CN109608970A - With excellent thixotropic baking-type water-borne acrylic coatings composition and preparation method thereof - Google Patents

With excellent thixotropic baking-type water-borne acrylic coatings composition and preparation method thereof Download PDF

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CN109608970A
CN109608970A CN201811411695.7A CN201811411695A CN109608970A CN 109608970 A CN109608970 A CN 109608970A CN 201811411695 A CN201811411695 A CN 201811411695A CN 109608970 A CN109608970 A CN 109608970A
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baking
water
type water
coatings composition
borne acrylic
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CN109608970B (en
Inventor
许飞
张汉青
庄振宇
胡中
周丽
张玉兴
陈卫东
王艳艳
刘汉功
祝宝英
刘明
刘睿
丁帮勇
刘益阳
陈兴兰
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China National Offshore Oil Corp CNOOC
CNOOC Energy Technology and Services Ltd
CNOOC Changzhou EP Coating Co Ltd
CNOOC Changzhou Paint and Coatings Industry Research Institute Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Energy Technology and Services Ltd
CNOOC Changzhou EP Coating Co Ltd
CNOOC Changzhou Paint and Coatings Industry Research Institute Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating 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
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/14Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

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Abstract

The present invention relates to technical field of coatings, and in particular to one kind has excellent thixotropic baking-type water-borne acrylic coatings composition and preparation method thereof.Coating composition of the invention, it is mainly made by the raw material of following weight percent: functional stuffing A 0.05~0.45%, deionized water 10~15%, hydroxy functionalized water-based acrylic resin 30~38% containing tertiary amine group, water-compatible amino resin 2.5~4.5%, cosolvent A 4.5~8%, dispersing agent 0.1~0.8%, levelling agent 0.1~0.55%, defoaming agent 0.1~0.65%, pH adjusting agent 0.05~0.4%, pigment 5~15%, filler B 10~40%, auxiliary rheological agents 0.1~0.85%, cosolvent B 3.5~9.7%;The functional stuffing A is hectorite or sheet silicate.Coating of the invention has excellent thixotropy, sag resistance and anti-stoning.

Description

With excellent thixotropic baking-type water-borne acrylic coatings composition and its preparation Method
Technical field
The present invention relates to technical field of coatings, and in particular to there is one kind excellent thixotropic baking-type water soluble acrylic acid to apply Feed composition and preparation method thereof.
Background technique
Aqueous amino is added mainly using water based acrylic resin as film-forming resin in baking-type water-borne acrylic coatings Resin adds pigments and fillers and aqueous promoter, is prepared after grinding distribution.Baking-type water-borne acrylic coatings were being constructed at present Cheng Zhong, since baking temperature is generally at 140 DEG C or more, paint viscosity is remarkably decreased since temperature rises in work progress, is led Current baking-type water-borne acrylic coatings are caused to be easy to generate sagging in the construction process.Flowing down problems are solved at present mainly to use Auxiliary rheological agents such as the thickener of polyurethane type, but in fact, auxiliary rheological agents anti-sag effect at high temperature and are paid no attention to Think.In addition, needing that a certain amount of cosolvent is added in baking-type water-borne acrylic coatings system, the presence of cosolvent can destroy poly- ammonia The thixotropic effects of type thickener, coating are more prone to produce sagging in the construction process, especially in facade spraying application, apply The problem of stream is hung is even more serious.Therefore, the flowing down problems of baking-type water-borne acrylic coatings in the construction process how are solved, It is industrial coating field urgent problem to be solved.The thixotropy for improving baking-type water-borne acrylic coatings, is especially applied in baking During work, it is the solution direction of baking-type water-borne acrylic coatings flowing down problems that the thixotropy of coating, which still keeps higher,.
Summary of the invention
The first purpose of this invention is to provide a kind of with excellent thixotropic baking-type water-borne acrylic coatings group Object is closed, which has excellent thixotropy and sag resistance.
Second object of the present invention is to provide a kind of above-mentioned with excellent thixotropic baking-type water soluble acrylic acid painting The preparation method of feed composition.
To achieve the above object, the technical scheme is that
One kind having excellent thixotropic baking-type water-borne acrylic coatings composition, mainly by following weight percent Raw material is made: functional stuffing A:0.05~0.45%, deionized water: 10~15%, it is hydroxy functionalized aqueous containing tertiary amine group Acrylic resin: 30~38%, water-compatible amino resin: 2.5~4.5%, cosolvent A:4.5~8%, dispersing agent: 0.1~ 0.8%, levelling agent: 0.1~0.55%, defoaming agent: 0.1~0.65%, pH adjusting agent 0.05~0.4%, pigment: 5~15%, Filler B:10~40%, auxiliary rheological agents: 0.1~0.85%, cosolvent B:3.5~9.7%;The functional stuffing A is that lithium illiteracy is de- Stone or sheet silicate.
The hectorite is aqueous hectorite.The sheet silicate is the sheet silicate of synthesis.
The auxiliary rheological agents are any one or two kinds in BYK-420, BYK-D 420.
The water-compatible amino resin be Resimene 717, Resimene 718, Resimene 741, Resimene745, Resimene 747、Maprenal MF 927、Resimene HM 2608、CYMEL 303LF、CYMEL325、CYMEL 327、 CYMEL 350, amino resins 5717, amino resins 5717W, amino resins 5847, in amino resins 5847L any one or It is several.
The cosolvent A be ethylene glycol ethyl ether, glycol propyl ether, butyl glycol ether, glycol hexyl ether, ethylene glycol phenyl ether, Propylene glycol monomethyl ether, propylene glycol propyl ether, propylene glycol phenylate, butyl, dipropylene glycol methyl ether, dipropylene, second two Any one or a few in alcohol monobutyl ether acetate, propylene glycol methyl ether acetate.
The dispersing agent be DISPERBYK 190, DISPERBYK 191, DISPERBYK 192, DISPERBYK194, AFCONA 4550、AFCONA 4560、EDAPLAN 490、Dispers 715W、Dispers 735W、Dispers 740W、Dispers 745W、Dispers 750W、Dispers 752W、Any one or a few in Dispers 760W.
The defoaming agent be 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、Foamex 805、Foamex 808、Foamex 810、Foamex 822、Any one or a few in Foamex 825.
The levelling agent is any in BYK-342, BYK-347, BYK-348, BYK-349, BYK-3455, BYK-378 It is one or more of.
The pH adjusting agent is N, N- dimethylethanolamine, triethylamine, 2-amino-2-methyl-1-propanol, appointing in ammonium hydroxide Meaning is one or more of.
The pigment be titanium dioxide, carbon black, iron oxide yellow, iron oxide red, phthalocyanine blue, in dark green any one or It is several.
The cosolvent B be ethylene glycol ethyl ether, glycol propyl ether, butyl glycol ether, glycol hexyl ether, ethylene glycol phenyl ether, Propylene glycol monomethyl ether, propylene glycol propyl ether, propylene glycol phenylate, butyl, dipropylene glycol methyl ether, dipropylene, second two Any one or a few in alcohol monobutyl ether acetate, propylene glycol methyl ether acetate.
The filler B is blanc fixe, kaolin, talcum powder, any one or a few in calcium carbonate.
The hectorite isDY CE、LT、DE、In EW Any one or a few.
The sheet silicate is one or both of Laponite RD, Laponite RDS.
The hydroxy functionalized water-based acrylic resin containing tertiary amine group is mainly by the raw material system of following weight percent At: cosolvent C:20~35%, hydrophilic monomer: 1.8~3.2%, hydroxy functional monomer: 2.5~6.5%, tertiary amines monomer: 0.5~2.5%, vinyl monomer: 18~38%, initiator: 0.05~0.8%, neutralizer: 2~4%, deionized water: 28.4~36.75%.
The tertiary amines monomer is acrylate, acrylic acid diethylamino ethyl ester, acrylic acid diformazan Base amino propyl ester, acrylic acid dibutylamino propyl ester, dimethylaminoethyl methacrylate, methacrylic acid diethylamino Ethyl ester, dimethylamine propyl ester, any one or a few in methacrylic acid dibutylamino propyl ester.
The hydroxy functional monomer is hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, metering system Sour hydroxypropyl acrylate, hy-droxybutyl, any one or a few in methacrylate.
The hydrophilic monomer is acrylic acid, methacrylic acid, any one or a few in maleic anhydride.
The vinyl monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylic acid second Ester, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid-2-ethyl caproite, propylene Sour n-octyl, n octyl methacrylate, benzyl acrylate, any one or a few in styrene.
The initiator is azodiisobutyronitrile, azobisisovaleronitrile, any one or a few in azobisisoheptonitrile.
The neutralizer is N, N- dimethylethanolamine, triethylamine, 2-amino-2-methyl-1-propanol, any in ammonium hydroxide It is one or more of.
The cosolvent C be ethylene glycol ethyl ether, glycol propyl ether, butyl glycol ether, glycol hexyl ether, ethylene glycol phenyl ether, Propylene glycol monomethyl ether, propylene glycol propyl ether, propylene glycol phenylate, butyl, dipropylene glycol methyl ether, dipropylene, second two Any one or a few in alcohol monobutyl ether acetate, propylene glycol methyl ether acetate.
The preparation method of the hydroxy functionalized water-based acrylic resin containing tertiary amine group, comprising the following steps:
1) preparation of mix monomer MM
By hydrophilic monomer, hydroxy functional monomer, tertiary amines monomer, vinyl monomer and initiator, after mixing evenly Mix monomer MM is obtained, it is spare;
2) preparation of the hydroxy functionalized water-based acrylic resin containing tertiary amine group
Cosolvent C is added as reaction bottom material, stirring is warming up to 70~90 DEG C and keeps the temperature, a dropping step 1) in Then mix monomer MM keeps the temperature 1~3 hour at 70~90 DEG C, after heat preservation, be cooled to 30~40 DEG C, neutralizer is added It neutralizes, adjusting speed of agitator is 500~1000rpm, and deionized water emulsification is added while stirring, obtains the hydroxyl containing tertiary amine group Functionalization water-based acrylic resin.
The dropwise addition of mix monomer MM is at 70~90 DEG C in completion of dropwise addition in 3~5 hours in step 2).
The above-mentioned preparation method with excellent thixotropic baking-type water-borne acrylic coatings composition, including following step It is rapid:
1) deionized water and functional stuffing A are mixed, obtains pregel liquid;
2) by containing tertiary amine group hydroxy functionalized water-based acrylic resin, water-compatible amino resin, cosolvent A, dispersing agent, Levelling agent, defoaming agent, pH adjusting agent, pigment, filler B are sequentially added in grinding pot, are added in step 1) after mixing Pregel liquid is ground to fineness≤40 micron, and discharging sequentially adds auxiliary rheological agents and cosolvent B later, mixes, filtering and discharging, Obtain baking-type water-borne acrylic coatings composition.
The present invention has excellent thixotropic baking-type water-borne acrylic coatings composition, fills out in raw material containing functional Material, hectorite or sheet silicate, after such functional stuffing disperses in coating, using the electrolyte among functional stuffing from Son forms 3 D stereo reticular structure (i.e. card room structure), and 3 D stereo reticular structure can promote the viscous of coating during storage It spends, in shear history, 3 D stereo reticular structure is destroyed, and viscosity reduces the spraying for being convenient for coating, when coating is sprayed on base When on material, shearing force disappears, and reticular structure restores, and viscosity increases, to achieve the effect that thickening and resist sagging;Raw material of the present invention In contain hydroxy functionalized water-based acrylic resin, it is in the coating composition, hydroxy functionalized aqueous wherein contain tertiary amine group The polyurea linkages and functional stuffing synergistic effect in tertiary amine group, auxiliary rheological agents in acrylic resin, it is intermolecular by being formed Hydrogen bond further strengthens the card room structure in functional stuffing, promotes the intensity of the structure, and during coating application, shearing force is broken Bad card room structure, viscosity reduces, and after construction, shearing force disappears, by hydroxy functionalized water-based acrylic resin, auxiliary rheological agents The card room structure cooperatively formed with functional stuffing is restored, and system viscosity increases, to achieve the effect that thickening and resist sagging, this hair The thixotropy of bright water-borne acrylic coatings composition is significantly enhanced;In addition, hydroxy functionalized water soluble acrylic acid in the present invention The hydrogen bond formed between the tertiary amine group and auxiliary rheological agents, functional stuffing of resin can further promote the anti-stoning of coating Energy.
Specific embodiment
Involved raw material include: in embodiment and comparative example
Propylene glycol methyl ether acetate, butyl glycol ether, propylene glycol monomethyl ether, technical grade, Nanjing Gutian Chemical Co., Ltd.;Third Olefin(e) acid, hydroxyethyl methacrylate, hydroxypropyl acrylate, acrylate, methacrylic acid lignocaine second Ester, methyl methacrylate, styrene, butyl acrylate, N, N- dimethylethanolamine, butanone, triethylamine, benzylamine, n-hexylamine, N-Methyl pyrrolidone, technical grade, Shanghai Ling Feng chemical reagent Co., Ltd;Azodiisobutyronitrile, azobisisoheptonitrile, industry Grade, Shanghai Ling Feng chemical reagent Co., Ltd;Isophorone diisocyanate, hexamethylene diisocyanate, technical grade, Cohan Create polymer (China) Co., Ltd;Amino resins Resimene 717, technical grade, Ineos;Amino resins CYMEL 325, Technical grade, profound new company;EDAPLAN 490, technical grade, the bright icepro of Germany;DISPERBYK190,BYK 348,BYK-025,BYK- 1710, technical grade, Bi Ke chemistry;Titanium dioxide R 902+, technical grade, E.I.Du Pont Company;Pu carbon black, technical grade, Cabot;Precipitated sulfur Sour barium, technical grade, south wind group.
Embodiment and comparative example raw materials are unless otherwise stated commercially available industrial goods, can be purchased by commercial channel ?.
Embodiment 1
The present embodiment has excellent thixotropic baking-type water-borne acrylic coatings composition, mainly by following raw material system : functional stuffing A 0.2gDY CE, 12g deionized water, hydroxy functionalized aqueous tree of the 35g containing tertiary amine group Rouge, 3.2g water-compatible amino resin Resimene 717,5g cosolvent A butyl glycol ether, 0.2g dispersing agent EDAPLAN 490, 0.2g levelling agent BYK-348,0.1g defoaming agent BYK-025,0.1g pH adjusting agent N, N- dimethylethanolamine, 9g titanium dioxide R 902+, 2g pu carbon black, 28.6g blanc fixe, 0.4g auxiliary rheological agents BYK-420,4g cosolvent B butyl glycol ether.
The preparation method with excellent thixotropic baking-type water-borne acrylic coatings composition of the present embodiment, including with Lower step:
1) functional stuffing pregel liquid GEL-1 is prepared:
12 grams of deionized waters are added in reaction flask, starts speed of agitator control in 500rpm, function is added while stirring 0.2 gram of filler ADY CE, stirs evenly, and obtains functional stuffing pregel liquid GEL-1;
2) baking-type water-borne acrylic coatings composition BAC-1 is prepared:
By 35 grams of hydroxy functionalized water-based acrylic resin, 3.2 grams of water-compatible amino resin Resimene containing tertiary amine group 717,5 grams of butyl glycol ethers, 0.2 gram of EDAPLAN, 490,0.2 grams of levelling agent BYK-348,0.1 gram of defoaming agent BYK-025,0.1 Gram pH adjusting agent N, N- dimethylethanolamine, 9 grams of titanium dioxide R 902+, 2 grams of pu carbon blacks, 28.6 grams of blanc fixes sequentially add In grinding pot, stir evenly, then 12.2 grams of functional stuffing pregel liquid GEL-1 by step 1) preparation are added in grinding pot, After mixing evenly, fineness≤40 micron are ground to, discharges, sequentially adds 0.4 gram of auxiliary rheological agents BYK-420 and 4 grams of ethylene glycol The mixture of butyl ether, is stirred 2 hours under 200rpm revolving speed, and filtering and discharging obtains baking-type water-borne acrylic coatings composition (BAC-1)。
The hydroxy functionalized water-base resin containing tertiary amine group of the present embodiment is made by the preparation method included the following steps:
1) preparation of mix monomer MM-1
By 2.3 grams of acrylic acid, 5.9 grams of hydroxyethyl methacrylates, 1.2 grams of acrylates, 12 grams of first Base methyl acrylate, 17 grams of butyl acrylates and 0.1 gram of azodiisobutyronitrile obtain mix monomer MM-1 after mixing evenly, spare;
2) preparation of the hydroxy functionalized water-based acrylic resin containing tertiary amine group
25 grams of propylene glycol methyl ether acetates are added as reaction bottom material, stirring is warming up to 80 DEG C and keeps the temperature, is added dropwise Mix monomer MM-1, in completion of dropwise addition in 5 hours at 80 DEG C;Then 3 hours are kept the temperature at 80 DEG C, after heat preservation, cooling To 30 DEG C, 2.5 grams of N are added, N- dimethylethanolamine neutralizes, and adjusting speed of agitator is 1000rpm, is added 34 grams while stirring and goes The hydroxy functionalized water-based acrylic resin containing tertiary amine group is prepared in ion water emulsification.
Embodiment 2
The present embodiment has excellent thixotropic baking-type water-borne acrylic coatings composition, mainly by following raw material system : 0.05g functional stuffing ALT, 10g deionized water, hydroxy functionalized water-base resin of the 30g containing tertiary amine group, 4.5g water-compatible amino resin CYMEL 325,1.5g cosolvent A butyl glycol ether, 3g cosolvent A propylene glycol monomethyl ether, 0.8g dispersion Agent DISPERBYK-190,0.1g levelling agent BYK-348,0.65g defoaming agentFoamex 810,0.05g pH adjusting agent Triethylamine, 4g titanium dioxide R 902+, 1g pu carbon black, 40g blanc fixe, 0.85g auxiliary rheological agents BYK-D 420,3.5g hydrotropy Agent B butyl glycol ether.
The preparation method with excellent thixotropic baking-type water-borne acrylic coatings composition of the present embodiment, including with Lower step:
1) functional stuffing pregel liquid GEL-2 is prepared:
10 grams of deionized waters are added in reaction flask, starts speed of agitator control in 200rpm, function is added while stirring 0.05 gram of fillerLT is stirred evenly, and obtains functional stuffing pregel liquid GEL-2;
2) baking-type water-borne acrylic coatings composition BAC-2 is prepared:
By 30 grams of hydroxy functionalized water-based acrylic resin, 4.5 grams of water-compatible amino resin CYMEL containing tertiary amine group 325,1.5 grams of butyl glycol ethers, 3 grams of propylene glycol monomethyl ethers, 0.8 gram of DISPERBYK-190,0.1 gram of levelling agent BYK-348,0.45 Gram defoaming agent810,0.05 grams of pH adjusting agent triethylamines of Foamex, 4 grams of titanium dioxide R 902+, 1 gram of pu carbon black, 40 grams Blanc fixe sequentially adds in grinding pot, stirs evenly, 10.05 grams of functional stuffing pregel liquid for then preparing step 1) GEL-2 is added in grinding pot, after mixing evenly, is ground to fineness≤40 micron, discharges, sequentially adds 0.85 gram of auxiliary rheological agents The mixture of BYK-D 420 and 3.7 grams of butyl glycol ether stirs 2 hours under 200rpm revolving speed, and filtering and discharging obtains baking-type Water-borne acrylic coatings composition (BAC-2).
Hydroxy functionalized water-base resin of the present embodiment containing tertiary amine group is made by the preparation method included the following steps:
1) preparation of mix monomer MM-2
By 1.8 grams of acrylic acid, 6.5 grams of hydroxypropyl acrylates, 1.2 grams of diethylaminoethyl methacrylates, 13 grams of methyl Methyl acrylate, 5 grams of styrene, 20 grams of butyl acrylates and 0.8 gram of azobisisoheptonitrile, obtain mix monomer after mixing evenly MM-2, it is spare;
2) preparation of the hydroxy functionalized water-based acrylic resin containing tertiary amine group
10 grams of propylene glycol methyl ether acetates and 10 grams of butanone are added as reaction bottom material, stirring is warming up to 70 DEG C and keeps temperature Degree, a dropping step 1) in mix monomer MM-2, in completion of dropwise addition in 5 hours at 70 DEG C, heat preservation is 3 small at 70 DEG C later When, after heat preservation, 30 DEG C are cooled to, 2 grams of N are added, N- dimethylethanolamine neutralizes, and adjusting speed of agitator is 800rpm, side It stirs side and 28.4 grams of deionized water emulsifications is added, the hydroxy functionalized water-based acrylic resin containing tertiary amine group is prepared.
Embodiment 3
The present embodiment has excellent thixotropic baking-type water-borne acrylic coatings composition, mainly by following raw material system : 0.45g functional stuffing ADY CE, 15g deionized water, hydroxy functionalized aqueous tree of the 38g containing tertiary amine group Rouge, 2.5g water-compatible amino resin Resimene 717,5g cosolvent A butyl glycol ether, 3g cosolvent A propylene glycol monomethyl ether, 0.1g Dispersing agent EDAPLAN 490,0.55g levelling agent BYK-348,0.2g defoaming agent BYK-025,0.4g pH adjusting agent N, N- diformazan Ethylethanolamine, 15g titanium dioxide R 902+, 10g calcium carbonate, 0.1g BYK-420,9.7g cosolvent B butyl glycol ether.
The preparation method with excellent thixotropic baking-type water-borne acrylic coatings composition of the present embodiment, including with Lower step:
1) functional stuffing pregel liquid GEL-3 is prepared:
15 grams of deionized waters are added in reaction flask, starts speed of agitator control in 300rpm, function is added while stirring 0.45 gram of fillerDY CE, stirs evenly, and obtains functional stuffing pregel liquid GEL-3;
3) baking-type water-borne acrylic coatings composition BAC-3 is prepared:
By 38 grams of hydroxy functionalized water-based acrylic resin, 2.5 grams of water-compatible amino resin Resimene containing tertiary amine group 717,5 grams of butyl glycol ethers, 3 grams of propylene glycol monomethyl ethers, 0.1 gram of EDAPLAN, 490,0.55 grams of levelling agent BYK-348,0.2 gram disappear Infusion BYK-025,0.4 gram of pH adjusting agent N, N- dimethylethanolamine, 15 grams of titanium dioxide R 902+, 10 grams of calcium carbonate sequentially add In grinding pot, stir evenly, then 15.45 grams of functional stuffing pregel liquid GEL-3 by step 1) preparation are added in grinding pot, After mixing evenly, fineness≤40 micron are ground to, discharges, sequentially adds 0.1 gram of auxiliary rheological agents BYK-420 and 9.7 grams of second two The mixture of alcohol butyl ether stirs 2 hours under 200rpm revolving speed, and filtering and discharging obtains baking-type water-borne acrylic coatings composition (BAC-3)。
The hydroxy functionalized water-base resin containing tertiary amine group of the present embodiment is made by the preparation method included the following steps:
1) preparation of mix monomer MM-3
By 3.2 grams of acrylic acid, 2.5 grams of hydroxyethyl methacrylates, 0.5 gram of acrylate, 5 grams of methyl Methyl acrylate, 5 grams of styrene, 8 grams of butyl acrylates and 0.05 gram of azodiisobutyronitrile obtain mix monomer after mixing evenly MM-3, it is spare;
2) preparation of the hydroxy functionalized water-based acrylic resin containing tertiary amine group
35 grams of propylene glycol methyl ether acetates are added as reaction bottom material, stirring is warming up to 90 DEG C and keeps the temperature, is added dropwise Mix monomer MM-3 keeps the temperature 3 hours at 90 DEG C later in completion of dropwise addition in 5 hours at 90 DEG C, after heat preservation, cooling To 30 DEG C, 4 grams of N are added, N- dimethylethanolamine neutralizes, and adjusting speed of agitator is 1000rpm, and 36.75 grams are added while stirring Deionized water emulsification, is prepared the hydroxy functionalized water-based acrylic resin containing tertiary amine group.
Comparative example 1
This comparative example baking-type water-borne acrylic coatings composition BAC-4 and the difference of embodiment 1 be only that, this comparative example Hydroxy functionalized water-base resin preparation process in be free of tertiary amines monomer, other are same as Example 1.
The preparation of the hydroxy functionalized water-base resin of this comparative example the following steps are included:
1) preparation of mix monomer MM-4
By 2.3 grams of acrylic acid, 5.9 grams of hydroxyethyl methacrylates, 13.2 grams of methyl methacrylates, 17 grams of acrylic acid fourths Ester and 0.1 gram of azodiisobutyronitrile, obtain mix monomer MM-4 after mixing evenly, spare;
2) preparation of hydroxy functionalized water-based acrylic resin
25 grams of propylene glycol methyl ether acetates are added as reaction bottom material, stirring is warming up to 80 DEG C and keeps temperature, is added dropwise mixed Monomer MM-4 is closed to keep the temperature 3 hours in completion of dropwise addition in 5 hours at 80 DEG C at 80 DEG C, after heat preservation, be cooled to 30 DEG C, 2.5 grams of N are added, N- dimethylethanolamine neutralizes, and adjusting speed of agitator is 1000rpm, and 34 grams of deionized waters are added while stirring Emulsification, is prepared hydroxy functionalized water-based acrylic resin.
Comparative example 2
The baking-type water-borne acrylic coatings composition BAC-5 of this comparative example and the difference of embodiment 1 are only that, will be implemented 0.2 gram of functional stuffing in example 1DY CE replaces with 0.2 gram of deionized water, other are same as Example 1.
Comparative example 3
The baking-type water-borne acrylic coatings composition BAC-6 of this comparative example and the difference of embodiment 1 are only that, will be implemented 0.4 gram of auxiliary rheological agents BYK-420 in example 1 replaces with 0.4 gram of butyl glycol ether, other are same as Example 1.
Experimental example
1) template is prepared
Use cold-rolled steel sheet as testing substrates.It polishes first cold-rolled steel sheet.It will according to construction requirement
Embodiment 1, embodiment 2, embodiment 3, comparative example 1, comparative example 2, the baking-type aqueous acrylamide prepared in comparative example 3 Sour coating composition BAC-1, BAC-2, BAC-3, BAC-4, BAC-5, BAC-6 coating be added appropriate amount of deionized water adjust viscosity to Template is then put under 140 DEG C of baking ovens and toasts 30 minutes by 38~45s, surface drying 30 minutes after spraying, and paint thickness is controlled 50 ~55 μm.Prepared template places test performance after 7 days under room temperature.
2) coating performance is tested
Coating property mainly investigates sag resistance, adhesive force, water resistance and anti-stoning energy.
Sag resistance test: sag resistance refers to coating in defined examination painting condition, defined ground and defined environment Under the conditions of, the maximum wet-film thickness (indicating with micron) of flow tendency is not generated during tilted-putted template re-dry.It applies The sag resistance of material is tested according to GB/T 9264-2012 " evaluation of paint and varnish sag resistance " test method.Using band The sagging spreader of scale applies.Test result assesses sag resistance according to the wet-film thickness of non-sagging.Will to tie convenient for comparing Fruit is divided into 3 grades: 1 grade: wet-film thickness >=150 micron, coating not sagging;150 μm of 2 grades: 100 μm≤wet-film thickness < is applied Expect not sagging;3 grades: wet-film thickness < 100 microns, coating not sagging.Sag resistance is 1 grade best, and 3 grades worst.
Thixotroping value: viscosity when at room temperature using 25 DEG C of I type rotary viscosity design determining coating of NDJ- tests revolving speed respectively For the viscosity of the coating under 6rpm and revolving speed 60rpm, thixotroping value=viscosity (6rpm)/viscosity (60rpm).
Adhesive force: coating adhesion is tested according to GB/T 9286-1998, is divided into 0~5 grade, 0 grade preferably, and 5 grades most Difference.Adhesive force test result is shown in Table 1.
Anti-stoning: instrument detection is hit using VDA-508 type stone, continuously strikes steel cuttings in spray-applied primer under authorized pressure On the template of middle painting, paint film appearance is observed, is divided into 0~9 grade, 0 grade of expression paint film is without breakdown, 9 grades of expression paint film large area Breakdown.0 grade preferably, and 9 grades worst.
Coating property test result is shown in Table 1.
The performance of baking-type water-borne acrylic coatings composition in table 1 embodiment 1-3 and comparative example 1-3
As shown in Table 1, the tertiary amine group in the hydroxy functionalized water-based acrylic resin in 1-3 of the embodiment of the present invention, stream The polyurea linkages and functional stuffing become in auxiliary agent act synergistically, and are further strengthened in functional stuffing by forming intermolecular hydrogen bond Card room structure, promotes the intensity of the structure, and during coating application, shearing force destroys card room structure, and viscosity reduces, construction knot Shu Hou, shearing force disappear, the card room knot cooperatively formed by hydroxy functionalized water-based acrylic resin, auxiliary rheological agents and functional stuffing Structure restores, and system viscosity increases, thus achieve the effect that thickening and resist sagging, the baking-type aqueous acrylamide of embodiment 1-3 preparation Sour coating composition BAC-1, BAC-2, BAC-3, thixotroping value are above 3.5, have good thixotropy, coating is in work progress In have good sag resistance energy, be 1 grade.Meanwhile coating shows excellent adhesive force and anti-stoning energy.It is comparing In example 1, tertiary amine group, three formed in BAC-4 coating by functional stuffing are not contained in hydroxy functionalized water-based acrylic resin It ties up space network to weaken, the thixotroping value of coating reduces, and sag resistance can be also reduced to 2 grades, and since hydrogen bond weakens, anti-stone is hit Performance also weakens.In comparative example 2, functional stuffing is not used in BAC-5 formulation for coating material, tridimensional network can not be formed (i.e. card room structure), thixotropy, sag resistance energy and the anti-stoning of coating can be obviously reduced.In comparative example 3, BAC-6 Auxiliary rheological agents are not used in formulation for coating material, thixotropy, sag resistance energy and the anti-stoning of coating can be also obviously reduced.
By above-mentioned analysis, the baking-type water-borne acrylic coatings composition in the present invention needs the hydroxyl containing tertiary amine group Functionalization water-based acrylic resin, functional stuffing and auxiliary rheological agents synergistic effect, can be only achieved excellent thixotropy and anti-sag Performance.
It will be apparent to those skilled in the art that can make various other according to the above description of the technical scheme and ideas Corresponding change and deformation, and all these changes and deformation all should belong to the protection scope of the claims in the present invention Within.

Claims (10)

1. one kind has excellent thixotropic baking-type water-borne acrylic coatings composition, which is characterized in that mainly by following heavy The raw material for measuring percentage is made: functional stuffing A:0.05~0.45%, deionized water: 10~15%, the hydroxyl containing tertiary amine group Functionalization water-based acrylic resin: 30~38%, water-compatible amino resin: 2.5~4.5%, cosolvent A:4.5~8%, dispersion Agent: 0.1~0.8%, levelling agent: 0.1~0.55%, defoaming agent: 0.1~0.65%, pH adjusting agent 0.05~0.4%, pigment: 5~15%, filler B:10~40%, auxiliary rheological agents: 0.1~0.85%, cosolvent B:3.5~9.7%;The functional stuffing A For hectorite or sheet silicate.
2. baking-type water-borne acrylic coatings composition according to claim 1, which is characterized in that the auxiliary rheological agents are Any one in BYK-420, BYK-D 420 or two kinds.
3. baking-type water-borne acrylic coatings composition according to claim 1, which is characterized in that the aqueous amino tree Rouge is Resimene 717, Resimene 718, Resimene 741, Resimene 745, Resimene 747, Maprenal MF 927, Resimene HM 2608, CYMEL 303LF, 325 CYMEL, CYMEL 327, CYMEL 350, amino resins 5717, amino resins 5717W, amino resins 5847, any one or a few in amino resins 5847L.
4. baking-type water-borne acrylic coatings composition according to claim 1, which is characterized in that the hectorite isDY CE、LT、DE、Any one or a few in EW.
5. baking-type water-borne acrylic coatings composition according to claim 1, which is characterized in that the sheet silicate For one or both of Laponite RD, Laponite RDS.
6. baking-type water-borne acrylic coatings composition according to claim 1, which is characterized in that the pigment is dioxy Change titanium, carbon black, iron oxide yellow, iron oxide red, phthalocyanine blue, any one or a few in dark green.
7. baking-type water-borne acrylic coatings composition according to claim 1, which is characterized in that described to contain tertiary amine group Hydroxy functionalized water-based acrylic resin be mainly made of the raw material of following weight percent: cosolvent C:20~35%, parent Water type monomer: 1.8~3.2%, hydroxy functional monomer: 2.5~6.5%, tertiary amines monomer: 0.5~2.5%, vinyl-based list Body: 18~38%, initiator: 0.05~0.8%, neutralizer: 2~4%, deionized water: 28.4~36.75%.
8. baking-type water-borne acrylic coatings composition according to claim 7, which is characterized in that the tertiary amines monomer For acrylate, acrylic acid diethylamino ethyl ester, acrylate propyl ester, acrylic acid dibutyl Amino propyl ester, dimethylaminoethyl methacrylate, diethyl aminoethyl methacrylate, dimethylaminoethyl acrylate methyl base ammonia Any one or a few in base propyl ester, methacrylic acid dibutylamino propyl ester.
9. baking-type water-borne acrylic coatings composition according to claim 7, which is characterized in that the hydroxyl functional list Body be hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, hy-droxybutyl, Any one or a few in methacrylate.
10. a kind of as described in claim 1 with the preparation of excellent thixotropic baking-type water-borne acrylic coatings composition Method, which comprises the following steps:
1) deionized water and functional stuffing A are mixed, obtains pregel liquid;
2) by hydroxy functionalized water-based acrylic resin, water-compatible amino resin, cosolvent A, dispersing agent, levelling containing tertiary amine group Agent, defoaming agent, pH adjusting agent, pigment, filler B are sequentially added in grinding pot, are added after mixing pre- solidifying in step 1) Glue is ground to fineness≤40 micron, and discharging sequentially adds auxiliary rheological agents and cosolvent B later, mixes, and filtering and discharging obtains Baking-type water-borne acrylic coatings composition.
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Citations (5)

* Cited by examiner, † Cited by third party
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
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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