CN1162322A - Paint coat composition useful in aqueous multilayer paint systems - Google Patents
Paint coat composition useful in aqueous multilayer paint systems Download PDFInfo
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- CN1162322A CN1162322A CN 95195898 CN95195898A CN1162322A CN 1162322 A CN1162322 A CN 1162322A CN 95195898 CN95195898 CN 95195898 CN 95195898 A CN95195898 A CN 95195898A CN 1162322 A CN1162322 A CN 1162322A
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Abstract
The present invention relates to a paint coat composition useful in multilayer paint systems, which contains a) a polyurethane resin as acementing agent, said resin can be diluted with water and has an acid number of 10-60 and a number average molecular weight of 400-25000 (preferably 8000-25000), said resin can be prepared by the interreaction of the following components: aa) a polyester-polyol having a number average molecular weight of 400-5000 and/or polyether-polyol or mixture thereof; bb) a polyisocyanic acid ester or mixture thereof; cc) a chemical compound containing at least one group capable of reacting with isocyanate group and at least one group capable of generating anions in molecules thereof and composition therefore; and optional dd) an organic compound having a molecular weight of 40-400 and containing hydroxyl group and/or amino therein or mixture thereof, and matter at least partly neutralizing the generated reaction products; and b) pigment and/or filling agent, wherein the ratio of the cementing agent to the pigment is 0.5:1-1.5:1.
Description
The present invention relates to a kind of new coating prescription that is used for water-based overbrushing layer paint systems, particularly it can be used for anti-stone and hits coating.
Prior art discloses and has been used for motor vehicle body, the whole bag of tricks that applies of body of a motor car particularly, the wherein coated and baking of electrocoating paint, middle anti-stone hits priming paint and is separated to toast or toast with the filler coatings that applies by optional the coating with each coating, coated and the baking of filler, and single coating or the coated and baking of overbrushing aspect lacquer system.
The 3rd coating particularly has the effect of the ununiformity of filling up and cover ground, so that make subsequently finish paint make that ground is even to be coated with.The ground ununiformity fill up and cover well more, the optical quality of whole paint systems is just good more.The optical quality of whole paint systems not only, and important machinery-technical feature such as non-corrosibility, particularly anti-hitting property of stone is relevant closely with the quality of filler coatings with anti-other mechanical impact properties, and if any, also to hit the filling perforation coating relevant closely with the anti-stone in centre.The correlation method that applies especially for body of a motor car is known, and is for example known from EP-A-238037.
In the past, be mainly used in paint industry, so that make filler coatings and middle anti-stone hits the filling perforation coating based on the baking finish of organic solvent.Because attempting use coating, economic cause and ecological consideration, paint industry in recent years replace the paint organic solvent.
The preparation method of such water-borne coatings is known, and is particularly known from DE-A-4005961.Described there coating is applicable to the method that filler coatings and/or middle anti-stone hit the filling perforation coating of making of initial description.This German Patent relates generally to the vibrin of the urethane resin that contains water-dilutable, water-dilutable and the aminoresin coating as tackiness agent.
But these coating are not suitable for the so-called wet wet technology of bumping.With the exception of this, resulting coat-thickness still can not be satisfactory.This is because owing to expense reason and environment reason, in recent years, automotive industry has attempted to use thin as far as possible paint films, and compares with thicker coating commonly used at present, does not make downgrade again.
So far, with the coating that above-mentioned the 3rd step applies, its thickness is about 35 microns.For the conservation and the energy in the multilayer paint systems is produced, particularly in the covering with paint of body of a motor car, particularly attempt to reduce the thickness of this coating.But, when using when becoming known for the aqueous coating system of these purposes at present, such effort all with obvious impaired the linking together of the performance of whole paint systems.
So, the purpose of this invention is to provide a kind of formulation for coating material that is used for the aqueous paint system, this prescription can be used for initial the 3rd step of describing, and can make high-quality paint systems in this way, even when with the 3rd coat-thickness that goes on foot coating during less than 35 microns.
The urethane resin of this purpose by containing a) a kind of water-dilutable is as tackiness agent and b) formulation for coating material of pigment and/or filler reaches, and tackiness agent and pigment ratio are 0.5: 1 to 1.5: 1.The acid number of the urethane resin of water-dilutable is 10～60, number-average molecular weight is 4000～25000, preferred 8000～25000, it can by following component react to each other and to the small part and the reaction product that generates prepare: aa) the number average molecule is 400～5000 polyester polyol and/or polyether polyol, perhaps their mixture, bb) polyisocyanates or its mixture, cc) has the group of an energy and responding property of isocyanate group and have a compound that can generate anionic group at least or the mixture of such compound in a kind of molecule at least, and optional dd) a kind of molecular weight is 40～400 the organic compound that contains hydroxyl and/or amino, or the mixture of such compound.
Opposite with prior art, for the present invention, it is very important can making under the situation that does not have polyester and aminoresin based on the formulation for coating material of the polyurethane dispersing liquid of physical dryness.It is shocking that the application that only contains the coating of urethane resin and pigment makes this material hit the filling perforation coating as filler coatings and middle anti-stone particularly well, because it is to mechanical load, particularly stone hits and impacts beyond thought stable.
The known polyurethane chemistry method of the available those skilled in the art of component (a) is by aa), bb), cc) and optional dd) prepare (referring to as US-A4719132, DE-A3628124, EP-A-89497, EP-A-256540 and WO87/03829).As component (aa), it is possible using saturated and undersaturated polyester polyol and/or polyether polyol, and particularly number-average molecular weight is 400～5000 polyester diol and/or polyether Glycols.The example of the polyether Glycols that is fit to is that general formula is H (O-(CHR
1)
n-)
mThe polyether Glycols of OH, R in the formula
1Be low-carbon alkyl hydrogen or replacement or unsubstituted, n is 2～6, preferred 3～4, and m is 2～100, preferred 5～50.Its example is the straight or branched polyether Glycols, as poly-(oxyethylene) glycol, poly-(inferior oxygen propyl group) two pure and mild poly-(inferior oxygen-butyl) glycol.Selected polyethers-glycol should not introduced excessive ether, otherwise the polymkeric substance that generates can swelling in water.Preferred polyethers-glycol is that number-average molecular weight Mn is poly-(inferior oxygen propyl group) glycol of 400～3000.
Polyester-dibasic alcohol prepares by organic di-carboxylic acid or its acid anhydride and organic dibasic alcohol ester, perhaps makes by hydroxycarboxylic acid or by lactone.In order to prepare the polyester polyol of side chain, using has on a small quantity more that the polyvalent alcohol or the polycarboxylic acid of high functionality are possible.Di-carboxylic acid and dibasic alcohol can be aliphatic series straight chain or side chain, cyclic aliphatic or aromatic dicarboxylate or dibasic alcohol.
The dibasic alcohol that is used to prepare polyester for example comprises aklylene glycol, as ethylene glycol, and propylene glycol, butyleneglycol, 1,4-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol; And other dibasic alcohol, as hydroxymethyl-cyclohexane.But adding a small amount of polyvalent alcohol also is possible as TriMethylolPropane(TMP), glycerine and/or tetramethylolmethane.The acid constituents of polyester mainly comprises 2～30 in the molecule, lower molecular weight di-carboxylic acid or its acid anhydride of preferred 4～18 carbon atoms.The example of the acid that is fit to is phthalic acid, m-phthalic acid, terephthalic acid, tetrahydrophthalic acid, cyclohexane dicarboxylic acid, succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, toxilic acid, fumaric acid, pentanedioic acid, chlordene dicarboxylic acid in heptan, tetrachlorophthalic acid and/or dimer (fatty acid) yl.Replace these acid, also can use their acid anhydrides, under the occasion that they exist.When generating polyester polyol, it also is possible that existence has the carboxylic acid of 3 or 3 above carboxyls quite on a small quantity, for example the adducts of trimellitic acid 1,2-anhydride or maleic anhydride and unsaturated fatty acids.
Polyester-dibasic alcohol that use is obtained by lactone and diol reaction also is possible.The feature of these polyester-dibasic alcohol is to have terminal hydroxyl and general formula (CO-(CHR
2)
n-CH
2-O) repetition polyester components.In the formula, n is preferably 4～6, substituent R
2Be hydrogen or alkyl, cycloalkyl or alkoxyl group.
Substituting group does not contain the carbon atom more than 12.The sum of carbon atom is no more than 12 in the substituting group of each lactonic ring.Its example is carboxyl caproic acid, hydroxybutyric acid, hydroxydecanoic acid and/or oxystearic acid.
In order to prepare polyester-dibasic alcohol, unsubstituted ∈-caprolactone is preferred, and wherein n is 4, and all R are hydrogen.Cause with low molecular weight polyols with the reaction of lactone, as ethylene glycol, 1, ammediol, 1,4-butyleneglycol or hydroxymethyl-cyclohexane.But other reactive components and caprolactone reaction also are possible, as quadrol, alkyl dioxane hydramine or urea.
The suitable high-molecular weight dibasic alcohol that has that other are fit to is the poly-lactam glycol that is for example made by ∈-hexanolactam and low molecular weight diol reaction.
As components b b), it is possible using aliphatic series and/or cyclic aliphatic and/or aromatic polyisocyanate.The example of aromatic polyisocyanate is phenylene vulcabond, inferior cresyl vulcabond, eylylene diisocyanate, biphenylene vulcabond, naphthalene diisocyanate and diphenylmethanediisocyanate.
Because (ring) aliphatic polyisocyanate has good ultraviolet resistance, so they obtain being difficult for the product of jaundice.Its example is the hydrogenated products of isophorone diisocyanate, cyclopentylidene vulcabond and aromatic diisocyanate, as cyclohexylidene vulcabond, methyl cyclohexylidene vulcabond and dicyclohexyl methane diisocyanate.Aliphatic vulcabond is formula OCN-(CR
3 2)
rThe compound of-NCO, r is an integer in 2～20 in the formula, particularly 6～8; R3 can be identical or different, for hydrogen or have 1～8, the low-carbon alkyl of preferred 1～2 carbon atom.Its example is trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylene diisocyanate, ethyl ethylidene diisocyanate, dimethyl ethylidene diisocyanate, methyl trimethylene vulcabond and trimethyl cyclohexane vulcabond.Particularly preferred vulcabond is isophorone diisocyanate and dicyclohexyl methane diisocyanate.
Consider the functionality of polyisocyanates, components b b) must consequently obtain uncrosslinked urethane resin by such forming.Except vulcabond, components b b) also can contain a certain proportion of functionality greater than 2 polyisocyanates, example is a triisocyanate.The product that has proved suitable triisocyanate is those compounds of vulcabond trimerization or oligomeric generation or those compounds that generated by vulcabond and the compound reaction that contains polyfunctional hydroxyl or NH-.They for example comprise the biuret of hexamethylene diisocyanate and water, the isocyanuric acid ester of hexamethylene diisocyanate, or the affixture of isophorone diisocyanate and TriMethylolPropane(TMP).If desired, can average functionality be reduced by adding monoisocyanates.The example of such chain termination monoisocyanates is phenylcarbimide, NSC 87419 and isocyanic acid stearyl.
In order to ensure the extent of dilution of used urethane in water, must introduce in the polyurethane molecular forming anionic group.Can form anionic group therein with after can guarantee that urethane resin can be dispersed in the water aptly.Urethane acid number a) should be 10～60, preferred 20～35.The introducing polyurethane molecular can be calculated by acid number and anionic group quantity can be formed.
Forming anionic group, to introduce polyurethane molecular be by compound c c) be incorporated into polyurethane molecular and realize compound c c) in molecule, contain at least one and can form anionic group with the group of isocyanic ester radical reaction and one.
As amount of component b c), preferably use the compound that in molecule, contains two energy and the group of isocyanic ester radical reaction.Can with the suitable group of isocyanic ester radical reaction particularly hydroxyl, primary amino and/or secondary amino group.Can form anionic suitable group is carboxylic acid group, sulfonic group and/or phosphate, and carboxyl is preferred in this respect.As amount of component b c), for example use that two substituent paraffinic acids are arranged is preferred on alpha-carbon atom.Substituting group can be hydroxyl, alkyl, or preferred hydroxyalkyl.These paraffinic acids have one at least in molecule, 1～3 carboxyl is arranged usually.They have 2 to about 25, preferred 3～10 carbon atoms.Amount of component b c) example is dihydroxypropionic acid, dihydroxysuccinic acid and resorcylic acid.Particularly preferred paraffinic acid is that general formula is R
4-C (CH
2OH)
2The α of COOH, α-dihydroxymethyl paraffinic acid, R in the formula
4For hydrogen atom or the alkyl of about at the most 20 carbon atoms is arranged.
The example of such compound is 2,2-dihydroxymethyl acetate, 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid and 2,2-dihydroxymethyl valeric acid.Preferred dihydroxyl paraffinic acid is 2, the 2-dimethylol propionic acid.The example that contains amino compound is α, δ-Ornithine, 3,4-diaminobenzoic acid, 2,4 di amino toluene sulfonic acid and 2,4-diaminodiphenyl oxide sulfonic acid.
If desired, according to the present invention, the urethane resin of use a) useful molecules amount is 40～400 hydroxyl and/or amino organic compound or the mixture (component dd) of these compounds) prepare.Component dd) use increases the molecular weight of urethane resin.As component dd), it is possible for example using per molecule that the polyvalent alcohol of 20 carbon atoms is arranged at the most, ethylene glycol for example, Diethylene Glycol, triethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 4-butyleneglycol, 1, the 2-butyleneglycol, 1, the 6-hexylene glycol, TriMethylolPropane(TMP), Viscotrol C or hydrogenated castor oil, two (TriMethylolPropane(TMP)) ether, tetramethylolmethane, 1, the 2-cyclohexane diol, 1,4 cyclohexane dimethanol, dihydroxyphenyl propane, Bisphenol F, neopentyl glycol, the hydroxy new pentane acid DOPCP, the dihydroxyphenyl propane of hydroxyethylated or hydroxypropylation, Hydrogenated Bisphenol A and composition thereof.
By component utilized aa) and quantity dd), the quantity of normally used polyvalent alcohol is at most 30% (weight), preferred 2～20% (weight).As component dd), also can use the diamines and/or the polyamines that contain primary amino and/or secondary amino group.Polyamines mainly is the alkylene polyamine that 1～40 carbon atom, preferred about 2 to 5 carbon atoms are arranged.They can have the substituting group that does not contain with the hydrogen atom of isocyanic ester radical reaction.Its example is the polyamines that straight or branched aliphatic series, cyclic aliphatic or the aromatic structure of at least two primary aminos are arranged.The diamines that can mention is hydrazine, quadrol, propylene diamine, 1,4-butanediamine, piperazine, 1,4-cyclohexyl dimethylamine, 1,6-hexamethylene-diamine, trimethylhexamethylenediamine, terpene diamines, isophorone diamine, 4,4 '-diamino cyclohexyl-methane and N-aminoethyl ethanolamine.Preferred diamines is hydrazine, alkyl-or cycloalkyl-diamines, as propylene diamine and 1-amino-3 aminomethyl-2,5,5-trimethyl-cyclohexane.Use contains polyamines amino more than two as component dd in molecule) also be possible.But under these circumstances, it must be for example by also using monoamine to guarantee to obtain not crosslinked urethane resin.These spendable polyamines are diethylenetriamine, Triethylenetetramine (TETA), dipropylenetriamine and two butylidene triamines.The example of monoamine is an ethylhexylamine.
Component preparation a) is the prior art part, and is for example open in detail in US-A4719132, DE-A36 28124, EP-A89497, EP-A256540 and WO87/03829.
For in and component a), use ammonia and/or amine (particularly alkylamine), amino alcohol and cyclammonium, be possible as diethylamine and triethylamine, dimethylaminoethanol amine, diisopropanolamine (DIPA), morpholine or N-alkyl morpholine.For neutralization, easy volatile amine is preferred.
Consider that the tackiness agent and the ratio of pigment and/or filler are particularly importants.According to the present invention, this ratio is 0.5: 1 to 1.5: 1.Preferred range is 0.6: 1 to 1.2: 1.
Certified pigment and/or filler are talcums.Its ratio is 20～80% (weight) in the total amount of pigment and filler.Preferred range is 30～70% (weight).
If desired, according to the present invention, it is possible adding a small amount of aminoresin.By the total amount of formulation for coating material of the present invention, aminoresin should be greater than 10% (weight).Be preferably in below 5% (weight).
For those skilled in the art, such aminoresin is that everybody is familiar with, and they are provided as commerical prod by many companies.Aminoresin is particularly formaldehyde and for example condensation product of urea, melamine, guanamines and benzoguanamine of aldehyde.Aminoresin contains alcohol radical, particular methanol base, usually it partially or even wholly with alcohol or imino-etherificate.It is preferred using the melamine-formaldehyde resin of aminoresin, the particularly water-dilutable of water-dilutable.
Polyisocyanate crosslinker also can be present in the formulation for coating material.Its ratio usually less than 30% (weight), preferably less than 10% (weight).The reactivity of linking agent is usually less than 130 ℃.
It is shocking that described material of the present invention is compared with the comparable material of prior art, can obtain much lower coat-thickness.Its thickness promptly is usually less than 15 microns far below 35 microns.Although the coat-thickness that this is low is 35 microns and anti-the hitting property of stone of thick coating more can obtain corresponding to thickness.
After predrying under about 70 ℃, material of the present invention can apply with priming paint or Clear paint, then 130 ℃ of bakings down.If the color of formulation for coating material of the present invention is consistent with priming paint, so even may further reduce the coat-thickness of priming paint, and can not cause any mass loss.
Except above-mentioned substance, formulation for coating material of the present invention can contain known all auxiliarys and additive in paint technology, as organic acid, other pigment and filler, even paint etc.Use coating of the present invention, those skilled in the art can produce and can be used as the water-based stoving enamel that middle anti-stone hits priming paint and/or is used as filler, do not have problem.But it also is possible producing the water-borne coatings that is fit to other application.
Formulation for coating material of the present invention can for example spray with known the whole bag of tricks itself, brushing, dipping, flow coat, blade coating or roller coat are coated on any required ground, as metal, plastics, timber or on glass.The ground that applies can have suitable priming paint.
Therefore, the invention still further relates to a kind of method of producing overbrushing layer paint systems, wherein 1) uses the electrocoating paint coated substrate, the randomly predrying and baking of electrodeposited coating that 2) will in the 1st step, apply, 3) with the electrodeposited coating of first water-borne coatings coating through baking, 4) coating that applies in the 3rd step is randomly predrying, and under the situation of no baking procedure, apply with second water-borne coatings, 5) coating that applies in the 4th step is randomly applied with Clear paint, and 6) toast whole paint systems.
In this method, use above-mentioned formulation for coating material of the present invention.Obtaining astonishing result is, can apply and obtain coat-thickness is 15 microns or thinner, and don't can cause any mass loss.
Illustrate in greater detail the present invention with following embodiment.Unless add explanation in addition, all umbers and percentage ratio is expression by weight all.
1. the preparation of the urethane resin of water-dilutable
1.1 urethane resin I
With 480.3 the gram 73% polyester polyol (acid number: 3.5～4.0, by 39.5 parts heavy two polyester fat acid (Pripol
Unichema company), 21.7 parts heavy by 1 1013, manufacturers:, 6-hexylene glycol and 11.7 parts heavy m-phthalic acid preparations) methyl ethyl ketone solution, 31.4 gram dimethylol propionic acids, 169.1 gram dicyclohexyl methane diisocyanate (Desmodur
W, manufacturers: BayerAG), 6.5 gram neopentyl glycol and 56.2 gram methylethylketones are weighed under nitrogen in the dry reaction container of thermometer and reflux exchanger, then with mixture heating up to 85 ℃.This temperature is remained to NCO content always reach 1.11%.After being cooled to 78 ℃, 17.8 gram TriMethylolPropane(TMP)s and 91.3 gram methylethylketones are added.In case is 12～15 fens handkerchief seconds with N-Methyl pyrrolidone by weight the viscosity of reaction mixture sample of dilution in 1: 1, just 57.6 gram butyldiglycol is added in the reaction mixture, and makes reaction mixture 78 ℃ of maintenances 1 hour down.For the urethane resin that will so make changes into the form of water-dilutable, 11.7 gram dimethylethanolamines and 1020 gram distilled water are added.Under vacuum, 50～60 ℃, from the aqueous dispersions that generates, steam methylethylketone then.With dimethylethanolamine the pH value of dispersion liquid is adjusted to 7.2 then, and the solid content of dispersion liquid is adjusted to 36.7% (weight) with distilled water.
2. the preparation of water-borne coatings of the present invention
A) aqueous paint I
It is heavy to press the part shown in the table 1, the even paint of the commerce of a kind of and deionized water in the above-mentioned aqueous polyurethane dispersing liquid, a kind of acrylic resin based on water-dilutable, a kind of commercial defoamer based on the unsaturated side chain dibasic alcohol are dissolved in butyldiglycol and N, the solution of N-dimethylethanolamine mixes, the titanium dioxide of the aftertreatment of mixture and rutile class and talcum and with the dim slurries of making of commerce.This mixture is drained in the sand mill of intermittent type laboratory, be distributed to the fineness of measuring with the Hegmann grindometer always and reach maximum 10 microns.
Prepare aqueous paint I by this mixture then, add other urethane resin dispersion liquid and butyldiglycol, use N, the N-dimethylethanolamine is adjusted to 7.2～7.5 with the pH value, with deionized water spray viscosity is adjusted to 33 seconds (DIN4).
B) aqueous paint II and III
I is the same to be prepared aqueous paint II by painting with III.Part heavily is very clearly from table.
3. the test of the coating of aqueous paint of the present invention and the paint films that makes
Paint of the present invention is being 15 microns with the dried film thickness on the phosphatization steel plate of commercial electrocoating paint coating with static high-speed rotating equipment (Behr Ecobell, 45000 rev/mins, flow velocity: 120 ml/min, voltage: 60 kilovolts) spraying once.Being coated in air themperature and being 23 ℃, relative humidity of atomsphere and be 60% time carries out.Will be following dry 5 minutes at 23 ℃ through the plate of spraying.They subsequently under 70 ℃, in convection furnace predrying 5 minutes.In order to produce formulation for coating material I and III, apply 14 microns of builds with commercial argentine priming paint.Evaporation after predrying 5 minutes, was using commercial two-pack Clear paint to apply the prime coat of generation in convection furnace under 70 ℃ in 5 minutes then under 23 ℃, and dried film thickness is 35～40 microns.Under 130 ℃, whole coating system was toasted 30 minutes then.
In order to produce the coating system of paint II, the red aqueous priming paint that the electrostatic coating colorant is compatible, dried film thickness are 16 microns.Step is with described different.
The paint systems that makes has fine even coating and electrodeposited primer is had the good interlayer binding property that is coated with on the works of electrodeposited coating.
Anti-the hitting property of stone of paint systems produced according to the invention anti-hitting property of stone with the paint systems of producing by DE-A4005961 at least is the same high; Although the former coat-thickness attenuation.
Can in table 2, see the result of relevant comparison test.
Table 1
Aqueous paint aqueous paint aqueous paint
I II III polyurethane dispersing liquid I 30.00 30.00 30.00 even paint 0.60 0.60 0.60 deionized waters 10.00 12; 00 10.00 defoamers 2.00 2; 00 2; 00N, N-dimethylethanolamine 0.10 0.10 0.10 titanium dioxide 5.00 1.00 5.00 talcums 10.00 10.00 10.00Blanc Fixe (Sachtleben) 4.00 0.00 4.00Bayferrox 180 (Bayer) 0.00 2.00 0.00Bayferrox 130 (Bayer) 0.00 4.00 0.00Paliogenmarron L4020 (BASF) 0.00 2.00 0.00Aerosil R972 (Degussa) 0.20 0.20 0.20 dim 0.50 0.20 0.50 dispersed mixture, 62.40 64.10 62.40 polyurethane resin dispersion liquid I, 34.00 34.00 32.00Cymel 327 (Cyanamide), 0.00 0.00 2.00 butyldiglycol, 2.00 1.90 2.00 deionized waters 1.60 0.00 1.60
Table 2 paint I II III IV
*) V
*) the coat-thickness 15 15 15 35 15 one-shots test of stone-impact-proof paint
*) 4/0 6/0 5/0 6/5 5/5
*) test for steel ball with 250 kms/hour speed be cooled to-23 ℃ japanning plate by an angle of 90 degrees impact.With the surface (m that removes
2)/extent of corrosion evaluation test.Extent of corrosion from 0 (fine, as not to be penetrated into ground) to 5 (all being penetrated into ground in the entire area)
*) the finish paint structure is corresponding to sample paint 1 and 3.
Claims (15)
1. formulation for coating material that is used for overbrushing layer paint systems, it contains: a) a kind of acid number be 10～60 and number-average molecular weight be that the urethane resin of 4000～25000, preferred 8000～25000 water-dilutable is as tackiness agent, this resin can be reacted to each other and the reaction product of generation is partly neutralized and prepare by following component
Aa) a kind of number-average molecular weight is 400～5000 polyester polyol and/or polyether polyol or its mixture,
Bb) a kind of polyisocyanates or its mixture,
Cc) have the group of an energy and responding property of isocyanate group and have compound or its mixture that can generate anionic group at least in a kind of molecule at least, and optional
Dd) a kind of molecular weight is 40～400 the organic compound or its mixture that contain hydroxyl and/or amino, and b) pigment and/or filler, tackiness agent is 0.5: 1 to 1.5: 1 with the ratio of pigment.
2. according to the formulation for coating material of claim 1, wherein tackiness agent is 0.6: 1 to 1.2: 1 with the ratio of pigment.
3. according to each formulation for coating material in claim 1 and 2, wherein pigment and/or filler contain talcum.
4. according to the formulation for coating material of claim 3, wherein by the total amount of pigment and filler, the steatitic ratio is 20～80% (weight).
5. according to the formulation for coating material of claim 4, wherein the steatitic ratio is 30～70% (weight).
6. according to each formulation for coating material in the claim 1～5, wherein contain aminoresin.
7. according to the formulation for coating material of claim 6, wherein contain the aminoresin of 10% (weight) at the most.
8. according to the formulation for coating material of claim 7, wherein contain the aminoresin of 5% (weight) at the most.
9. according to each formulation for coating material in the claim 1～8, wherein contain polyisocyanate crosslinker.
10. according to the formulation for coating material of claim 9, wherein contain the polyisocyanate crosslinker of 30% (weight) at the most.
11., wherein contain the polyisocyanate crosslinker of 10% (weight) at the most according to the formulation for coating material of claim 10.
12. according to each formulation for coating material in the claim 1～11, wherein the reactivity of linking agent is lower than 130 ℃.
13. method of producing overbrushing layer paint systems, wherein 1) uses the electrocoating paint coated substrate, 2) the randomly predrying and baking of electrodeposited coating that the 1st step was applied, 3) with the electrodeposited coating of first water-borne coatings coating through baking, 4) coating that applies in the 3rd step is randomly predrying, under the situation that baking does not go on foot, apply with second water-borne coatings, 5) coating that applies in the 4th step is randomly applied with Clear paint, and 6) with whole paint systems baking.This method comprises that each formulation for coating material in the claim 1～12 is used for the 3rd to be gone on foot.
14. according to the method for claim 13, wherein with bed thickness be below 35 microns, preferred 15 microns apply formulation for coating material.
15. each formulation for coating material hits the application of coating in the claim 1～12 as the anti-stone in the water-based overbrushing layer paint systems.
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|---|---|---|---|
| CN 95195898 CN1162322A (en) | 1994-10-28 | 1995-10-25 | Paint coat composition useful in aqueous multilayer paint systems |
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|---|---|---|---|
| DE4438504.8 | 1994-10-28 | ||
| CN 95195898 CN1162322A (en) | 1994-10-28 | 1995-10-25 | Paint coat composition useful in aqueous multilayer paint systems |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101374920B (en) * | 2006-01-23 | 2011-02-09 | 关西涂料株式会社 | Water-based intermediate coating composition and method for the formation of multilayer coating film |
| CN102292166A (en) * | 2009-02-05 | 2011-12-21 | 巴斯夫涂料有限公司 | Coating agent for corrosion-resistant coatings |
| CN102341190A (en) * | 2009-04-24 | 2012-02-01 | 巴斯福涂料股份有限公司 | Method for the formation of multi-layer paint films |
| US8563634B2 (en) | 2009-02-03 | 2013-10-22 | Hewlett-Packard Development Company, L.P. | Inkjet ink including polyurethane |
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| CN102292366B (en) * | 2009-02-05 | 2015-07-22 | 巴斯夫涂料有限公司 | Coating agent for corrosion-stable paints |
| US9120924B2 (en) | 2006-11-17 | 2015-09-01 | Mitsui Chemicals, Inc. | Aqueous thermosetting composition |
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| CN107646041A (en) * | 2015-05-22 | 2018-01-30 | 巴斯夫涂料有限公司 | The method for preparing laminated coating |
| US10137476B2 (en) | 2009-02-05 | 2018-11-27 | Basf Coatings Gmbh | Coating agent for corrosion-resistant coatings |
| CN109627417A (en) * | 2018-10-25 | 2019-04-16 | 湖南湘江关西涂料有限公司 | The aqueous anti-stone of one kind hits dispersions of polyurethanes and preparation method thereof |
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1995
- 1995-10-25 CN CN 95195898 patent/CN1162322A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101374920B (en) * | 2006-01-23 | 2011-02-09 | 关西涂料株式会社 | Water-based intermediate coating composition and method for the formation of multilayer coating film |
| US9120924B2 (en) | 2006-11-17 | 2015-09-01 | Mitsui Chemicals, Inc. | Aqueous thermosetting composition |
| CN102300941B (en) * | 2009-02-03 | 2014-06-25 | 惠普开发有限公司 | An inkjet ink including polyurethane |
| US8563634B2 (en) | 2009-02-03 | 2013-10-22 | Hewlett-Packard Development Company, L.P. | Inkjet ink including polyurethane |
| CN102292366B (en) * | 2009-02-05 | 2015-07-22 | 巴斯夫涂料有限公司 | Coating agent for corrosion-stable paints |
| CN102292166B (en) * | 2009-02-05 | 2014-12-03 | 巴斯夫涂料有限公司 | Coating agent for corrosion-resistant coatings |
| CN102292166A (en) * | 2009-02-05 | 2011-12-21 | 巴斯夫涂料有限公司 | Coating agent for corrosion-resistant coatings |
| US10137476B2 (en) | 2009-02-05 | 2018-11-27 | Basf Coatings Gmbh | Coating agent for corrosion-resistant coatings |
| CN102341190A (en) * | 2009-04-24 | 2012-02-01 | 巴斯福涂料股份有限公司 | Method for the formation of multi-layer paint films |
| CN107646041A (en) * | 2015-05-22 | 2018-01-30 | 巴斯夫涂料有限公司 | The method for preparing laminated coating |
| TWI707006B (en) * | 2015-05-22 | 2020-10-11 | 德商巴斯夫塗料有限責任公司 | Method for producing a multicoat coating |
| CN105238251A (en) * | 2015-11-13 | 2016-01-13 | 无锡桥阳机械制造有限公司 | Coating for preventing and controlling haze |
| CN109627417A (en) * | 2018-10-25 | 2019-04-16 | 湖南湘江关西涂料有限公司 | The aqueous anti-stone of one kind hits dispersions of polyurethanes and preparation method thereof |
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