CN1285684C - High-polymer polyester water dispersed liquid for breakstone impacting resistant ground coating - Google Patents
High-polymer polyester water dispersed liquid for breakstone impacting resistant ground coating Download PDFInfo
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- CN1285684C CN1285684C CNB01823609XA CN01823609A CN1285684C CN 1285684 C CN1285684 C CN 1285684C CN B01823609X A CNB01823609X A CN B01823609XA CN 01823609 A CN01823609 A CN 01823609A CN 1285684 C CN1285684 C CN 1285684C
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- polyester
- aqueous liquid
- salt
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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- Application Of Or Painting With Fluid Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to water dispersed liquid of polyester salt, and polymer paint which contains the water dispersed liquid of the polyester salt. The polymer paint has special effect on coating adhesives formed in a solidified bottom coating. The bottom paint composition can be used for multilayer coating films which have at least two layers of coating films which comprise the solidified bottom coating composition film. The bottom coating polymer paint of the present invention can be used with one layer or multiple layers of other covering surface coating films to provide multilayer coating which improves the properties of adhesion and anti-rubble impact.
Description
The present invention relates to stabilized aqueous polyester dispersion liquid as base paint.More particularly, the waterborne polyester dispersion liquid has equilibrated high molecular and low hydroxyl value, to form the undercoat of the anti-rubble impact that can effectively improve the paint coatings that covers on the undercoat, keep the volatile organic compounds and the low viscosity of binding property and low levels simultaneously.
Background of invention
Automobile and other durable coating are complicated multilayer systems, and it relies on each other specified property standard of level and achieves success.The most of factor that improves anti-rubble impact is the base paint top layer.But the raising automotive coatings or the protectiveness of other type or the anti-rubble impact of ornamental durable coating obviously are and the system related task.For many systems, there are many The key factor can make it to be improved.Originally, anti-rubble impact test was exactly whether test has high stress, impact-resistance and shearing force, and these character intuitively go up can produce such hypothesis, and promptly described undercoat has the character that softish is similar to rubber.Base paint improves the reduction that brittle any effect finally can cause anti-rubble impact.This is relevant with degree of crosslinking.In these systems, very low and very high degree of crosslinking can cause relatively poor anti-rubble impact.Under the situation of low crosslinking degree, described coating does not have impact and the necessary strength characteristics of shearing force that the opposing gravel applies.Basis (base) molecular weight is too low usually and can not obtain the suitable elasticity relevant with photo-crosslinking.Viscous deformation (flow) and split (scission) when consequently gravel impacts.Very high cross-linking density can access a large amount of covalent cross-linkings that described coating is become fragile, and because coating can not absorb and these intensive power owing to gravel impact generation of uniform distribution are destroyed.Described material can not plastic deformation, can not elastic deformation, but it is cracked but can fragility to take place.And, because the crosslinking reaction between linking agent and the fluoropolymer resin can discharge by product VOC, so linking agent can produce VOC usually.And, in the complex system that uses various linking agents, the tendency of linking agent and himself reaction is arranged.For example, melamine crosslinker be exactly a kind of potential competing reaction from condensation, it causes the cross-linking highly of high crosslinked melamine resin to concentrate on regional area.This can produce the part and becomes fragile, thereby causes cracked or adhesion failure.For the anti-rubble impact of success, another key factor is bonding between described undercoat and the described base material, and bonding (must be exactly be coated with interlayer bonding) between other paint coatings subsequently and the described undercoat.The principal element that influences described effect is the functional group of functional group's one polar group of described undercoat resin, and described polar group is included in hydroxyl and the carboxyl that plays a crucial role in the interaction with base material and other coating.
In order to obtain best anti-rubble impact, the coating and described undercoat basis (base) resin that cover described undercoat must all pass to final coating with described equilibrated character.The easiest method that makes the mechanical property maximum of described undercoat resin is to improve molecular weight.But, improve the viscosity that molecular weight can improve described resin usually.And high viscosity resins can reduce its viscosity with organic solvent, has so just improved unwanted volatile organic compounds (VOC) amount
Summary of the invention
The present invention relates to the aqueous liquid dispersion and the polymkeric substance paint vehicle (vehicle) that comprises the polyester salt dispersion liquid of polyester salt.Described polymkeric substance paint vehicle is effective especially for obtain paint adhesive in cured base coating (solidified bottom coating film).Described primer composition (the also known coatings formulated composition that can be used as) can be used for multilayer film, and described filming has at least two coating films that comprise cured base coating composition film.Basecoat polymers paint vehicle of the present invention is filmed to be used in combination to provide with one or more layers other covering surfaces and is had the multilayer coating system that improves binding property and anti-rubble impact.
Basecoat polymers paint vehicle of the present invention allows to use less linking agent to come crosslinked described polyester salt.Use less linking agent can in cross-linking process, discharge less VOC, and form lower cross-linking density in the solidified coating adhesive films in described cured base coating composition.Have at described polyester salt under the condition of higher molecular weight, the cross-linking density of described minimizing provides improved anti-rubble impact.Though and without wishing to be bound by theory, but polyester salt of the present invention has higher molecular weight, thereby improve anti-rubble impact, and compare the polyester of forming identical (and not being metal or ammonium salt) but having lower molecular weight, only need less linking agent (they also can improve anti-rubble impact) to be solidified into useful filming.These low-molecular(weight)polymers can be used in the high solid system, and can be dispersed in organic solvent or with blended solvent solvent/water solvent system in.And, in the high solid system hereinafter, the molecular weight of described polyester does not improve, and do not improve the viscosity (improve molecular weight be exactly the viscosity that improves these systems) of described polymer dispersion liquid or solution from essence, therefore, polymkeric substance paint vehicle of the present invention comprise have that unique high molecular, lower hydroxyl value or array are closed, the polyester salt of unique hydroxyl value and the water-dispersion of the ratio of number-average molecular weight, and polyester with the acid number that can form water dispersible salt.
Described polyester salt is crosslinkable, in bottom coating film, to form the solidified coating tackiness agent, when described undercoat was a part of in the multilayer coating system, it had anti-rubble impact, and wherein said multilayer coating system has at least two coating film layers that comprise cured base coating film layer.The solidified coating tackiness agent of undercoat of the present invention also makes described multilayer coating system have anti-rubble impact.Therefore, the polymkeric substance paint vehicle balance of described primer composition the hydroxyl value and the number-average molecular weight of the polyester salt in the described aqueous liquid dispersion, reduce VOC with the water-based system that has less linking agent by use, and the binding property that improves the cured base coating film of anti-rubble impact and primer composition.
In order to improve the anti-rubble impact of the coating system that has used base paint of the present invention, required hydroxyl value is oppositely relevant with the molecular weight of polyester usually.For example, the polymkeric substance paint vehicle that described primer composition or preparation coating are used comprises the aqueous liquid dispersion of polyester salt, and described polyester salt is the residue of the polyester of about 1500 dalton of number-average molecular weight, hydroxyl value about 90.In this case, the hydroxyl equivalent of described polyester about 600.This aqueous liquid dispersion can provide the polyester paint vehicle that has less than the organic solvent of about 5 weight % effectively.For higher molecular weight, the polymkeric substance paint vehicle that described primer composition or preparation coating are used comprises the aqueous liquid dispersion of polyester salt, and described polyester salt is the residue of the polyester of about 2800 dalton of number-average molecular weight, hydroxyl value about 50.In this case, the hydroxyl equivalent of described polyester about 1100.Described aqueous liquid dispersion can provide the polymkeric substance paint vehicle that has less than the organic solvent of about 5 weight % effectively.
The anti-rubble impact of described multilayer coating system (it comprises the binders for coatings of undercoat of the present invention) is better than comprising the anti-rubble impact of the multilayer coating system of following undercoat, and above-mentioned undercoat has to be formed identical but molecular weight is lower and be not the polyester of salt.Low-molecular-weight polyester described later uses with organic solvent or blended organic solvent/water solvent system usually.Compare polymkeric substance paint vehicle of the present invention, they have a large amount of VOC, and need more linking agent to solidify usually.
In an importance of the present invention, the polymkeric substance paint vehicle that described primer composition or preparation coating are used comprises the aqueous liquid dispersion of polyester salt, and described polyester salt is that number-average molecular weight at least 1500 dalton, hydroxyl value are no more than 90 polyester residue.On the one hand, the hydroxyl equivalent of described polyester is about 600-about 1100.Described aqueous liquid dispersion can provide the polymkeric substance paint vehicle that has less than the organic solvent of 5 weight % effectively.Another importance, the granularity of the polyester salt in the described aqueous liquid dispersion is less than 400 nanometers.
On the other hand, described polyester salt is that acid number is at least 30 polyester residue, an importance, described acid number is about 40-about 50, the hydroxyl value of described polyester salt is about 90-about 50, the number-average molecular weight of described salt is about 1500-2800 dalton (cationic moiety that does not comprise described salt, promptly described salt comprise that molecular weight is about 1500-about 2800 daltonian polyester residues).Polymkeric substance paint vehicle curing when described base paint, and be when comprising two-layer at least multilayer coating system a part of of undercoat tackiness agent, polymkeric substance paint vehicle of the present invention can provide multilayer coating system and undercoat tackiness agent effectively, its have at least about 5 two pints (pint) rubble grade and at least about the two pints rubble size of A (using the No.J400 of automobile engineering rubble test association).Although used the higher molecular weight polyester, polymkeric substance paint vehicle of the present invention and aqueous liquid dispersion are at the organic solvent that uses less than about 5 weight %, and an importance, when using the organic solvent less than about 2 weight %, in about 25 ℃ viscosity less than about 10 pools.。
As mentioned above, compare identical molecular weight less than 1500 daltonian low-molecular-weight polyesters (it is not a salt), described polyester salt needs less normal linking agent, and the molecular weight of described polyester is usually less than about 800 dalton.Suitable crosslinking agent comprises multifunctional aminoresin and blocked isocyanate compounds.Polymkeric substance paint vehicle of the present invention generally includes the linking agent of the about 25 weight % of about 15-, in the polymkeric substance paint vehicle.The polymkeric substance paint vehicle that has used aforementioned low-molecular-weight polyester is not to be the polyester of salt, and it can be used in the high solid system, needs the linking agent of the about 50 weight % of about 35-usually.
In the present invention, only synthetic ionic functional polyester polymers mixes hydrophilic organic solvent subsequently.Formation has the polyester of enough ionogens, so that the polyester of the about 30-of acid number about 50 to be provided, thereby makes the waterborne polymeric dispersion liquid.The solubleness of described polymkeric substance in hydrophilic solvent is at least about 50 weight %, and the solubleness of described organic hydrophilic solvent in water is at least about 5 weight %.As described above, underway and reaction to be forming before the salt, and the number-average molecular weight of described polyester is at least about 1500, and an importance, and the about 1500-of number-average molecular weight is about 2800, and the about 50-of hydroxyl value about 90.In described solvent, the ionogen at least about 30% of described polyester polymers neutralizes with a certain amount of neutralizing agent, with in forming effectively and the solution of polyester salt.After this, in described and the solution of polyester salt mixes with water with formation water/organic solvent/in the mixture of polyester.Then, described organic solvent under being no more than about 65 ℃ temperature from mixture described later stripping go out, with in water, forming and the dispersion liquid of polyester salt.Described dispersion liquid is moored less than about 10 in about 25 ℃ viscosity.Described neutralizing agent can be any can the salifiable alkali of shape, but described alkali can with the ionic functional polymer-compatible, as sodium hydroxide or amine.One very important aspect, described neutralizing agent is an amine, it is selected from ammonia, trolamine, dimethylethanolamine and 2-amino-2-methyl-1-propanol.Not all ionogen on described polymkeric substance all needs and described alkali reaction (or neutralization).
According to the type of the ionogen in the described polymkeric substance, importantly described polymkeric substance be with neutral before water mixes, the neutral ionogen of water-dispersion is evenly distributed in the whole polymkeric substance usually like this.Also be very importantly described organic solvent and some water within a certain period of time, from described mixture, remove under certain temperature and the pressure or stripping is removed, to obtain the aqueous liquid dispersion that the resin mean particle size is not more than about 400 nanometers.An importance, described polyester salt concentration is at least about 30 weight %, and described organic solvent concentration is less than 5 weight %, even less than 2 weight %.An importance, when described neutralizing agent is amine or ammonia, in the mean particle size that is no more than about 65 ℃ stripping temperature and allows to keep under the pressure of described stripping temperature described resin.
On the other hand, the invention provides coatings formulated, it comprises aqueous liquid dispersion of the present invention and cosolvent, described cosolvent be selected from butyl cellosolve, diglycol monotertiary butyl ether, sec-butyl alcohol, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, propylene glycol n-propyl ether, glycol tertiary propyl ether, and composition thereof.These preparation coating compositions generally include rheology modifier, as pyrogenic silica and wilkinite.
Detailed Description Of The Invention
Definition
" hydroxyl value " or " hydroxyl value " (also be called " acetylation value) is the numerical value of a kind of material of expression degree that can be acetylation; It is in and the milligram number of the required potassium hydroxide of the acetate that in the process of saponification 1 gram acetylize sample, discharges.Concerning the application, hydroxyl value depends on solid polyester rather than the solution in the system.
" hydroxyl equivalent " calculated by hydroxyl value (OHN) according to following A STM D1957.
Hydroxyl equivalent=56100/OHN
The unit of hydroxyl value is a milligram KOH/ gram resin solid.
" polymkeric substance paint vehicle " refers to all polymkeric substance and the resin Composition in preparation coating (before promptly forming film), and it includes but not limited to the water dispersible salt of polymkeric substance.Described polymkeric substance paint vehicle can comprise linking agent.
" binders for coatings " refers to after solvent evaporation and after crosslinked, the polymer moieties of filming.
" preparation coating composition " refers to polymkeric substance paint vehicle and solvent, tinting material, catalyzer and additive, described additive can be chosen adding wantonly, so that described preparation coating obtains required application characteristic and make described film obtain required character such as opacity and color.
Described term " aqueous medium " refers to the mixture of water and water and hydrophilic organic solvent, and in described mixture, the content of water is 10 weight % at least.The example of hydrophilic solvent comprises alkyl alcohol (as Virahol, methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol and isopropylcarbinol), ether alcohol (as methylcyclohexane, ethyl cellosolve, propyl cellosolve, ethylene glycol butyl ether, methyl carbitol and ethyl carbitol), ether-ether (as methylcellosolve acetate and ethyl cellosolve acetate), two alkane, dimethyl formamide, diacetone alcohol, methyl ethyl ketone, acetone and tetrahydrofurfuryl alcohol.
" ionogen " refers to can influence the functional group of the water dispersible of described polymkeric substance on polymkeric substance.The example of ionogen comprises-COOH.
" neutralizing agent " refers to and can react with the ionogen on the described polymkeric substance, to influence the composition of water dispersible.The example of neutralizing agent of the present invention comprises amine, ammonia and metal hydroxides (comprising NaOH and KOH).In an importance of the present invention, described neutralizing agent is amine and ammonia.
" polyester salt residue " refers to the reaction product of ionizable polyester and neutralizing agent.
" linking agent " or " crosslinking reaction agent " refer to can with the polyfunctional compound of hydroxyl groups or phenolic hydroxyl group or both reactions.These reagent comprise having two or the compound or the multifunctional aminoresin of polyfunctional isocyanate's group.Described isocyanate compound or aminoresin comprise isocyanic ester or can form other crosslinking functionality of covalent linkage with described hydroxyl, and described hydroxyl is arranged on the polyester polyol of described polymkeric substance paint vehicle.Described linking agent can be a mixture; Therefore, can have a kind of material of surpassing to form mixture, described material can form covalent linkage with the hydroxyl of described polyester polyol.The linking agent that aminoresin and polyisocyanates come to this.
" isocyanate compound " refers to such compound, promptly forms amino-formate bond when with hydroxyl reaction.Described isocyanate compound can be end capped polyisocyanates, end capped biuret, end capped nitrogen urea diketone (uretdione) and end capped isocyanuric acid ester.
The vulcabond of the present invention that can be used for that joins among the HDI comprises isophorone diisocyanate (IPDI), tetramethylxylene diisocyanate (TMXDI), with other aliphatic diisocyanate (as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 1, the 2-trimethylene diisocyanate, 2,3-butylidene vulcabond, 1,3-butylidene vulcabond, 2,4,4-or 2,2, the 4-trimethyl hexamethylene diisocyanate), the cycloalkylidene vulcabond is (as 1,3-pentamethylene-vulcabond, 1,4-hexanaphthene-vulcabond and 1,3-hexanaphthene-vulcabond), and aromatic diisocyanate is (as the metaphenylene vulcabond, to phenylene vulcabond, 4,4 '-diphenyl diisocyanate, 1, the 5-naphthalene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 2,4-or 2,6-toluene (tolulene) vulcabond.
" polyisocyanates " can be to have two or more isocyanate groups (compound N=C=O), described compound can be biuret and isocyanuric acid ester.Described polyisocyanates can be dimerization or trimerization vulcabond (as trimerization HDI or IPDI) and triisocyanate (as triphenyl methane-4,4 ', 4 "-triisocyanate, 1; 3,5-three isocyanato-benzene, 1,3; 5-three isocyanato-hexanaphthenes, 2; 4,6-three isocyanato-toluene and ω-isocyanatoethyl-2,6-two isocyanato-capronates) and tetraisocyanate (as 4; 4 '-phenylbenzene dimethylmethane-2; 2 ', 5,5 '-tetraisocyanate).
" amino-formate bond " refer to-OC (=O) N (H)-, it can be a urethane bonds.
" biuret " refers under the ratio of three equivalent isocyanic ester and 1 mole of water, the material that the reaction of isocyanic ester and water generates, as the biuret of following HDI:
" isocyanuric acid ester " is to have nitrogen-atoms and at 2,4,6 six-rings with ketone group, described nitrogen-atoms replaces with isocyanate groups, HDI isocyanuric acid ester described as follows at 1,3,5.
Methylol (alkoxy methyl) amino crosslinker is applicable to the present invention, and is known commerical prod, and the reaction by two (many) acid amides (amine) compounds and formaldehyde and optional lower alcohol makes usually.
" aminoresin " comprises melamine resin, and also can refer to " melamine-formaldehyde resin " or " melamine-formaldehyde resin of alcoholization ".The example of suitable amino-cross-linked resin comprises a kind of following material or following mixtures of material:
Melamine base resin:
R such as following wherein:
R＝CH
3(Cymel)
300，301，303)；
R＝CH
3，C
2H
5(Cymel
1116)；
R＝CH
3，C
4H
9(Cymel
1130，1133)；
R=C
4H
9(Cymel
1156); Or
R＝CH
3，H(Cymel
370，373，380，385)。
Preferred melamine is a hexamethoxy methyl cyanuramide.
The benzo guanamine resin:
R=CH wherein
3, C
2H
5(Cymel
1123).
The urea groups resin:
Wherein:
R=CH
3, H (Beetle
TM60, Beetle
TM65); Perhaps
R＝C
4H
9(Beetle
TM80)。
Gycoluryl base resin:
Wherein:
R=CH
3, C
2H
5(Cymel
1171); Perhaps
R＝C
4H
9(Cymel
1170)。
" polyester " refers to have in main polymer chain
The polymkeric substance of key.
As described, the reaction product of alkali metal base or amine or ammonia and carboxylic acid group or other ionogen (it is the part of polyester) forms " salt ".
" essentially no solvent " refers to that polymkeric substance paint vehicle or preparation coating composition contain the organic solvent that is no more than about 5 weight %.
" solvent " refers to organic solvent.
" organic solvent " refers to the liquid including but not limited to carbon and hydrogen, and the boiling point of described liquid is no more than about 150 ℃ under about 1 normal atmosphere.
" hydrophilic solvent " refers at room temperature, and the solubleness in water is at least about the solvent of 5 weight %.
" volatile organic compounds " (VOC) defined in federal regulations 40 C.F.R 51.000 by EPA.
" Gao Gu " or " height is prepared coating composition admittedly " refers to comprise greater than about 30 weight % solid water-based coatings formulated compositions, and in an important aspect of the invention, the solids content that records according to ASTM test D-2369-92 is the about 70 weight % of about 35-." film " is by will preparing on substrate of coating composition paint or the base material, evaporating solvent (if any), and crosslinked (if necessary) forms.
When " the preparation coating composition of baking " refers under being higher than envrionment temperature heating or baking, can provide the preparation coating composition of best film character.
Refer to that about " dispersion liquid " of polymkeric substance paint vehicle, preparation coating composition or its component described composition must comprise liquid and can the detected particle of light scattering apparatus.
" dissolving " about polymkeric substance paint vehicle, preparation coating composition or its component refers to that there is not particle form in the dissolved material in liquid, and described particle is greater than unit molecule, and can be detected by light scattering apparatus.
" soluble " refers to partly or entirely to be dissolved in the liquid or solid in the liquid." easily miscible " refers to have the liquid of mutual solubility." suction " refers to that liquid can be miscible with water.
" acid number " or " acid number " refer to neutralization or with 1 gram material (as resin) in the milligram number of the required potassium hydroxide of the ionogen reaction that exists.
" do not contain emulsifying agent substantially " and refer to that composition contains the emulsifying agent that is no more than about 0.5 weight %.Aqueous liquid dispersion of the present invention is substantially free of emulsifying agent.
Described term " anti-phase " refers to that mobile phase becomes the phase transformation of disperse phase.For example, anti-phase usually occurring under such situation, promptly enough oil be added into oil-in-water mutually in, oil-in-water is with regard to the anti-phase water-in-oil phase that becomes like this.On the contrary, in " no anti-phase " system, mobile phase can not become disperse phase, and viscosity can be along with dispersion liquid correspondingly increases.In an importance of the present invention, in treating processes, the viscosity of described system under 25 ℃, remain on less than 20 the pool, one very important aspect, less than 10 the pool.
The first step: preparation polyester
In the first step of the present invention, only the synthesizing polyester polymkeric substance is sneaked into it in organic hydrophilic solvent subsequently, and described solvent is limited to the solvent that has infinitely great solubleness in water.The used polyester polymers of the present invention comprises the polymkeric substance that can form polyester salt, and described polyester salt is that number-average molecular weight is about 1500-about 2800 daltonian polyester residues.In an importance of the present invention, the acid number of described polyester polymers is less than about 50, one very important aspect, the about 30-of acid number about 50.
Used polyester is the reaction product of polyvalent alcohol and polycarboxylic acid.The example of suitable polyvalent alcohol comprises three pure and mild tetrols (as TriMethylolPropane(TMP), trimethylolethane, three (hydroxyethyl) isocyanuric acid ester, glycerine and tetramethylolmethane) and dibasic alcohol or glycol, described dibasic alcohol or glycol can comprise neopentyl glycol, dihydroxymethyl glycolylurea, ethylene glycol, propylene glycol, 1,3-butyleneglycol, glycol ether, dipropylene glycol, 1,4-cyclohexanedimethanol, Esterdiol204 (trade mark of Union Carbide), 1, ammediol, 1,6-hexylene glycol and dimethylol propionic acid (DMPA).Can find out that by DMPA polyvalent alcohol can have-the COOH group.
The used carboxylic acid of the present invention can be aromatic carboxylic acid (as m-phthalic acid, terephthalic acid, phthalic acid, Tetra hydro Phthalic anhydride, dimethyl terephthalic acid, naphthalene decarboxylate, tetrachlorophthalic acid, bis-glycol terephthalate and benzophenone dicarboxylic acid) and alicyclic, aliphatic carboxylic acid and polyprotonic acid (as trimellitic acid 1,2-anhydride (TMA)).Can find out that by TMA diacid can have other-the COOH group.
In another importance of the present invention, only synthetic polyester polymers and solvent, described solvent is selected from alkyl alcohol (as Virahol, methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol and isopropylcarbinol), ether alcohol (as methylcyclohexane, ethyl cellosolve, propyl cellosolve, ethylene glycol butyl ether, methyl carbitol and ethyl carbitol), ether-ether (as methylcellosolve acetate and ethyl cellosolve acetate), two alkane, dimethyl formamide, diacetone alcohol, methyl ethyl ketone, acetone and tetrahydrofurfuryl alcohol.Under treatment temp, the solubleness of polymkeric substance of the present invention in hydrophilic solvent is at least about 50 weight %, more preferably at least about 80 weight %, in the gross weight of composition.
The first step provides the resin that can be kept in the hydrophilic solvent, and it can further be handled in second step.One important aspect, the storage stability of the resin that provides in the first step was at least about 6 months.
Second step: polyester dispersion liquid
In and resin:
Original position forms described polyester salt in described organic solvent, and wherein water mixes with the mixture of polyester salt/organic solvent.In the present invention, the neutralizing agent of significant quantity is joined in the organic solvent solution that contains polyester, with in and polyester make it to form enough salt described polyester be dispersed in the water.The used neutralizing agent of the present invention includes but not limited to ammonia, trolamine, dimethylethanolamine, 2-amino-2-methyl-1-propanol, NaOH and KOH.
The add-on of neutralizing agent depends on acid number and molecular weight.On the one hand, the hydroxy-acid group of about 30-about 100% is neutralized, with solids content and the low VOC content that obtains dispersion liquid of the present invention.On the other hand, the neutralizing agent of significant quantity mixes with polyester polymers to form the polymer salt at least about 70 parts in less than about 30 parts solvent, wherein for subsequently with the mixing step of water, described neutral polymkeric substance can form and comprise the dispersion liquid that is no more than about 70 weight % water, in the weight of dispersion liquid.
Of the present invention one very important aspect, when ionogen was carboxyl, it is about 100% that described polyester need be neutralized about 70%-, to stablize described dispersion liquid.In another importance of the present invention, the particle that described method provides mean particle size to be no more than about 400 nanometers, and the mean particle size that usually records with laser light scattering instrument is in the scope of about 200 nanometers of about 40-.
Described polyester polymers (carries out pre-neutralization as-COOH) metal, amine or ammonium salt by making its formation have ionogen.If form the ionogen neutral words not of the part of described polymkeric substance, the acid number (recording by titration) of the polymkeric substance that is formed by these " pre-neutralization " monomers is at least about 30.In this aspect of the invention, monomer has polyfunctionality (as two functionality), so just can make them can form the polymkeric substance of the salt form with ionogen.
A this monomeric example is
Wherein A and B be-OH and/or-COOH, they can form polyester with condensation reaction, C is-COOX that wherein X is basic metal such as sodium or potassium.
Add entry
In next step of treatment process second step, temperature is that about 25 ℃-Yue 65 ℃ water is added in the neutral resin solution.Lesser temps provides less mean particle size.
In an importance of the present invention, for polyester polymers, solvent and water be about 0.15-about 0.45 initially than (solvent/water).The initial ratio of solvent and water is very important, and it can guarantee not take place in stripping dissolving agent process subsequently anti-phase.The add-on of water can be greater than the amount that needs for the required solid that obtains final dispersion liquid.The loss of some water usually occurs in the still-process of solvent.Before adding entry, described system is needing enough solvents to stablize described salt at first.
In another aspect of this invention, the polymkeric substance in hydrophilic solvent is added in the water that comprises neutralizing agent.
Remove and desolvate
In the next step of described method, from described neutral resin/water/solvent mixture, remove or stripping is gone out organic solvent and water (if necessary).On described mixture, apply less than atmospheric pressure, to help to remove described solvent and water.One important aspect, vacuum tightness is about 22 inches-Yue 29 inches mercury pressure.For lower temperature, must use higher vacuum tightness to remove and desolvate.Lower temperature of reaction causes forming less foam, and helps to stave these bubbles with higher vacuum that the surface tension of bubble interrelates.In another aspect of this invention, solvent/water uses heat exchanger to heat, to carry out stripping.The use of heat exchanger can reduce distillation time and temperature, thereby further makes the destruction minimum of salt.
Of the present invention one very important aspect, for polyester, can obtain solids content at least about the about 45 weight % of 30 weight %-.
In another aspect of this invention, the solvent of removing can carry out purifying and reuse.Simple flash distillation or multistep distillation are enough to remove any pollutent in the described solvent.
On the other hand, the present invention can use single reaction vessel to make aqueous liquid dispersion from described polymkeric substance.After distilling described solvent, aqueous liquid dispersion of the present invention does not need emulsifying agent, and the content of organic solvent is no more than about 2 weight %, with composition weight meter.One important aspect, described aqueous liquid dispersion comprises the organic solvent of the about 2 weight % of about 0.2-.
Aqueous liquid dispersion of the present invention comprises the polymkeric substance amine salt and the not salifiable polymkeric substance of water dispersible, but, in one aspect of the invention, when described ionogen is carboxyl, in the polymkeric substance of aqueous liquid dispersion of the present invention, be not neutralized or become salt less than the free carboxy of 30 weight %.When the acid number of described polymkeric substance descended, the carboxyl of the more percentage ratios on the described polymkeric substance must be neutralized.When ionogen be-during COOH, for described dispersion liquid is maintained at about 15 acid number, about 100% carboxyl should be neutralized into described salt on the polymkeric substance.In an importance of the present invention, about 100% carboxyl is neutralized salify on the polymkeric substance, and in the dispersion liquid of the present invention, and the per gallon dispersion liquid comprises and is no more than about 1 pound VOC (120 grams per liter), one important aspect, the per gallon dispersion liquid comprises about 0.2 pound VOC.Aqueous liquid dispersion of the present invention (per gallon comprises 0.2 pound of VOC) freezes the molten cycle and can freeze in the molten cycle at about 4 at most at least one is stable.Can increase by a spot of solvent that is generally used for the latex system or glycol and to freeze the molten cycle.
The preparation coating composition
The polymkeric substance paint vehicle is sneaked into the preparation coating composition, and described composition can form the preparation coating composition or the cured compositions of baking when heating.Toast with linking agent being higher than under the room temperature, to obtain paint adhesive.The polymkeric substance paint vehicle that comprises aqueous liquid dispersion of the present invention provides a kind of preparation coating composition, contain VOC in the per gallon preparation coating composition less than 1 pound, described composition comprises aqueous dispersion polymers and the salt thereof with above-mentioned molecular weight, and does not only need but also be substantially free of emulsifying agent, tensio-active agent and coalescing agent.
The aqueous liquid dispersion of this high-molecular weight polymer provides has the binders for coatings that improves membrane property and the preparation coating composition of baking, and described improvement membrane property includes but not limited to that the film-forming properties of the same good, the wet film blade coating improved performance of the raising of anti-rubble impact, binding property and lower molecular weight, high VOC system, per pass film is stronger, accelerate time of drying, the erosion resistance of per pass film increases, the film erosion resistance increases, film is hard, the film wear resistance improves and the raising of film wet fastness.Polymkeric substance paint vehicle of the present invention also provides the binders for coatings that is used for improved outside " UV resistant " durable membranes, and described " UV resistant " durable membranes derives from the low VOC preparation coating composition of water-based.But compare the water reductive system of the crosslinked thermosetting polymer of water-based thermoplastic emulsion or low molecular weight thermoplastic plastics or needs, film of the present invention has certain improvement.
Following embodiment has described and has implemented method of the present invention, and should think that they just are used to the scope of the present invention that illustrates that appended claims limits, rather than limits the scope of the invention.
Embodiment
Embodiment 1: the polyester dispersion liquid
A. synthesizing polyester polymkeric substance:
1. with 218.9 gram neopentyl glycol (NPG), 77.2 gram TriMethylolPropane(TMP)s (TMP) and 248.4 grams 1,6-hexylene glycol (HDO) is put into the round-bottomed flask that packed column, fractional distillating tube, susceptor and nitrogen protection are housed.
2. heat described flask and melt, and under the situation of stirring, add 322.8 diacid (AA) and 322.8 of restraining oneself and restrain m-phthalic acids (IPtA) up to described glycol.
3. with described temperature-stable and progressively bring up to 220 ℃, and remove the water that esterification produces.
4. when acid number is 6.8, described temperature is reduced to 170 ℃.
5. in described flask, add 80 gram trimellitic acid 1,2-anhydrides (TMA), and described temperature remains on 170 ℃.
6. remove the water that esterification produces, reach 46.3 up to acid number.
7. described temperature is reduced to 90 ℃, with methyl ethyl ketone (MEK) dissolving (cut) described polymkeric substance.
The character of described polyester liquid:
Percent solids (NVM) 70
Acid number (milligram KOH/ gram) 45
Molecular weight (Mn) 2350
Hydroxyl value (milligram KOH/ gram) 65
B. prepare the polyester dispersion liquid
1. the polyester liquid and the 26.4 gram AMP-95 that 635 grams are arranged in MEK put into the round-bottomed flask that total condenser and susceptor are housed.
2. under the condition of stirring, described flask is heated to 40 ℃.
3. when arriving described temperature, in about 30 minutes time, add 666 gram deionized waters.
4. described flask is vacuumized, and slowly bring up to 26 inches mercury pressures of maximum value.
5. continue to keep vacuum up in described dispersion liquid, obtaining required percent solids.
6. after the distillment of removing desired number, stop described vacuum, and analyze the product that obtains.
The character of described polyester dispersion liquid:
Percent solids (NVM) 41.0
Viscosity (centipoise) 45
PH (unit) 6.0
Granularity (nanometer)＜80
Weight/gallon (pound) 8.9
Embodiment 2: the polyester dispersion liquid
A. synthesizing polyester polymkeric substance:
1. 1170.0 gram neopentyl glycol (NPG), 412.5 gram TriMethylolPropane(TMP)s (TMP) and 1687.5 gram butyl-ethyl-propylene glycol (BEPD) are put into the round-bottomed flask that packed column, fractional distillating tube, susceptor and nitrogen protection are housed.
2. heat described flask and melt, and under the situation of stirring, add 1725.0 restrain oneself diacid (AA) and 1725.0 m-phthalic acids (IPtA) that restrain up to described glycol.
3. with described temperature-stable and bring up to 220 ℃ step by step, and remove the water that esterification produces.
4. when described acid number is 3.1, described temperature is reduced to 170 ℃.
5. in described flask, add 427.5 gram trimellitic acid 1,2-anhydrides (TMA), and described temperature is remained on 170 ℃.
6. remove the water that esterification produces, reach 41.2 up to acid number.
7. described temperature is reduced to 90 ℃, and dissolves (cut) described polymkeric substance with Virahol (IPA).
The character of described polyester liquid:
Percent solids (NVM) 69.4
Acid number (milligram KOH/ gram) 41.1
Molecular weight (Mn) 2050
Hydroxyl value (milligram KOH/ gram) 65
B. prepare the polyester dispersion liquid
1. with polyester liquid and the 26.4 gram Ns of 1352 grams in IPA, N-dimethylethanolamine (DMEA) is put into the round-bottomed flask that total condenser and susceptor are housed.
2. under the condition of stirring, described flask is heated to 40 ℃.
3. when reaching described temperature, in about 30 minutes, add 1476 gram deionized waters.
4. described flask is vacuumized, and slowly bring up to 26 inches mercury pressures of maximum value.
5. continue to keep vacuum up in described dispersion liquid, obtaining required percent solids.
6. after the distillment of removing desired number, stop described vacuum, and analyze the product that obtains.
The character of described polyester dispersion liquid:
Percent solids (NVM) 42.6
Viscosity (centipoise) 45
PH (unit) 7.0
Granularity (nanometer)＜80
Weight/gallon (pound) 8.9
Embodiment 3: the formulation for coating material that contains the polyester dispersion liquid
Preparation coating:
Be mixed with base paint as the following dispersion polyester that will derive from embodiment 1:
1. the resin dispersion liquid of the 228 gram parts that will prepare in embodiment 1 is put into 1 liter of stainless steel mixing vessel.
2. then in described resin dispersion liquid, add 9 gram propylene glycol single-butyl ethers and 36 gram deionized waters.
3. insert vertical decollator then.
4. under stirring, add 195 gram TiO
2(R-960 is DuPont) with 5 gram Raven 16.
5. 3 millimeters granulated glass spherees of about 300 grams of adding in described container, and described mixture high speed dispersion 30 minutes are to disperse described pigment to 7Hegman.
6. the speed with described shredder is reduced to mixing velocity, and adds following component under stirring at a slow speed:
143 gram polyester dispersion liquids
40 gram Cymel 301
7.2 gram Nacure 3525
0.5 gram Surfynol 104BC
7. after sneaking into these components, cross pan (cone) by 25 microns and filter described mixture, to remove described granulated glass sphere.With AMP-95 the pH value is adjusted to 8.2-8.5 then, then its ford cup viscosity (Ford cup) is reduced to 34-36 second (second) #4 with deionized water.
In the coating that obtains, the calculating content of VOC is less than 2.0 pounds/gallon, and the content of non-volatile substance is 51 weight %.
The character of described coating:
By spraying to the high rim protection test coatings formulated is arranged on the steel plate galvanized of cataphoretic coating.The build of base paint is 1.0 Mills.The plate that applies at room temperature dodges to be done 5 minutes, dodged in the stove of 180 then again and did 10 minutes.The plate that applies toasted 25 minutes under 330 .Mask 3 inches on the top of described plate, described then plate carries out surface-coated with the system that commercially available automobile water causes basic coating/Clear paint, and 275 baking 20 minutes.Then, with on the plate only electropaining 3 millimeters cross hatches (crosshatch) of covering the zone of base paint and surface-coated zone check bonding.On two zones of described plate, all have good bonding.Under 20 ℃, in Q-plate gravel abrasion tester (panel gravelometer machine), impact the bottom of this plate with 2 pints gravel.Described plate has good anti-rubble impact.
Bonding grade: gravel abrasion tester
Grade: GM8
Has only undercoat 0
Top coat 1
Wherein 0=does not have defective
1=is less than 5% defective
Embodiment 4: the formulation for coating material that contains the polyester dispersion liquid
Preparation coating:
Be mixed with base paint as the following dispersion polyester that will derive from embodiment 2:
1. will put into 1 liter stainless steel mixing vessel by the 201 grams resin dispersion liquid partly of embodiment 2 preparations.
2. then in described resin dispersion liquid, add 15 gram butyl cellosolves and 26 gram deionized waters.
3. insert vertical decollator then.
4. under stirring, add 151 gram TiO
2(R-920 is DuPont) with 3 gram Raven 16.
5. 3 millimeters granulated glass spherees of about 300 grams of adding in described container, and described mixture high speed dispersion 30 minutes are to disperse described pigment to 7Hegman.
6. the speed with described shredder is reduced to mixing velocity, and adds following component under stirring at a slow speed:
106 gram polyester dispersion liquids
56 gram BL-3175
5.4 gram Cymel 303
6.8 gram Nacure 5528
2.2 gram DC-14
7. after sneaking into these components, cross pan (cone) by 25 microns and filter described mixture, to remove described granulated glass sphere.With DMEA the pH value is adjusted to 8.2-8.5 then, then its ford cup viscosity is reduced to 30-32 second (second) #4 with deionized water.
In the coating that obtains, the calculating content of VOC is less than 2.0 pounds/gallon, and the content of non-volatile substance is 53 weight %.
The character of described coating:
On the cold-rolled steel sheet that sprays to cataphoretic coating, the test coatings formulated.The build of base paint is 1.0 Mills.The plate that applies at room temperature dodges to be done 5 minutes, dodged in the stove of 180 then again and did 10 minutes.The plate that applies toasted 25 minutes under 330 .Described then plate carries out surface-coated with the system that commercially available automobile water causes basic coating/Clear paint, and 250 baking 30 minutes.
Then, check bonding with 3 millimeters cross hatches in surface-coated zone.On described plate, have good bonding.Then at room temperature, lower part of in the cracked test machine of Erichsen, impacting this plate with 1 kilogram steel sand.Described plate has good crumpling resistance.
Bonding grade: Erichsen
Grade: 7
Wherein 10 is best
Top coat 00 is the poorest
Wherein 0=does not have defective
Embodiment 5: binding property grade result
Test according to SAE J400.
| Symbol | The baking of electropaining layer | The undercoat baking |
| U/U U/T U/H T/U T/T T/H H/U H/T H/H | 10×330F 10×330F 10×330F 10×360F 10×360F 10×360F 10×390F 10×390F 10×390F | 25×275F 25×330F 60×375F 25×275F 25×330F 60×375F 25×275F 25×330F 60×375F |
U=toasts not enough
The baking of T=target
The H=paint baking over
10 * 330F=toasted 10 minutes under 330 .
| Polyester type | Hydroxyl value | U/U | U/T | U/O | T/U | T/T | T/O | O/U | O/T | O/O |
| NPG NPG/ HDO NPG | 118 73 55 | 9/4 1/2 0/0 | 3/4 0/1 0/1 | 5/9 0/0 3/0 | 9/8 3/1 0/1 | 9/8 1/1 0/1 | 1/1 0/1 0/0 | 7/4 0/1 0/1 | 1/3 0/1 0/1 | 0/1 0/1 0/1 |
Annotate: 0=removes 0%
2=removes 5%
6=removes 25%
7=removes 45%
10=removes 95%
Embodiment 6: the fragment grade
Test according to ASTM D3359
| Polyester type | Hydroxyl value | 2 pints of rubbles number | 2 pints of macome-scales | 3 pints of rubbles number | 3 pints of macome-scales | Note |
| NPG | 118 | 5 grades | B | 4 grades | B | The lower end of standard hydroxyl value scope (100-200) |
| BEPD | 110 | 4 grades | B | 3 grades | B | The lower end of standard hydroxyl value scope (100-200) |
| NPG/HDO | 117 | 5 grades | B | 3 grades | B | The lower end of standard hydroxyl value scope (100-200) |
| BEPD | 117 | 4 grades | B | 4 grades | B | The lower end of standard hydroxyl value scope (100-200) |
| NPG/BEP | 66 | 5 grades | A | 4 grades | A | Target zone less than mean value |
| NPG/HDO | 73 | 5 grades | A | 4 grades | A | Target zone less than mean value |
| NPG/BEP | 72 | 5 grades | A | 4 grades | A | Target zone less than mean value |
| NPG | 55 | 5 grades | A | 4 grades | A | Target zone less than mean value |
| BEPD | 65 | 5 grades | A | 4 grades | A | Target zone less than mean value |
| NPG | 38 | 5 grades | A | 4 grades | A | Low-down hydroxyl value |
In the every standard area of rubble grade: 5=25-49 rubble arranged
Those of ordinary skill in the art can make many improvement and change to the present invention under understanding foregoing description situation of the present invention.Therefore, these improvement and change are also included within the scope of the present invention.
Claims (16)
1. polyester salt aqueous liquid dispersion, described dispersion liquid does not contain emulsifying agent substantially, the acid number of the polyester residue of described polyester salt is that 30-50, number-average molecular weight are that 1500-2800 and hydroxyl value are no more than 90, the median size of described polyester salt in described aqueous liquid dispersion is less than 400 nanometers, and the organic solvent content of described aqueous liquid dispersion is less than 5 weight %.
2. aqueous liquid dispersion as claimed in claim 1, it is characterized in that described polyester comprise can be neutralized form water dispersible salt-the COOH group.
3. aqueous liquid dispersion as claimed in claim 1 is characterized in that described aqueous liquid dispersion also comprises the linking agent that is selected from aminoresin, isocyanate compound and composition thereof.
4. waterborne polymeric dispersion liquid that forms by following method, described method comprises:
Formation has enough-polyester of COOH group, and be that 1500-2800 and hydroxyl value are 50-90 so that the acid number of polyester is 30-50, number-average molecular weight,
Described polyester is blended in the organic hydrophilic solvent, the solubleness at least 50 weight %s of described polyester polymers in hydrophilic solvent, and the solubleness at least 5 weight %s of described organic hydrophilic solvent in water,
With in the neutralizing agent and described polyester at least 30% can ionogen, during the amount of described neutralizing agent is enough to form and the solution of polyester salt,
With in described and the solution of polyester salt mixes with water, with formation water/organic solvent/in the mixture of polyester, and
Be no more than under 65 ℃ the temperature, with described organic solvent from water/organic solvent/and in the polyester mixture stripping go out, with in forming and the aqueous liquid dispersion of polyester salt,
Described dispersion liquid does not contain emulsifying agent substantially, and median size is less than 400 nanometers, and the viscosity of described dispersion liquid under 25 ℃ is less than 10 pools.
5. waterborne polymeric dispersion liquid as claimed in claim 4 is characterized in that described neutralizing agent is selected from ammonia, trolamine, 2-amino-2-methyl-1-propanol and dimethylethanolamine.
6. waterborne polymeric dispersion liquid as claimed in claim 4, it is characterized in that in described and the solution of polyester in add entry, it is 0.15-0.45 that the amount of adding is enough to make the organic solvent and the initial ratio of water.
7. the aqueous liquid dispersion of a polyester salt, described dispersion liquid does not contain emulsifying agent substantially and contains organic solvent less than 5 weight %, the number-average molecular weight of the polyester residue of described polyester salt in the 1500-2800 scope, hydroxyl value is that 90-50 and acid number are 40-50, described polyester have can be neutralized form water-dispersible polyester salt-the COOH group.
8. polyester salt aqueous liquid dispersion as claimed in claim 7, the number-average molecular weight that it is characterized in that described polyester be 1500 and hydroxyl value be 90.
9. polyester salt aqueous liquid dispersion as claimed in claim 7, the number-average molecular weight that it is characterized in that described polyester salt be 2800 and hydroxyl value be 50.
10. as claim 7 or 8 or 9 described polyester salt aqueous liquid dispersions, the median size that it is characterized in that described dispersion liquid is less than 400 nanometers.
11. polyester salt aqueous liquid dispersion as claimed in claim 10 is characterized in that described aqueous liquid dispersion also comprises the linking agent that is selected from aminoresin, isocyanate compound and composition thereof.
12. the aqueous liquid dispersion of a polyester salt, the polyester residue of described polyester salt has carboxyl, it is that 30-50, number-average molecular weight are that 1500-2800 and hydroxyl value are the polyester of 90-50 that described polyester residue can provide acid number, the median size of described polyester salt in described aqueous liquid dispersion is less than 400 nanometers, and the organic solvent content of described aqueous liquid dispersion is less than 5 weight % and do not contain emulsifying agent substantially.
13. aqueous liquid dispersion as claimed in claim 12 is characterized in that described aqueous liquid dispersion also comprises the linking agent that is selected from aminoresin, isocyanate compound and composition thereof.
14. the aqueous liquid dispersion of a polyester salt, the acid number of the polyester residue of described polyester salt is that 30-50, number-average molecular weight are that 1500-2800 and hydroxyl value are 90-50, the median size of described polyester salt in described aqueous liquid dispersion is less than 400 nanometers, and the organic solvent content of described aqueous liquid dispersion is less than 2 weight % and do not contain emulsifying agent substantially.
15. aqueous liquid dispersion as claimed in claim 14, it is characterized in that described polyester comprise can be neutralized form water dispersible salt-the COOH group.
16., it is characterized in that described aqueous liquid dispersion also comprises the linking agent that is selected from aminoresin, isocyanate compound and composition thereof as claim 14 or 15 described aqueous liquid dispersions.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2001/028284 WO2003022946A1 (en) | 2001-09-10 | 2001-09-10 | Aqueous dispersion of high molecular weight polyester for chip resistant primer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1549849A CN1549849A (en) | 2004-11-24 |
| CN1285684C true CN1285684C (en) | 2006-11-22 |
Family
ID=21742827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB01823609XA Expired - Fee Related CN1285684C (en) | 2001-09-10 | 2001-09-10 | High-polymer polyester water dispersed liquid for breakstone impacting resistant ground coating |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1427789A1 (en) |
| JP (1) | JP2005527645A (en) |
| KR (1) | KR20040062944A (en) |
| CN (1) | CN1285684C (en) |
| WO (1) | WO2003022946A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7666951B2 (en) | 2005-02-24 | 2010-02-23 | Ppg Industries Ohio, Inc. | Coating compositions that include a polyester polyol, related coated substrates, multi-layer coating and methods |
| CN107001815B (en) * | 2014-08-22 | 2020-02-07 | 巴斯夫涂料有限公司 | Aqueous dispersion of polyester and low acid number polyamide and coating composition for applying base coat comprising said aqueous dispersion |
| FR3037589B1 (en) * | 2015-06-17 | 2020-02-28 | Arkema France | HYDROXYLATED AND / OR CARBOXYLATED POLYESTER RESIN WITH HIGH EXTRACT DRIED AND HIGH COVERING FOR METAL SHEET COATING |
| KR102290742B1 (en) * | 2017-12-08 | 2021-08-18 | 도요보 가부시키가이샤 | Polyester resin, polyester resin aqueous dispersion, and method for producing polyester resin aqueous dispersion |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4036378A1 (en) * | 1990-11-15 | 1992-05-21 | Basf Lacke & Farben | Aq. coil-coating compsn. for metal substrates - contains polyester(s) with carboxyl and hydroxyl gps., opt. acrylate¨ resin(s), amino resin(s) and wax(es) |
-
2001
- 2001-09-10 CN CNB01823609XA patent/CN1285684C/en not_active Expired - Fee Related
- 2001-09-10 KR KR10-2004-7003454A patent/KR20040062944A/en not_active Application Discontinuation
- 2001-09-10 JP JP2003527013A patent/JP2005527645A/en active Pending
- 2001-09-10 EP EP01968756A patent/EP1427789A1/en not_active Withdrawn
- 2001-09-10 WO PCT/US2001/028284 patent/WO2003022946A1/en active Application Filing
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| Publication number | Publication date |
|---|---|
| KR20040062944A (en) | 2004-07-09 |
| EP1427789A1 (en) | 2004-06-16 |
| JP2005527645A (en) | 2005-09-15 |
| CN1549849A (en) | 2004-11-24 |
| WO2003022946A1 (en) | 2003-03-20 |
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