CN106147588A - One group is applied to the aqueous finish paint of 25 type passenger vehicles, varnish and preparation method thereof - Google Patents
One group is applied to the aqueous finish paint of 25 type passenger vehicles, varnish and preparation method thereof Download PDFInfo
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- CN106147588A CN106147588A CN201610580005.5A CN201610580005A CN106147588A CN 106147588 A CN106147588 A CN 106147588A CN 201610580005 A CN201610580005 A CN 201610580005A CN 106147588 A CN106147588 A CN 106147588A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Inorganic Chemistry (AREA)
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Abstract
The present invention relates to one group and be applied to the aqueous finish paint of 25 type passenger vehicles, varnish and preparation method thereof, belong to technical field of coatings.Finish paint includes waterborne acrylic ester-polyurethane resin emulsion, pigment, nano barium sulfate, aqueous dispersion, aqueous defoamer, surfactant, nertralizer, aqueous anti ultraviolet agent, aqueous polyamide wax slurry, deionized water, coalescents；Varnish includes waterborne acrylic ester-polyurethane resin emulsion, aqueous flatting silica, aqueous dispersion, aqueous defoamer, waterborne organic silicon levelling agent surfactant, nertralizer, aqueous anti ultraviolet agent, aqueous polyamide wax slurry, deionized water, coalescents.This kind of product has drying speed, hardness is high, resist sagging is good, the feature that weatherability, resistance to butanone performance, chemical resistance and composite bed salt fog resistance are the most excellent.
Description
Technical field
The present invention relates to one group and be applied to the aqueous finish paint of 25 type passenger vehicles, varnish and preparation method thereof, belong to coating technology
Field.
Background technology
In order to improve Steel Structure of Passenger Car anticorrosive quality, specification bus anticorrosion coating process, shipping office of Chinese Railway head office
Vehicle portion has organized bus anticorrosion coating process specification seminar on January 22nd, 2015 in Beijing, has promulgated " 25 type visitors
Car anticorrosive coating technological specification (trying) " and the trail run notice of " 25 type passenger vehicles with coating technology condition (trying) ", notice rule
Determine to be applied to outside car body side, end wall panel steel construction use " anti-corrosive primer+(putty)+floating coating+base coat+coating varnish "
Coating process, in this coating four kinds paints all list the execution standard of oleaginous system, and wherein anti-corrosive primer salt spray resistance reaches
500h, base coat and coating varnish require the highest, repair in shop standard requires gloss control 70 ± 5%, varnish fineness requirement≤
10 microns, and require that the wipe test of resistance to butanone 50 times paint film back and forth is the most unchanged, and require resistance to acids and bases and weather-proof
Property reaches 1000h.
Summary of the invention
In response to the call that country is to environmental requirement, the present invention is directed to be satisfied with this standard-required and designed and developed one
The corresponding product of a whole set of aqueous, environmental protective system, combination property is entirely capable of being satisfied with standard-required, can be widely used in 25 type visitors
The application on car surface.
It is applied to the aqueous finish paint of 25 type passenger vehicles, varnish,
Finish paint wherein includes following component by weight percentage:
Waterborne acrylic ester-polyurethane resin emulsion 50～60%, pigment 3～26%, nano barium sulfate 5～20%, aqueous dispersion 0.3
～0.5%, aqueous defoamer 0.2～0.4%, surfactant 0.1～0.2%, nertralizer 0.2～0.6%, aqueous anti ultraviolet agent
0.5～1%, aqueous polyamide wax slurry 2～4%, deionized water 11～13%, coalescents 1～2%；
Varnish wherein includes following component by weight percentage:
Waterborne acrylic ester-polyurethane resin emulsion 70～80%, aqueous flatting silica 0～12%, aqueous dispersion 0.3～0.5%, aqueous
Defoamer 0.1～0.2%, waterborne organic silicon levelling agent 0.2～2%, surfactant 0.2～0.4%, nertralizer 0.4～0.6%,
Aqueous anti ultraviolet agent 0.5～1%, aqueous polyamide wax slurry 1～2%, deionized water 7～14%, coalescents 2～4%.
Coating composition, includes above-mentioned aqueous finish paint, varnish, and first coordinated respectively with finish paint and varnish solid
Agent and the second firming agent, the weight ratio of described finish paint and the first firming agent is 100:(10～70)；Described varnish
It is 100:(10～70 with the weight ratio of the second firming agent)；First firming agent and the second firming agent are hydrophilic isocyanates
Resin curing agent.
Above-mentioned aqueous finish paint, the preparation method of varnish,
Wherein the preparation method of finish paint, comprises the steps:
1, deionized water, aqueous dispersion, aqueous defoamer, coalescents are added together employing 300～400 revs/min stirring 5
～10 minutes；
2, add pigment, nano barium sulfate, aqueous polyamide wax slurry, use 400～600 revs/min to stir 5～10 minutes, use
Sand mill is ground to fineness and reaches less than 20 microns；
3, adding aqueous acrylic urethane resins uses 400～600 revs/min to stir 15～20 minutes；
4, limit use 400～600 revs/min add surfactant, aqueous anti ultraviolet agent while stirring, use 400～600 turns/
Dispersion 15～20 minutes, uses nertralizer to adjust pH value between 8～9.
Wherein the preparation method of varnish, comprises the steps:
1, waterborne acrylic ester-polyurethane resin emulsion is added in production cylinder；
2, deionized water is used to add after aqueous dispersion, aqueous defoamer, waterborne organic silicon levelling agent, surface activity dilution agent
Enter and produce in cylinder, use 300～400 revs/min to stir 5～10 minutes；
3, add aqueous flatting silica, aqueous polyamide wax slurry uses 500～600 revs/min to stir 15～20 minutes；
4, add aqueous anti ultraviolet agent, use nertralizer adjust pH value between 8～9, uses 400～500 revs/min stir 5～
10 minutes.
Beneficial effect
The finish paint of this kind of product has drying speed, hardness is high, resist sagging is good, and weatherability can reach more than 2000 hours, resistance to fourth
Ketone performance can reach more than 1000 times, and chemical resistance is the most excellent；Varnish has drying speed, hardness is high, resist sagging is good,
Weatherability can reach more than 2000 hours, and resistance to butanone performance can reach more than 1 000 times, and chemical resistance and composite bed are resistance to
Salt fog the most excellent.
Detailed description of the invention
Below by detailed description of the invention, the present invention is described in further detail.But those skilled in the art will manage
Solving, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Unreceipted concrete skill in embodiment
Art or condition person, according to the technology described by the document in this area or condition or carried out according to product description.Examination used
Agent or instrument unreceipted production firm person, be can by city available from conventional products.
Additionally, the ordinal number used in the claims and specification such as " first ", " second ", " the 3rd " etc., it is used for
Modify claim rather than due to itself containing any preferentially, the order of formerly or one claim wants in another right
Before asking or perform method step time sequencing.But, use with difference such as with specific names as just label
Element and the another one of claim with the element (rather than belonging to for succession) of same names, distinguish power
The element that profit requires.Thus, define " first ", the feature of " second " can be expressed or implicitly include one or more
Individual this feature.
Word used herein " includes ", " comprising ", " having " or its any other variant are intended to non-exclusionism
Including.Such as, it is not necessarily limited by those key elements including listing the technique of key element, method, article or equipment, but can include
Other are not expressly set out or belong to the key element that this technique, method, article or equipment are intrinsic.
The value expressed using range format should be interpreted as in a flexible way not only including clearly listing as scope
The numerical value of limit value, but also include containing all single numerical value within the range or subinterval, just as each numerical value and Zi Qu
Between be expressly recited out.Such as, the concentration range of " about 0.1% to about 5% " should be understood to not only to include clearly to list
The concentration of about 0.1% to about 5%, also includes the single concentration (e.g., 1%, 2%, 3% and 4%) in the range of indication and subinterval (example
As, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).
Propose in the present invention is applied to the aqueous finish paint of 25 type passenger vehicles, varnish, is to be combined by finish compositions and varnish
The thing use that matches forms.
Wherein, finish paint includes following component by weight percentage: waterborne acrylic ester-polyurethane resin emulsion 50
～60%, pigment 3～26%, nano barium sulfate 5～20%, aqueous dispersion 0.3～0.5%, aqueous defoamer 0.2～0.4%, table
Face activating agent 0.1～0.2%, nertralizer 0.2～0.6%, aqueous anti ultraviolet agent 0.5～1%, aqueous polyamide wax slurry 2～4%, go
Ionized water 11～13%, coalescents 1～2%；
Varnish includes following component by weight percentage: waterborne acrylic ester-polyurethane resin emulsion 70～80%, aqueous
Flatting silica 0～12%, aqueous dispersion 0.3～0.5%, aqueous defoamer 0.1～0.2%, waterborne organic silicon levelling agent 0.2～2%,
Surfactant 0.2～0.4%, nertralizer 0.4～0.6%, aqueous anti ultraviolet agent 0.5～1%, aqueous polyamide wax slurry 1～2%,
Deionized water 7～14%, coalescents 2～4%.
Heretofore described acrylic ester-polyurethane resin emulsion, refers to acrylic monomer, polyhydric alcohol and isocyanates
Monomer copolymerization reacts the water-based emulsion obtained.
Here acrylic monomer, there is no particular limitation, can illustrate such as: (methyl) acrylic acid methyl ester. (refers to third
Any one of e pioic acid methyl ester or methyl methacrylate, lower with), (methyl) ethyl acrylate, (methyl) n-butyl acrylate,
(the first containing alkyl such as (methyl) Isobutyl 2-propenoate, (methyl) acrylic acid-2-ethyl caproite, (methyl) cyclohexyl acrylate
Base) acrylic monomer；(methyl) acrylic monomer containing hydroxyl such as (methyl) acrylic acid 2-hydroxy methacrylate；(methyl) third
The ethylene unsaturated carboxylic acids such as olefin(e) acid；(methyl) acrylate, (methyl) acrylate propyl ester
Deng (methyl) acrylic monomer containing amino；(methyl) acrylamide, ethyl (methyl) acrylamide etc. are containing amide
(methyl) acrylic monomer；(methyl) acrylic monomer containing itrile group such as acrylonitrile；(methyl) glycidyl
(methyl) acrylic monomer etc. containing epoxy radicals such as ester.
The polyol compound of the present invention is diol compound and three alcoholic compounds etc., the polyhydric alcohol used as the present invention
Composition, mainly uses PEPA, polycarbonate polyol or polyether polyol etc., wherein can use as polyurethane
The raw-material ordinary matter of resin, the most particularly specifies.More particularly, as PEPA, it is possible to use adjacent benzene
Dioctyl phthalate, M-phthalic acid, p-phthalic acid, naphthalene dicarboxylic acids, succinic acid, tartaric acid, malonic acid, ethanedioic acid, 1,3-propanedicarboxylic acid, oneself two
Acid, 1,5-pentanedicarboxylic acid., Azelaic Acid, Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α, β-diethyl
Base succinic acid, maleic acid, fumaric acid, other binary acid etc. one kind or two or more with ethylene glycol, 1,2-PD, 1,3-the third two
Alcohol, 1,2-butanediol, 1,3 butylene glycol, BDO, 1,5-PD, 1,6-hexanediol, 1,8-ethohexadiol, 1,9-nonyl two
Alcohol, 3-methyl isophthalic acid, 5-pentanediol, 3,3-dihydroxymethyl heptane, diethylene glycol, dipropylene glycol, neopentyl glycol, hexamethylene-Isosorbide-5-Nitrae-
Addition product, double (beta-hydroxyethyl) benzene, the benzene diformazans such as glycol, hexamethylene-Isosorbide-5-Nitrae-dimethanol, the oxirane of bisphenol-A, expoxy propane
The PEPA that the polycondensation reaction of the polyalcohols such as alcohol, other glycol or glycerol, trimethylolpropane, tetramethylolmethane obtains.
Further, it is also possible to it is (interior to enumerate the cyclic esters such as 6-caprolactone, alkyl replacement 6-caprolactone, δ-valerolactone, alkyl replacement δ-valerolactone
Ester) etc. the PEPA of lactone that obtains of the ring-opening polymerisation of monomer, it is also possible to use a part for low molecular polylol
Become the low molecule amines such as hexamethylene diamine, isophorone diamine, monoethanolamine, low molecule amino alcohol polyesteramide polynary
Alcohol etc..As polyether polyol, it is possible to use with glycols as mentioned, polyalcohols or they with ethylenediamine, propane diamine,
The amines such as toluenediamine, m-diaminobenzene., diphenylmethanediamiand, benzene dimethylamine have more than 2 like that, preferably 2-3 activity
The compound of hydrogen group as initiator, the alkylene such as the one kind or two or more oxirane of addition polymerization, expoxy propane, epoxy butane
The ring-type ethers such as alkyl or aryl (+)-2,3-Epoxy-1-propanol ethers, oxolane such as oxygen class, methyl glycidyl ether, phenyl glycidyl ether
The polyether polyol that monomer etc. obtain.As polycarbonate polyol, it is possible to use by low-molecular-weight diol class described above, low
The reaction of molecule triol and ethylene carbonate, diethyl carbonate, diphenyl carbonate etc. and the polycarbonate polyol that obtains.Separately
Outward, it is also possible to be suitably used the polyhydric alcohol generated by the ester exchange of polycarbonate polyol and PEPA.Other are also
Can use the polyol prepared by polyether polyol and omega-dicarboxylic acids and by polyester, Merlon and epoxide,
The polyester ether polylol that the reaction of cyclic ether obtains, it is also possible to use and there are more than 2 hydroxyls, polybutadiene, the poly-fourth of hydrogenation
The polyolefin polyhydric alcohol of diene, polyisoprene, hydrogenated polyisoprene etc..
As isocyanate-monomer, can list hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate,
The aliphatic diisocyanate compound such as dimer acid diisocyanate, lysinediisocyanate；These diisocyanate chemical combination
The biuret form addition product of thing, isocyanurate ring addition product；Isophorone diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl
Isocyanates), hexahydrotoluene-2,4-(or-2,6-) diisocyanate, 1,3-(or 1,4-) two (isocyanatomethyl)
Hexamethylene, 1,4-cyclohexane diisocyanate, 1,3-Pentamethylene. diisocyanate, 1,2-cyclohexane diisocyanate etc. are alicyclic
Diisocyanate cpd；The biuret form addition product of these diisocyanate, isocyanurate ring addition product；Dimethylbenzene two is different
Cyanate, m xylene diisocyanate, tetramethylxylene diisocyanate, toluene di-isocyanate(TDI), 4,4 '-diphenyl-methane
Diisocyanate, 1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 4,4 '-toluidine diisocyanate, 4,4 '-hexichol
Base ether isocyanates, (or to) phenylene diisocyanate, 4,4 '-biphenylene diisocyanate, 3,3 '-dimethyl-4,4 '-sub-
The aromatic series two such as biphenylene diisocyanate, double (4-isocyanatophenyi) sulfone, isopropylidene double (4-phenyl isocyanate)
Isocyanate compound；The biuret form addition product of these diisocyanate cpds, isocyanurate ring addition product；Triphenyl
Methane-4,4 ', 4 "-triisocyanate, 1,3,5-tri-isocyanato-benzene, 2,4,6-tri-isocyanato-toluene, 4,4 '-diformazan
Base diphenyl methane-2,2 ', 5,5 '-tetraisocyanate etc. has the polyisocyanic acid of more than three NCOs in 1 molecule
Ester compounds；The biuret form addition product of these polyisocyanate compounds, isocyanurate ring addition product；With relative to second two
The polyhydric alcohol such as alcohol, propylene glycol, 1,4-butanediol, dihydromethyl propionic acid, poly alkylene glycol, trimethylolpropane, hexane triol
Hydroxyl for NCO become the ratio of excess so that polyisocyanate compound and these polyhydric alcohol carry out reacting and
The urethane addition product become；The biuret form addition product of these urethane addition products, isocyanurate ring add
Become thing etc..
It addition, in the course of the polymerization process, it is also possible to add as can be permissible with other monomers of acrylic monomer copolymerization
Illustration has the aromatic hydrocarbon vinyl monomers such as styrene, methyl styrene, chlorostyrene, vinyl toluene；Maleic acid, itaconic acid,
α, the β-ethylene unsaturated carboxylic acids such as .beta.-methylacrylic acid, fumaric acid, citraconic acid；The second containing sulfonic acid such as styrene sulfonic acid, vinyl sulfonic acid
Alkene monomer；The anhydride of maleic anhydride, itaconic anhydride etc.；The chloride monomers such as vinyl chloride, vinylidene chloride, chlorobutadiene；Ethoxy
The alkyl vinyl ether containing hydroxyl such as vinyl ethers, hydroxypropyl vinyl ethers；Ethylene glycol monoallyl ether, propylene glycol monoene third
The alkylene glycol mono allyl ethers such as base ether diethylene glycol mono allyl ether；The alpha-olefins such as ethylene, propylene, isobutene.；Vinyl acetate
The vinyl acetate such as ester, propionate, vinyl butyrate, vinyl pivalate；Ethylene methacrylic ether, ethyl vinyl ether, butyl
The vinyl Ether such as vinyl Ether, cyclohexyl vinyl ether；The allyl ethers etc. such as ethyl allyl ether, butyl allyl ether.
About the manufacture of above-mentioned carbamate prepolymer, can carry out based on existing known method.
Above-mentioned acrylic monomers, isocyanates, monomeric polyol are gathered under the effect of catalyst and initiator
Close, after reaction terminates, then mix with defoamer, nertralizer, deionized water, emulsion can be prepared, be preferably used and turn
Phase emulsion process.First, in the oil adding emulsifying agent divides (containing the organic solvent of resin), add a small amount of water, mix, thus
W/o type emulsion can be obtained.Then, being slowly added into water, while making its phase inversion, O/W type emulsion may finally be obtained.
Device for mixing can enumerate the shaft mixer with rotating vane and homogenizer, homomixer, colloid mill etc..Separately
Outward, emulsifying temperature is preferably the scope of 10-80 DEG C, more preferably the scope of 20-30 DEG C.The mean diameter of emulsion is the most particularly
Limit, usually about 0.01-10 μm, about preferably 0.1-1 μm.Mean diameter, more than the occasion of 10 μm, is susceptible to sink
Fall, bad stability.
As polymerization initiator, existing known polymerization initiator can be used without restriction, include, for example out hexamethylene
Double (the t-butyl peroxy of ketone peroxide, 3,3,5 trimethyl hexanone peroxide, methyl cyclohexanone peroxide, 1,1-
Base)-3,3,5-trimethyl-cyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, the double (t-butyl peroxy of normal-butyl-4,4-
Base) valerate, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydro-peroxidase, the double (t-butyl peroxy of 1,3-
A change-isopropyl) benzene, 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, dicumyl peroxide, the tert-butyl group be withered
Base peroxide, decanol peroxide, lauroyl peroxide, benzoyl peroxide, 2,4 dichloro benzene formyl peroxidating
Thing, two t-amyl peroxy compounds, double (tert-butylcyclohexyl) peroxy dicarbonate, tert butyl peroxy benzoate, 2,
The peroxide type polymerization such as 5-dimethyl-2,5-two (benzoylperoxy) hexane, peroxidating-2-ethylhexanate
Initiator；Double-2-the methylbutyronitrile of 2,2 '-azo double (isopropyl cyanide), 2,2 '-azo, the double (hexamethylene-1-first of 1,1 '-azo
Nitrile), azocumene, 2,2 '-azo double (2-methylbutyronitrile), the double-2,4-methyl pentane nitrile of 2,2 '-azo, 4,4 '-azo double
(4-cyanopentanoic acid), 2-(tert-butyl group azo)-2-dicyanopropane, 2,2 '-azo double (2,4,4-trimethylpentane), 2,2 '-idol
Nitrogen double (2-methylpropane), 2,2 '-azo double [2-methyl-N-(2-ethoxy)-propionic acid amide .], dimethyl 2,2 '-azo are double
(2 Methylpropionic acid ester), 1,1 '-azo double (1-hexamethylene-1-formonitrile HCN), the double [2-(2-imidazoline-2-base) third of 2,2 '-azo
Alkane], dimethyl-2,2 ' the azo type polymerization initiator such as-azobisisobutylonitrile acid esters.
As nertralizer, if the nertralizer that carboxyl is neutralized then can be not particularly limited, such as, hydrogen can be enumerated
Sodium oxide, potassium hydroxide, trimethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propanol, triethylamine, ammonia etc..
It addition, the defoamer carrying out being used during emulsion polymerization is not particularly limited, include, for example dialkyl sulfosuccinate amber
Meticortene Solu-Delta-cortef, dodecylbenzene sodium sulfonate, sodium lauryl sulfate, polyethylene glycol oxide alkyl phenyl ether sodium sulfate and alkyl diphenyl base
The anionic emulsifiers such as ether sodium disulfonate, the nonionic such as polyoxyethylene higher alcohol ether and polyethylene glycol oxide alkyl phenyl ether
Property emulsifying agent and there is the anionic property of free-radical polymerised double bond or the reactive emulsifier of cationic.
Reactive emulsifier refers to the most together have nonionic group, anionic property group and cation
Property group in the group of wantonly more than a kind and the emulsifying agent of polymerism unsaturated group, as polymerism unsaturated group, tool
Body lists (methyl) pi-allyl, (methyl) acryloyl group, acrylic, cyclobutenyl etc..
Many usual coalescents can increase flowing, minimizing foam, and sometimes coalesces contributing to being spread coating
Freeze/thaw stability can also be improved while (this promotes to be formed more continuous print coating).Some coalescents are: lactate, 2-fourth
Ethoxy-ethanol, phthalic acid ester, 2-(2-Butoxyethoxy) ethanol, methyl phenyl carbinol, ethylene glycol, diethylene glycol, double
The monoesters of pyruvic alcohol, propylene glycol, ethylene glycol or propylene glycol and diester, etc..
Surfactant used in the present invention, such as, can enumerate dodecylbenzene sodium sulfonate, lauryl sulphate acid
The anion surfactants such as sodium；The nonionic surfactants such as polyoxyethylene laurel ether, ethylene nonyl phenylate；16
The cationic surfactant such as alkyl trimethyl ammonium bromide, cetylpyridinium chloride；The amphoteric surfaces such as lauryl betaine live
Property agent.
Delustering agent used in the present invention such as can enumerate white carbon, aluminium hydroxide, magnesium carbonate, brium carbonate, sulphuric acid
Barium, zinc sulfide have the function as delustering agent.
Wherein, as coloring pigment, the material can being matched with in coating typically can be used.Specifically, can be with example
Lift such as: titanium oxide, zinc oxide, white carbon black, dim, boneblack, graphite, black iron oxide, copper-chrome black, cobalt black, copper ferromanganese are black, oxidation
Iron oxide red, molybdate orange, permanent bordeaux, forever consolidate carmine, anthraquinone is red, red, quinacridone is red, yellow iron oxide, titan yellow, firmly yellow,
Benzimidazolone yellow, chrome green, cobalt green, phthalocyanine green, ultramarine, dark purple, cobalt blue, phthalocyanine blue, quinacridone violet, diazine purple, aluminum face
Material, pearl pigment etc., it is possible to use in them a kind or two or more.
In the components of waterborne paint of the present invention, in addition to mentioned component, it is also possible to mixing coloring pigment, filling face
Material, aggregate, other various compositions that can use in common coating, such as, membrane producing promoter, plasticizer, antifreeze, anticorrosion
Agent, antifungus agent, antibacterial, defoamer, pigment dispersing agent, viscosifier, levelling agent, wetting agent, pH regulator, fiber-like, disappear
Photo etching, UV absorbent, antioxidant, light stabilizer, adsorbent, catalyst, cross-linking agent etc..
The water-based paint compositions of the present invention can be containing the organic solvent dissolved in water.Tool as this organic solvent
Style, can list, ethylene glycol, propylene glycol, ethylene glycol monobutyl ether, glycol monobutyl ether, diethylene glycol, a contracting dipropyl two
Alcohol, diethylene glycol monobutyl ehter etc..From the viewpoint of reducing use VOC, the amount preferably making organic solvent is the fewest as far as possible.
The coating composition of the present invention has the metal deposit of excellent appearance by coating can be formed on various base material.
With coating composition of the present invention coatingBase materialDo not limit.PreferablyBase materialThe for example, car of automobile, motorcycle etc.
Body.Other available base material includes the material for forming above-mentioned car body, such as cold-rolled steel sheet, galvanized steel plain sheet, galvanized alloy steel
Plate, corrosion resistant plate, tin plate, other steel plate, aluminium sheet, aluminium alloy plate and other metal base；Various plastic materials；Deng.Base
Material can be that its metal surface has carried out the upper of surface process such as phosphate treated, chromate process, composite oxides process etc.
State car body or metal base.Additionally, base material can be to have the priming coat of various electrodeposition coating composition and/or middle painting
The above-mentioned car body of layer or metal substrate etc..
The method being coated with coating composition of the present invention does not limit, can be such as calm the anger spraying process, apneumatic spraying method,
Rotary-atomizing rubbing method, curtain coating method etc..Wet coating can be formed by above-mentioned coating process.Wherein, particularly preferably calm the anger spraying process
Deng.When applied coating composition, electrostatic can be applied as required.The amount of coating composition of the present invention to be coated with is
Compositions is made to form about 3,000 to about 8,000nm thick films when solidification.This amount is preferably so that compositions is when solidification
Form the film of thick about 3,000 to about 6,000nm.Additionally, the viscosity of adjusting coating compositions makes when by being coated with on base material
When the deposition coating that cloth coating composition is formed has 40wt% solid component content, deposition coating is at 20 DEG C and 0.1 s-1's
The viscosity measured under shear rate is 4 × 102To 1 × 104In the range of mPa s.Above-mentioned deposition coating viscosity is following mensuration
's.Coating composition sprayed on tin plating base material and stands 1 minute, then collecting deposition coating.Measure consolidating of deposition coating
Body component content and at 20 DEG C and 0.1s-1Viscosity under shear rate.Except making coating composition stand 2,5 or 10 minutes
Outward, the same solid component content measuring deposition coating as formed above and viscosity.The solid component content that will be measured respectively
(weight) and viscosity are indicated on abscissa and vertical coordinate, utilize the function obtained by method of least square to draw curve chart.By
Reading solid component content on this curve chart is deposition coating viscosity during 40wt%.Although the viscosity of deposition coating is with coating
Condition such as temperature, humidity etc. and change, but generally such as can regulate in the following way to above-mentioned scope: with organic molten
When the viscosity of agent and/or water suitable adjusting coating compositions makes to be coated with, the viscosity of coating composition is under 20 DEG C and 60rpm
By Brookfield viscometer mensuration about 50 to about 400cP, preferably from about 100 to about 200cP.
Can be by heating by the deposition curing of coatings on base material.Heating can be carried out by known heating means, such as, use
Drying oven such as hot-air furnace, electric furnace, infrared furnace etc. are carried out.Heating-up temperature is preferably from about 80 to about 180 DEG C, more preferably from about
100 to about 160 DEG C.Heat time heating time does not limit, typically about 20 to about 40 minutes.
The preparation of embodiment 1～4 priming paint
Raw material is as follows:
Aqueous acrylic urethane resins (2695Covestro)
Rutile type titanium dioxide (706 Du Pont)
Carbon black (the solid Sa of 6# carbon black enlightening)
Medium chrome yellow (south of the River, 103-2A GB medium chrome yellow Chongqing)
Phthalein dark green (the double happy chemical industry of G)
Permanent bordeaux (F5RK Hangzhou power standing grain)
Nano barium sulfate (BS80 Beijing gold zebra)
Aqueous polyamide wax slurry (it is prosperous that AQH-630 founds Hua in Shenzhen)
Aqueous dispersion (755W enlightening is high)
Aqueous defoamer (DF7072 engrave in sea this and DF675 Hai Mingsi mix according to 1:1)
Surfactant (OF Chengdu favour grace chemical industry)
Aqueous anti ultraviolet agent (1406 Beijing addition)
Coalescents (PDGA LG-DOW)
Nertralizer (AMP-95 engrave in sea this chemistry)
Hydrophilic isocyanate resin firming agent (N-3900Covestro)
Table 1: embodiment 1～embodiment 4 component formula proportioning
Preparation method is:
1, deionized water, aqueous dispersion, aqueous defoamer, coalescents are added together employing 300～400 revs/min stirring 5
～10 minutes；
2, add pigment, nano barium sulfate, aqueous flatting silica, aqueous polyamide wax slurry, uses 400～600 revs/min stir 5～
10 minutes, use sand mill to be ground to fineness and reach less than 20 microns；
3, adding aqueous acrylic urethane resins uses 400～600 revs/min to stir 15～20 minutes；
4, limit uses 400～600 revs/min of additions while stirring, aqueous wetting agent, surfactant, aqueous anti ultraviolet agents, uses
400～600 revs/min are disperseed 15～20 minutes.Nertralizer is used to adjust pH value between 8～9.
Dry plate realizes: use 1000 mesh fine sandpapers to carry out grinding process sheet metal (50mm × 120mm × 0.5mm)；On
State paint base composition: hydrophilic isocyanate curing agent=3:1 weight ratio proportioning, employing deionized-distilled water carries out spray viscosity
Adjustment, spray viscosity is adjusted to 20～25S(T～4 glasss), on sheet metal spray 2～3 layers, dry plate place 25 DEG C of constant temperature
From dry 48 hours detection traditional performances in case, test, after ripening 7d, the wipe test of resistance to butanone.
Test result is as follows:
As can be seen from the above table, this kind of product has drying speed, hardness is high, resist sagging is good, and weatherability can reach 2000 hours
Above, resistance to butanone performance can reach more than 1000 times, and chemical resistance is the most excellent；It addition, reference examples 1 adds aqueous due to water
Polyamide wax pulp, the weatherability that result in priming paint is bad.
The preparation of embodiment 5～9 varnish
In following example, the varnish of preparation, is mainly used in priming paint supporting.
Raw material is as follows:
Aqueous acrylic urethane resins (2470 Covestro)
Styrene-acrylic emulsion (Acronal7035, BASF)
Aqueous polyamide wax slurry (it is prosperous that AQH-630 founds Hua in Shenzhen)
Aqueous flatting silica (M2 Singapore is resistance to rich)
Aqueous dispersion (211 YCK)
Aqueous organic modified polyorganosiloxane polyether antifoam agent (Xingda's chemical industry is closed in 6700 Chengdu)
Waterborne organic silicon class levelling agent (3300 Chongqing wheat figure)
Surfactant (OF Chengdu favour grace chemical industry)
Aqueous anti ultraviolet agent (1406 Beijing addition)
Coalescents (PDGA LG-DOW)
Nertralizer (AMP-95 engrave in sea this chemistry)
Hydrophilic isocyanate resin firming agent (2695 Covestro)
The weight of raw material:
Preparation method is:
1, waterborne acrylic ester-polyurethane resin emulsion is added in production cylinder；
2, deionized water is used to add after aqueous dispersion, aqueous defoamer, waterborne organic silicon levelling agent, surface activity dilution agent
Enter and produce in cylinder, use 300-400 rev/min to stir 5-10 minute；
2, add aqueous flatting silica, aqueous polyamide wax slurry uses 500-600 rev/min to stir 15-20 minute；
4, add aquosity ultraviolet light absorbent, use nertralizer adjustment pH value between 8-9, use 400-500 rev/min of stirring 5-
10 minutes.
Dry plate realizes: by the varnish obtained made above with hydrophilic isocyanate curing agent according to weight ratio 3:1 proportioning,
Use deionized-distilled water to carry out the adjustment of spray viscosity, spray viscosity be adjusted to 20-25S(T-4 cup), according in upper table
Matching in embodiment 1～4 and the lacquer painting spraying layer 2-3 that obtains of reference examples 1, dry plate is placed in 25 DEG C of calorstats from inspection in dry 48 hours
Survey traditional performance, after ripening 7d, test the wipe test of resistance to butanone and chemical resistance test.It is simultaneously spraying at aqueous double-component background color
Painting, the composite bed obtained, its gross thickness controls at 90-130 m.
Testing result is as follows:
Note: high-low temperature resistant repeat experimental condition: 80 ± 2 DEG C, 95%RH4h, 80 DEG C to-40 DEG C 2h(ramp rates 1 DEG C/
Min) ,-40 ± 2 DEG C of 4h ,-40 DEG C to 80 DEG C, 1 DEG C/min of 95%RH2h(ramp rates), above 12h is a cycle, and model is 60
Periodic test is answered ambient temperatare to put more than 16h and is tested after completing；Carry out when coating layer thickness is for≤300 m drawing lattice examination
Test, during thickness≤80 below m, draw compartment away from for 1mm, during thickness 80-150 m, draw compartment away from for 2mm, thickness 150-300 m
Time, draw compartment away from for 3mm, during coating layer thickness ＞ 300 m, carry out X-cutting test.Because of its thickness all 150-300 micron it
Between, so using stroke compartment to test away from for 3mm.
As can be seen from the above table, this kind of product has drying speed, hardness is high, resist sagging is good, and weatherability can reach
More than 2000 hours, resistance to butanone performance can reach more than 1 000 times, and chemical resistance and composite bed salt fog resistance are the most excellent
Different.Wherein embodiment 8 is identical with the varnish of embodiment 9 composition, but is that the priming paint with embodiment 4 and reference examples 1 matches respectively
Set, owing to not adding aqueous polyamide wax slurry in reference examples 1, causes the matching between varnish bad, there is adhesive force
Low bad with effect in composite bed cross cut test, additionally there is also low temperature resistant and high temperatures bad.And embodiment 10 and enforcement
The difference of example 8 is by adding styrene-acrylic emulsion, improve varnish and high-low temperature resistant circulation between priming paint performance, through 60
It is maintained to after individual circulation that preferable paint film is complete and tack.
Claims (3)
1. it is applied to the aqueous finish paint of 25 type passenger vehicles, varnish, it is characterised in that
Finish paint wherein includes following component by weight percentage:
Waterborne acrylic ester-polyurethane resin emulsion 50～60%, pigment 3～26%, nano barium sulfate 5～20%, aqueous dispersion 0.3
～0.5%, aqueous defoamer 0.2～0.4%, surfactant 0.1～0.2%, nertralizer 0.2～0.6%, aqueous anti ultraviolet agent
0.5～1%, aqueous polyamide wax slurry 2～4%, deionized water 11～13%, coalescents 1～2%；
Varnish wherein includes following component by weight percentage:
Waterborne acrylic ester-polyurethane resin emulsion 70～80%, aqueous flatting silica 0～12%, aqueous dispersion 0.3～0.5%, aqueous
Defoamer 0.1～0.2%, waterborne organic silicon levelling agent 0.2～2%, surfactant 0.2～0.4%, nertralizer 0.4～0.6%,
Aqueous anti ultraviolet agent 0.5～1%, aqueous polyamide wax slurry 1～2%, deionized water 7～14%, coalescents 2～4%.
2. coating composition, it is characterised in that include the aqueous finish paint described in claim 1, varnish, and respectively with finish paint
The first firming agent coordinated with varnish and the second firming agent, the weight ratio of described finish paint and the first firming agent is 100:
(10～70)；The weight ratio of described varnish and the second firming agent is 100:(10～70)；First firming agent and second is admittedly
Agent is hydrophilic isocyanate resin firming agent.
3. it is applied to the aqueous finish paint of 25 type passenger vehicles, the preparation method of varnish described in claim 1, it is characterised in that include
Following steps:
Aqueous finish paint, the preparation method of varnish, comprise the steps:
1, deionized water, aqueous dispersion, aqueous defoamer, coalescents are added together employing 300～400 revs/min stirring 5
～10 minutes；
2, add pigment, nano barium sulfate, aqueous polyamide wax slurry, use 400～600 revs/min to stir 5～10 minutes, use
Sand mill is ground to fineness and reaches less than 20 microns；
3, adding aqueous acrylic urethane resins uses 400～600 revs/min to stir 15～20 minutes；
4, limit use 400～600 revs/min add surfactant, aqueous anti ultraviolet agent while stirring, use 400～600 turns/
Dispersion 15～20 minutes, uses nertralizer to adjust pH value between 8～9；
The preparation method of varnish, comprises the steps:
1, waterborne acrylic ester-polyurethane resin emulsion is added in production cylinder；
2, deionized water is used to add after aqueous dispersion, aqueous defoamer, waterborne organic silicon levelling agent, surface activity dilution agent
Enter and produce in cylinder, use 300～400 revs/min to stir 5～10 minutes；
3, add aqueous flatting silica, aqueous polyamide wax slurry uses 500～600 revs/min to stir 15～20 minutes；
4, add aqueous anti ultraviolet agent, use nertralizer adjust pH value between 8～9, uses 400～500 revs/min stir 5～
10 minutes.
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|---|---|---|---|
| CN201610580005.5A CN106147588A (en) | 2016-07-22 | 2016-07-22 | One group is applied to the aqueous finish paint of 25 type passenger vehicles, varnish and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610580005.5A CN106147588A (en) | 2016-07-22 | 2016-07-22 | One group is applied to the aqueous finish paint of 25 type passenger vehicles, varnish and preparation method thereof |
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|---|---|---|---|
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| CN107699121A (en) * | 2017-09-19 | 2018-02-16 | 运研材料科技（上海）有限公司 | A kind of aqueous polyurethane coating and its film build method of resistance to butanone |
| CN107732154A (en) * | 2017-11-10 | 2018-02-23 | 江苏华富储能新技术股份有限公司 | Small lithium ion battery of loss of capacitance and preparation method thereof after a kind of circulation electric discharge |
| CN107910520A (en) * | 2017-11-10 | 2018-04-13 | 江苏华富储能新技术股份有限公司 | A kind of lithium ion battery cathode slurry, negative material and preparation method thereof |
| CN109679479A (en) * | 2018-12-29 | 2019-04-26 | 东来涂料技术（上海）股份有限公司 | A kind of environment-friendly water-based varnish of high durable acid and alkali-resistance and preparation method thereof |
| CN110003785A (en) * | 2019-05-09 | 2019-07-12 | 浙江幸福之家门业有限公司 | A kind of security door aqueous metallic paint |
| CN111763440A (en) * | 2020-05-25 | 2020-10-13 | 贵州省昊越新型材料科技有限公司 | Special putty paste for aluminum film wall |
| CN114806379A (en) * | 2019-12-31 | 2022-07-29 | 江西贝特利新材料有限公司 | High-flexibility coating applied to ethylene propylene diene monomer and preparation method thereof |
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| CN107699121A (en) * | 2017-09-19 | 2018-02-16 | 运研材料科技（上海）有限公司 | A kind of aqueous polyurethane coating and its film build method of resistance to butanone |
| CN107732154A (en) * | 2017-11-10 | 2018-02-23 | 江苏华富储能新技术股份有限公司 | Small lithium ion battery of loss of capacitance and preparation method thereof after a kind of circulation electric discharge |
| CN107910520A (en) * | 2017-11-10 | 2018-04-13 | 江苏华富储能新技术股份有限公司 | A kind of lithium ion battery cathode slurry, negative material and preparation method thereof |
| CN109679479A (en) * | 2018-12-29 | 2019-04-26 | 东来涂料技术（上海）股份有限公司 | A kind of environment-friendly water-based varnish of high durable acid and alkali-resistance and preparation method thereof |
| CN110003785A (en) * | 2019-05-09 | 2019-07-12 | 浙江幸福之家门业有限公司 | A kind of security door aqueous metallic paint |
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| CN111763440A (en) * | 2020-05-25 | 2020-10-13 | 贵州省昊越新型材料科技有限公司 | Special putty paste for aluminum film wall |
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Application publication date: 20161123 |