CN109608970B - Baking type water-based acrylic coating composition with excellent thixotropy and preparation method thereof - Google Patents
Baking type water-based acrylic coating composition with excellent thixotropy and preparation method thereof Download PDFInfo
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- CN109608970B CN109608970B CN201811411695.7A CN201811411695A CN109608970B CN 109608970 B CN109608970 B CN 109608970B CN 201811411695 A CN201811411695 A CN 201811411695A CN 109608970 B CN109608970 B CN 109608970B
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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
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Abstract
The invention relates to the technical field of coatings, and particularly relates to a baking type water-based acrylic coating composition with excellent thixotropy and a preparation method thereof. The coating composition is mainly prepared from the following raw materials in percentage by weight: 0.05-0.45% of functional filler A, 10-15% of deionized water, 30-38% of hydroxyl functionalized water-based acrylic resin containing tertiary amine groups, 2.5-4.5% of water-based amino resin, 4.5-8% of cosolvent A, 0.1-0.8% of dispersing agent, 0.1-0.55% of flatting agent, 0.1-0.65% of defoaming agent, 0.05-0.4% of pH regulator, 5-15% of pigment, 10-40% of filler B, 0.1-0.85% of rheological additive and 3.5-9.7% of cosolvent B; the functional filler A is hectorite or sheet silicate. The coating disclosed by the invention has excellent thixotropy, sagging resistance and stone chip resistance.
Description
Technical Field
The invention relates to the technical field of coatings, and particularly relates to a baking type water-based acrylic coating composition with excellent thixotropy and a preparation method thereof.
Background
The baking-type water-based acrylic coating is prepared by mainly taking water-based hydroxyl acrylic resin as film-forming resin, adding water-based amino resin, adding pigment, filler and water-based auxiliary agent, grinding and dispersing. In the construction process of the current baking type water-based acrylic paint, because the baking temperature is generally over 140 ℃, the viscosity of the paint is obviously reduced due to the temperature rise in the construction process, so that the current baking type water-based acrylic paint is easy to sag in the construction process. At present, rheological additives such as polyurethane type thickening agents are mainly used for solving the sagging problem, but actually, the sagging resistance effect of the rheological additives at high temperature is not ideal. In addition, a certain amount of cosolvent is required to be added into a baking type water-based acrylic paint system, the thixotropic effect of the polyurethane thickener can be damaged due to the existence of the cosolvent, the paint is more prone to sagging in the construction process, and the problem of sagging of the paint is more serious particularly in vertical spraying construction. Therefore, how to solve the problem of sagging of the baking type water-based acrylic paint in the construction process is a problem to be solved urgently in the field of industrial paint. The thixotropy of the baking type water-based acrylic paint is improved, particularly, the thixotropy of the paint is still kept high in the baking construction process, and the baking type water-based acrylic paint is a solution direction for solving the sagging problem of the baking type water-based acrylic paint.
Disclosure of Invention
A first object of the present invention is to provide a baking-type aqueous acrylic coating composition having excellent thixotropy, which has excellent thixotropy and sag resistance.
A second object of the present invention is to provide a method for preparing the above baking-type aqueous acrylic coating composition having excellent thixotropy.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a baking type water-based acrylic coating composition with excellent thixotropy is mainly prepared from the following raw materials in percentage by weight: functional filler A: 0.05-0.45%, deionized water: 10-15%, and hydroxyl functional water-based acrylic resin containing tertiary amine groups: 30-38%, aqueous amino resin: 2.5-4.5%, cosolvent A: 4.5-8%, dispersing agent: 0.1-0.8%, leveling agent: 0.1-0.55%, defoaming agent: 0.1-0.65%, pH regulator 0.05-0.4%, pigment: 5-15%, filler B: 10-40%, rheological additive: 0.1-0.85% of cosolvent B, 3.5-9.7% of cosolvent B; the functional filler A is hectorite or sheet silicate.
The hectorite is a water-based hectorite. The sheet silicate is a synthetic sheet silicate.
The rheological additive is one or two of BYK-420 and BYK-D420.
The water-based amino resin is any one or more of Resimene717, Resimene 718, Resimene 741, Resimene745, Resimene 747, Maprenal MF 927, Resimene HM 2608, CYMEL 303LF, CYMEL325, CYMEL 327, CYMEL 350, amino resin 5717W, amino resin 5847 and amino resin 5847L.
The cosolvent A is any one or more of ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol propyl ether, propylene glycol phenyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, ethylene glycol butyl ether acetate and propylene glycol methyl ether acetate.
The dispersant is DISPERBYK190, DISPERBYK 191, DISPERBYK 192, DISPERBYK194, AFCONA 4550, AFCONA 4560, EDAPAN 490, or,
Dispers 715W、
Dispers 735W、
Dispers 740W、
Dispers 745W、
Dispers 750W、
Dispers752W、
Any one or more of Dispers 760W.
The defoaming agent is BYK-025, BYK-028, BYK-093, BYK-022, BYK-044, BYK-019, BYK-017, BYK-1760, BYK-1781, BYK-011, BYK-1711, BYK-015, BYK-1710, BYK-1740, BYK-016, BYK-014, BYK-012, Surfynol 104E, BYK-015, BYK-1710, Surfynol 104E, BYK-1740, BYK-016, BY,
Foamex 805、
Foamex 808、
Foamex 810、
Foamex 822、
Foamex 825.
The leveling agent is any one or more of BYK-342, BYK-347, BYK-348, BYK-349, BYK-3455 and BYK-378.
The pH regulator is one or more of N, N-dimethylethanolamine, triethylamine, 2-amino-2-methyl-1-propanol and ammonia water.
The pigment is any one or more of titanium dioxide, carbon black, iron oxide yellow, iron oxide red, phthalocyanine blue and phthalocyanine green.
The cosolvent B is any one or more of ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol propyl ether, propylene glycol phenyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, ethylene glycol butyl ether acetate and propylene glycol methyl ether acetate.
The filler B is any one or more of precipitated barium sulfate, kaolin, talcum powder and calcium carbonate.
The hectorite is
DY CE、
LT、
DE、
And any one or more of EWs.
The sheet silicate is one or two of Laponite RD and Laponite RDS.
The hydroxyl functional water-based acrylic resin containing the tertiary amine group is mainly prepared from the following raw materials in percentage by weight: and (3) a cosolvent C: 20-35%, hydrophilic monomer: 1.8-3.2%, hydroxyl functional monomer: 2.5-6.5%, tertiary amine monomer: 0.5-2.5%, vinyl monomer: 18-38%, initiator: 0.05-0.8%, neutralizer: 2-4%, deionized water: 28.4 to 36.75 percent.
The tertiary amine monomer is any one or more of dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, dibutyl aminopropyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate and dibutyl aminopropyl methacrylate.
The hydroxyl functional monomer is any one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate.
The hydrophilic monomer is any one or more of acrylic acid, methacrylic acid and maleic anhydride.
The vinyl monomer is any one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, n-octyl methacrylate, benzyl acrylate and styrene.
The initiator is any one or more of azodiisobutyronitrile, azodiisovaleronitrile and azodiisoheptanonitrile.
The neutralizing agent is one or more of N, N-dimethylethanolamine, triethylamine, 2-amino-2-methyl-1-propanol and ammonia water.
The cosolvent C is any one or more of ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol propyl ether, propylene glycol phenyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, ethylene glycol butyl ether acetate and propylene glycol methyl ether acetate.
The preparation method of the hydroxyl-functionalized water-based acrylic resin containing the tertiary amine group comprises the following steps:
1) preparation of Mixed monomer MM
Uniformly stirring a hydrophilic monomer, a hydroxyl functional monomer, a tertiary amine monomer, a vinyl monomer and an initiator to obtain a mixed monomer MM for later use;
2) preparation of hydroxyl functional water-based acrylic resin containing tertiary amine group
Adding cosolvent C as a reaction bottom material, stirring and heating to 70-90 ℃, keeping the temperature, dropwise adding the mixed monomer MM obtained in the step 1), then preserving heat at 70-90 ℃ for 1-3 hours, cooling to 30-40 ℃ after heat preservation, adding a neutralizing agent for neutralization, adjusting the stirring speed to 500-1000 rpm, and adding deionized water for emulsification while stirring to obtain the hydroxyl functionalized water-based acrylic resin containing the tertiary amine group.
The step 2) of dripping the mixed monomer MM is finished within 3-5 hours at the temperature of 70-90 ℃.
The preparation method of the baking type water-based acrylic coating composition with excellent thixotropy comprises the following steps:
1) uniformly mixing deionized water and the functional filler A to obtain a pre-gel solution;
2) sequentially adding hydroxyl functional water-based acrylic resin containing tertiary amine groups, water-based amino resin, cosolvent A, dispersant, flatting agent, defoaming agent, pH regulator, pigment and filler B into a grinding tank, uniformly mixing, then adding the pre-gelling liquid obtained in the step 1), grinding until the fineness is less than or equal to 40 micrometers, discharging, then sequentially adding rheological additive and cosolvent B, uniformly mixing, filtering and discharging to obtain the baking-type water-based acrylic coating composition.
The baking type water-based acrylic coating composition with excellent thixotropy comprises a functional filler, namely hectorite or sheet silicate, wherein the functional filler is dispersed in the coating, and an electrolyte ion in the middle of the functional filler is utilized to form a three-dimensional net structure (namely a cabin structure), the three-dimensional net structure can improve the viscosity of the coating in the storage process, the three-dimensional net structure is damaged in the shearing process, the viscosity is reduced, the spraying of the coating is facilitated, when the coating is sprayed on a base material, the shearing force disappears, the net structure is recovered, the viscosity is increased, and therefore the effects of thickening and sagging prevention are achieved; the raw materials of the water-based acrylic coating composition contain hydroxyl functional water-based acrylic resin, wherein the raw materials contain tertiary amine groups, in the coating composition, the tertiary amine groups in the hydroxyl functional water-based acrylic resin, polyurea bonds in rheological additives and functional fillers act synergistically, a cabin structure in the functional fillers is further strengthened by forming intermolecular hydrogen bonds, the strength of the structure is improved, in the coating construction process, shearing force destroys the cabin structure, the viscosity is reduced, after the construction is finished, the shearing force disappears, the cabin structure formed by the cooperation of the hydroxyl functional water-based acrylic resin, the rheological additives and the functional fillers recovers, the system viscosity is increased, and the thickening and sagging prevention effects are achieved; in addition, hydrogen bonds formed among the tertiary amine groups of the hydroxyl functionalized water-based acrylic resin, the rheological additive and the functional filler can further improve the stone-impact resistance of the coating.
Detailed Description
The raw materials referred to in the examples and comparative examples include:
propylene glycol methyl ether acetate, ethylene glycol butyl ether, propylene glycol methyl ether, technical grade, Nanjing Cutian chemical Co., Ltd; acrylic acid, hydroxyethyl methacrylate, hydroxypropyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, methyl methacrylate, styrene, butyl acrylate, N-dimethylethanolamine, butanone, triethylamine, benzylamine, N-hexylamine, N-methylpyrrolidone, technical grade, Shanghai Lingfeng Chemicals Co., Ltd; azobisisobutyronitrile, azobisisoheptonitrile, technical grade, shanghai Lingfeng Chemicals, Inc.; isophorone diisocyanate, hexamethylene diisocyanate, technical grade, koshichu polymer (china) limited; amino resin Resimene717, technical grade, Enlishi; amino resin CYMEL325, technical grade, tradesman corporation; EDAPLAN 490, industrial grade, german mingming; DISPERBYK190, BYK 348, BYK-025, BYK-1710, technical grade, Pico Chemicals; titanium dioxide R902+, technical grade, dupont company; pu carbon black, technical grade, cabot; precipitated barium sulfate, technical grade, Nanfeng group.
The raw materials used in the examples and comparative examples were commercially available commercial products and were commercially available from commercial sources, unless otherwise specified.
Example 1
The baking type water-based acrylic coating composition with excellent thixotropy of the embodiment is mainly prepared from the following raw materials: functional Filler A0.2 g
DY CE, 12g of deionized water, 35g of hydroxyl functional water-based resin containing tertiary amine groups, 3.2g of water-based amino resin Resimene717, 5g of cosolvent A ethylene glycol butyl ether, 0.2g of dispersant EDAPAN 490, 0.2g of flatting agent BYK-348, 0.1g of defoaming agent BYK-025, 0.1g of pH regulator N, N-dimethylethanolamine, 9g of titanium dioxide R902+, 2g of pu carbon black, 28.6g of precipitated barium sulfate, 0.4g of rheological additive BYK-420, and 4g of cosolvent B ethylene glycol butyl ether.
The preparation method of the baking-type aqueous acrylic coating composition having excellent thixotropy of the present example comprises the following steps:
1) preparing functional filler pre-GEL liquid GEL-1:
adding 12g of deionized water into a reaction bottle, starting stirring at a rotating speed of 500rpm, and adding 0.2g of functional filler A while stirring
DYCE is uniformly stirred to obtain functional filler pre-GEL liquid GEL-1;
2) preparation of baking-type waterborne acrylic coating composition BAC-1:
adding 35g of hydroxyl functional water-based acrylic resin containing tertiary amine groups, 3.2g of water-based amino resin Resimine 717, 5g of ethylene glycol butyl ether, 0.2g of EDAPAN 490, 0.2g of flatting agent BYK-348, 0.1g of defoaming agent BYK-025, 0.1g of pH regulator N, N-dimethylethanolamine, 9g of titanium dioxide R902+, 2g of pu carbon black and 28.6g of precipitated barium sulfate into a grinding tank in sequence, stirring uniformly, then adding 12.2 g of functional filler pregel liquid GEL-1 prepared in the step 1) into the grinding tank, stirring uniformly, grinding to the fineness of less than or equal to 40 microns, discharging, then adding a mixture of 0.4g of rheological aid BYK-420 and 4g of ethylene glycol butyl ether in sequence, stirring for 2 hours at the rotating speed of 200rpm, filtering and discharging to obtain the baking water-based acrylic coating composition (BAC-1).
The hydroxyl-functionalized water-based resin containing the tertiary amine group is prepared by the preparation method comprising the following steps:
1) preparation of Mixed monomer MM-1
Uniformly stirring 2.3 g of acrylic acid, 5.9 g of hydroxyethyl methacrylate, 1.2 g of dimethylaminoethyl acrylate, 12g of methyl methacrylate, 17 g of butyl acrylate and 0.1g of azobisisobutyronitrile to obtain a mixed monomer MM-1 for later use;
2) preparation of hydroxyl functional water-based acrylic resin containing tertiary amine group
Adding 25 g of propylene glycol methyl ether acetate serving as a reaction bottom material, stirring, heating to 80 ℃, keeping the temperature, dropwise adding the mixed monomer MM-1, and finishing dropwise adding within 5 hours at 80 ℃; and then preserving heat at 80 ℃ for 3 hours, after the heat preservation is finished, cooling to 30 ℃, adding 2.5g of N, N-dimethylethanolamine for neutralization, adjusting the stirring speed to 1000rpm, adding 34 g of deionized water while stirring for emulsification, and preparing the hydroxyl functional water-based acrylic resin containing the tertiary amine group.
Example 2
The baking type water-based acrylic coating composition with excellent thixotropy of the embodiment is mainly prepared from the following raw materials: 0.05g of functional filler A
LT, 10g of deionized water, 30g of hydroxyl functional water-based resin containing tertiary amine groups, 4.5g of water-based amino resin CYMEL325, 1.5g of cosolvent A ethylene glycol butyl ether, 3g of cosolvent A propylene glycol methyl ether, 0.8g of dispersant DISPERBYK-190, 0.1g of flatting agent BYK-348, 0.65g of defoaming agent
Foamex 810, 0.05g of pH regulator triethylamine, 4g of titanium dioxide R902+, 1g of pu carbon black, 40g of precipitated barium sulfate, 0.85g of rheological additive BYK-D420 and 3.5g of cosolvent B ethylene glycol butyl ether.
The preparation method of the baking-type aqueous acrylic coating composition having excellent thixotropy of the present example comprises the following steps:
1) preparing functional filler pre-GEL liquid GEL-2:
adding 10g of deionized water into a reaction bottle, starting stirring at the rotating speed of 200rpm, and adding 0.05g of functional filler while stirring
LT, stirring uniformly to obtain functional filler pregel liquid GEL-2;
2) preparation of baking-type waterborne acrylic coating composition BAC-2:
30g of hydroxyl functional water-based acrylic resin containing tertiary amine groups, 4.5g of water-based amino resin CYMEL325, 1.5g of ethylene glycol butyl ether, 3g of propylene glycol methyl ether, 0.8g of DISPERBYK-190, 0.1g of flatting agent BYK-348 and 0.45g of defoaming agent
Foamex 810, 0.05g of pH regulator triethylamine, 4g of titanium dioxide R902+, 1g of pu carbon black and 40g of precipitated barium sulfate are sequentially added into a grinding tank and uniformly stirred, then 10.05 g of functional filler pre-GEL liquid GEL-2 prepared in the step 1) is added into the grinding tank and uniformly stirred, the mixture is ground until the fineness is less than or equal to 40 micrometers, discharging is carried out, then a mixture of 0.85g of rheological additive BYK-D420 and 3.7 g of ethylene glycol butyl ether is sequentially added, stirring is carried out at the rotating speed of 200rpm for 2 hours, and discharging is filtered to obtain the baking type water-based acrylic coating composition (BAC-2).
This example of a hydroxyl-functionalized aqueous resin containing tertiary amine groups was prepared by a method comprising the steps of:
1) preparation of Mixed monomer MM-2
Uniformly stirring 1.8 g of acrylic acid, 6.5 g of hydroxypropyl acrylate, 1.2 g of diethylaminoethyl methacrylate, 13 g of methyl methacrylate, 5g of styrene, 20 g of butyl acrylate and 0.8g of azobisisoheptonitrile to obtain a mixed monomer MM-2 for later use;
2) preparation of hydroxyl functional water-based acrylic resin containing tertiary amine group
Adding 10g of propylene glycol methyl ether acetate and 10g of butanone as reaction bottom materials, stirring and heating to 70 ℃, keeping the temperature, dropwise adding the mixed monomer MM-2 in the step 1), finishing dropwise adding within 5 hours at 70 ℃, then preserving heat for 3 hours at 70 ℃, cooling to 30 ℃ after finishing preserving heat, adding 2g of N, N-dimethylethanolamine for neutralization, adjusting the stirring speed to 800rpm, adding 28.4 g of deionized water while stirring for emulsification, and preparing the hydroxyl functional water-based acrylic resin containing the tertiary amine group.
Example 3
The baking type water-based acrylic coating composition with excellent thixotropy of the embodiment is mainly prepared from the following raw materials: 0.45g of functional filler A
DY CE, 15g deionized water, 38g hydroxyl-functionalized aqueous resin containing tertiary amine groups, 2.5g aqueous amino resin Resimene717, 5g helpedThe paint comprises a solvent A, ethylene glycol monobutyl ether, a cosolvent A, propylene glycol methyl ether, a dispersant EDAPAN 490, a flatting agent BYK-348, a defoaming agent BYK-025, a pH regulator N, N-dimethylethanolamine, a titanium dioxide R902+, a calcium carbonate, a cosolvent B, a dispersant B, a.
The preparation method of the baking-type aqueous acrylic coating composition having excellent thixotropy of the present example comprises the following steps:
1) preparing functional filler pre-GEL liquid GEL-3:
adding 15g of deionized water into a reaction bottle, starting stirring at the rotating speed of 300rpm, and adding 0.45g of functional filler while stirring
DYCE is uniformly stirred to obtain functional filler pre-GEL liquid GEL-3;
3) preparation of baking-type waterborne acrylic coating composition BAC-3:
adding 38g of hydroxyl functional water-based acrylic resin containing tertiary amine groups, 2.5g of water-based amino resin Resimene717, 5g of ethylene glycol butyl ether, 3g of propylene glycol methyl ether, 0.1g of EDAPAN 490, 0.55g of flatting agent BYK-348, 0.2g of defoaming agent BYK-025,0.4g of pH regulator N, N-dimethylethanolamine, 15g of titanium dioxide R902+ and 10g of calcium carbonate into a grinding tank in sequence, stirring uniformly, then adding 15.45 g of functional filler pre-GEL liquid GEL-3 prepared in the step 1) into the grinding tank, grinding to the fineness of less than or equal to 40 microns after stirring uniformly, discharging, then adding a mixture of 0.1g of rheological aid BYK-420 and 9.7g of ethylene glycol butyl ether in sequence, stirring for 2 hours at the rotating speed of 200rpm, filtering and discharging to obtain the baking water-based acrylic coating composition (BAC-3).
The hydroxyl-functionalized water-based resin containing the tertiary amine group is prepared by the preparation method comprising the following steps:
1) preparation of Mixed monomer MM-3
Uniformly stirring 3.2g of acrylic acid, 2.5g of hydroxyethyl methacrylate, 0.5 g of dimethylaminoethyl acrylate, 5g of methyl methacrylate, 5g of styrene, 8g of butyl acrylate and 0.05g of azobisisobutyronitrile to obtain a mixed monomer MM-3 for later use;
2) preparation of hydroxyl functional water-based acrylic resin containing tertiary amine group
Adding 35g of propylene glycol methyl ether acetate serving as a reaction bottom material, stirring, heating to 90 ℃, keeping the temperature, dropwise adding a mixed monomer MM-3, finishing dropwise adding within 5 hours at 90 ℃, then preserving heat for 3 hours at 90 ℃, cooling to 30 ℃ after finishing preserving heat, adding 4g of N, N-dimethylethanolamine for neutralization, adjusting the stirring speed to 1000rpm, adding 36.75 g of deionized water while stirring, and emulsifying to prepare the hydroxyl functional water-based acrylic resin containing the tertiary amine group.
Comparative example 1
Comparative example baked waterborne acrylic coating composition BAC-4 differs from example 1 only in that the hydroxyl-functionalized waterborne resin of the comparative example was prepared without the tertiary amine monomer and was otherwise the same as in example 1.
The preparation of the hydroxyl functional waterborne resin of this comparative example included the following steps:
1) preparation of Mixed monomer MM-4
Uniformly stirring 2.3 g of acrylic acid, 5.9 g of hydroxyethyl methacrylate, 13.2 g of methyl methacrylate, 17 g of butyl acrylate and 0.1g of azobisisobutyronitrile to obtain a mixed monomer MM-4 for later use;
2) preparation of hydroxyl functional water-based acrylic resin
Adding 25 g of propylene glycol methyl ether acetate serving as a reaction bottom material, stirring, heating to 80 ℃, keeping the temperature, dropwise adding a mixed monomer MM-4, finishing dropwise adding within 5 hours at 80 ℃, preserving heat for 3 hours at 80 ℃, cooling to 30 ℃ after finishing preserving heat, adding 2.5g of N, N-dimethylethanolamine for neutralization, adjusting the stirring speed to 1000rpm, adding 34 g of deionized water while stirring, and emulsifying to prepare the hydroxyl functionalized water-based acrylic resin.
Comparative example 2
The baking-type aqueous acrylic coating composition BAC-5 of this comparative example differs from example 1 only in that 0.2g of the functional filler of example 1 was added
DY CE was replaced with 0.2g deionized water, and the rest was the same as in example 1.
Comparative example 3
The baking-type aqueous acrylic coating composition BAC-6 of this comparative example differs from example 1 only in that 0.4g of the rheology aid BYK-420 in example 1 was replaced with 0.4g of butyl glycol ether, and the other was the same as in example 1.
Examples of the experiments
1) Preparation of a template
Cold rolled steel sheets were used as test substrates. The cold rolled steel sheet is first ground. According to the construction requirements
The baking type water acrylic paint compositions BAC-1, BAC-2, BAC-3, BAC-4, BAC-5 and BAC-6 prepared in the examples 1, 2 and 3, the comparative examples 1 and 2 and the comparative examples 3 are added with a proper amount of deionized water to adjust the viscosity to 38-45 s, and are dried for 30 minutes after being sprayed, and then the sample plate is put into an oven at 140 ℃ to be baked for 30 minutes, and the thickness of the paint is controlled to be 50-55 mu m. The prepared sample plate is placed for 7 days at room temperature and then the performance is tested.
2) Testing of coating Properties
The performances of the coating are mainly investigated on the sagging resistance, the adhesive force, the water resistance and the stone impact resistance.
And (3) sag resistance test: sag resistance refers to the maximum wet film thickness (in microns) of the coating that does not have a tendency to flow during re-drying of an inclined panel under specified test coating conditions, specified substrate and specified environmental conditions. The sag resistance of the coatings was tested according to GB/T9264-2012 "evaluation of sag resistance of paints and varnishes". Applied using a graduated sag coater. Test results sag resistance was evaluated in terms of wet film thickness without sagging. For ease of comparison, the results were classified into 3 classes: level 1: the thickness of the wet film is more than or equal to 150 microns, and the coating does not sag; and 2, stage: the thickness of the wet film is more than or equal to 100 mu m and less than 150 mu m, and the coating does not sag; and 3, level: the thickness of the wet film is less than 100 microns, and the coating does not sag. Sag resistance is best at level 1 and worst at level 3.
The thixotropic value is: the viscosity of the dope at 25 ℃ was measured at room temperature using an NDJ-i type rotational viscometer, and the dope viscosity at 6rpm and 60rpm, thixotropic value being viscosity (6 rpm)/viscosity (60rpm), was measured, respectively.
Adhesion force: the coating adhesion is tested according to GB/T9286-1998 and is divided into 0-5 grades, the best grade 0 and the worst grade 5. The adhesion test results are shown in table 1.
Stone chip resistance: and (3) detecting by adopting a VDA-508 stone impact instrument, continuously impacting steel chips on sample plates for spraying the base paint and the intermediate paint under specified pressure, and observing the appearance of the paint film, wherein the total level is 0-9, the 0 level indicates that the paint film is not punctured, and the 9 level indicates that the paint film is punctured in a large area. Best at level 0 and worst at level 9.
The results of the coating performance tests are shown in table 1.
TABLE 1 Properties of baking-type aqueous acrylic coating compositions in examples 1 to 3 and comparative examples 1 to 3
As can be seen from Table 1, the tertiary amine group in the hydroxyl-functionalized water-based acrylic resin, the polyurea bond in the rheological aid and the functional filler in examples 1-3 of the present invention act synergistically to further strengthen the cabin structure in the functional filler by forming intermolecular hydrogen bonds, thereby enhancing the strength of the cabin structure, during the coating construction process, the shear force destroys the cabin structure, the viscosity is reduced, after the construction is finished, the shear force disappears, the cabin structure formed by the hydroxyl-functionalized water-based acrylic resin, the rheological aid and the functional filler synergistically recovers, the system viscosity increases, thereby achieving the thickening and sagging prevention effects, the baking-type water-based acrylic coating compositions prepared in examples 1-3 have the thixotropic value higher than 3.5, have good thixotropy, and the coating has good sagging resistance during the construction process, all are 1 grade. Meanwhile, the coating shows excellent adhesion and stone-impact resistance. In comparative example 1, the hydroxyl-functionalized aqueous acrylic resin did not contain a tertiary amine group, the three-dimensional network structure formed by the functional filler in the BAC-4 coating was weakened, the thixotropic value of the coating was reduced, the sag resistance was also reduced to level 2, and the stone chip resistance was also weakened due to the weakening of the hydrogen bond. In comparative example 2, no functional filler was used in the BAC-5 coating formulation, a three-dimensional network structure (i.e., a cabin structure) could not be formed, and the thixotropy, sag resistance, and stone chip resistance of the coating were significantly reduced. In comparative example 3, no rheological aid was used in the BAC-6 coating formulation, and the thixotropy, sag resistance, and stone chip resistance of the coating were also significantly reduced.
Through the analysis, the baking type water-based acrylic coating composition disclosed by the invention can achieve excellent thixotropy and anti-sagging performance only by the synergistic effect of the hydroxyl functionalized water-based acrylic resin containing the tertiary amine group, the functional filler and the rheological additive.
Various other modifications and changes may be made by those skilled in the art based on the above-described technical solutions and concepts, and all such modifications and changes should fall within the scope of the claims of the present invention.
Claims (10)
1. The baking type water-based acrylic coating composition with excellent thixotropy is characterized by being mainly prepared from the following raw materials in percentage by weight: functional filler A: 0.05-0.45%, deionized water: 10-15%, and hydroxyl functional water-based acrylic resin containing tertiary amine groups: 30-38%, aqueous amino resin: 2.5-4.5%, cosolvent A: 4.5-8%, dispersing agent: 0.1-0.8%, leveling agent: 0.1-0.55%, defoaming agent: 0.1-0.65%, pH regulator 0.05-0.4%, pigment: 5-15%, filler B: 10-40%, rheological additive: 0.1-0.85% of cosolvent B, 3.5-9.7% of cosolvent B; the functional filler A is hectorite or sheet silicate.
2. The baking-type aqueous acrylic coating composition according to claim 1, wherein the rheological aid is one or both of BYK-420 and BYK-D420.
3. The baking-type water-based acrylic coating composition according to claim 1, wherein the water-based amino resin is any one or more of Resimene717, Resimene 718, Resimene 741, Resimene745, Resimene 747, MaprenalMF 927, Resimene HM 2608, CYMEL 303LF, CYMEL325, CYMEL 327, CYMEL 350, amino resin 5717W, amino resin 5847, and amino resin 5847L.
4. The baking-type aqueous acrylic coating composition according to claim 1, wherein the hectorite is hectorite
DY CE、
LT、
DE、
And any one or more of EWs.
5. The baking-type waterborne acrylic coating composition of claim 1, wherein the sheet silicate is one or both of Laponite RD, Laponite RDs.
6. The baking-type aqueous acrylic coating composition according to claim 1, wherein the pigment is any one or more of titanium dioxide, carbon black, yellow iron oxide, red iron oxide, phthalocyanine blue and phthalocyanine green.
7. The baking-type aqueous acrylic coating composition according to claim 1, wherein the hydroxyl-functionalized aqueous acrylic resin containing a tertiary amine group is mainly prepared from the following raw materials in percentage by weight: and (3) a cosolvent C: 20-35%, hydrophilic monomer: 1.8-3.2%, hydroxyl functional monomer: 2.5-6.5%, tertiary amine monomer: 0.5-2.5%, vinyl monomer: 18-38%, initiator: 0.05-0.8%, neutralizer: 2-4%, deionized water: 28.4 to 36.75 percent.
8. The baking-type aqueous acrylic coating composition according to claim 7, wherein the tertiary amine monomer is one or more selected from the group consisting of dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, dibutylaminopropyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, and dibutylaminopropyl methacrylate.
9. The baking-type aqueous acrylic coating composition according to claim 7, wherein the hydroxyl functional monomer is any one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate.
10. A method for preparing a baking-type aqueous acrylic coating composition having excellent thixotropy according to claim 1, comprising the steps of:
1) uniformly mixing deionized water and the functional filler A to obtain a pre-gel solution;
2) sequentially adding hydroxyl functional water-based acrylic resin containing tertiary amine groups, water-based amino resin, cosolvent A, dispersant, flatting agent, defoaming agent, pH regulator, pigment and filler B into a grinding tank, uniformly mixing, then adding the pre-gelling liquid obtained in the step 1), grinding until the fineness is less than or equal to 40 micrometers, discharging, then sequentially adding rheological additive and cosolvent B, uniformly mixing, filtering and discharging to obtain the baking-type water-based acrylic coating composition.
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| JP2002155232A (en) * | 2000-11-20 | 2002-05-28 | Toyo Ink Mfg Co Ltd | Water-based coating composition |
| CN1814663A (en) * | 2005-02-05 | 2006-08-09 | 广州慧谷化学有限公司 | Thermo-setting acrylic-acid emulsion, its preparing method and paint containing same |
| CN101698771A (en) * | 2009-09-24 | 2010-04-28 | 中国海洋石油总公司 | Water-based primer-topcoat braking paint and preparation method thereof |
| CN106478860A (en) * | 2016-11-29 | 2017-03-08 | 广州慧谷化学有限公司 | One kind has excellent aluminium powder directionality water-borne acrylic resin and preparation and its coating |
| CN108395797A (en) * | 2018-04-28 | 2018-08-14 | 湖州富美材料科技有限公司 | A kind of aqueous amino-stoving varnish |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002155232A (en) * | 2000-11-20 | 2002-05-28 | Toyo Ink Mfg Co Ltd | Water-based coating composition |
| CN1814663A (en) * | 2005-02-05 | 2006-08-09 | 广州慧谷化学有限公司 | Thermo-setting acrylic-acid emulsion, its preparing method and paint containing same |
| CN101698771A (en) * | 2009-09-24 | 2010-04-28 | 中国海洋石油总公司 | Water-based primer-topcoat braking paint and preparation method thereof |
| CN106478860A (en) * | 2016-11-29 | 2017-03-08 | 广州慧谷化学有限公司 | One kind has excellent aluminium powder directionality water-borne acrylic resin and preparation and its coating |
| CN108395797A (en) * | 2018-04-28 | 2018-08-14 | 湖州富美材料科技有限公司 | A kind of aqueous amino-stoving varnish |
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