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CN1094428A - Water base paint compositions - Google Patents

Water base paint compositions Download PDF

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CN1094428A
CN1094428A CN 94100502 CN94100502A CN1094428A CN 1094428 A CN1094428 A CN 1094428A CN 94100502 CN94100502 CN 94100502 CN 94100502 A CN94100502 A CN 94100502A CN 1094428 A CN1094428 A CN 1094428A
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郭钊明
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Eastman Chemical Co
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Eastman Chemical Co
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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
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • 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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
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Abstract

Provide curable water-based resin composition, in its available amine and generate quaternary ammonium salt with phenol functional group.Coating by these preparation of compositions shows fabulous performance and can be used as coating composition as car paint, instrument coating and mechanical coating.

Description

Water base paint compositions
The invention belongs to organic chemistry filed.More particularly the present invention relates to be applicable to the polymer blend of water base paint compositions.
Recently, because the concern of environment and government department are used for the regulation of volatile organic compounds (VOCs) quantity of coating composition to reduction, water-based paint has become an important research field.Compare with the other technologies that develop for the regulation that meets VOC (for example high solids content, pulvis and uv curing coating), water-based paint is owing to adopting a considerable amount of water to replace this volatile organic compounds to represent a kind of practicable substitute.Yet for the trial that obtains satisfied water-based paint is usually failed, this is because the wetting ability of paint adhesive.Though water-based paint will be produced with hydrophilic resin, be used in when outdoor, should have water-proof solidified coating.Therefore, how to reach these two purposes simultaneously and especially the coating scientist has been proposed challenge.In the present invention, the crosslinkable polyester that employing has the phenol end group obtains cabisan salt, this salt is scattered in the water then and is mixed with industry and cures coated material (baking enamel), Zhi Bei thermosetting coating shows excellent water tolerance like this, also show other premium properties simultaneously, and be suitable as high-performance coating, for example car paint, instrument coating and mechanical coating.
The common water base neutralizing effect of curing coated material based on the curable resin that contains carboxyl functional group that is used for industrial coating, these resins can produce the quaternary ammonium salt of water-dispersion.This amine neutralisation commonly used is quite explained.(referring to: for example, Olding and Hayward edit, " Resins for Surface Coatings " the 3rd " SITA Technology ", London, 1987, the 171 pages).
Above-mentioned common aqueous composition is by adding polyprotonic acid in solidifiable polyester resin synthetic, benzene tricarboxylic acid and generate the composition that is rich in carboxyl for example, and said composition then neutralizes with amine and is scattered in the water and makes.Perhaps, the polymer blend that is rich in hydroxyl can react with benzene tricarboxylic acid or acid anhydrides (for example benzene tricarboxylic acid, benzene front three acid anhydride (TMA) or phthalic acid), the curable polyester of carboxyl is rich in generation, polyester can further be used amine (for example N, N-dimethylethanolamine, triethylamine) or ammoniacal liquor neutralization.For preparing satisfied water-based coating material (water-borne enamel) composition, solidifiable polyester resin should have about 40 to about 70 acid number.The amine that is used to form hydrophilic salts can cure in the process at solidified and evaporate.Yet the coating that makes like this is owing to have remaining amine, unreacted TMA and wetting ability carboxyl end groups in cured film and to water sensitive.
Open in many reference with phenolic group end capped (end-capped) crosslinkable resin.Yet this resin also is not used to obtain to be used for the hydrophilic cabisan salt of water-based paint.European patent application 419,088 discloses the end capped liquid polymers of ester phenol and polyhydric alcohol composition cooperates with amino crosslinker, obtains to have filming of superperformance.United States Patent (USP) 2,993,873 time of drying and the coating properties that disclose the Synolac of oily modification can improve with following manner: with the part unsaturated fatty acids in the carboxyl phenylformic acid replacement resin formula.Coating is in the presence of cross-linking agent-free, through air-dry or cure and solidify.United States Patent (USP) 4,267,239 and 4,298,658 have illustrated that Synolac is through obtaining modification with the para-hydroxybenzoic acid reaction.The resin that generates can at room temperature solidify rapidly with isocyanic ester in the presence of tertiary amine steam.United States Patent (USP) 4,343,839 and 3,836,491 disclose in the presence of tertiary amine catalyst steam, at room temperature rapid a kind of coating composition of solidified.This coating composition is the polyester and the polyisocyanate curing agent of phenol end group.United States Patent (USP) 4,331,782 disclose improving one's methods of the polyester that adopts hydroxy-benzoic acid and epoxy compounds and pre-adducts anamorphic zone phenolic group functional group.Japanese Patent 75 40,629,76 56,839,76 44,130 and 77 73,929 disclose the powder paint compositions that comprises the phenolic group hydroxyl end groups.These resins have high softening-point and are used for the surface with powder form.
The invention provides and have the curable resin composition that generates the phenolic group functional group of quaternary ammonium salt with in the amine and back.The salt of these resins is hydrophilic, therefore, can be scattered in the water and further be mixed with industry cure coated material.The end group of resin described herein be rich in hydroxyl and resin have about 5 to about 39 low acid number.During acid number described herein is meant and the milligram number of the required potassium hydroxide of the carboxyl end groups of 1 gram in the resin sample.According to ASTM Method(method) D.1639 analyze, but terminal point is determined so that the outrun of terminal point with phenolic group functional group separated with potentiometric titration.These resins with acid number of about 5 to about 39 can directly be used amine (for example N, N-dimethylethanolamine or triethylamine) neutralization.Therefore, need not to adopt to benzene tricarboxylic acid acid anhydride water sensitive, highly toxic as the composition in the resin combination.When paint solidification, amine can easily be removed from cabisan salt, and phenolic group and suitable linking agent react rapidly.As a result, the coating of being made by coated material composition of the present invention shows fabulous water tolerance.The coating that makes with composition of the present invention can be used as car paint, instrument coating and mechanical coating.
The invention provides a kind of water-based coating material compositions, comprising:
(I) contains the ammonium salt that at least one aryl hydroxy functional group and acid number are about 5 to about 39 curable polymer, and described polymkeric substance has following structure:
Wherein Z is the residue of curable polymer; Ar is the aryl moiety on the end of the chain, skeleton or the side chain that is connected on the described polymer residue; R ' is hydrogen, C 1-C 6The C of alkyl or replacement 1-C 6Alkyl; N is equal to or greater than 1 integer;
(II) contains can be with component (I) reaction and form the suitable functional group of filming, the dispersible linking agent of water; With
(III) is enough to an amount of water of dispersed component (I) and (II).
Above-mentioned composition is provided in a preferred embodiment of the invention, wherein the scope of component (I) existence is: about 25 to about 65%(weight), the scope that component (II) exists is about 5 to about 20%(weight), the scope that component (III) exists is about 30 to about 70%(weight), the summation of (I), (II), (III) is 100%.
Above-mentioned coated material composition also can comprise an amount of organic cosolvent.This kind solvent comprises: the solvent that ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, isopropylcarbinol, ethylene glycol monobutyl ether, propylene glycol n-butyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol methyl ether, Pyranton and other and water dissolve each other.
The polymkeric substance of component (I) comprises, for example: polyester, alkyd, epoxy compounds and acrylic polymers.
Amine salt in the component (I) is polymkeric substance (as polyester) and the amine by the tool phenol functional group, prepared in reaction under room temperature, stirring.At polymkeric substance is under the situation of polyester, also can be oil-free polyester or alkyd.Reactant (for example, glycol, triol/polyvalent alcohol, diacid and aryl alcohol acid) preferably in the presence of the condensation catalyzer, mixes purely, and is heated to about 175 to about 230 ℃.The general reaction times about 5 was to about 20 hours.Generally, reaction requires to use a steam-heated fractional distillating tube, condensation product-water and/or alcohol is removed, and volatile reactant is condensed.Reaction is preferably carried out in the nitrogen of constant flow rate.
In above-mentioned polyester synthetic, also preferably triol/polyvalent alcohol is mixed with the aryl alcohol acid in the fs of reaction, with the generation glycol adducts, add glycol and diacid again.
In the curable polyester of this class, suitable diol residue is preferably from the residue of following compound: ethylene glycol, propylene glycol, 1, ammediol, 2,4-dimethyl-2-ethyl-1,3-hexylene glycol, 2,2-dimethyl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 2-ethyl-2-isobutyl--1, ammediol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 2,2,4-trimethylammonium-1, the 3-pentanediol, thiodiethanol (thiodiethanol), 1,2-cyclohexyl dimethanol, 1,3-cyclohexyl dimethanol, 1,4-cyclohexyl dimethanol, 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol, to an xylylene glycol, Diethylene Glycol, triethylene glycol, TEG and amyl group ethylene glycol, hexyl ethylene glycol, heptyl ethylene glycol, octyl group ethylene glycol, nonyl ethylene glycol and decyl ethylene glycol; The suitable triol and/or the residue of polyvalent alcohol are selected from the residue of following compounds: trihydroxymethyl propane, methyltrimethylolmethane, glycerol, 2,2-dihydroxymethyl-1, ammediol, 1,2,3,4,5,6-hexahydroxy-hexane and two (2, the 2-dihydroxymethyl)-3-propyl alcohol ether.
The carboxylic acid residues of curable polyester is preferably from the residue of following compounds: oxalic acid; propanedioic acid; dimethyl malonic acid; succsinic acid; pentanedioic acid; hexanodioic acid; trimethyladipic acid; pimelic acid; 2; the 2-dimethylated pentanedioic acid; nonane diacid; sebacic acid; fumaric acid; toxilic acid; methylene-succinic acid; 1; 3-encircles pentanedioic acid; 1; the 2-cyclohexane diacid; 1; the 3-cyclohexane diacid; 1; the 4-cyclohexane diacid; phthalic acid; terephthalic acid; m-phthalic acid; 2; 5-norbornane diacid; 1; 4-naphthalene diacid; diphenic acid; 4; 4 '-the oxygen dibenzoic acid; diglycollic acid; thiodipropionic acid; 4; 4 '-alkylsulfonyl dibenzoic acid and 2,6-naphthalene diacid or their acid anhydrides.
In this kind polyester, the residue of aryl alcohol acid is preferably from the residue of following acid: right-hydroxy-benzoic acid ,-hydroxy-benzoic acid, Whitfield's ointment, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 1-hydroxyl-4-naphthoic acid, 1-hydroxyl-5-naphthoic acid, 1-hydroxyl-6-naphthoic acid, 1-hydroxyl-7-naphthoic acid, 1-hydroxyl-8-naphthoic acid, 2-hydroxyl-4-naphthoic acid, 2-hydroxyl-5-naphthoic acid, 2-hydroxyl-6-naphthoic acid, 2-hydroxyl-7-naphthoic acid and 2-hydroxyl-8-naphthoic acid.
Alcohol acid constituents (I) is above-mentioned a kind of polyester, further unsaturated fatty acids or oil, introduces polymer chain as Toenol 1140, Yatall MA, soya-bean oil, Oleum Cocois or the like.
Epoxy component (I) is preferably the diglycidylether of the dihydroxyphenyl propane that makes by dihydroxyphenyl propane and epichlorohydrin (as DER330,331,332,337, can available from Dow Chemical company) condensation.The polymkeric substance that contains phenol functional group gets by these epoxy polymers and aryl alcohol acid (as listed above) reaction.
Acrylic polymers component (I) is preferably monomer by hydroxyl (as methacrylic acid hydroxyl ethyl ester, Hydroxyethyl Acrylate, the own ester of vinylformic acid hydroxyl, the own ester of methacrylic acid hydroxyl, the vinylformic acid hydroxy propyl ester, methacrylic acid hydroxyl propyl ester, vinylformic acid hydroxyl butyl ester, methacrylic acid hydroxyl butyl ester or the like) or contain the epoxy group(ing) monomer (as glycidyl acrylate, glycidyl methacrylate) polymkeric substance that polyreaction makes or resin, optional and other monomer are (as methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate, isobutyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, EHA, ethylhexyl methacrylate, vinylbenzene, vinyl-acetic ester, vinylformic acid, methacrylic acid or the like) polymerization.The acrylic polymers that contains phenol functional group can make by the acrylic polymers of above-mentioned hydroxyl or epoxy group(ing) and aryl alcohol acid reaction as listed above.
Aryl moiety in the component (I) is preferably phenyl or naphthyl and also can further be selected from C respectively by 1 to 3 1-C 4Alkyl, C 1-C 4The group of alkoxy or halogen replaces.
The example of linking agent comprises: amino crosslinker, as HMMM, methoxymethyl/methylol-trimeric cyanamide mixture, butoxy/methoxyl group-methyl melamine mixture, tetramethoxy-methylbenzo quanamine, tetramethoxy methyl urea or the like; The isocyanates linking agent, as tolylene diisocyanate, hexamethylene diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate or the like; The epoxies linking agent is as bisphenol A epoxide resin or the like.The preferred carbamide class of linking agent linking agent promptly has a large amount of-N(CH 2OR 3) 2(R wherein 3Be C 1-C 4Alkyl or hydrogen, preferable methyl) linking agent of functional group.
Generally, linking agent can be selected from the compound of following formula, wherein R 3Be respectively C 1-C 4Alkyl or hydrogen:
Figure 94100502X_IMG2
In the ammonium salt preparation of component (I), adopt formula N(R ') 3Compound, wherein R ' is hydrogen, C 1-C 6The C of alkyl or replacement 1-C 6Alkyl.Described " C 1-C 6Alkyl " example comprise: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, n-pentyl, sec.-amyl sec-pentyl secondary amyl, hexyl, Sec-Hexyl or the like.Described " the C of replacement 1-C 6Alkyl " comprising: be selected from halogen, nitro, hydroxyl, C by 1 to 3 1-C 6The abovementioned alkyl group that the group of alkoxyl group and cyano group replaces.
Formula N(R ') 3The amine preferred examples comprises: N, N-dimethylethanolamine, triethylamine, diethylamine, ammonium hydroxide, trolamine, diethanolamine, thanomin, Yi Bingchunan, N, N-diethylethanolamine, 2-N, N-dimethylamino-2-methyl-propyl alcohol, 2-amino-2-methyl propyl alcohol, N-ethylmorpholine or the like.Special preferred tertiary amine.
As mentioned above, n is the integer more than or equal to 1, preferred 1 to about 10.
A kind of water-based coating material compositions is provided in another embodiment of the invention, has comprised:
(I) 25% is to about 65%(weight) the ammonium salt of the curable polyester that contains phenol functional group, the acid number of wherein said polyester is about 5 to about 39, number-average molecular weight be about 800 to about 3,500 and weight-average molecular weight be about 3,000 to about 70,000, comprise:
(a) for (a) and (b), (c), (d) and (e) total mole number be about 20% to about 45%(mole) diol residue;
(b) for (a) and (b), (c), (d) and (e) total mole number be about 4% to about 21%(mole) the triol residue;
(c) for (a) and (b), (c), (d) and (e) total mole number be about 5% to about 20%(mole) the aliphatic diacid residue;
(d) for (a) and (b), (c), (d) and (e) total mole number be about 20% to about 35%(mole) the aryl diacid residues;
(e) for (a) and (b), (c), (d) and (e) total mole number be about 12% to about 20%(mole) aryl alcohol acid residue;
(II) about 5% is to about 20%(weight) amino crosslinker;
(III) about 0 is to about 10%(weight) the organic solvent that can dissolve each other with water; With
(IV) about 30% is to about 70%(weight) water.
The overall weight percent of (I), (II), (III) and (IV) is 100.
As another aspect of the present invention, a kind of water-based coating material compositions is provided, comprise:
(I) about 25% is to about 65%(weight) the ammonium salt of the curable polyester that contains phenol functional group, the acid number of wherein said polyester is about 5 to about 39, number-average molecular weight is about 800 to about 3,500, weight-average molecular weight is about 3,000 to about 70,000, comprises:
(a) for (a) and (b), (c), (d) and (e) total mole number be about 20% to about 45%(mole) diol residue;
(b) for (a) and (b), (c), (d) and (e) total mole number be about 4% to about 21%(mole) the triol residue;
(c) for (a) and (b), (c), (d) and (e) total mole number be about 0 to about 20%(mole) non-cycloaliphatic diacid residue;
(d) for (a) and (b), (c), (d) and (e) total mole number be about 20% to about 35%(mole) the cyclic aliphatic diacid residues;
(e) for (a) and (b), (c), (d) and (e) total mole number be about 12% to about 20%(mole) aryl alcohol acid residue;
(II) about 5% is to about 20%(weight) amino crosslinker;
(III) about 0 is to about 10%(weight) the organic solvent that can dissolve each other with water;
(IV) about 30% is to about 70%(weight) water.
The overall weight percent of (I), (II), (III) and (IV) is 100.
The most preferred acid number scope of polyester of the present invention is about 10 to about 25.
The example of cyclic aliphatic diacid component comprises: 1, and 2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid and 1,3-pentamethylene dicarboxylic acid and their acid anhydrides.1, the 4-cyclohexane dicarboxylic acid is very preferred.
Coated material among the present invention can at high temperature be dissolved in the organic cosolvent by making pure vibrin, then with amine and water dispersed resin solution, adds linking agent again and makes.Coated material also can be by occupying machine solvent 70%-80%(weight) resins.This heavy-gravity, flowable resin by resin is synthetic finish after, in reaction mixture, add suitable organic solvent and make, and store.Under agitation, in this resin, add amine, water and linking agent, generate aqueous dispersions, need not heating.
Coating is being higher than 150 ℃ of curing down, thereby need not acid catalyst.For obtaining the best coatings performance and being curing, also usable acid catalyzer at a lower temperature.Suitable acid catalyst comprises: tosic acid, NACURE 5076,155,1051(King Industries) and contain amine segmental acid catalyst, as BYK-catalyzer 450,460,470(BYK-Chemie USA).
As another aspect of the present invention, a kind of foregoing crosslinkable coated material composition is provided, it also comprises one or more levelling agents, rheological agent and flowing regulator (as polysiloxane, fluorocarbon or Mierocrystalline cellulose), flatting agent, pigment wetting agent and dispersion agent, tensio-active agent, ultraviolet (UV) light absorber, UV light stabilizing agent, tinting pigment, defoamer and foam inhibiting agent, antisettling agent, anti-sagging agent, reaches viscosifying agent, anti-skinning agent, anti-floating and anti-flooding agent, sterilant, mould inhibitor, stopping agent, thickening material or coalescing agent.
The specific examples of these additives can be from Raw Materials Index(by National Paint ﹠amp; Coatings Association publishes, 1500 Rhode Island Avenue, N.W; Washihgton finds in D.C.20005).
The example of flatting agent comprises: synthetic silicon-dioxide (can be from Davison Chemical Division of W.R.Grace ﹠amp; Company buys, and registered trademark is SYLDID
Figure 94100502X_IMG3
), (can buy from Hercules Inc., registered trademark is HERCOFLAT to polypropylene
Figure 94100502X_IMG4
), (can buy from J.M.Huber Corporation, registered trademark is ZEOLEX to synthetic silicate ).
The example of dispersion agent and tensio-active agent comprises: double tridecyl sulfo-sodium succinate, two (2-ethylhexyl) sulfo-sodium succinate, dihexyl sulfo-sodium succinate, dicyclohexyl sulfo-sodium succinate, diamyl sulfo-sodium succinate, diisobutyl sulfo-sodium succinate, isodecyl sulfo-disodium succinate, the ethoxylation ethanol Carbenoxolone Sodium salt of sulfo-succsinic acid, many oxyethyl groups of alkyl amido sulfo-disodium succinate, just-(1,2-dicarboxyl-ethyl 3-Octadecane base sulfo-succsinic acid four sodium, n-octyl sulfo-disodium succinate, the sulfonated ethoxylated nonylphenol, 2-amino-2-methyl-1-propanol, and can be from BYK-Chemie, U.S.A buys, and registered trademark is BYKUMEN , DISPERBYK
Figure 94100502X_IMG7
, LACTIMON
Figure 94100502X_IMG8
Product or the like.
The example of viscosity, suspension and mobile conditioning agent comprises: the alkylamino salt of polyaminoamide phosphoric acid, high-molecular weight polyaminoamide carboxylate salt and unsaturated fatty acids, and these products can be buied from BYK Chemie U.S.A, and registered trademark is ANTI TERRA
Figure 94100502X_IMG9
Other example comprises: the Natvosol of polysiloxane copolymer, polyacrylate solution, cellulose ester, Natvosol, hydrophobically modified, hydroxypropylcellulose, polyamide wax, polyolefin-wax, carboxymethyl cellulose, ammonium polyacrylate, sodium polyacrylate and polyoxyethylene.
For example, several patented foam inhibiting agents, what buy on the market is: the registered trademark of Buckman Laboratories Inc. is BRUBREAK, BYK Chemie, and the registered trademark of U.S.A is BYK
Figure 94100502X_IMG10
, Henkel Corp., Coating Chemicals registered trademark be FOAMASTER
Figure 94100502X_IMG11
And Nopco
Figure 94100502X_IMG12
, Drew Industrial Division of Ashland Chemical Compny registered trademark be DREWPLUS
Figure 94100502X_IMG13
, Troy Chemical Corporation registered trademark be TROYSOL
Figure 94100502X_IMG14
And TROYKYD
Figure 94100502X_IMG15
And the registered trademark of Union Carbide Corporation is SAG Foam inhibiting agent.
Sterilant, the example of mould inhibitor and sterilant comprises: 4,4-dimethyl-1, the 3-oxazolidine, 3,4,4-trimethylammonium-1, the 3-oxazolidine, the barium metaborate of modification, N-hydroxyl-methyl-N-methyl dithiocarbamic acid potassium, 2-(sulfo-cyano group-methylthio group) benzothiazole, potassium dimethyldithiocarbamate, diamantane, the N-(trichloro-methylthio) phthalic imidine, 2,4,5, the different phthalonitrile of 6-tetrachloro, orthoxenol, 2,4, the 5-Trichlorophenol, dehydroacetic acid (DHA), copper naphthenate, cupric octoate, organic arsenide, tributyltin oxide, zinc naphthenate and 8-quinolinic acid copper.
The example of uv-absorbing agent and UV light stabilizing agent comprises: substituted benzophenone, substituted benzo three thiazoles, hindered amine and the benzoic ether that is obstructed (can be buied from American Cyanamide Company; registered trademark is Cyasorb UV, and also can buy registered trademark from Ciba Geigy is Tinuvin) and diethyl-3-ethanoyl-4-hydroxyl-phenyl-phosphoric acid ester, 4-dodecyloxy-2-dihydroxy benaophenonel and resorcinol monobenzoate.
The additive of foregoing these paint or coating accounts for less relatively ratio in the coated material composition, preferred about 0.05% to about 5.00%(weight).
As another aspect of the present invention, a kind of curable coated material composition is provided, it is optional to comprise in the above-mentioned additive one or more, also comprises one or more pigment.
Be applicable to that the pigment in the coated material composition that the present invention estimates is common organic and mineral dye (any one those of ordinary skill that is the topcoating field is known), particularly list in Colour Index, the third edition, those dyestuff examples in the revised edition (1982, by the Society of Dyers and Colourists and the American Association of Textile Chemists and Colorists combined publication) include, but is not limited to for the second time: CI Pigment white 6(titanium dioxide), CI Pigment Red 101(red iron oxide), CI Pigment Yellow 42, CI Pigment Blue 15,15: 1,15: 2,15: 3,15: the 4(CuPc), CI Pigment Red 49: 1 and CI Pigment Red 57: 1.
In a manner described after the preparation, curable coated material composition is used for required base material or goods, for example steel, aluminium or zinc coated sheet (priming or not priming), heating (promptly solidifying) makes temperature reach about 130 ℃ to about 175 ℃, and the time cycle is the 5-60 branch, then cooling, therefore, as another aspect of the present invention, a kind of setting or formed article are provided, it is coated by thermosetting coating compositions of the present invention and solidifies.
Other example of typical application and curing can be consulted United States Patent (USP) 4,737, and 551 and 4,698,391(lists in this as a reference).
As one side more of the present invention, provide the coating of using aforementioned curable coated material composition also to solidify and obtaining.
Experimental section
The preparation of embodiment 1-resin 1
In the three neck round-bottomed flasks that mechanical stirrer, vapor portion condenser, Dean-Stark collector and water condenser are housed, add following reactant: trihydroxymethyl propane (TMP) 121.1g(0.90mol), right-hydroxy-benzoic acid (PHBA) 146.5g(1.06mol), catalyzer FASCAT 4100 0.5g and colour stabilizer WESTON 618 1g.With mixture heating up to 150 ℃ and in nitrogen atmosphere, stir.In one hour by a definite date, temperature rises to 220 ℃ and overhead product gradually and is collected in the Dean-Stark collector.When collecting (more than 1.5 hours) less than overhead product, show that the reaction of fs is finished, add neopentyl glycol (NPG) 222.0g(2.13mol then) and m-phthalic acid (IPA) 358.6g(2.16mol).After the restir eight hours, add hexanodioic acid (AD) 81.8g(0.56mol).Four hours afterreactions of restir are finished, and obtaining a kind of is the resin of 59 pools 175 ℃ of following ICI Cone and Plate viscosity.Be collected in this resin in the metal vessel and it can be cooled to room temperature (rt).
The preparation of embodiment 2-water-based coating material 1
With resin 1(40g) be heated to 125 ℃, in being housed, stirs by the round-bottomed flask of water condenser.In resin, add ethylene glycol monobutyl ether (10g) (EKTASOLVE ethylene glycol monobutyl ether (EB) can be buied from the Eastman Chemical Company of branch of Eastman Kodak Company), add N then, N-dimethylethanolamine (1.25g).Mixture was stirred 20 minutes, be cooled to 50 ℃ then, (60g) progressively adds in the mixture distilled water, obtains a kind of lactous aqueous dispersion.In above-mentioned aqueous dispersion, add CYMEL 303(American Cyanamid) (10g) and add water (10g) and make the water-based coating material.
Embodiment 3-solid content is the preparation of 70% resin 2
In the three neck round-bottomed flasks that mechanical stirrer, vapor portion condenser, Dean-Stark collector and water condenser are housed, add following reactant: TMP 70.19g(0.52mol), PHBA 84.90g(0.62mol), catalyzer FASCAT 4100 0.45g and colour stabilizer WESTON 618 0.92g.With mixture heating up to 150 ℃ and in nitrogen atmosphere, stir.Temperature rises to 200 ℃ and overhead product gradually and is collected in the Dean-Stark collector.The fs reaction is finished after three hours, adds NPG 120.00g(1.15mol) and IPA 207.81g(1.25mol).After four hours, add AD 47.40g(0.32mol at 220 ℃ of following restir).3.5 hours afterreactions of restir are finished, and obtaining 175 ℃ of following ICI Cone and Plate viscosity is the resin of 43 pools.This resin is cooled to 145 ℃, adds 196g ethylene glycol monobutyl ether (EB), obtains solid content and be 70% resin.
The preparation of embodiment 4-water-based coating material 2
To above-mentioned (solid content is 70% in EB) resin 2(28.6g) in add DMEA(0.55g) and distilled water (30g).Stir the mixture and obtain aqueous dispersion.Adding CYMEL 303(5.0g in this dispersed system), (content 20% in Virahol, 0.3g) with extra water (17g), obtains the water-based coating material for FLOURAD FC-430 flowing regulator (3M Company).
Embodiment 5-solid content is the preparation of 75% resin 3
In the three neck round-bottomed flasks that mechanical stirrer, vapor portion condenser, Dean-Stark collector and water condenser are housed, add following reactant: TMP 70.19g(0.52mol), PHBA 84.90g(0.62mol), catalyzer FASCAT 4100 0.45g and colour stabilizer WESTON 618 0.92g.With this mixture heating up to 150 ℃ and in nitrogen atmosphere, stir.Temperature rises to 200 ℃ and overhead product is collected in the Dean-Stark collector gradually.The fs reaction is finished after three hours, adds NPG 120.00g(1.15mol then) and 1,4-cyclohexyl dicarboxylic acid 270.94g(1.58mol).Stir six hours afterreactions down at 220 ℃ again and finish, obtaining a kind of 175 ℃ of following ICI Cone and Plate viscosity is the resin of 29 pools.This resin is cooled to 145 ℃, adds 160g ethylene glycol monobutyl ether (EB), obtain solid content and be 75% resin.
The preparation of embodiment 6-water-based coating material 3
To above-mentioned resin 3(solid content in EB is 75%) add DMEA(0.75g in (40.0g)) and distilled water (30g).Stir this mixture and obtain aqueous dispersion.Adding CYMEL 303(American Cyanamid in this dispersed system) (7.5g), (content 20% in Virahol for FLOURAD FC-430 flowing regulator (3M Company), 0.4g) and extra water (30g), obtain a kind of water-based coating material.
The preparation of embodiment 7-comparative resin
In the three neck round-bottomed flasks that mechanical stirrer, vapor portion condenser, Dean-Stark collector and water condenser are housed, add following reactant: NPG 267.40g(2.57mol), TMP 38.20g(0.29mol), IPA 203.69g(1.23mol), AD179.00g(1.23mol) and catalyzer FASCAT 4100 0.8g.With mixture heating up to 150 ℃ and in nitrogen atmosphere, stir.Temperature rises to 175 ℃ gradually, and continues three hours in this temperature, and overhead product is collected in the Dean-Stark collector.Reaction can down continue 2.5 hours at 200 ℃, provides a kind of acid number and be 22 resin.
Repeat above-mentioned reaction, obtain acid number and be 14 resin.Although these two kinds of comparative resin have similar acid number to resin 1,2 with 3, find that stable, homogeneous aquifer coating material can not be according to the method preparation of embodiment 2.
The preparation of embodiment 8-coating
By various coated materials are applied on the cold-rolled steel brassboard (according to Advanced Coating Technologies ACT 3 * 9 * 032) and under 175 ℃ in baking oven baking made coating in 30 minutes.The thickness of coated membrane is about 1.0 to 1.5 mils (mil).After 1000 hours Cleveland moisture-proof experiment (ASTM Method D2247), the coating no change of coated material I.The character of various resins and coating is listed in table I and II.Acid number and phenolic group OH number are measured according to ASTM Method D1639, and terminal point is determined by the method for potentiometric titration.Molecular weight can pass through gel permeation chromatography.Viscosity ICI Cone and Plate viscometer determining.The acid-resistant corrosion of coating is by adding several 10% sulfuric acid (as six) on the film coated surface of coated coated plate, baking was tested in 0.5 hour in baking oven under 50 ℃ or 60 ℃.Other coating test carries out according to following standard method:
1, film thickness (Fisher.Deltascope MP2)
2, solvent resistance (MEK Double Rub, ASTM D1308)
3, glossiness (BYK-micro-gloss, ASTM D523)
4, pencil hardness (ASTM D3362)
5, shock resistance (BYK-Gavdner Impact Tester, ASTM D2794)
Figure 94100502X_IMG17

Claims (14)

1, a kind of water-based coating material compositions comprises:
(I) a kind of to contain the ammonium salt that an aryl hydroxy functional group and acid number are about 5 to about 39 curable polymer at least.Described polymkeric substance has following structure:
Wherein Z is a curable polymer residue, and Ar is the aryl moiety that is connected with end chain, skeleton or the side chain of described polymer residue; R ' is hydrogen, C 1-C 6The C of alkyl or replacement 1-C 6Alkyl; N is equal to or greater than 1 integer;
(II) a kind of to contain the water dispersible linking agent that can film with the suitable functional group and the formation of component (I) reaction; With
(III) is enough to an amount of water of dispersed component (I) and (II).
2, by the composition of claim 1, wherein Ar is a phenyl or naphthyl.
3, by the composition of claim 1 or 2, wherein Ar is at the group that has on the polymer backbone of following formula
Figure 94100502X_IMG1
4, by the arbitrary composition in the claim 1 to 3, wherein n is 1 to about 10.
5, by the arbitrary composition in the claim 1 to 4, wherein Z is the residue of polyester or acrylic polymers.
6, by the arbitrary composition in the claim 1 to 5, wherein the scope that exists of component (I) is about 25 to about 65%(weight); The scope that component (II) exists is about 5 to about 20%(weight); The scope that component (III) exists is about 30 to about 70%(weight); (I), (II) and (III) summation are 100%.
7, a kind of water-based coating material compositions comprises:
(I) about 25% is to about 65%(weight) the ammonium salt of the curable polyester that contains phenol functional group, the acid number of wherein said polyester is about 5 to 39, number-average molecular weight be about 800 to about 3,500 and weight-average molecular weight be about 3,000 to about 70,000, comprise:
(a) for (a) and (b), (c), (d) and (e) total mole number be about 20%-45%(mole) diol residue;
(b) for (a) and (b), (c), (d) and (e) total mole number be about 4%-21%(mole) the triol residue;
(c) for (a) and (b), (c), (d) and (e) total mole number be about 5%-20%(mole) the aliphatic diacid residue;
(d) for (a) and (b), (c), (d) and (e) total mole number be about 20%-35%(mole) the aryl diacid residues;
(e) for (a) and (b), (c), (d) and (e) total mole number be about 12%-20%(mole) aryl alcohol acid residue;
(II) about 5 is to about 20%(weight) amino crosslinker;
(III) about 0 is to about 10%(weight) suitable organic solvent; With
(IV) about 30% is to about 70%(weight) water; The overall weight percent of (I), (II), (III) and (IV) is 100.
8, by the composition of claim 7, wherein aryl alcohol acid residue is the para-hydroxybenzoic acid residue.
9, by the composition of claim 7, wherein component (a) is that neopentyl glycol, component (b) are that m-phthalic acid and component (e) are para-hydroxybenzoic acid for trihydroxymethyl propane, component (c) for hexanodioic acid, component (d).
10, a kind of water-based coating material compositions comprises:
(I) about 25 is to about 65%(weight) the curable polyester ammonium salt that contains phenol functional group, the acid number of wherein said polyester is about 5 to 39, number-average molecular weight is about 3000-70 for about 800-3500 and weight-average molecular weight, 000, comprise:
(a) for (a) and (b), (c), (d) and (e) total mole number be about 20%-45%(mole) diol residue;
(b) for (a) and (b), (c), (d) and (e) total mole number be about 4%-21%(mole) the triol residue;
(c) for (a) and (b), (c), (d) and (e) total mole number be about 0%-20%(mole) non-cycloaliphatic diacid residue;
(d) for (a) and (b), (c), (d) and (e) total mole number be about 20%-35%(mole) the cyclic aliphatic diacid residues;
(e) for (a) and (b), (c), (d) and (e) total mole number be about 12%-20%(mole) aryl alcohol acid residue;
(II) about 5% is to about 20%(weight) amino crosslinker;
(III) about 0% is to about 10%(weight) suitable organic solvent; With
(IV) about 30% is to about 70%(weight) water; The total percentage of (I), (II), (III) and (IV) is 100.
11, by the composition of claim 10, wherein the cyclic aliphatic diacid residues comprises 1.4-cyclohexane dicarboxylic acid residue.
12, by the composition of claim 10, wherein the aryl alcohol acid can be selected from the para-hydroxybenzoic acid residue.
13, by the composition of claim 10, wherein component (a) is that neopentyl glycol, component (b) are 1 for trihydroxymethyl propane, component (c) for hexanodioic acid, component (d), and 4-cyclohexane dicarboxylic acid and component (e) are para-hydroxybenzoic acid.
14, be coated with a kind of goods that are shaped or formalize of solidified by the composition of claim 1.
CN 94100502 1993-01-15 1994-01-15 Water base paint compositions Pending CN1094428A (en)

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* Cited by examiner, † Cited by third party
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CN106752228A (en) * 2015-11-24 2017-05-31 浙江捷能汽车零部件有限公司 A kind of water-based anticorrosive paint and preparation method thereof

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DE2146754C3 (en) * 1971-09-18 1982-05-27 Chemische Werke Hüls AG, 4370 Marl Coating agents
US4517322A (en) * 1983-09-22 1985-05-14 Ppg Industries, Inc. Acrylated alkyd and polyester resins
JPH0699662B2 (en) * 1986-12-22 1994-12-07 日本油脂株式会社 Aqueous dispersion type paint

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106752228A (en) * 2015-11-24 2017-05-31 浙江捷能汽车零部件有限公司 A kind of water-based anticorrosive paint and preparation method thereof

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