersoid in water to prepare an aqueous dispersion mixed solution;
sequentially adding the photoinitiator, the cosolvent, the water-based leveling agent and the water-based aluminum powder liquid into the dispersion mixed liquid, dispersing while adding, stirring for 30min at the rotating speed of 600r/min, finally adding the water-based rheological auxiliary agent, and re-dispersing and stirring for 10min to obtain the water-based single-coating UV aluminum powder paint.
Spraying and curing process and test of the aqueous single-coating UV aluminum paint:
(1) The thickness of the spray coating film of the water-based aluminum paint is controlled to be 10-15 mu m, the water-based aluminum paint is baked for 15min at 60 ℃, and then UV curing is carried out, wherein the curing energy is 1000mj/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Then, the coating film is subjected to secondary spraying, the thickness of the recoating film is 10-15 mu m, and other processes are the same as the above.
(2) Paint film performance testing, comprising:
film thickness: and (3) testing by ball-head type thickness measurement specification (execution standard: GB/T22520-2008) after film thickness spraying.
Water-resistant adhesion/heavy-duty adhesion: the adhesion was tested by the hundred method and by Scotch 3m 600 tape.
Paint film hardness: the Mitsubishi pencil marked with various hardness values is used, the pencil mark is wiped clean by an eraser after being pushed for 5-6mm on the surface of aluminum paint at an angle of 1000 g and 45 degrees, the surface of the product is checked to be free from tearing, the surface layer is not damaged, and the hardness value of the test is recorded.
Paint film RCA: the aluminum paint surface was checked for black spots using ASTM F2357, norman test, force 150 g.
Recoating properties: after the cured paint film is placed for different time, the water-based single-coating UV cured aluminum paint is sprayed for the second time, and the adhesive force of the paint film is tested, when the adhesive force is 5B, the aluminum paint film has good recoating performance in the time, and can be expressed by recoating time.
Paint film resistance:
humidity resistance, i.e. a constant temperature and humidity box test, 60 ℃/90% RH for 100 hours, and whether the appearance of the aluminum paint is changed or not and whether the adhesive force is changed or not;
artificial sweat resistance: acid, ph=5.0; alkaline, ph=8.8, respectively soaking for 48 hours, with or without change in appearance, and with or without change in adhesion;
hand cream resistant to hand cream: testing in a constant temperature and humidity box, wherein 50 ℃/95% RH,48h, and applying Nivea hand cream Anti-Age Q10 on the surface of aluminum powder paint, and judging whether the appearance is changed;
QUV resistance to yellowing: by ASTM D4674, UVA-340,0.7W/m 2 The test is carried out for 100h, whether the appearance is changed or not, and whether the delta E is changed or not.
Flash index (Fi) of parallel alignment: the test was performed by using a MA68 II spectrophotometer.
Table 1 examples 1 to 6 coating materials in parts by weight
Table 2 test results after application of the aqueous single-coat UV aluminum paint of examples 1 to 6
The test results are shown in Table 2, the comprehensive performance of the example 3 shows the best performance, the recoating time is the longest, the RCA can reach 180 times, the Fi value is higher, the metal texture is good, the performances of artificial sweat resistance, hand cream resistance, wet heat resistance, QUV yellowing resistance and the like are outstanding, and the resistance and recoating performance are considered.
The above description of the embodiments is provided to facilitate the understanding and use of the invention by those skilled in the art, and appropriate alterations and modifications of the above described embodiments may be made by those skilled in the art to which the invention pertains. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention.
Claims (6)
1. The water-based single-coating UV curing aluminum paint is characterized by comprising the following raw material components in parts by weight:
30-60% of aqueous polyurethane acrylate dispersion
Aqueous acrylic resin secondary fraction 10-30
1-5 photo-initiator
Cosolvent 1-5
0.5-1% of aqueous wetting agent
0.5-1.5% of aqueous rheological additive
3-7 parts of aqueous aluminum powder liquid
10-30 parts of water;
the aqueous polyurethane acrylate dispersion comprises the following raw material components in parts by weight:
dimethylolpropionic acid 1-5
8-15 parts of 4,4' -dicyclohexylmethane diisocyanate
10-25 parts of polycarbonate diol
10-30% of 3-functional or 6-functional acrylate monomer
Polyamine chain extender 0.1-2
50-60 parts of water;
the aqueous acrylic resin secondary fraction is prepared by copolymerizing acrylic acid ester or methyl acrylic acid ester monomers by a solvent method; removing solvent, neutralizing amine, adding water and emulsifying to obtain aqueous acrylic resin secondary fraction;
the number average molecular weight of the aqueous acrylic resin is 8000-30000;
the glass transition temperature of the aqueous acrylic resin is 50-120 ℃;
the preparation method of the aqueous polyurethane acrylate dispersion comprises the following steps:
mixing dimethylolpropionic acid, 4' -dicyclohexylmethane diisocyanate and polycarbonate diol for reaction until the residual NCO% is less than or equal to 4, and stopping the reaction to obtain aqueous polyurethane resin;
adding 3-functional or 6-functional acrylate monomers to carry out end-capping reaction until NCO% is less than or equal to 2, and stopping the reaction to obtain aqueous polyurethane acrylate resin;
and neutralizing the aqueous polyurethane acrylate resin with triethylamine, and adding water and a polyamine chain extender to carry out chain extension self-emulsification to obtain the aqueous polyurethane acrylate dispersion.
2. The aqueous single-coat UV-curable aluminum paint of claim 1, wherein the aqueous urethane acrylate has a number average molecular weight of 75000 to 180000 and a viscosity of 1000 to 8000 mpa.s at 60 ℃;
the solid content of the aqueous polyurethane acrylate dispersion is 30-50wt%.
3. The aqueous single-coat UV-curable aluminum paint of claim 1, wherein the aqueous acrylic resin has an acid value of 45-75 mgKOH/g and a hydroxyl value of 20-45 mgKOH/g;
the solid content of the aqueous acrylic resin secondary fraction is 20-50wt%.
4. The aqueous single-coat UV-curable aluminum paint of claim 1, wherein the aqueous acrylic resin has a glass transition temperature of 80-95 ℃.
5. The aqueous single-coating UV-curable aluminum paint according to claim 1, which comprises the following raw material components in parts by weight:
35-55 of aqueous polyurethane acrylate dispersion
Aqueous acrylic resin secondary fraction 15-25
1-5 photo-initiator
Cosolvent 1-5
0.5-1% of aqueous wetting agent
1-1.5 parts of aqueous rheological additive
4-6 parts of aqueous aluminum powder liquid
10-30 parts of water.
6. The method for preparing the aqueous single-coating UV-curable aluminum paint according to claim 1, which comprises the following steps:
mixing aluminum powder, propylene glycol methyl ether, a dispersing agent and water to prepare aqueous aluminum powder liquid;
mixing and dispersing the aqueous polyurethane acrylate dispersion and the aqueous acrylate resin secondary dispersion in water to prepare a dispersion mixed solution;
mixing a photoinitiator, a cosolvent, an aqueous wetting agent, aqueous aluminum powder liquid and an aqueous rheological aid with the dispersion mixed liquid to prepare the aqueous single-coating UV-cured aluminum powder paint.
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