CN102702958B - Water-based paint compositions, preparation method and its usage - Google Patents
Water-based paint compositions, preparation method and its usage Download PDFInfo
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- CN102702958B CN102702958B CN201210178866.2A CN201210178866A CN102702958B CN 102702958 B CN102702958 B CN 102702958B CN 201210178866 A CN201210178866 A CN 201210178866A CN 102702958 B CN102702958 B CN 102702958B
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Abstract
The present invention relates to water base paint compositions, it comprises the resin combination of at least one for water base paint compositions and at least one polymeric amide as auxiliary rheological agents and at least one acrylic resin modified epoxy thickening material.
Description
Technical field
The present invention relates to paint field, particularly, the present invention relates to a kind of novel water-based coating composition, prepare the method for described coating composition and the purposes of described coating composition.
Background technology
Now know, in automotive paints, and expect there is good decorative effect and the coating field simultaneously with good non-corrosibility at other, the base material with multiple coatings of arranging that overlap each other should be equipped with.
Preferably apply multilayer japanning according to so-called " primary coat/varnish " method, namely first apply one deck colored primer, and just apply varnish thereon without the need to baking step (wet and touch wet method) after of short duration flash-off time.Subsequently priming paint is dried together with varnish.
In applying automobile metal effect paint, " primary coat/varnish " method obtains meaning great especially.
Cause with the reason in ecology economically and attempt using water-borne primer coating composition when producing laminated coating.
Coating composition for generation of these undercoats must be processed according to rational " wetting, it is wet to touch " method conventional at present, namely they just must apply transparent top coat layer thereon without the need to baking step in pre-drying-time short as far as possible, and the defect do not shown on visual appearance, such as so-called " pin hole ".
In addition, coating also must demonstrate sufficient storage stability.A kind of detection of routine stores this material at 40 DEG C.
In addition, in primary coat/varnish shaped metal effect paint, also other problem must be solved.Metal effect depends primarily on the orientation of the metallic pigment particulate in paint film.Therefore such paint film can must be provided with the metal effect priming paint of " wetting, it is wet to touch " method processing, in this paint film, metallic pigment exist with favourable space after applied, and in this paint film, so fix these orientations fast, they can not be interfered in the process of further enamelling process.Suitable parameter for characterizing metal effect is brightness and the Flop Index of tone.
By the known water-dilutable coating composition of open text DE4028386A1, it contains as the water-dilutable polyurethane resin of base-material, pigment particle, thickening material and the polymeric amide as auxiliary rheological agents.The precipitation tendency that this kind of coating demonstrates not enough metal effect and increases after storing at the temperature (40 DEG C) raised.
US2004/0039097A1 discloses a kind of water-base metal paint, and it comprises the polymeric amide as auxiliary rheological agents equally.
EP1153989A1 discloses water-base metallic coating composition, and it is except resin combination and pigment, also forms by metal silicate with as the polyamide resin of auxiliary rheological agents.But depend on base composition, the existence of layered silicate can cause pin hole.
CN101945956A discloses a kind of water base paint compositions, and it comprises the resin combination of at least one for water base paint compositions and at least one polymeric amide as auxiliary rheological agents and at least one based on poly-(methyl) acrylic acid acrylate thickening agent.But it is in luminance brightness, settling stability, mobility and cause pin hole is further improved.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of novel coating composition, and it does not have the shortcoming of prior art.What these compositions had an improvement applies performance.Therefore can reduce pin hole to be formed, and should not cause metal effect simultaneously and affect negatively.The settling stability of composition should be ensured in addition.
Term " pin hole " and " metal effect " are known for technical personnel, and such as exist
defined in Lexikon, LackeundDruckfarben, GeorgThiemeVerlag1998.
Find surprisingly, these objects can realize by polymeric amide with as the combination of the acrylic resin modified epoxy of auxiliary rheological agents.
Therefore, theme of the present invention is a kind of water base paint compositions, and it comprises the resin combination of at least one for water base paint compositions and at least one polymeric amide as auxiliary rheological agents and at least one acrylic resin modified epoxy thickening material.
Described acrylic resin modified epoxy thickening material makes the bisphenol-type epoxy resin of number-average molecular weight 2000 ~ 35000 and carries out esterification containing carboxy acrylic resinoid and the resin that formed or will containing containing the resin that the polymerizability unsaturated monomer composition graft polymerization to this bisphenol-type epoxy resin of carboxyl polymerizability unsaturated monomer is formed.
Acrylic resin modified epoxy can be following resin (1), resin (2) any one.
Resin (1) makes bisphenol-type epoxy resin (al) (following, be called " epoxy resin (a1) ") and the resin carrying out ester addition reaction containing carboxy acrylic resinoid (a2) (hereinafter referred to as " acrylic resin (a2) ") and formed.In resin (1), by such as in organic solvent solution, under the existence of esterifying catalyst, heating ring epoxy resins (al) and acrylic resin (a2), easily can carry out ester addition reaction.
Resin (2) to contain the polymerizability unsaturated monomer composition graft polymerization of carboxyl polymerizability unsaturated monomer to bisphenol-type epoxy resin (al) the above resin formed.In resin (2), such as can in organic solvent, under the existence of the radical initiators such as benzoyl peroxide, will containing the graft polymerization of carboxyl polymerizability unsaturated monomer composition on epoxy resin (al).
As the bisphenol-type epoxy resin (al) used in above-mentioned resin (1), resin (2), can be any one of following resin: such as, as required under the existence of the catalyzer such as basic catalyst, make Epicholorohydrin and bis-phenol be condensed to epoxy equivalent (weight) 2000 ~ 10000(number-average molecular weight 4000 ~ 30000) high molecular and the resin formed; As required under the existence of the catalyzer such as basic catalyst, make Epicholorohydrin and bis-phenol condensation, forming epoxy equivalent (weight) is 180 ~ 1000(number-average molecular weight 360 ~ 2000) epoxy resin, and make the resin that this epoxy resin and bis-phenol carry out polyaddition reaction and obtain; And the epoxy ester resin making these resins of diprotic acid and gained or above-mentioned low-molecular-weight epoxy resin react and be formed.
Polymeric amide refers to the organic compound containing at least two amide structures in molecule.This compounds by the reaction of poly carboxylic acid and polyamines and/or monoamine or can be prepared by the reaction of polyamines and monocarboxylic acid and/or polyacid.The polymeric amide that preferred use is obtained by polyamines and fatty acid response, particularly by polyamines and per molecule containing the polymeric amide that the fatty acid response of 16 to 20 C atoms obtains.The particularly preferably reaction product of 12-oxystearic acid and 1,6-hexanediamine.The suitable polymeric amide thickening material be obtained commercially is such as by trade name Disparlon
aQ630 (manufacturers Kusumoto, Japan) buys.
The auxiliary rheological agents of coating composition of the present invention usually containing 0.5 to 15 quality %, based on total binder solids material meter.When not containing metallic pigment, use 0.5 to 10 quality %, preferably use the auxiliary rheological agents of 1.5 to 8 quality %, based on total binder solids material meter.Containing in the coating composition of metallic pigment, use 2 to 15 quality %, the preferably auxiliary rheological agents of 4 to 12 quality %, based on total binder solids material meter.
Polymeric amide: the mass ratio of acrylic resin modified epoxy thickening material is 15: 1 to 1: 1, preferably 7: 1 to 3: 1.
Coating composition of the present invention can contain other auxiliary rheological agents of at least one.This auxiliary rheological agents is preferably selected from based on the associative thickener of urethane, carboxymethyl cellulose acetobutyric acid ester thickener, metal silicate and silicon-dioxide.Other auxiliary rheological agents described are preferably metal silicate.
Polymeric amide: acrylic resin modified epoxy thickening material: solid part mass ratio of other thickening material is 15: 1: 1 to 1: 1: 1, preferably 7: 1: 1 to 3: 0.5: 1.
Metal silicate is preferably selected from montmorillonite.Particularly preferably described montmorillonite is selected from polynite and hectorite.Described polynite and hectorite are especially selected from aluminium-magnesium silicate and sodium-magnesium-and sodium-magnesium-fluoro-lithium layered silicate.Inorganic laminated silicate such as by Rockwood company with Laponite
trademark Soynatto.The massfraction of metal silicate is preferred not higher than 2.5 quality %, based on total binder solids material meter.
Associative thickener based on urethane is such as open in DE19945574A1.Associative thickener based on urethane also can be conventional with known compound, such as by Henkel company with Nopco
trademark Soynatto.Carboxymethyl cellulose acetobutyric acid ester thickener is such as sold with trade(brand)name CMCAB641-0.2 by Eastman company, and silicon-dioxide is such as sold with trade(brand)name Aerosil by Evonik company.
Coating composition of the present invention also can contain other conventional additives separately or as a mixture, as weighting agent, softening agent, stablizer, wetting agent, dispersing auxiliary, flow agent, defoamer and catalyzer.
Coating composition of the present invention can be given color containing at least one and/or give the pigment of effect.Mention titanium dioxide, graphite, carbon black, phthalocyanine blue, chromic oxide Yi as an example Ji perylene tetracarboxylic acid imide.The pigment optimization ground given color and/or give effect be selected from organic with mineral dye, tint permanence pigment, fillibility pigment, rheology control pigment, visual effect pigments, conductive pigment, electromagnetic shielding performance pigment and high-visibility pigment, metallic pigment or metal-powder, organic and inorganic filler, transparent or opacifying property weighting agent and nanoparticle.Coating composition is preferably containing metallic pigment.Particularly preferably, metallic pigment are selected from the coated silicon-dioxide of the coated mica of aluminium, pearl white, mica, the mica of coated by titanium dioxide, ferric oxide, micaceous ferric oxide, the silicon-dioxide of coated by titanium dioxide, the aluminium of coated by titanium dioxide, ferric oxide and the coated aluminium of ferric oxide.As long as besides the metallic pigments containing other tinting pigments in coating composition of the present invention, then so select kind and the consumption of tinting pigment, make desired metal effect not be suppressed.The mass parts of metal-powder is 32 quality %, preferably 12 to 28 quality %, based on total binder solids material meter.
The present invention also comprises the coating composition of not containing metal pigment.These compositions are referred to as monochromatic priming paint or single color finish.
Coating composition of the present invention contains the water as liquid diluent, and it optionally can also contain organic solvent.The ratio of organic solvent remains on bottom line.
Example as the organic solvent that may reside in water can mention heterocyclic, aliphatic series or aromatic hydrocarbon, unitary or polyvalent alcohol, ether, ester, ketone and acid amides, such as N-Methyl pyrrolidone, N-ethyl pyrrolidone, dimethyl formamide, toluene, dimethylbenzene, butanols, ethyl glycol and butyl glycol, and their acetic ester, butyl diglycol, diglyme, pimelinketone, methyl ethyl ketone, acetone, different fluorine that ketone or their mixtures.
Resin combination for coating composition of the present invention comprises the base-material that can be dissolved or dispersed in water and linking agent.Example as available water-dilutable base-material mentions water-dilutable acrylic resin modified epoxy, water-reducible polyester, water-dilutable polyethers, water-dilutable trimeric cyanamide or urea-formaldehyde resin and water-dilutable polyurethane resin.
Preferably such coating composition, it contains the water-dilutable polyurethane resin as base-material.Be positioned at side containing at least one and/or at least one is positioned at the urethane of the vinyl arylene of end if used, then obtain particularly preferred coating composition.These water-based base-materials are such as described in German patent application DE19948004A1.
In addition, coating composition particularly preferably contains acid number is the urethane resin of 5 to 70.It is such as disclosed in German patent application DE03545618A1.
Coating composition containing urethane resin preferably contains water-dilutable melamine resin as extra base ingredient.Particularly advantageously the ratio of 1 to 80 quality %, the very particularly advantageously ratio of 30 to 70 quality %, based on the ratio meter of water-dilutable polyurethane resin.Water-dilutable melamine resin is such as the carbamide condensation product of etherificate.Except alap condensation degree, the water-soluble of them depends on etherificate component, and the lowermost level member that wherein only alkanol is serial or ethylene glycol mono-ether is serial produces water-soluble condensate.With the melamine resin of methanol etherification, there is maximum meaning.When using solubilizing agent, also the melamine resin of butanol etherification can be dispersed in aqueous phase.
Also there is such possibility, carboxyl is inserted in condenses.The formaldehyde condensation products of high etherificate and the anti-etherification product of hydroxycarboxylic acid are water miscible due to their carboxyl after the neutralization, and can be contained in coating composition of the present invention.
Also can use the water-soluble of other or water dispersible aminoresin, such as urea-formaldehyde resin replaces described melamine resin.
If coating composition contains melamine resin, then it can advantageously also containing as the water-dilutable polyether resin of other base ingredient and/or water-dilutable acrylic resin modified epoxy resin.At this, the mass ratio of preferred melamine resin and polyester/acrylic resin modified epoxy resin is 2: 1 to 1: 4, and preferably melamine resin adds the mass ratio of polyester and/or acrylic resin modified epoxy resin and urethane resin is 4: 1 to 1: 4, more preferably 2: 1 to 1: 2, particularly preferably 1.3: 1 to 1: 1.3.As water-reducible polyester resin, preferably use with the saturated of hydroxyl and unsaturated polyester resin, mention as open text DE4028386A1 and DE4437535A1 those.
Vibrin is not preferably containing polymerisable double bond.Particularly preferably be polyester glycol.Especially particularly preferably mumber average molar mass is the polyester glycol of 400 to 5000.
As solubilizing group, vibrin used in the present invention is preferably containing carboxyl.
The polyurethane-modified polyacrylic ester of preferred use is as water-dilutable polyacrylate resin.It is such as disclosed in open text DE4437535A1.
Coating composition of the present invention contains 5 to 30 quality %, preferably the water-dilutable base ingredients of 10 to 25 quality %.
The example of suitable linking agent is aminoresin, compound containing anhydride group or resin, compound containing epoxide group or resin, three (alkoxycarbonyl amino) triazine, compound containing carbonate group or resin, dead front type or non-blocked polyisocyanate, beta-hydroxyalkylamides and on average there are at least two can the compound of group of anti-esterification, the ester of the reaction product of such as diester malonate and polyisocyanates or the polyhydroxy-alcohol of propanedioic acid and the reaction product of part ester and monoisocyanates, it is described in European patent document EP0596460A1.
If select non-blocked polyisocyanate as linking agent, then water base paint compositions of the present invention is mixed with 2 components compositions.
Such linking agent is known for technical personnel, and by many companies as commodity selling.
The mass ratio of base-material and linking agent is preferably 50 to 90 quality %, based on the total amount of these two kinds of components.The more preferably scope of 65 to 85 quality %.
In addition, the present invention relates to the method preparing coating composition of the present invention.
Coating composition of the present invention can obtain as follows: in aqueous medium, such as, mix by high-speed mixer, dissolver or online dissolver (InLineDissolver) and disperse each component of coating composition mentioned above.
In addition, the application relates to the purposes of coating composition of the present invention, be used as at article to be coated, as the japanning on the vehicle body of automobile (as car, bogie, motorcycle and motorbus) that manufactured by metal or plastics and part thereof and the part of household electrical appliance that manufactured by metal or plastics, or rather, direct use or applying ground coating composition in advance, as cationic electro-dipcoat paint composition, and if if required, apply midcoat composition on article to be coated, and use after making the solidification of these coated membrane subsequently.Coating composition is preferably applied on body of a motor car and part thereof as japanning.Metal to be painted preferably stands the chemical conversion treatment of phosphoric acid salt and chromic salt in advance.In addition, known traditional material can be used as bottom-coating composition and as midcoat composition.
Coating composition of the present invention can pass through electrostatic coating, by aerial spraying and by airfree spraying to be applied on these article to be coated (comprise use ground coating composition coating and in addition properly with those of midcoat composition coating).The thickness of their coated membrane compatibly falls into as the coated membrane of solidification and is generally 5 to 35 μm, especially in the scope of 10 to 25 μm.It can be made to solidify by coated membrane being heated to about 100 to about 180 DEG C within the time of about 10 to about 40 minutes.
In the coated membrane formed by the coating composition containing metallic pigment of the present invention, metallic pigment are on the uniform surface ground of coating and be parallel to the surface alignment of coating, and the coated membrane obtained has changeable colors along with angle character more outstanding compared with traditional metallic coating film.But also obtaining outstanding effect, these metallic pigment disperse equably and almost do not observe metal lines.
Can by " 2 coatings-1 solidification " (2C1B) method or " 2 coatings-2 solidifications " (2C2B) method, in the coated membrane be made up of coating composition of the present invention (after described coated membrane solidification or time uncured), on the face applied, namely apply the coating composition of layer of transparent.
In addition, coated material of the present invention be also suitable for of short duration predrying after (wet touch wet coating paint) applies varnish applying for 2 times, and together to dry (3C1B) with the layer applied in advance.
Can by advance coating composition of the present invention is applied to by method as described above and mode need japanning article on, and by through heating make its coated membrane solidify after or under its uncured state, with electrostatic coating, aerial spraying and airfree be sprayed on this coating upper surface apply have solids content control coating composition about 30 to about 80 quality % clear coating composition apply clear coating composition.Based on the coated membrane of solidification, the coated membrane thickness of clear coating composition falls into suitably and is generally 5 to 100 μm, more preferably the scope of 20 to 80 μm.It can be made to solidify by coated membrane being heated to about 100 to about 180 DEG C within the time of about 10 to about 40 minutes.
The present invention is explained in more detail below by means of preparation embodiment.
Compared with prior art, the present invention has the following advantages:
(1) there is excellent settling stability;
(2) luminance brightness is excellent;
(3) not easily pin hole is caused.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Understand " part " alleged in hereinafter composition with " mass fraction ".
I. water-based metal priming paint
The preparation of Ia. painting
The preparation of embodiment 1 acrylic resin modified epoxy
(1) manufacture (al) of epoxy resin solution: add 558 mass parts Epikote828EL in the four-hole boiling flask being provided with return line, thermometer, stirrer, 329 mass parts dihydroxyphenyl propanes, 0.6 mass parts Tetrabutyl amonium bromide, and react in 160 DEG C under stream of nitrogen gas.Reaction by following the tracks of with epoxy equivalent (weight), and carries out the reaction of about 5 hours, obtains number-average molecular weight about 11000, the bisphenol A type epoxy resin of epoxy equivalent (weight) about 8000.
In addition, Epikote828EL is bisphenol A type epoxy resin (epoxy equivalent (weight) about 190, molecular weight about 350, japan epoxy resin Co., Ltd. manufacture).
(2) containing the manufacture (a2) of carboxy acrylic resinoid solution: be provided with return line, thermometer, dropping funnel, 882 mass parts propyl carbinols are added in the four-hole boiling flask of stirrer, by 180 mass parts methacrylic acids, 240 mass parts vinylbenzene, 180 mass parts ethyl propenoates, the mixture of the 18 mass parts peroxidation 2 ethyl hexanoic acid tert-butyl esters is heated to 100 DEG C and uses from dropping funnel and about within 3 hours, drips under stream of nitrogen gas, stirring 2 hours is continued at the same temperature again after dropping, then cool, obtain the acrylic resin solution that solids component is 40 quality %.The resinous acid value of the resin (solids component) obtained is 196mgKOH/g, number-average molecular weight about 19000.
(3) manufacture of acrylic modified epoxy dispersion: add 80 mass parts (solids component) bisphenol A type epoxy resin, 50 mass parts (solids component 20 mass parts) 40 quality % acrylic resin solution, 33 mass parts diethylene glycol monobutyl ethers in the four-hole boiling flask being provided with return line, thermometer, stirrer, be heated to 100 DEG C make it dissolve after, add 2 mass parts N, N-dimethylaminoethanol, react about 2 hours, then add 3 mass parts N, N-dimethylaminoethanol continues reaction 20 minutes.Then, dripped 165 mass parts deionized waters with 1 hour, carry out water-dispersion, obtain the acrylic modified epoxy dispersion that acid number is 34mgKOH/g, solids component is 30 quality %.
Embodiment 2
Under vigorous stirring, to 17.5 parts according to DE19948004A1, add 4.5 parts of acrylic acid modified polyurethane resins (DE4437535A1, the 7th page the 55th is walked to the 8th page of the 23rd row) in the water-based binder dispersion of the 20th page of the 9 to 21 row, 1.8 parts by 50 parts of Surfinol
the solution of 104 (AirProducts) and 50 parts of butyl glycol compositions, and 4.5 parts of melamine resin Luwipal
052 (BASF), 2 parts of butyl glycols, 4 parts of DE4009858A1, the polyester described in the 16th hurdle 37-59 is capable and the polymeric amide thickening material Disparlon of 30 part 20%
the water-based pre-composition of AQ 630 in water and the mixture be made up of 0.75 part of acrylic resin modified epoxy thickening material and 0.75 part of water.
Be added on the 5.4g aluminium pigment Stapa in 8 parts of butyl glycols subsequently
the mixture of the uniform stirring of Hydrolux2192 (Eckart).With dimethylethanolamine (in water 10%) by pH regulator to 8.0 water use regulation to 1000s
-1with 23 DEG C at be the viscosity (RheolabMC1 of Physica company, measuring system Z2) of 70mPas.
Embodiment 3
Under vigorous stirring, to 17.5 parts according to DE19948004A1, add 4.5 parts of acrylic acid modified polyurethane resins (DE4437535A1, the 7th page the 55th is walked to the 8th page of the 23rd row) in the water-based binder dispersion of the 20th page of the 9 to 21 row, 1.8 parts by 50 parts of Surfinol
the solution of 104 (Air Products) and 50 parts of butyl glycol compositions, and 4.5 parts of melamine resin Luwipal
052 (BASF), 2 parts of butyl glycols, 4 parts of DE4009858A1, the polyester described in the 16th hurdle 37-59 is capable and the polymeric amide thickening material Disparlon of 30 part 20%
the water-based pre-composition of AQ630 in water and the mixture be made up of 4.5 parts of acrylic resin modified epoxy acrylate thickening agents and 0.75 part of water.
Be added on the 5.4g aluminium pigment Stapa in 8 parts of butyl glycols subsequently
the mixture of the uniform stirring of Hydrolux2192 (Eckart).With dimethylethanolamine (in water 10%) by pH regulator to 8.0 water use regulation to 1000s
-1with 23 DEG C at be the viscosity (RheolabMC1 of Physica company, measuring system Z2) of 70mPas.
Comparative example 1
Under vigorous stirring, to 17.5 parts according to DE19948004A1, in the water-based binder dispersion of the 20th page of the 9 to 21 row, add 4.5 parts of s
-1, 1.8 parts by 50 parts of Surfinol
the solution of 104 (AirProducts) and 50 parts of butyl glycol compositions, and 4.5 parts of melamine resin Luwipal
052 (BASF), 2 parts of butyl glycols, 4 parts of DE4009858A1, the polyester described in the 16th hurdle 37-59 is capable and the polymeric amide thickening material Disparlon of 30 part 20%
the water-based pre-composition of AQ630 in water and by 0.75 part of acrylate thickening agent Viscalex
the mixture that HV30 and 0.75 part water forms.
Be added on the 5.4g aluminium pigment Stapa in 8 parts of butyl glycols subsequently
the mixture of the uniform stirring of Hydrolux 2192 (Eckart).With dimethylethanolamine (in water 10%) by pH regulator to 8.0 water use regulation to 1000s
-1with 23 DEG C at be the viscosity (RheolabMC1 of Physica company, measuring system Z2) of 70mPas.
The inspection of Ib. painting
By obtain aqueous priming paint and commercially available water-based floating coat (as SecuBloc, BASF coating company limited) be applied on the metal sheet of 30cmx60cm with the film thickness of 12 μ, at room temperature maintenance 5 minutes and 80 DEG C of maintenances make it predrying in 10 minutes subsequently.Pre-dried metal sheet coated commercially available varnish (as Evergloss, BASFAG) subsequently and dry 30 minutes at 140 DEG C.
The mensuration of luminance brightness
The evaluation of tone is realized by colour measurement.Luminance brightness (carrying out colour measurement with the XRiteMA68II of XRite company) is evaluated 15 ° take measurement of an angle.
The mensuration of Flop Index
According to formula, the chrominance distortion Flop Index that the brightness value recorded by different measuring angle is corresponding:
Flop Index=2.69 (L*15L*110) 1.11/ (L*45) 0.86,
Wherein, L is the corresponding respective brightness value taken measurement of an angle measured by (15 °, 45 ° and 110 °).
The mensuration of pin hole
For checking anti-pin hole, priming paint wedge shape is coated with method and is applied on metal sheet (30cm × 60cm) with the film thickness of 10-30 μm, at room temperature maintenance 5 minutes and 80 DEG C of maintenances make it predrying in 10 minutes subsequently.Subsequently pre-dried metal sheet coated commercially available varnish (as Evergloss, BASFAG) with the film thickness of 30-35 μ and dry 30 minutes at 140 DEG C.The sum of visual mensuration pin hole.
The mensuration of settling stability
The coating obtained is stored 10 days in 40 DEG C in Glass Containers (diameter 5cm, loading height 10cm).The height of supernatant liquor is calculated subsequently by precipitation.
Result
| Embodiment | Luminance brightness | Flop Index | Pin hole sum | Precipitation/cm |
| 2 | 138 | 22 | 0 | 0 |
| 3 | 140 | 21 | 0 | 0 |
| Comparative example 1 | 134 | 17 | 1 | 0.5 |
Aqueous priming paint of the present invention, compared with comparative example 1, shows the better characteristic of (by luminance brightness and Flop Index represented) relevant to metallic appearance, anti-pin hole and antisolvent precipitation.
II. the monochromatic aqueous priming paint of water-based
The preparation of IIa. painting
Embodiment 4: the preparation of pigment paste
Under vigorous stirring, the millbase that 39 parts are prepared according to DEA4010176 embodiment 1 and 6 portions of commercially available dispersing additives, 25 parts of water and 30 parts of Irgazin
rotA2BN (Ciba company) mixes, and dissolves 30 minutes and grinds 40 minutes on ball mill at the highest 50 DEG C subsequently.
Embodiment 5
Under agitation in the dispersion of 6 parts of 3%LaponiteRD in water, add 1.7 parts according to DE 4437535A1, the acrylic acid modified urethane resin walking to the 8th page of the 23rd row for the 7th page the 55th, 1.5 parts by 50 parts of Surfinol
the solution of 104 (AirProducts) and 50 parts of butyl glycol compositions and 29 parts of EP0228003B2, the urethane resin described by the 8th page of 6-18 is capable.Under agitation add 5.5 parts of commercially available melamine resin (Luwipal subsequently
052, BASF), 4.5 parts of DE4009858A1, the polyester described by the 16th hurdle 37-59 is capable, 8 parts of butyl glycols and 1.5 part of 10% aqueous dimethylethanolamine.After this 18 parts of pigment paste according to embodiment 4 and 2.5 parts of 2-Ethylhexyl Alcohols are added.Then 20 parts of 20%Disparlon are under agitation added
the dispersion of AQ630 in water and by 0.5 part of acrylic resin modified epoxy thickening material and 0.5 part of water mixture and be the viscosity (RheolabMC1 of Physica company, measuring system Z2) of 90mPas under water use regulation to 1000s-1.
Comparative example 2
Under agitation in the dispersion of 6 parts of 3%LaponiteRD in water, add 1.7 parts according to DE 4437535A1, the acrylic acid modified urethane resin walking to the 8th page of the 23rd row for the 7th page the 55th, 1.5 parts by 50 parts of Surfinol
the solution of 104 (AirProducts) and 50 parts of butyl glycol compositions and 29 parts of EP0228003B2, the urethane resin described by the 8th page of 6-18 is capable.Under agitation add 5.5 parts of commercially available melamine resin (Luwipal subsequently
052, BASF), 4.5 parts of DE4009858A1, the polyester described by the 16th hurdle 37-59 is capable, 8 parts of butyl glycols and 1.5 part of 10% aqueous dimethylethanolamine.After this 18 parts of pigment paste according to embodiment 4 and 2.5 parts of 2-Ethylhexyl Alcohols are added.Then 20 parts of 20%Disparlon are under agitation added
the dispersion of AQ630 in water and by the mixture of 0.5 part of acrylate thickening agent ViscalexHV30 and 0.5 part water and water use regulation to 1000s
-1it is down the viscosity (RheolabMC1 of Physica company, measuring system Z2) of 90mPas.
The inspection of IIb. painting
The mensuration of pin hole
For checking anti-pin hole, be applied on metal sheet (30cmx60cm) by priming paint with 10-35 μm of film thickness, at room temperature maintenance 5 minutes and 80 DEG C of maintenances make it predrying in 10 minutes subsequently.Subsequently pre-dried metal sheet coated commercially available varnish (as Evergloss, BASFAG) with the film thickness of 30-35 μm and dry 30 minutes at 140 DEG C.The sum of visual mensuration pin hole.
Fluidity evaluating
For evaluating resistance to flow, with the film thickness of 10-35 μm priming paint being applied over and being longitudinally equipped with on the metal sheet (30cm × 60cm) of a round, at room temperature maintain 5 minutes with vertical attitude subsequently and 80 DEG C of maintenances make it predrying in 10 minutes.Subsequently pre-dried metal sheet is dried 30 minutes in 140 DEG C.The film thickness that visual mensuration fluid is formed around hole.
Result
| Embodiment | Pin hole sum | Flowing boundary/μm |
| 5 | 0 | 12 |
| Comparative example 2 | 0 | 28 |
The fact shows, the present invention shows best relevant anti-pin hole and the character of flowing.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (13)
1. water base paint compositions, it comprises the resin combination of at least one for water base paint compositions and at least one polymeric amide as auxiliary rheological agents and at least one acrylic resin modified epoxy thickening material;
Described polymeric amide obtains by the reaction of polyamines and lipid acid;
Described acrylic resin modified epoxy thickening material makes the bisphenol-type epoxy resin of number-average molecular weight 2000 ~ 35000 and carries out esterification containing carboxy acrylic resinoid and the resin that formed or will containing containing the resin that the polymerizability unsaturated monomer composition graft polymerization to this bisphenol-type epoxy resin of carboxyl polymerizability unsaturated monomer is formed;
Polymeric amide: the mass ratio of acrylic resin modified epoxy thickening material is 15: 1 ~ 1: 1.
2. coating composition according to claim 1, is characterized in that, it contains the pigment that at least one is given color and/or given effect.
3. coating composition according to claim 2, is characterized in that, the pigment of described imparting color and/or imparting effect is organic and mineral dye.
4. the coating composition according to any one of claim 1-3, is characterized in that, it is monochromatic priming paint or single color finish.
5. coating composition according to claim 3, is characterized in that, the pigment of described imparting color and/or imparting effect is metallic pigment.
6. coating composition according to claim 3, it is characterized in that, described pigment is the combination of in the coated aluminium of the coated silicon-dioxide of the coated mica of aluminium, pearl white, mica, the mica of coated by titanium dioxide, ferric oxide, micaceous ferric oxide, the silicon-dioxide of coated by titanium dioxide, the aluminium of coated by titanium dioxide, ferric oxide and ferric oxide a kind or at least 2 kinds.
7. the coating composition according to any one of claim 1-3, is characterized in that, based on total binder solids material, described coating composition contains the auxiliary rheological agents of 0.5 ~ 15 quality %.
8. the coating composition according to any one of claim 1-3, is characterized in that, it contains other auxiliary rheological agents of at least one.
9. coating composition according to claim 8, it is characterized in that, other auxiliary rheological agents described is the combination based on a kind in the associative thickener of urethane, carboxymethyl cellulose acetobutyric acid ester thickener, metal silicate and silicon-dioxide or at least 2 kinds.
10. coating composition according to claim 9, is characterized in that, polymeric amide: acrylic resin modified epoxy thickening material: the mass ratio of other thickening material is 15: 1: 1 to 1: 1: 1.
11. coating compositions according to any one of claim 1-3, is characterized in that, described resin combination comprises can the base-material that maybe can be scattered in water soluble in water, and linking agent.
The method of the coating composition of 12. preparations according to any one of claim 1-3, is characterized in that, each component mixed in an aqueous medium and disperse.
The purposes of 13. coating compositions according to any one of claim 1-3, as the japanning on article to be coated.
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| JP6688300B2 (en) * | 2014-08-22 | 2020-04-28 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ | Aqueous coating composition comprising a thickening agent producible from at least one polyamide and at least one further polymer |
| CN109233493B (en) * | 2017-05-10 | 2020-09-25 | 上海大学 | High-reflectivity acrylic acid heat-shielding coating and preparation method thereof |
| CN116970326B (en) * | 2023-09-23 | 2023-12-05 | 江西永通科技股份有限公司 | Water-based paint composition and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077957A (en) * | 2006-05-22 | 2007-11-28 | 关西涂料株式会社 | Water coating composition |
| CN101945956A (en) * | 2008-02-15 | 2011-01-12 | 巴斯夫涂料有限公司 | Water-based paint compositions, preparation method and its usage |
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| CN101077957A (en) * | 2006-05-22 | 2007-11-28 | 关西涂料株式会社 | Water coating composition |
| CN101945956A (en) * | 2008-02-15 | 2011-01-12 | 巴斯夫涂料有限公司 | Water-based paint compositions, preparation method and its usage |
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