CN108977051A - A kind of water-fast stain-resistant exterior wall coating - Google Patents
A kind of water-fast stain-resistant exterior wall coating Download PDFInfo
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- CN108977051A CN108977051A CN201810695024.1A CN201810695024A CN108977051A CN 108977051 A CN108977051 A CN 108977051A CN 201810695024 A CN201810695024 A CN 201810695024A CN 108977051 A CN108977051 A CN 108977051A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a kind of water-fast stain-resistant exterior wall coating, raw material includes: 30-50 parts of fluorinated acrylate modified polyurethane emulsion, 20-35 parts of organosilicon modified crylic acid resin, 1-5 parts of methacrylic acid polydimethylsiloxanes base Arrcostab, 1-5 parts of modified calcinated kaolin, 2-6 parts of titanium dioxide, 0.5-4 parts of zinc oxide, 2-6 parts of ceramic hollow microballon, 2-8 parts of natural porous konilite, 0.5-3 parts of coalescing agent, 1-3 parts of anti-settling agent, 1-3 parts of levelling agent, 1-3 parts of defoaming agent, 60-80 parts of deionized water by weight；Water-fast stain-resistant exterior wall coating proposed by the present invention has the characteristics that hardness height, water-tolerant, stain resistance be good and long service life.
Description
Technical field
The present invention relates to exterior coating technical field more particularly to a kind of water-fast stain-resistant exterior wall coating.
Background technique
Exterior coating is a kind of outer layer ornament materials the effects of playing beautiful and protection brushed outside building.
Due to its have in use Color Expression effect abundant and its can be showed flexible and changeablely in decoration coating surface it is each
It plants the decoration style of various kinds and is liked deeply by people.However, being exposed in atmospheric environment for a long time easily after exterior coating is coated
By the pollution of atmosphere, the pollution cause of exterior coating is that metope is rough and uneven in surface, and the dust in rainwater entrainment air falls on paint film table
Face, there are gap, tiny pollutants to invade in coating with rainwater for surface of the paint film, and after moisture evaporation, pollutant will be stayed
In paint film, permanent pollution is formed；For China's atmosphere pollution than more serious, dust in air content is high, and coating surface is easy
Accumulate dust, just occur " dragging nasal mucus " phenomenon when serious, for the decorative effect and service life for improving coating, improves the resistance to of coating
Contamination is necessary.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of water-fast stain-resistant exterior wall coating, the coating
Have the characteristics that hardness height, water-tolerant, stain resistance be good and long service life.
A kind of water-fast stain-resistant exterior wall coating proposed by the present invention, raw material include: that fluorinated acrylate changes by weight
Property 30-50 parts of polyaminoester emulsion, 20-35 parts of organosilicon modified crylic acid resin, methacrylic acid polydimethylsiloxanes base alkyl
It is 1-5 parts of ester, 1-5 parts of modified calcinated kaolin, 2-6 parts of titanium dioxide, 0.5-4 parts of zinc oxide, 2-6 parts of ceramic hollow microballon, natural
Porous konilite 2-8 parts, 0.5-3 parts of coalescing agent, 1-3 parts of anti-settling agent, 1-3 parts of levelling agent, 1-3 parts of defoaming agent, deionized water
60-80 parts.
Preferably, the fluorinated acrylate modified polyurethane emulsion is prepared according to following technique: first with Toluene-2,4-diisocyanate, 4-
Diisocyanate and poly- ethanedioic acid butyl glycol ester diol are that raw material carries out prepolymerization reaction, be then added 2,2- dihydromethyl propionic acid,
Diglycol, dibutyl tin dilaurate, diamine 2, bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of 2- carry out
Chain extending reaction, and acetone is added and adjusts viscosity, 2- hydroxyethyl methacrylate phosphate is then added and carries out end capping reaction,
After reaction, triethylamine is added to neutralize, obtains polyurethane macromolecular；By obtained polyurethane macromolecular and methyl methacrylate
Ester and the mixing of five fluorine propyl ester of methacrylic acid, carry out emulsion polymerization by initiator of perfluor dicapryl peroxide, obtain fluorine-containing
Polymerization of acrylic modified polyurethane lotion.
Preferably, the weight ratio of the Toluene-2,4-diisocyanate, 4- diisocyanate and poly- ethanedioic acid butyl glycol ester diol is 3-8:2-
7。
Preferably, the polyurethane macromolecular, perfluor dicapryl peroxide, methyl methacrylate and methacrylic acid
The weight ratio of five fluorine propyl ester is 3-20:0.3-0.6:5-15:5-20.
Preferably, the organosilicon modified crylic acid resin is prepared according to following technique: trim,ethylchlorosilane, silane is even
Join agent KH-550, hydroquinone, ethyl alcohol to be uniformly mixed, deionized water is then added, heats up, insulation reaction is quiet after reaction
Layering is set, water layer is removed and washed organic layer is to neutrality, vacuum distillation obtains intermediate product；By obtained intermediate product and ring four
Siloxanes mixing, is added dropwise dense H2SO4After reacted, be evaporated under reduced pressure after reaction, obtain organosiloxane oligomers；Will
To organosiloxane oligomers, anionic emulsifier, methyl methacrylate and butyl acrylate be added to deionized water
In, caused with peroxide type initiators and carry out emulsion polymerization, obtains the organosilicon modified crylic acid resin.
Preferably, the organosiloxane oligomers are the 6- of methyl methacrylate and butyl acrylate total weight
8wt%.
Preferably, the modified calcinated kaolin is silane coupler modified calcined kaolin, and the silane coupling agent is
KH-570。
Preferably, the modified calcinated kaolin is prepared according to following technique: by weight that 10-15 parts of calcinings are high
Ridge soil is dispersed in 200-300 parts of water, and 0.2-2.0 parts of sodium metnylene bis-naphthalene sulfonate and 5-10 parts of silane coupling agents is then added
KH-570, ball milling 30-60min are dried at 80-90 DEG C, and sieving obtains the modified calcinated kaolin.
Preferably, the anti-settling agent is organobentonite；The coalescing agent is Lauryl Alcohol ester；The defoaming agent is to disappear
Infusion BYK028；The levelling agent is levelling agent BYK333.
Water-fast stain-resistant exterior wall coating of the present invention is prepared according to following technique: by the deionized water of formula ratio, titanium white
Powder, natural porous silica flour, modified calcinated kaolin, zinc oxide, ceramic hollow microballon and anti-settling agent mixing, are uniformly mixing to obtain
Then methacrylic acid polydimethylsiloxanes base Arrcostab, fluorinated acrylate is added in mixture, the mixture ball milling that will be obtained
Modified polyurethane emulsion, organosilicon modified crylic acid resin, defoaming agent, levelling agent and coalescing agent, stir evenly.
The present invention prepares the process of fluorinated acrylate modified polyurethane emulsion are as follows: uses seed emulsion polymerization system first
The standby polyurethane macromolecular containing unsaturated double-bond, i.e., pass through Toluene-2,4-diisocyanate, 4- diisocyanate and poly- ethanedioic acid fourth in organic phase
The reaction of glycol esterdiol, is made base polyurethane prepolymer for use as, and base polyurethane prepolymer for use as and dihydromethyl propionic acid carry out chain extension later, passes through control
The ratio of-NCO and-OH in polymerization system processed, base polyurethane prepolymer for use as after making chain extension with-NCO sealing end, later with 2- hydroxyl second
Methyl acrylate phosphate reaction, to obtain the polyurethane macromolecular containing unsaturated double-bond, then to contain unsaturated double-bond
Polyurethane macromolecular, five fluorine propyl ester monomer of methacrylic acid and methyl methacrylate are raw material, by using suitable initiation
System causes copolymerization, thus the fluorinated acrylate modified polyurethane emulsion for the core-shell structure being had good stability；Wherein, gather
Urethane segment is shell structure, and the segment that polymethyl methacrylate and five fluorine propyl ester of polymethylacrylic acid are formed is nuclear structure, by
There is different glass transition temperatures in stratum nucleare and shell, soft phase can deform to form continuous phase in film forming, and hard phase is then assigned
The higher hardness of film is given, to increase substantially the surface hardness of film in the case where keeping good filming performance；This hair
It is bright fluorine element to be introduced while fluorinated acrylate modified polyurethane by chain extender, it is modified, it is further to improve
The water resistance and corrosion resistance of paint film.
On the other hand, the present invention prepares organosiloxane in the process for preparing organosilicon modified crylic acid resin first
Trim,ethylchlorosilane, silane resin acceptor kh-550, hydroquinone, ethyl alcohol are uniformly mixed by oligomer, deionized water is added,
Heating, insulation reaction, stratification, removes water layer and washed organic layer is to neutrality, vacuum distillation obtains centre after reaction
Product mixes obtained intermediate product with cyclotetrasiloxane, and dense H is added dropwise2SO4After reacted, after reaction decompression steam
It evaporates, so that the organosiloxane oligomers are obtained, using the organosiloxane oligomers, the polysiloxanes segment contained by it
Density is higher, can increase organosilicon in the distribution density of surface of the paint film, further enhance the hard of organosilicon modified crylic acid resin
Degree and compactness, weaken the sucking contact scar of paint film, to further increase the stain resistance of paint film；It will be above-mentioned organic-silicon-modified
Acrylic resin in fluorinated acrylate modified polyurethane emulsion mixing film forming procedure, it is cooperation modified calcinated kaolin, natural
Porous konilite, zinc oxide and ceramic hollow microballon are remarkably improved the heat-proof quality, hardness and wearability of paint film；And due to
Contain zirconium dioxide in natural porous konilite, property is stablized, and hardness is high, in addition porous structure has coating preferably
Hardness shows higher shock resistance, and inexpensive can reduce the cost of coating, while substituting barium sulfate to reduce
The content of soluble barium, meet the requirement of environmental protection in product, then cooperate the appropriate low surface energy auxiliary agent coalescing agent of selection, levelling agent and
Anti-settling agent, and the surface energy and water absorption rate of paint film can be reduced, dust is sticked to be effectively reduced exterior coating, improves it
Contaminated resistance；Exterior coating proposed by the present invention has hardness height, water-tolerant, stain resistance good and with long service life
Feature.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of water-fast stain-resistant exterior wall coating proposed by the present invention, raw material include: that fluorinated acrylate changes by weight
40 parts of polyaminoester emulsion of property, 35 parts of organosilicon modified crylic acid resin, 2 parts of methacrylic acid polydimethylsiloxanes base Arrcostab,
5 parts of modified calcinated kaolin, 2 parts of titanium dioxide, 3 parts of zinc oxide, 2 parts of ceramic hollow microballon, 2 parts of natural porous konilite, film forming
0.5 part of auxiliary agent, 2 parts of anti-settling agent, 2 parts of levelling agent, 2 parts of defoaming agent, 60 parts of deionized water.
Embodiment 2
A kind of water-fast stain-resistant exterior wall coating proposed by the present invention, raw material include: that fluorinated acrylate changes by weight
50 parts of polyaminoester emulsion of property, 25 parts of organosilicon modified crylic acid resin, 5 parts of methacrylic acid polydimethylsiloxanes base Arrcostab,
3 parts of modified calcinated kaolin, 6 parts of titanium dioxide, 4 parts of zinc oxide, 6 parts of ceramic hollow microballon, 8 parts of natural porous konilite, film forming
2 parts of auxiliary agent, 3 parts of anti-settling agent, 3 parts of levelling agent, 1 part of defoaming agent, 80 parts of deionized water.
Embodiment 3
A kind of water-fast stain-resistant exterior wall coating proposed by the present invention, raw material include: that fluorinated acrylate changes by weight
30 parts of polyaminoester emulsion of property, 20 parts of organosilicon modified crylic acid resin, 1 part of methacrylic acid polydimethylsiloxanes base Arrcostab,
1 part of modified calcinated kaolin, 5 parts of titanium dioxide, 0.5 part of zinc oxide, 4 parts of ceramic hollow microballon, 6 parts of natural porous konilite, at
3 parts of film auxiliary agent, 1 part of anti-settling agent, 1 part of levelling agent, 3 parts of defoaming agent, 70 parts of deionized water；
Wherein, the fluorinated acrylate modified polyurethane emulsion is prepared according to following technique: by Toluene-2,4-diisocyanate, bis- isocyanide of 4-
Acid esters and the mixing of poly- ethanedioic acid butyl glycol ester diol, are warming up to 80 DEG C of progress prepolymerization reaction 2h, are cooled to 70 DEG C, are then added 2,
2- dihydromethyl propionic acid, diglycol, dibutyl tin dilaurate, diamine 2, bis- [4- (4- amino-benzene oxygen) benzene of 2-
Base] hexafluoropropane carries out chain extending reaction 2h, and acetone is added and adjusts viscosity, 2- hydroxyethyl methacrylate phosphorus is then added
Acid esters after reaction, is added triethylamine and neutralizes, obtain polyurethane macromolecular in 60 DEG C of progress end capping reaction 4h；By what is obtained
Polyurethane macromolecular is mixed with methyl methacrylate, five fluorine propyl ester of methacrylic acid, and perfluor dicapryl peroxide is added, in
80 DEG C of progress emulsion polymerization 6h, obtain fluorinated acrylate modified polyurethane emulsion；
The weight ratio of the Toluene-2,4-diisocyanate, 4- diisocyanate and poly- ethanedioic acid butyl glycol ester diol is 3:7；
The polyurethane macromolecular, five fluorine third of perfluor dicapryl peroxide, methyl methacrylate and methacrylic acid
The weight ratio of ester is 10:0.3:5:15.
Embodiment 4
A kind of water-fast stain-resistant exterior wall coating proposed by the present invention, raw material include: that fluorinated acrylate changes by weight
40 parts of polyaminoester emulsion of property, 30 parts of organosilicon modified crylic acid resin, 3 parts of methacrylic acid polydimethylsiloxanes base Arrcostab,
2 parts of modified calcinated kaolin, 5 parts of titanium dioxide, 2 parts of zinc oxide, 3 parts of ceramic hollow microballon, 6 parts of natural porous konilite, film forming
3 parts of auxiliary agent, 1 part of anti-settling agent, 1 part of levelling agent, 2 parts of defoaming agent, 70 parts of deionized water；
Wherein, the fluorinated acrylate modified polyurethane emulsion is prepared according to following technique: by Toluene-2,4-diisocyanate, bis- isocyanide of 4-
Acid esters and the mixing of poly- ethanedioic acid butyl glycol ester diol, are warming up to 80 DEG C of progress prepolymerization reaction 2h, are cooled to 70 DEG C, are then added 2,
2- dihydromethyl propionic acid, diglycol, dibutyl tin dilaurate, diamine 2, bis- [4- (4- amino-benzene oxygen) benzene of 2-
Base] hexafluoropropane carries out chain extending reaction 2h, and acetone is added and adjusts viscosity, 2- hydroxyethyl methacrylate phosphorus is then added
Acid esters after reaction, is added triethylamine and neutralizes, obtain polyurethane macromolecular in 60 DEG C of progress end capping reaction 4h；By what is obtained
Polyurethane macromolecular is mixed with methyl methacrylate, five fluorine propyl ester of methacrylic acid, and perfluor dicapryl peroxide is added, in
Emulsion polymerization 6h is carried out at 80 DEG C, obtains fluorinated acrylate modified polyurethane emulsion；
The weight ratio of the Toluene-2,4-diisocyanate, 4- diisocyanate and poly- ethanedioic acid butyl glycol ester diol is 8:2；
The polyurethane macromolecular, five fluorine third of perfluor dicapryl peroxide, methyl methacrylate and methacrylic acid
The weight ratio of ester is 20:0.3:5:5；
The organosilicon modified crylic acid resin is prepared according to following technique: by trim,ethylchlorosilane, silane coupling agent KH-
550, hydroquinone, ethyl alcohol are uniformly mixed, and deionized water is then added, and are heated up, insulation reaction, after reaction stratification,
It removes water layer and washed organic layer is to neutrality, vacuum distillation obtains intermediate product；By obtained intermediate product and cyclotetrasiloxane
Mixing, is added dropwise dense H2SO4After reacted, be evaporated under reduced pressure after reaction, obtain organosiloxane oligomers；Have what is obtained
Organic siloxane oligomer, anionic emulsifier, methyl methacrylate and butyl acrylate are added into deionized water, with mistake
Oxide-based initiator, which causes, carries out emulsion polymerization, obtains the organosilicon modified crylic acid resin.
The organosiloxane oligomers are the 7wt% of methyl methacrylate and butyl acrylate total weight；
The modified calcinated kaolin is silane coupler modified calcined kaolin, and the silane coupling agent is KH-570.
Embodiment 5
A kind of water-fast stain-resistant exterior wall coating proposed by the present invention, raw material include: that fluorinated acrylate changes by weight
45 parts of polyaminoester emulsion of property, 25 parts of organosilicon modified crylic acid resin, 3 parts of methacrylic acid polydimethylsiloxanes base Arrcostab,
2 parts of modified calcinated kaolin, 5 parts of titanium dioxide, 1 part of zinc oxide, 3 parts of ceramic hollow microballon, 6 parts of natural porous konilite, 12
3 parts of carbon alcohol ester, 1 part of organobentonite, 2 parts of levelling agent BYK333,2 parts of defoaming agent BYK028,70 parts of deionized water；
Wherein, the fluorinated acrylate modified polyurethane emulsion is prepared according to following technique: by Toluene-2,4-diisocyanate, bis- isocyanide of 4-
Acid esters and the mixing of poly- ethanedioic acid butyl glycol ester diol, are warming up to 80 DEG C of progress prepolymerization reaction 2h, are cooled to 70 DEG C, are then added 2,
2- dihydromethyl propionic acid, diglycol, dibutyl tin dilaurate, diamine 2, bis- [4- (4- amino-benzene oxygen) benzene of 2-
Base] hexafluoropropane carries out chain extending reaction 2h, and acetone is added and adjusts viscosity, 2- hydroxyethyl methacrylate phosphorus is then added
Acid esters after reaction, is added triethylamine and neutralizes, polyurethane macromolecular is obtained, by what is obtained in 60 DEG C of progress end capping reaction 4h
Polyurethane macromolecular is mixed with methyl methacrylate, five fluorine propyl ester of methacrylic acid, is to draw with perfluor dicapryl peroxide
Emulsion polymerization 6h is carried out at 80 DEG C of agent of hair, obtains fluorinated acrylate modified polyurethane emulsion；
The weight ratio of the Toluene-2,4-diisocyanate, 4- diisocyanate and poly- ethanedioic acid butyl glycol ester diol is 3:7；
The polyurethane macromolecular, five fluorine third of perfluor dicapryl peroxide, methyl methacrylate and methacrylic acid
The weight ratio of ester is 3:0.6:15:12；
The organosilicon modified crylic acid resin is prepared according to following technique: by trim,ethylchlorosilane, silane coupling agent KH-
550, hydroquinone, ethyl alcohol are uniformly mixed, and deionized water is then added, is warming up to 75 DEG C, insulation reaction 3h, quiet after reaction
Layering is set, water layer is removed and washed organic layer is to neutrality, vacuum distillation obtains intermediate product；By obtained intermediate product and ring four
Siloxanes mixing, is added dropwise dense H2SO4After carry out reaction 2h, be evaporated under reduced pressure after reaction, obtain organosiloxane oligomers；It will
Obtained organosiloxane oligomers, anionic emulsifier, methyl methacrylate and butyl acrylate is added to deionization
In water, with peroxide type initiators in 80 DEG C of progress emulsion polymerization 6h, organosilicon modified crylic acid resin is obtained；
The organosiloxane oligomers are the 6wt% of methyl methacrylate and butyl acrylate total weight；
The modified calcinated kaolin is prepared according to following technique: 10 parts of calcined kaolins are dispersed to 200 parts of water
In, 0.2 part of sodium metnylene bis-naphthalene sulfonate then is added and 5 parts of Silane coupling reagent KH-570s, ball milling 40min dry at 85 DEG C
Dry, sieving obtains modified calcinated kaolin.
Embodiment 6
A kind of water-fast stain-resistant exterior wall coating proposed by the present invention, raw material include: that fluorinated acrylate changes by weight
40 parts of polyaminoester emulsion of property, 30 parts of organosilicon modified crylic acid resin, 4 parts of methacrylic acid polydimethylsiloxanes base Arrcostab,
2 parts of modified calcinated kaolin, 5 parts of titanium dioxide, 1 part of zinc oxide, 2 parts of ceramic hollow microballon, 3 parts of natural porous konilite, 12
2 parts of carbon alcohol ester, 1 part of anti-settling agent, 2 parts of levelling agent, 3 parts of defoaming agent, 70 parts of deionized water；
Wherein, the fluorinated acrylate modified polyurethane emulsion is prepared according to following technique: by Toluene-2,4-diisocyanate, bis- isocyanide of 4-
Acid esters and the mixing of poly- ethanedioic acid butyl glycol ester diol, are warming up to 80 DEG C of progress prepolymerization reaction 2h, are cooled to 70 DEG C, are then added 2,
2- dihydromethyl propionic acid, diglycol, dibutyl tin dilaurate, diamine 2, bis- [4- (4- amino-benzene oxygen) benzene of 2-
Base] hexafluoropropane carries out chain extending reaction 2h, and acetone is added and adjusts viscosity, 2- hydroxyethyl methacrylate phosphorus is then added
Acid esters after reaction, is added triethylamine and neutralizes, polyurethane macromolecular is obtained, by what is obtained in 60 DEG C of progress end capping reaction 4h
Polyurethane macromolecular is mixed with methyl methacrylate, five fluorine propyl ester of methacrylic acid, is to draw with perfluor dicapryl peroxide
Emulsion polymerization 6h is carried out at 80 DEG C of agent of hair, obtains fluorinated acrylate modified polyurethane emulsion；
The weight ratio of the Toluene-2,4-diisocyanate, 4- diisocyanate and poly- ethanedioic acid butyl glycol ester diol is 8:5；
The polyurethane macromolecular, five fluorine third of perfluor dicapryl peroxide, methyl methacrylate and methacrylic acid
The weight ratio of ester is 3:0.6:15:10；
The organosilicon modified crylic acid resin is prepared according to following technique: by trim,ethylchlorosilane, silane coupling agent KH-
550, hydroquinone, ethyl alcohol are uniformly mixed, and deionized water is then added, and are heated up, insulation reaction, after reaction stratification,
It removes water layer and washed organic layer is to neutrality, vacuum distillation obtains intermediate product；By obtained intermediate product and cyclotetrasiloxane
Mixing, is added dropwise dense H2SO4After reacted, be evaporated under reduced pressure after reaction, obtain organosiloxane oligomers；Have what is obtained
Organic siloxane oligomer, anionic emulsifier, methyl methacrylate and butyl acrylate are added into deionized water, with mistake
Oxide-based initiator, which causes, carries out emulsion polymerization, obtains the organosilicon modified crylic acid resin；
The organosiloxane oligomers are the 8wt% of methyl methacrylate and butyl acrylate total weight；
The modified calcinated kaolin is prepared according to following technique: being by weight dispersed to 15 parts of calcined kaolins
In 300 parts of water, it is then added 2.0 parts of sodium metnylene bis-naphthalene sulfonate and 10 parts of Silane coupling reagent KH-570s, ball milling 60min,
It is dried at 90 DEG C, is sieved, obtains modified calcinated kaolin.
Embodiment 7
A kind of water-fast stain-resistant exterior wall coating, raw material include: fluorinated acrylate modified polyurethane emulsion by weight
48 parts, 32 parts of organosilicon modified crylic acid resin, 5 parts of methacrylic acid polydimethylsiloxanes base Arrcostab, modified calcining kaolinite
4 parts of soil, 3 parts of zinc oxide, 3 parts of ceramic hollow microballon, 6 parts of natural porous konilite, 2 parts of Lauryl Alcohol ester, has 4 parts of titanium dioxide
1 part of machine bentonite, 1 part of levelling agent BYK333,2 parts of defoaming agent BYK028,80 parts of deionized water；
Wherein, the fluorinated acrylate modified polyurethane emulsion is prepared according to following technique: by Toluene-2,4-diisocyanate, bis- isocyanide of 4-
Acid esters and the mixing of poly- ethanedioic acid butyl glycol ester diol, are warming up to 80 DEG C of progress prepolymerization reaction 2h, are cooled to 70 DEG C, are then added 2,
2- dihydromethyl propionic acid, diglycol, dibutyl tin dilaurate, diamine 2, bis- [4- (4- amino-benzene oxygen) benzene of 2-
Base] hexafluoropropane carries out chain extending reaction 2h, and acetone is added and adjusts viscosity, 2- hydroxyethyl methacrylate phosphorus is then added
Acid esters after reaction, is added triethylamine and neutralizes, polyurethane macromolecular is obtained, by what is obtained in 60 DEG C of progress end capping reaction 4h
Polyurethane macromolecular is mixed with methyl methacrylate, five fluorine propyl ester of methacrylic acid, is to draw with perfluor dicapryl peroxide
Emulsion polymerization 6h is carried out at 80 DEG C of agent of hair, obtains fluorinated acrylate modified polyurethane emulsion；
The weight ratio of the Toluene-2,4-diisocyanate, 4- diisocyanate and poly- ethanedioic acid butyl glycol ester diol is 3:2；
The polyurethane macromolecular, five fluorine third of perfluor dicapryl peroxide, methyl methacrylate and methacrylic acid
The weight ratio of ester is 20:0.5:5:20；
The organosilicon modified crylic acid resin is prepared according to following technique: by trim,ethylchlorosilane, silane coupling agent KH-
550, hydroquinone, ethyl alcohol are uniformly mixed, and deionized water is then added, is warming up to 75 DEG C, insulation reaction 3h, quiet after reaction
Layering is set, water layer is removed and washed organic layer is to neutrality, vacuum distillation obtains intermediate product；By obtained intermediate product and ring four
Siloxanes mixing, is added dropwise dense H2SO4After carry out reaction 2h, be evaporated under reduced pressure after reaction, obtain organosiloxane oligomers；It will
Obtained organosiloxane oligomers, anionic emulsifier, methyl methacrylate and butyl acrylate is added to deionization
In water, with peroxide type initiators in 80 DEG C of progress emulsion polymerization 6h, the organosilicon modified crylic acid resin is obtained；
The organosiloxane oligomers are the 7wt% of methyl methacrylate and butyl acrylate total weight；
The modified calcinated kaolin is prepared according to following technique: 12 parts of calcined kaolins being dispersed to 150 by weight
In part water, 0.5 part of sodium metnylene bis-naphthalene sulfonate and 8 parts of Silane coupling reagent KH-570s, ball milling 60min, at 90 DEG C is then added
Drying crosses 80 meshes, obtains modified calcinated kaolin.
Paint film after the paint solidification obtained to embodiment 1-7 is tested for the property, wherein uses deionized water and coating
Contact angle characterize the water resistance of coating；The contact angle instrument produced using Shanghai Zhongchen digital technology equipment Co., Ltd
The contact angle of testing coating and water, the planarization of iron matrix is extremely important when test, so should ensure that the smooth of matrix before test
Property, make it on tester horizontal platform without inclination and gap, is also cleaned using ethyl alcohol before coating test.
1, water resistance test
The latex film dried completely is cut into 30mm × 30mm size, claims its mass M1, impregnate in water at room temperature
For 24 hours, taking-up dries surface moisture with filter paper, claims its mass M2, then water absorption rate=(M2-M1)/M1× 100%.
2, contact angle test
Polymer emulsion is applied on glass slide, is placed on after natural drying on the objective table of contact angle instrument, with distillation
For aquametry glue film to the static contact angle of water, the test result of water resistance and contact angle is shown in Table 1
Table 1
As can be known from Table 1, the water resistance and hydrophobicity of latex film are higher, this is because the low-surface-energy of fluorine make its
To the surface migration of film during polymer film forming, it is enriched in film surface, the surface energy of paint film is reduced, improves hydrophobic
Property.
3, stain resistance is tested
The test of paint film stain resistance is carried out referring to national standard GB/T 9780-2005, and flyash is standard flyash.Test knot
Fruit shows that at room temperature the loss of whiteness rate for the paint film that the present invention obtains is respectively less than 5%, and contaminated resistance is good.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of water-fast stain-resistant exterior wall coating, which is characterized in that its raw material includes: that fluorine-containing is ester modified poly- by weight
30-50 parts of urethane lotion, 20-35 parts of organosilicon modified crylic acid resin, methacrylic acid polydimethylsiloxanes base Arrcostab 1-5
Part, 1-5 parts of modified calcinated kaolin, 2-6 parts of titanium dioxide, 0.5-4 parts of zinc oxide, 2-6 parts of ceramic hollow microballon, natural porous powder
2-8 parts quartzy, 0.5-3 parts of coalescing agent, 1-3 parts of anti-settling agent, 1-3 parts of levelling agent, 1-3 parts of defoaming agent, deionized water 60-80
Part.
2. water-fast stain-resistant exterior wall coating according to claim 1, which is characterized in that the fluorine-containing is ester modified poly-
Urethane lotion is prepared according to following technique: first with Toluene-2,4-diisocyanate, 4- diisocyanate and poly- ethanedioic acid butyl glycol ester diol are original
Material carries out prepolymerization reaction, and 2,2- dihydromethyl propionic acid, diglycol, dibutyl tin dilaurate, diamine is then added
2,2- bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane carry out chain extending reaction, and acetone is added and adjusts viscosity, are then added
2- hydroxyethyl methacrylate phosphate carries out end capping reaction, after reaction, triethylamine is added and neutralizes, obtains polyurethane
Macromolecular；Obtained polyurethane macromolecular is mixed with methyl methacrylate, five fluorine propyl ester of methacrylic acid, it is pungent with perfluor two
Base peroxide is that initiator carries out emulsion polymerization, obtains fluorinated acrylate modified polyurethane emulsion.
3. water-fast stain-resistant exterior wall coating according to claim 2, which is characterized in that the Toluene-2,4-diisocyanate, 4- diisocyanate
The weight ratio of ester and poly- ethanedioic acid butyl glycol ester diol is 3-8:2-7.
4. water-fast stain-resistant exterior wall coating according to claim 2, which is characterized in that the polyurethane macromolecular, perfluor
The weight ratio of five fluorine propyl ester of dicapryl peroxide, methyl methacrylate and methacrylic acid is 3-20:0.3-0.6:5-15:
5-20。
5. water-fast stain-resistant exterior wall coating according to claim 1-4, which is characterized in that described organic-silicon-modified
Acrylic resin is prepared according to following technique: trim,ethylchlorosilane, silane resin acceptor kh-550, hydroquinone, ethyl alcohol are mixed
Uniformly, deionized water is then added, heats up, insulation reaction, stratification, removes water layer and washed organic layer extremely after reaction
Neutrality obtains intermediate product after vacuum distillation；Obtained intermediate product is mixed with cyclotetrasiloxane, dense H is added dropwise2SO4After carry out
Reaction, is evaporated under reduced pressure after reaction, obtains organosiloxane oligomers；By obtained organosiloxane oligomers, anion
Type emulsifier, methyl methacrylate and butyl acrylate are added into deionized water, cause cream with peroxide type initiators
Liquid polymerization, obtains organosilicon modified crylic acid resin.
6. water-fast stain-resistant exterior wall coating according to claim 5, which is characterized in that the organosiloxane oligomers are
The 6-8wt% of methyl methacrylate and butyl acrylate total weight.
7. water-fast stain-resistant exterior wall coating according to claim 1-6, which is characterized in that the modified calcining is high
Ridge soil is silane coupler modified calcined kaolin, and the silane coupling agent is KH-570.
8. water-fast stain-resistant exterior wall coating according to claim 1-7, which is characterized in that the anti-settling agent is to have
Machine bentonite, the coalescing agent are Lauryl Alcohol ester, and the defoaming agent is defoaming agent BYK028, and the levelling agent is levelling agent
BYK333。
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