CN113372511A - Acrylic resin, water-based amino baking paint, and preparation method and application thereof - Google Patents
Acrylic resin, water-based amino baking paint, and preparation method and application thereof Download PDFInfo
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- CN113372511A CN113372511A CN202110739602.9A CN202110739602A CN113372511A CN 113372511 A CN113372511 A CN 113372511A CN 202110739602 A CN202110739602 A CN 202110739602A CN 113372511 A CN113372511 A CN 113372511A
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- parts
- water
- resin
- acrylic resin
- amino baking
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 53
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 53
- 239000003973 paint Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002966 varnish Substances 0.000 claims abstract description 54
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 239000002562 thickening agent Substances 0.000 claims abstract description 27
- 229920003180 amino resin Polymers 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 12
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- -1 neutralizer I Substances 0.000 claims description 10
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 9
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 7
- 239000000080 wetting agent Substances 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 239000006184 cosolvent Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 239000004640 Melamine resin Substances 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- JHRDMNILWGIFBI-UHFFFAOYSA-N 6-diazenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(N=N)=N1 JHRDMNILWGIFBI-UHFFFAOYSA-N 0.000 claims description 2
- BBBDKKJVYCAVTO-UHFFFAOYSA-N 6-diazenyl-1,3,5-triazine-2,4-diamine;formaldehyde Chemical compound O=C.NC1=NC(N)=NC(N=N)=N1 BBBDKKJVYCAVTO-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- 238000005260 corrosion Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 claims 1
- 239000011253 protective coating Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000945 filler Substances 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910000861 Mg alloy Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000005028 tinplate Substances 0.000 description 3
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
- C09D7/43—Thickening agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses acrylic resin, a water-based amino baking paint and a preparation method and application thereof, wherein the water-based amino baking paint comprises the following preparation raw materials: acrylic resin, amino resin, a thickening agent and an auxiliary agent. By introducing epoxy resin into acrylic resin, a paint film after the curing is more compact, so that the adhesive force and chemical resistance of the waterborne amino baking paint on various substrates are improved; meanwhile, the acrylic resin and the amino resin are crosslinked and cured at high temperature, so that the compactness and the protection of the water-based amino baking varnish are further improved; meanwhile, the decorative effect of the amino baking varnish is improved; the associative thickener and the resin form a more stable net structure, so that the associative thickener has better wrapping property on color paste and filler, thereby improving the storage stability of the water-based amino baking paint.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to acrylic resin, a water-based amino baking varnish, and a preparation method and application thereof.
Background
The traditional amino baking varnish is mainly solvent-type amino baking varnish, the solvent-type amino baking varnish is mainly composed of solvent-type resin and organic solvent, a large amount of organic volatile matters can be generated in the production and use processes, the pollution to the ecological environment is caused, and the health of constructors is harmed. In order to reduce the use of organic solvents, aqueous amino baking lacquers have been developed in the related art.
The water-based amino baking paint mainly comprises water-based resin, water, a water-based auxiliary agent and a cosolvent, is safe and environment-friendly, has small harm to the health of constructors, and accords with the development trend of green environment-friendly coatings, but the existing water-based amino baking paint has the defects of poor adhesive force on some base materials, long baking time, poor chemical resistance, unstable storage and the like.
Therefore, it is necessary to develop an acrylic resin, and the aqueous amino baking varnish prepared by the acrylic resin has good substrate adhesion and chemical resistance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the acrylic resin, and the water-based amino baking varnish prepared from the acrylic resin has good adhesive force and chemical resistance.
The invention also provides a preparation method of the acrylic resin.
The invention also provides application of the acrylic resin.
The invention also provides the water-based amino baking paint, and the water-based amino baking paint has good base material adhesion and good chemical resistance.
The invention also provides a preparation method of the water-based amino baking paint.
The invention also provides application of the water-based amino baking paint.
The invention provides acrylic resin in a first aspect, which comprises the following preparation raw materials: epoxy resin, acrylate compound, styrene, acrylic compound and tertiary carboxylic acid glycidyl ester (E-10P).
The epoxy group has good adhesion to metal materials; the flexibility of the acrylic resin is improved by the acrylate compound; the styrene improves the hardness of the acrylic resin; hydrophilic groups are introduced into the acrylic acid compounds, so that the hydrophilicity of the acrylic resin is improved; the glycidyl versatate improves the chemical resistance and weather resistance of the resin.
According to some embodiments of the invention, the acrylic resin comprises the following preparation raw materials: initiator, neutralizer I, cosolvent and regulator.
According to some embodiments of the invention, the acrylate compound consists of methyl methacrylate, butyl acrylate and hydroxyethyl acrylate.
According to some embodiments of the invention, the acrylic compound is methacrylic acid.
According to some embodiments of the invention, the initiator is benzoyl peroxide.
The initiator excites free radicals in the synthesis process of the acrylic resin to initiate polymerization reaction.
According to some embodiments of the invention, the neutralizing agent i is N, N-dimethylethanolamine.
According to some embodiments of the invention, the co-solvent is isopropanol.
According to some embodiments of the invention, the modulator is dodecyl mercaptan (DDM).
According to some embodiments of the invention, the acrylic resin comprises the following preparation raw materials in parts by weight: 10-15 parts of epoxy resin (E-44), 5-35 parts of Methyl Methacrylate (MMA), 15-20 parts of Styrene (ST), 10-20 parts of Butyl Acrylate (BA), 10-15 parts of hydroxyethyl acrylate (HEA), 5-9 parts of methacrylic acid (MAA), 0.5-0.9 part of Benzoyl Peroxide (BPO), 2-10 parts of Isopropanol (IPA), 0.2-2 parts of N, N-Dimethylethanolamine (DMEA), 1-15 parts of glycidyl versatate (E-10P) and 1-1.5 parts of dodecyl mercaptan (DDM).
The second aspect of the present invention provides a method for preparing the acrylic resin, comprising the steps of:
s1, uniformly mixing the epoxy resin, the methyl methacrylate, the styrene, the butyl acrylate, the hydroxyethyl acrylate, the methacrylic acid, the glycidyl versatate, the dodecyl mercaptan and the benzoyl peroxide to obtain a precursor;
s2, adding part of the precursor into the isopropanol under inert atmosphere; reacting for 1-2 h at 75-85 ℃ to obtain prepolymer; adding the rest of the precursor into the prepolymer, and reacting at 75-85 ℃ for 6-7 h; and cooling, and adding the N, N-dimethylethanolamine and water to obtain the acrylic resin.
According to some embodiments of the invention, the portion of the precursor in step S2 is 15% to 25% of the precursor.
According to some embodiments of the invention, the temperature of the temperature reduction in step S2 is 65 ℃ to 70 ℃.
The third aspect of the invention provides the application of the acrylic resin in preparing the water-based amino baking paint.
The fourth aspect of the invention provides water-based amino baking paint, which comprises the following preparation raw materials: the acrylic resin, the amino resin, the thickening agent and the auxiliary agent.
According to some embodiments of the invention, the additives include color paste, neutralizer ii, talc, a film forming additive, and an aqueous additive.
According to some embodiments of the present invention, the aqueous amino baking varnish comprises the following preparation raw materials in parts by weight: 45 to 60 parts of acrylic resin, 4 to 10 parts of amino resin, 25 to 45 parts of color paste, 0.1 to 0.5 part of neutralizer II, 5 to 20 parts of talcum powder, 2 to 6 parts of film-forming additive, 0.5 to 1.5 parts of thickening agent and 0.5 to 5 parts of water-based additive.
According to some embodiments of the invention, the amino resin is at least one of a homo-imino melamine formaldehyde resin and a methyl-etherified homo-imino melamine resin; preferably, the high imino melamine formaldehyde resin is cyanogen-Te 327 resin; preferably, the methyl etherified high imino melamine resin is cyanogen 325 resin.
The amino resin can react with hydroxyl and carboxyl, so that the compactness of a paint film is better, the adhesion to a material is better, and the impact property, the hard pen hardness, the tolerance and other properties of the paint film are better.
According to some embodiments of the invention, the color paste comprises one of a white color paste, a black color paste, a red color paste, a yellow color paste, and a blue color paste; preferably, the White color paste is Crainen White TQ 100-CN.
According to some embodiments of the invention, the neutralizing agent ii is N, N-Dimethylethanolamine (DMEA).
According to some embodiments of the invention, the talc powder has a mesh size of 2500 to 3500.
Compared with the thicker talcum powder, the superfine talcum powder can be better dispersed in the system, and meanwhile, the pencil hardness of a paint film is improved to a certain degree, and the storage stability of the system is also facilitated.
According to some embodiments of the invention, the coalescent consists of dipropylene glycol butyl ether (DPNB) and ethylene glycol butyl ether (BG); preferably, the mass ratio of the dipropylene glycol butyl ether to the ethylene glycol butyl ether is 0.5-2: 1.
The film-forming auxiliary agent is selected from low-boiling point solvents and high-boiling point solvents for matching use, and according to the characteristics that the low-boiling point film-forming auxiliary agent is fast in volatilization and the high-boiling point film-forming auxiliary agent is slow in volatilization, the system can be used at high temperature and low temperature.
According to some embodiments of the invention, the thickener is an associative thickener; preferably, the associative thickener comprises OMG-0620.
The associative thickener and the resin component form a more stable net structure, so that the associative thickener has better wrapping property on color paste and filler, thereby improving the storage stability of the water-based amino baking paint.
According to some embodiments of the invention, the aqueous adjuvant is a defoamer, a substrate wetting agent and a leveling agent.
According to some embodiments of the invention, the defoamer comprises at least one of BYK-024, AIR Product AD-01, AIR Product MD-02, and TEGO-901W.
According to some embodiments of the present invention, the substrate wetting agent comprises at least one of TEGO-4100 and TEGO-270.
According to some embodiments of the invention, the leveling agent comprises at least one of TEGO-410, BYK-3410, and BYK-381.
The fifth aspect of the invention provides a preparation method of the water-based amino baking paint, which comprises the following steps:
s01, adding the acrylic resin, the amino resin, the color paste and water, and uniformly mixing; obtaining a mixture;
s02, sequentially adding the N, N-dimethylethanolamine, the talcum powder, the film-forming aid, the thickener and the water-based aid into the mixture; solid-liquid separation, and solid phase collection; and obtaining the water-based amino baking paint.
The invention provides an application of the water-based amino baking paint in preparation of a metal substrate anticorrosive coating.
According to some embodiments of the invention, the metal substrate comprises one of stainless steel, an aluminum alloy, a magnesium alloy, and tinplate.
The invention at least obtains the following beneficial effects: the amino baking varnish is a water-based system, and belongs to a green and environment-friendly product capable of being developed sustainably; meanwhile, the acrylic resin used by the waterborne amino baking paint is modified waterborne hydroxyl acrylic resin, and the epoxy resin is introduced into the modified waterborne hydroxyl acrylic resin, so that a paint film after the epoxy resin is cured is more compact, and the adhesive force and the chemical resistance of the waterborne amino baking paint on various substrates are improved; meanwhile, the baking time is reduced, so that the process is simpler and more convenient; meanwhile, the modified water-based hydroxyl acrylic resin with hydroxyl and the amino resin are crosslinked and cured at high temperature, so that the compactness and the protection (preventing materials from being scratched, corroded, aged and oxidized) of the finally prepared water-based amino baking paint are further improved; meanwhile, the decorative effect of the amino baking varnish is improved; the associative thickener and the resin component form a more stable net structure, so that the associative thickener has better wrapping property on color paste and filler, thereby improving the storage stability of the water-based amino baking paint. The water-based amino baking paint has wide application range and can be used for various metal base materials such as stainless steel, aluminum alloy, magnesium alloy, tinplate and the like.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
The preparation method of the aqueous amino baking varnish in the embodiment of the invention comprises the following steps:
s1, adding the self-made acrylic resin, the amino resin, the white color paste and the water into a dispersion tank, and stirring for 10-15 min at 600-800 r/min;
s2, adjusting the rotating speed to 800 r/min-1000 r/min, adding the N, N-dimethylethanolamine into a dispersion tank, and stirring for 5 min-10 min;
s3, adjusting the rotating speed to 800 r/min-1000 r/min, slowly adding talcum powder, and stirring for 20 min-30 min;
s4, adjusting the rotating speed to 1000 r/min-1200 r/min, adding a film-forming aid, wherein the film-forming aid is a mixture of DPNB and BG with the weight ratio of 0.5-2, and stirring for 5-10 min;
s5, adjusting the rotating speed to 800 r/min-1000 r/min, adding a thickening agent, and stirring for 5 min-10 min;
s6, adjusting the rotating speed to 1000 r/min-1200 r/min, adding the water-based auxiliary agent, and stirring the other auxiliary agents including the defoaming agent, the base material wetting agent and the flatting agent for 20 min-30 min;
and S7, filtering and packaging the dispersed materials.
The defoaming agent comprises at least one of BYK-024, AIR Product AD-01, AIR Product MD-02 and TEGO-901W.
The substrate wetting agent includes at least one of TEGO-4100 and TEGO-270.
The leveling agent comprises at least one of TEGO-410, BYK-3410 and BYK-381.
Example 1
The embodiment is a preparation method of acrylic resin, which comprises the following steps:
s1, 10 parts of epoxy resin (E-44 barite), 5 parts of methyl methacrylate, 15 parts of styrene, 15 parts of butyl acrylate, 10 parts of hydroxyethyl acrylate, 8 parts of methacrylic acid, 2 parts of glycidyl versatate, 0.8 part of dodecyl mercaptan and 0.5 part of benzoyl peroxide are mixed and added into a dropping funnel to obtain a mixed solution.
S2, adding 8 parts of isopropanol into a four-neck flask with a water bath heating device, a stirrer, a condenser tube, a dropping funnel and a thermometer device, introducing nitrogen into the four-neck flask, keeping the temperature to 80 ℃, slowly dropping 20% (volume) of the mixed solution in the dropping funnel (1mL/min), after heat preservation reaction for 1h, dropping the rest mixed solution at a constant speed (4mL/min), after dropping for 3-4h, heat preservation reaction for 2h, reducing the temperature to 70 ℃, adding 0.5 part of N, N-dimethylethanolamine and a certain amount of water (10 parts), stirring for 30min, and discharging to obtain the acrylic resin.
Example 2
The embodiment is a waterborne amino baking paint and a preparation method thereof.
The aqueous amino baking varnish of the embodiment comprises the following raw materials in parts by weight:
the preparation method of the water-based amino baking paint comprises the following steps:
s1, adding acrylic resin, amino resin, white color paste and water into a dispersion tank, and stirring for 15min at the speed of 600 r/min;
s2, adjusting the rotating speed to 800r/min, adding the N, N-dimethylethanolamine into a dispersion tank, and stirring for 10 min;
s3, adjusting the rotating speed to 1000r/min, slowly adding talcum powder into the dispersion tank, and stirring for 30 min;
s4, adjusting the rotation speed to 1200r/min, adding the DPNB and the BG into a dispersion tank, and stirring for 10 min;
s5, adjusting the rotating speed to 800 r/min-1000 r/min, adding the thickening agent into a dispersion tank, and stirring for 10 min;
s6, adjusting the rotation speed to 1200r/min, adding the defoaming agent, the base material wetting agent and the flatting agent into a dispersion tank, and stirring for 30 min;
s7, filtering and packaging the dispersed materials to obtain the waterborne amino baking varnish.
Example 3
This example is an aqueous amino baking varnish and a preparation method thereof, and the difference from example 2 is that: raw materials and parts by weight of the water-based amino baking varnish.
The aqueous amino baking varnish of the embodiment comprises the following raw materials in parts by weight:
50.0 parts of acrylic resin (prepared in example 1);
6.5 parts of amino resin (Cyanote 327);
30.0 parts of White color paste (Clainen White TQ 100-CN);
0.2 part of N, N-dimethylethanolamine;
5.0 parts of talcum powder (3000 meshes, New materials Youbang, Hunan);
4.0 parts of film-forming additive (DPNB/BG mass ratio is 1: 1);
0.4 part of base material wetting agent (TEGO-4100);
0.2 part of defoaming agent (BYK-024);
0.5 part of thickener (OMG-0620);
0.1 part of leveling agent (BYK-381);
and 3.1 parts of water.
Example 4
This example is an aqueous amino baking varnish and a preparation method thereof, and the difference from example 2 is that: raw materials and parts by weight of the water-based amino baking varnish.
The aqueous amino baking varnish of the embodiment comprises the following raw materials in parts by weight:
example 5
This example is an aqueous amino baking varnish and a preparation method thereof, and the difference from example 2 is that: raw materials and parts by weight of the water-based amino baking varnish.
The aqueous amino baking varnish of the embodiment comprises the following raw materials in parts by weight:
example 6
This example is an aqueous amino baking varnish and a preparation method thereof, and the difference from example 2 is that: raw materials and parts by weight of the water-based amino baking varnish.
The aqueous amino baking varnish of the embodiment comprises the following raw materials in parts by weight:
comparative example 1
This example is an aqueous amino baking varnish and a preparation method thereof, and the difference from example 2 is that: raw materials and parts by weight of the water-based amino baking varnish.
The aqueous amino baking varnish of the embodiment comprises the following raw materials in parts by weight:
comparative example 2
This example is an aqueous amino baking varnish and a preparation method thereof, and the difference from example 2 is that: raw materials and parts by weight of the water-based amino baking varnish.
The aqueous amino baking varnish of the embodiment comprises the following raw materials in parts by weight:
comparative example 3
This example is an aqueous amino baking varnish and a preparation method thereof, and the difference from example 2 is that: raw materials and parts by weight of the water-based amino baking varnish.
The aqueous amino baking varnish of the embodiment comprises the following raw materials in parts by weight:
comparative example 4
This example is an aqueous amino baking varnish and a preparation method thereof, and the difference from example 2 is that: raw materials and parts by weight of the water-based amino baking varnish.
The aqueous amino baking varnish of the embodiment comprises the following raw materials in parts by weight:
comparative example 5
This example is an aqueous amino baking varnish and a preparation method thereof, and the difference from example 2 is that: raw materials and parts by weight of the water-based amino baking varnish.
The aqueous amino baking varnish of the embodiment comprises the following raw materials in parts by weight:
the performance of the aqueous amino baking paint prepared in the embodiments 2-6 and the comparative examples 1-5 of the invention is tested by experiments, in the testing process, an aluminum plate without greasy dirt is selected as a base material for spraying, after the spraying, the aqueous amino baking paint is baked for 20min in an oven at 150 ℃ after being leveled for 15min, and then the performance test is carried out; the performance test method comprises the following steps:
appearance, IPA resistance, MEK resistance, oleic acid resistance, and artificial sweat resistance: visual inspection was carried out.
Conventional adhesion and boiled adhesion test reference: GB/T9286-1998.
Pencil hardness test reference: GB/T6739-2006.
Flexibility test reference: GB/T1731-1993.
Positive and negative impact strength references: GB/T1732-1993.
Storage stability (5 ℃, room temperature (25 ℃), 40 ℃ and 50 ℃) reference: GB/T6753.3-86.
The performance test results of the aqueous amino baking varnish prepared in the embodiments 2 to 6 and the comparative examples 1 to 5 are shown in tables 1 to 3:
TABLE 1 test results of the performance of the aqueous amino baking varnish prepared in examples 2 to 6
TABLE 2 test results of the properties of the aqueous amino baking varnish prepared in example 4 and comparative examples 1 to 3
TABLE 3 storage stability test results for aqueous amino baking paints prepared from the coatings of example 4 and comparative examples 4 to 5
In the embodiments 2 to 6 of the present invention, the modified aqueous hydroxy acrylic resin prepared in the embodiment 1 is selected and matched with amino resins of different weight parts, and as shown in table 1, when the amino resin is 7.5 weight parts, the comprehensive performance of the aqueous amino baking varnish is the best. When the content of the amino resin is too low, the paint film is not sufficiently cured, and the performances such as the adhesive force, the tolerance and the like of the paint film are influenced to a certain extent; when the content of the amino group is too high, the amino group reacts completely, so that the paint film is brittle, and the adhesion, the resistance and the like of the paint film are affected.
According to the invention, the modified waterborne hydroxy acrylic resin prepared in the embodiment 1 is selected in the embodiment 4, and the commercially available waterborne hydroxy acrylic resins (Coltsingchu 2470, Wanhua 2043 and Wanhua U2145H) are respectively selected in the comparative examples 1 to 3, and from experimental results, the comprehensive performance of the waterborne amino baking paint prepared from the modified waterborne hydroxy acrylic resin prepared in the embodiment 1 is obviously superior to that of the waterborne amino baking paint prepared from the commercially available waterborne hydroxy acrylic acid. The molecular weight and the hydroxyl content of the modified waterborne hydroxyl acrylic resin prepared in the embodiment 1 of the invention are different from those of the commercial resin; the resin finally forms a paint film, and the paint film characteristics are determined to a certain extent by the molecular structure of the resin; meanwhile, the hydroxyl content is increased, and the compactness of the paint film can be influenced to a certain extent, so that various performances of the paint film are influenced.
The OMG-0620 thickener is selected in the embodiment 4 of the invention and is an associative polyurethane thickener, and can form a spatial three-dimensional network structure with the modified water-based hydroxy acrylic acid prepared in the embodiment 1 of the invention, so that the pigment and filler in a water-based amino baking varnish system can be better wrapped, and the water-based amino baking varnish system has better storage stability; the RD thickener from hamming was chosen for comparative example 4 and the BYK-420 thickener was chosen for comparative example 5, which produced coatings that were significantly less stable on storage than the coating produced in example 3.
In conclusion, the amino baking varnish disclosed by the invention is a water-based system, and belongs to a green and environment-friendly product capable of being developed continuously; meanwhile, the acrylic resin used by the waterborne amino baking paint is modified waterborne hydroxyl acrylic resin, and the epoxy resin is introduced into the modified waterborne hydroxyl acrylic resin, so that a paint film after the epoxy resin is cured is more compact, and the adhesive force and the chemical resistance of the waterborne amino baking paint on various substrates are improved; meanwhile, the baking time is reduced, so that the process is simpler and more convenient; meanwhile, the modified water-based hydroxyl acrylic resin with hydroxyl and the amino resin are crosslinked and cured at high temperature, so that the compactness and the protection of the finally prepared water-based amino baking paint are further improved; meanwhile, the decorative effect of the amino baking varnish is improved; the associative thickener and the resin component form a more stable net structure, so that the associative thickener has better wrapping property on color paste and filler, thereby improving the storage stability of the water-based amino baking paint. The water-based amino baking paint has wide application range and can be used for various metal base materials such as stainless steel, aluminum base, magnesium alloy, tinplate and the like.
While the embodiments of the present invention have been described in detail with reference to the description, the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. An acrylic resin characterized by: the method comprises the following preparation raw materials: epoxy resin, acrylate compounds, styrene, acrylic compounds and glycidyl versatate.
2. The acrylic resin according to claim 1, wherein: the method comprises the following preparation raw materials: the acrylic resin comprises the following preparation raw materials: initiator, neutralizer I, cosolvent and regulator; preferably, the acrylate compound consists of methyl methacrylate, butyl acrylate and hydroxyethyl acrylate; preferably, the acrylic compound is methacrylic acid, preferably, the initiator is benzoyl peroxide; preferably, the neutralizing agent I is N, N-dimethylethanolamine; preferably, the cosolvent is isopropanol; preferably, the regulator is dodecyl mercaptan.
3. The acrylic resin according to claim 2, wherein: the preparation method comprises the following raw materials in parts by weight: 10 to 15 parts of epoxy resin, 5 to 35 parts of methyl methacrylate, 15 to 20 parts of styrene, 10 to 20 parts of butyl acrylate, 10 to 15 parts of hydroxyethyl acrylate, 5 to 9 parts of methacrylic acid, 0.5 to 0.9 part of benzoyl peroxide, 2 to 10 parts of isopropanol, 0.2 to 2 parts of N, N-dimethylethanolamine, 1 to 15 parts of glycidyl versatate and 1 to 1.5 parts of dodecyl mercaptan.
4. A method for preparing the acrylic resin as defined in claim 3, wherein: the method comprises the following steps:
s1, uniformly mixing the epoxy resin, the methyl methacrylate, the styrene, the butyl acrylate, the hydroxyethyl acrylate, the methacrylic acid, the glycidyl versatate, the dodecyl mercaptan and the benzoyl peroxide to obtain a precursor;
s2, adding part of the precursor into the isopropanol under inert atmosphere; reacting for 1-2 h at 75-85 ℃ to obtain prepolymer; adding the rest of the precursor into the prepolymer, and reacting at 75-85 ℃ for 6-7 h; and cooling, and adding the N, N-dimethylethanolamine and water to obtain the acrylic resin.
5. The water-based amino baking paint is characterized in that: the method comprises the following preparation raw materials: the acrylic resin, the amino resin, the thickener and the auxiliary according to any one of claims 1 to 3.
6. The aqueous amino baking varnish according to claim 5, wherein: the auxiliary agent comprises color paste, a neutralizer, talcum powder, a film-forming auxiliary agent and a water-based auxiliary agent.
7. The aqueous amino baking varnish according to claim 6, wherein: the preparation method comprises the following raw materials in parts by weight: 45 to 60 portions of acrylic resin, 4 to 10 portions of amino resin, 25 to 45 portions of color paste, 0.1 to 0.5 portion of neutralizer II, 5 to 20 portions of talcum powder, 2 to 6 portions of film forming additive, 0.5 to 1.5 portions of thickening agent and 0.5 to 5 portions of water-based additive.
8. An aqueous amino baking varnish according to claim 6 or 7, characterised in that: the amino resin is at least one of high imino melamine formaldehyde resin and methyl etherified high imino melamine resin; preferably, the color paste comprises one of white color paste, black color paste, red color paste, yellow color paste and blue color paste; (ii) a Preferably, the neutralizing agent II is N, N-Dimethylethanolamine (DMEA); preferably, the mesh number of the talcum powder is 2500 meshes to 3500 meshes; preferably, the coalescent consists of dipropylene glycol butyl ether (DPNB) and ethylene glycol butyl ether (BG); preferably, the thickener is an associative thickener; preferably, the aqueous auxiliary agent is a defoaming agent, a substrate wetting agent and a leveling agent.
9. A process for the preparation of the aqueous amino baking varnish according to any one of claims 7 to 8, characterized in that: the method comprises the following steps:
s01, adding the acrylic resin, the amino resin, the color paste and water, and uniformly mixing; obtaining a mixture;
s02, sequentially adding the N, N-dimethylethanolamine, the talcum powder, the film-forming aid, the thickener and the water-based aid into the mixture; solid-liquid separation, and solid phase collection; and obtaining the water-based amino baking paint.
10. Use of an aqueous amino baking varnish according to any one of claims 5 to 8 for the preparation of a corrosion protective coating.
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Application publication date: 20210910 |