CN101541846B - Coating composition - Google Patents
Coating composition Download PDFInfo
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- CN101541846B CN101541846B CN2007800430277A CN200780043027A CN101541846B CN 101541846 B CN101541846 B CN 101541846B CN 2007800430277 A CN2007800430277 A CN 2007800430277A CN 200780043027 A CN200780043027 A CN 200780043027A CN 101541846 B CN101541846 B CN 101541846B
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- coating composition
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- carboxylic acid
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/089—Reaction retarding agents
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a coating composition comprising one or more polythiols, one or more polyisocyanates, and a base compound, e.g., an amine catalyst, and a carboxylic acid compound, e.g., cyanoacetic acid and/or a halogenated acetic acid, such as dichloroacetic acid or thfluoroacetic acid. The molar ratio of the acid compound to the basic compound is preferably at least 2:1, e.g. at least 10:1.
Description
The present invention relates to a kind of coating composition, it contains one or more polythiols, one or more POLYMETHYLENE POLYPHENYLISOCYANATE and alkali cpd.
WO 2004/018115 discloses based on mercaptan-isocyanate-crosslinked coating composition.The cross-linking chemistry reaction is usually through alkaline catalysts catalysis.For delay cross linking and raising shelf lives, these alkaline catalystss can be closed.WO 06/030029 discloses the NCO-SH system, and it has can be by the alkali cpd Li such as the oxazolidine of moisture-activated.Shortcoming is the moisture content that solidification rate depends on ambiance.In addition, coating is in its surface than catalysis more consumingly under coating surface.
WO 01/92362 disclose make with light potentiality alkali based on mercaptan-isocyanate-crosslinked compsn.In order to solidify this coating, the new layer that applies must be with the photic radiation of correct wavelength.Therefore, this coating is not too useful in the time will applying big area, for example garage floor etc.In addition, some points on surface possibly more be difficult to irradiation.Curing speed on these shadow spots is low.
The purpose of this invention is to provide the coating composition based on NCO-SH with controllable cured speed, it does not rely on Externality for example ambient moisture content or light.Shelf lives should be preferably at least 30 minutes, on the other hand for great majority are used, preferably less than set time of 3 hours.
The object of the invention realizes that through a kind of coating composition it contains one or more polythiols, one or more POLYMETHYLENE POLYPHENYLISOCYANATE, alkali cpd and carboxylic acid cpd.
The combination of acid cpd and alkaline catalysts is used and is learnt from the NCO-OH curing system, for example referring to US 4,617,286.In the system of these prior aries, acid causes forming CO through being removed with isocyanate reaction
2As a result, the catalyzer that these acid seals are closed only can be used for foaming system, and can not obtain slick filming.Surprised is to find in based on NCO-SH solidified coating composition CO now
2Formation significantly reduce, and can form slick film.
Carboxylic acid cpd has less than 25 carbon atoms usually, preferred following 10 carbon atoms, and can be unsubstituted or replaced by other functional group.Beta-keto acid and dicarboxylicacid (for example propanedioic acid) also can be used for the present invention.But preferred, carboxylic acid is replaced by electron-withdrawing group, wherein preferred especially cyanoacetic acid or halogenated acetic acids.Suitable halogenated acetic acids for example is Mono Chloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA) or trifluoroacetic acid.
In specific embodiments, based on the excessive acid of content meter use of alkali cpd.Acid cpd and alkali cpd can be for example use according to the mol ratio greater than 2: 1, for example at about 10: 1 to about 15: 1 scope.
Usually, alkali cpd is as catalyzer, for example amine.But,, also can use the catalyzer of other type if compsn contains for example basic color of other alkaline additive.
Appropriate catalyst comprises amine, for example triethylamine, three iso-octyl amine, aldimine, or metal complexes or metal-salt, and wherein metal is selected from aluminium, titanium, zirconium, manganese and hafnium.When the title complex of the zirconium that uses catalytic amount or hafnium and diketone or alkyl ethanoyl acetic ester, obtained excellent results.Other suitable example is aluminum complex K-
XC5218 (from King Industries); Organic titanate is diisopropanol titanium 10 2-2 for example; 4-diacetylmethane hydrochlorate obtains from DuPont as
M; N, N-dimethyl-octyl group amine (DMOA), from Acros Organics, and N, N-dimethyl decyl amine (DMDA) is from Sigma-Aldrich.The example of the catalyzer that other is satisfied is referring to US-A-5, and 846,897.
If use amine catalyst, then acid: the part by weight of amine is as can be in 5: 1 to 7: 1 scope.Acid content can for example be at least 0.06 weight %, for example 0.09 weight % or higher.
The polythiol that in coating composition, uses should have at least two thiol groups.Similarly, POLYMETHYLENE POLYPHENYLISOCYANATE should have at least two isocyanate groups.The equivalence ratio of NCO: SH, being the number of NCO group with respect to SH group meter, can for example be 1: 2 to 2: 1.
Suitable polythiol can be through the compound and the acid-respons preparation that contains thiol group of hydroxyl, and said acid for example is 3-thiohydracrylic acid, 2 mercaptopropionic acid, thiosalicylic acid, mercaptosuccinic acid, Thiovanic acid or halfcystine.The compound of suitable hydroxyl for example is glycol, three pure and mild tetrols, for example 1, and 4-butyleneglycol, 1,6-pinakon, 2,2-dimethyl--1; Ammediol, 2-ethyl-2-propyl group-1, ammediol, 1,2-, 1,3-and 1; 4-cyclohexane diol and corresponding cyclohexanedimethanol, 1,1, the 1-TriMethylolPropane(TMP); 1,2,3-TriMethylolPropane(TMP), and tetramethylolmethane.The compound of preparation comprises tetramethylolmethane four (3-mercaptopropionic acid ester) according to the method; Tetramethylolmethane four (2 mercaptopropionic acid ester); Trimethylolpropane tris (3-mercaptopropionic acid ester), trimethylolpropane tris (2 mercaptopropionic acid ester), and trimethylolpropane tris (2-mercaptoacetate).Use trimethylolpropane tris (3-mercaptopropionic acid ester) and tetramethylolmethane four (3-mercaptopropionic acid ester) to obtain excellent results.Other compound of preparation for example comprises the hyperbranched polyvalent alcohol core based on initial polyvalent alcohol, for example TriMethylolPropane(TMP), and dimethylol propionic acid according to the method.This polyvalent alcohol is used 3-thiohydracrylic acid and different n-nonanoic acid esterification subsequently.These methods are described among EP-A 0448224 and the WO 93/17060.
The method that other synthetic preparation contains the compound of polythiol relates to:
-aryl halide or alkylogen and NaHS reaction, thus the side chain thiol group is introduced respectively in alkyl and the aryl compound;
-Grignard reagent and reaction of Salmon-Saxl, thus the side chain thiol group is introduced in the structure;
-polythiol and polyene hydrocarbon react according to Michael reaction, nucleophilic reaction, cationoid reaction or free radical reaction;
The reaction of the alcohol of-thiol-functional and the compound of isocyanate-functional and
-reduction disulphide.
Polythiol can for example have one or more hydroxyls, and has the structure of following formula: T [(C
3H
6O)
nCH
2CHOHCH
2SH]
3, wherein T is a triol, for example TriMethylolPropane(TMP) or glycerine.The example of this compound can obtain with trade(brand)name Henkel
3/800 from Henkel.
Perhaps, polythiol can for example be the resin with polyester, urethane, polyacrylic ester or polyether backbone.These isocyanate-reactive compounds also can contain hydroxyl.
Polythiol for example can be the polyester from following component preparation: (a) at least a poly carboxylic acid or its reactive derivatives, (b) at least a polyvalent alcohol and (c) carboxylic acid of at least a thiol-functional.Polyester preferably has branched structure.When at least a reactant had at least 3 functionality, the polyester of branching passed through poly carboxylic acid or its reactive derivatives (for example corresponding acid anhydrides or lower alkyl esters) usually and the condensation reaction of polyvalent alcohol obtains.The suitable poly carboxylic acid or the example of its reactive derivatives are tetrahydrophthalic acid, Tetra Hydro Phthalic Anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, methylhexahydrophthaacid acid, methylhexahydrophthalic anhydride, dimethyl cyclohexane dicarboxylic ester, 1; 4-cyclohexane dicarboxylic acid, 1; 3-cyclohexane dicarboxylic acid, phthalic acid, Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, 5-tert-butyl isophthalic acid, 1; 2,4-benzenetricarboxylic acid, toxilic acid, maleic anhydride, fumaric acid, succsinic acid, succinyl oxide, dodecenyl succinic anhydride, Succinic acid dimethylester, pentanedioic acid, hexanodioic acid, dimethyl adipate, nonane diacid and their mixture.The example of suitable polyvalent alcohol comprises TriMethylolPropane(TMP), trimethylolethane, glycerine, 1,2,6-hexanetriol, terepthaloyl moietie, 1,2-Ucar 35,1, ammediol, 2-methyl-prop-1; 3-glycol, NSC 6366,2-butyl-2-ethyl-1, ammediol, 1,4-hydroxymethyl-cyclohexane, the monoesters of NSC 6366 and NSC 115936, Hydrogenated Bisphenol A 99; 1,5-pentanediol, 3-methyl-pentanediol, 1,6-pinakon; 2,2,4-trimethylammonium penta-1,3-glycol, dimethylol propionic acid; Tetramethylolmethane, dihydroxy methylpropane, Dipentaerythritol, and their mixture.The organic acid example of suitable thiol-functional comprises 3-thiohydracrylic acid, 2 mercaptopropionic acid, thiosalicylic acid, mercaptosuccinic acid, Thiovanic acid, halfcystine and their mixture.Randomly, monocarboxylic acid and single alcohol can use in the preparation of polyester.The preferred C that uses
4-C
18Monocarboxylic acid and C
6-C
18Single alcohol.C
4-C
18The example of monocarboxylic acid comprises PIVALIC ACID CRUDE (25), caproic acid, enanthic acid, sad, n-nonanoic acid, 2 ethyl hexanoic acid, different n-nonanoic acid, capric acid, LAURIC ACID 99 MIN, tetradecanoic acid, palmitinic acid, Unimac 5680, Triple Pressed Stearic Acid, oxystearic acid, phenylformic acid, 4-p t butylbenzoic acid and their mixture.C
6-C
18The example of single alcohol comprises hexalin, 2-Ethylhexyl Alcohol, VLTN 6 and 4-tertiary butyl hexalin.
Perhaps, polythiol can be the polyacrylic ester of thiol-functional.This polyacrylic ester can be derived from following material: (methyl) acrylic monomer, for example (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) Bing Xisuandingzhi; Ethenyl derivatives, for example vinylbenzene; And the acrylic monomer of optional hydroxyl-functional; For example (methyl) vinylformic acid hydroxyethyl ester, (methyl) vinylformic acid hydroxy-propyl ester, (methyl) vinylformic acid hydroxybutyl ester etc.; Or their mixture; Wherein term (methyl) propenoate is represented methacrylic ester and propenoate respectively with (methyl) vinylformic acid, and methylacrylic acid and vinylformic acid.Thiol group can pass through dimethyl---reaction product of pseudoallyl benzyl isocyanate ester and mercaptoethanol introduces.Perhaps, SY-Monomer G be directed in the polymkeric substance to prepare epoxy functionalized polyacrylic ester.Epoxide group then with the organic acid reaction of suitable thiol-functional, for example above-mentioned organic acid.Polyacrylic ester can be through the ordinary method preparation, and for example through proper monomer slowly being added in the solution of suitable polymerization initiators, polymerization starter for example is azo initiator or peroxy initiator.
The thinner that in coating composition of the present invention, also can comprise dithiol official ability, three thiol-functional or more senior thiol-functional, for example ethane two mercaptan or two-β-mercaptoethyl sulphur.Preferably use more high-molecular weight thiol-functional compound, it can obtain through polythiol functional compound and POLYMETHYLENE POLYPHENYLISOCYANATE reaction.
Suitable organic multiple isocyanate comprises polyfunctional, preferred free POLYMETHYLENE POLYPHENYLISOCYANATE, and its average N CO functionality is 2.5-5, and can be (ring) aliphatic series, araliphatic or aromatics.Organic multiple isocyanate can be by end-blocking.POLYMETHYLENE POLYPHENYLISOCYANATE can comprise biuret, carbamate, urea diketone and isocyanurate derivative.The example of these organic multiple isocyanates comprises 1, the diisocyanate based hexane of 6-, isophorone diisocyanate, 2,4 toluene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethanediisocyanate, 4; 4 '-two (NCO-cyclohexyl) methane, 1, the diisocyanate based butane of 4-, 1,5-is diisocyanate based-2,2-dimethylpentane, 2; 2,4-trimethylammonium-1, the diisocyanate based hexane of 6-, 1; The diisocyanate based decane of 10-, 4,4-is diisocyanate based-hexanaphthene, 2; 4-hexahydrotoluene vulcabond, 2,6-hexahydrotoluene vulcabond, norbornene alkyl diisocyanate, 1,3-xylylene diisocyanate, 1; 4-xylylene diisocyanate, 1-NCO-3-(NCO-methyl)-1-methyl-cyclohexyl alkane, m-α, α, α '; α '-tetramethyl-xylylene diisocyanate, their said derivative, and their mixture.Usually, these products are liquid at ambient temperature, and can in wide region, be purchased.Specially suitable isocyanate curing agent is triisocyanate and adducts.Its example is 1,8-is diisocyanate based-and 4-(NCO-methyl) octane, the adducts of 3 moles of toluene diisocyanate and 1 mole of trimethylol propane; 1, the isocyanurate trimer of the diisocyanate based hexane of 6-, the isocyanurate trimer of isophorone diisocyanate; 1, the urea diketone dimer of the diisocyanate based hexane of 6-, 1; The biuret tripolymer of the diisocyanate based hexane of 6-, 3 moles of m-α, α; α ', the adducts of α '-tetramethyl-xylylene diisocyanate and 1 mole of trimethylol propane, and their mixture.Also can use 1, cyclic trimer of 6-hexane diisocyanate and isophorone diisocyanate (isocyanuric acid ester) and urea diketone.These useful compounds contain a spot of their higher homologue.
Randomly, the hydroxy functional compound of containing at least two hydroxy functional groups may reside in the curable material.The hydroxy functional compound of containing at least two hydroxy functional groups can be selected from polyester polyol, polyether glycol, polyacrylate polyol, polyurethane polyol, Mierocrystalline cellulose ethanoyl butyric ester, hydroxyl-functional epoxy resin, Synolac; And the dendroid polyvalent alcohol, for example referring to WO93/17060.The oligopolymer and the monomer that also can comprise hydroxyl-functional, for example Viscotrol C and TriMethylolPropane(TMP).Suitable polyvalent alcohol is the propenoate polyvalent alcohol;
1157 for example is from Nuplex.
POLYMETHYLENE POLYPHENYLISOCYANATE can mix through any suitable technique with polythiol.But simple stirring is generally just enough.Sometimes, can be usefully with organic solvent ETHYLE ACETATE, butylacetate or acetate 1-methoxyl group-2-propyl diester dilution POLYMETHYLENE POLYPHENYLISOCYANATE for example, thereby reduce its viscosity.
The coating composition shelf lives at ambient temperature is generally greater than 15 minutes, for example greater than half a hour, reach about 5 hours or even the longer time, this depends on used catalyzer.
Compsn of the present invention can be solvent-based compositions or not solvent-laden compsn.If the use liquid oligomer, then compsn is especially suitable for use as high solids content compsn or not solvent-laden compsn.Coating composition also can use with the form of powder paint compositions, water base paint compositions and hot melts coating composition.Preferably, the theoretical volatile organic content (VOC) in compsn is more preferably less than about 350g/l less than about 450g/l, most preferably less than about 250g/l, or even less than 100g/l.
For solvent borne formulations, suitable solvent comprises for example acetate methoxy-propyl ester and acetone.For aqueous composition, can use solubility promoter or wetting agent when needed.
Coating composition can also contain other composition, additive or auxiliary agent, for example pigment, dyestuff, emulsifying agent (tensio-active agent), pigment dispersion aids, photosensitizers, flow agent, anti-cratering agent, foam preventer, anti-sag agent, thermo-stabilizer, UV absorption agent, inhibitor and filler.
When coating composition of the present invention prepared as bicomponent system, promptly first component contained (many) mercaptan compounds and second component contains (many) isocyanic ester, then preferably pigment is introduced in the compsn in first (many) thiol component.
Coating composition of the present invention can be applied on any base material.Base material can for example be metal, plastics, timber, glass, pottery or some other coatings.Other coating can be made up of coating composition of the present invention, maybe can be different coating compositions.Coating composition of the present invention is particularly useful as floor coating, for example on the cement flooring, or as coating or reparation, for example as priming paint or as Clear coating, is used for the vehicles, for example automobile, train, aircraft etc.
Coating composition can apply through conventional equipment, for example spray gun, brush or roller.Solidification value is normally-30 ℃ to 100 ℃, for example-10 ℃ to 30 ℃.
Through embodiment the present invention is described below.In these embodiment, use following component.
In an embodiment, the shelf lives is detected as follows: after mixing all three kinds of components, at several paint brush at interval, and observe paint and whether can have no to be coated onto also whether after curing, obtain having filming of excellent appearance on any base material difficultly.
In an embodiment, coating composition is coated onto on hardboard, MDF or the cement, and dry under envrionment conditions.When can will be placed on blowing off and when in coating, not staying any hair, think that coating is " touching dried " on the coating and with 10 seconds cotton wool thin slice of 1kg counterweight load.Can not be wiped, when in coating, not leaving a trace, thought coating completely solidified in walking on the coating and with any marking that the mass loading sample of people's list pin obtains after very hard and film solidifies when coating.
Embodiment 1
Tetramethylolmethane-four-3-mercaptopropionic acid ester of stoichiometric quantity is mixed with
HDT-LV2; And add the liquid catalyst agent solution of 0.6% (m/m) to this mixture; This solution contains the cyanoacetic acid of 3.6g, the N of 0.5g; The acetate methoxy-propyl ester of N-dimethyl-octyl group amine and 16.7g, and fully stir.
Discovery is under 20-25 ℃ envrionment temperature, and the shelf lives is 35-45 minute.Film touched dried after 1-1.5 hour, and after 1.5-2 hour completely solidified.
Embodiment 2
Thixotropic liquid catalyst agent solution passes through the cyanoacetic acid of 3.0g, the N of 0.5g, and
410 of N-dimethyl-octyl group amine and 10.0g is dissolved in the 50.0g acetone and prepares.This catalyst solution of 3.2% (m/m) is added in the stoichiometric quantity mixture like tetramethylolmethane-four-3-mercaptopropionic acid ester of embodiment 1 said preparation and
HDT-LV2.
The shelf lives of finding this thixotropic scheme is 30 minutes.Film touched dried after 1-1.5 hour, and after 1.5-2 hour completely solidified.When with brush or roller paint being coated onto vertical surface, paint can sagging.
Embodiment 3
With containing the tetramethylolmethane-four (3-mercaptopropionic acid ester) of 990.0g, the acetate methoxy-propyl ester of 22.5g,
310 of 12.5g,
100E of 0.5g, the cyanoacetic acid of 3.0g and the N of 0.5g, first component of N-dimethyl-octyl group amine is mixed with Clear paint fully.Second component is made up of
HDT-LV2.First component and second component are mixed together, and its amount makes that thiol functionalities and isocyanate functional group's amount is equal basically.
When with brush or roller when envrionment temperature applies, the shelf lives of gained Clear coating and set time be respectively 35-45 minute with 1.5-2 hour.
Embodiment 4
Through adding the acetate methoxy-propyl ester of extra 157.5g, the Clear coating scheme of embodiment 3 is diluted to spray viscosity.Reach shelf lives, remained set time about 2 hours above 1 hour.Because still lower VOC and extraordinary mobile after coating can reach high layer thickness through spraying.
Embodiment 5
Cyanoacetic acid through using 0.1g and the N of 6mg, N-dimethyl-octyl group amine replaces above-mentioned consumption, can the shelf lives of the Clear paint scheme that sprays of embodiment 4 be extended to greater than 5 hours, and remains set time at only night (≤16 hours).
Embodiment 6-10
Prepare five double-component paint compositions; For each compsn; First component contains tetramethylolmethane-four (3-mercaptopropionic acid ester) and pigment, and second component is pure POLYMETHYLENE POLYPHENYLISOCYANATE
HDT-LV2.According to after mixing these components with respect to the stoichiometric quantity mode of tackiness agent meter; Liquid catalyst (LC) solution that adds 0.2% (m/m) to this mixture; This solution contains the N of one of five kinds of listed in the following table 1 of 13.32g carboxylic acids, 2.22g, N-dimethyl decyl amine (DMDA, Aldrich; >=90%) and the acetate methoxy-propyl ester (MPA) of 84.46g, and fully stirs.
Detect the shelf lives and the set time of these five kinds of compsns then, and the ratio of shelf lives/set time.The result is listed in the table 1.
Table 1
| Embodiment | Carboxylic acid | Shelf lives (P/ minute) | Set time (C/ minute) | P/C |
| 6 | Cyanoacetic acid (CAA, A CROS O RGANICS，98％) | 30 | 75 | 0.40 |
| 7 | Phenylacetic acid (PAA, S IGMA-A LDRICH， 99％) | 5 | 22 | 0.23 |
| 8 | Propanedioic acid (MA, S IGMA-A LDRICH， 99％) | 90 | 170 | 0.53 |
| 9 | Mono Chloro Acetic Acid (C HLAA， S IGMA-A LDRICH，99％) | 33 | 70 | 0.47 |
| 10 | Trichoroacetic acid(TCA) (TC HLAA， S IGMA-A LDRICH，98％) | 255 | 480 | 0.53 |
Embodiment 11
Preparation water two-component coating composition; Wherein first component contain rare aqueous polyacrylic acid ester as emulsifying agent, as the tetramethylolmethane-3-mercaptopropionic acid ester and 0.65% (m/m) of tackiness agent at liquid catalyst (LC) solution described in the embodiment 6; Second component is hydrophilic polyisocyanate Rhodocoat EZ-D 803, is diluted to the viscosity of coupling with acetate methoxy-propyl ester.
Prepare other double-component paint composition different with above-mentioned compsn, difference is liquid catalyst (LC) solution that replaces the liquid catalyst agent solution use embodiment 7-10 among the embodiment 6.
When these coating compositions according to mixing with respect to the stoichiometric quantity mode of tackiness agent and when being coated onto on the base material with brush subsequently, dry with solidify after obtain smooth and transparent coating.When in these coating compositions, using POLYMETHYLENE POLYPHENYLISOCYANATE Rhodocoat EZ-M 502 to replace Rhodocoat EZ-D 803, also obtain this result with Bayhydur XP 2655.
Embodiment 12
First component and second component of preparation two-component composition.First component contains rare liquid catalyst agent solution of tetramethylolmethane-3-mercaptopropionic acid ester of 97%, 0.25% Byk 310 and 2.75 (m/m); This catalyst solution contains 17.36% cyanoacetic acid, 0.64% N, N-dimethyl decyl amine and 82% butylacetate.Second component is pure Tolonate HDT-LV2.
In the first part of this embodiment, two components are mixed according to the stoichiometric quantity mode with respect to tackiness agent, with butylacetate mixture diluted are arrived spray viscosity subsequently.The shelf lives of this system and set time are respectively about 45 minutes and 3 hours.
In the second section of this embodiment, only dilute first component with butylacetate.First component and second component of so dilution are added in the bi-component spray automatic doubler surface glouer according to the stoichiometric quantity with respect to tackiness agent, and first component and second component are during spraying mixed in this equipment.Reach shelf lives, and remained set time about 3 hours above 1 hour.
Claims (9)
1. coating composition, it contains one or more polythiols, one or more POLYMETHYLENE POLYPHENYLISOCYANATE and alkali cpd, and wherein alkali cpd is an alkaline catalysts, it is characterized in that said compsn also contains carboxylic acid cpd.
2. the coating composition of claim 1 is characterized in that carboxylic acid cpd has less than 25 carbon atoms.
3. the coating composition of claim 2 is characterized in that carboxylic acid cpd is replaced by electron-withdrawing group.
4. the coating composition of claim 3 is characterized in that carboxylic acid is selected from beta-keto acid, propanedioic acid, cyanoacetic acid and halogenated acetic acids.
5. the coating composition of claim 4 is characterized in that said halogenated acetic acids is to be selected from dichloro acetic acid and trifluoroacetic acid.
6. the coating composition of claim 1 is characterized in that the molar weight of carboxylic acid cpd is excessive with respect to the molar weight of alkali cpd.
7. the coating composition of claim 6, it is characterized in that carboxylic acid cpd: the mol ratio of alkali cpd is at least 2: 1.
8. the coating composition of claim 7, it is characterized in that carboxylic acid cpd: the mol ratio of alkali cpd is at least 10: 1.
9. the coating composition of claim 1 is characterized in that alkali cpd is an amine catalyst.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06124402 | 2006-11-20 | ||
| EP06124402.6 | 2006-11-20 | ||
| US86189506P | 2006-11-29 | 2006-11-29 | |
| US60/861,895 | 2006-11-29 | ||
| PCT/EP2007/060512 WO2008061839A1 (en) | 2006-11-20 | 2007-10-03 | Coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101541846A CN101541846A (en) | 2009-09-23 |
| CN101541846B true CN101541846B (en) | 2012-08-08 |
Family
ID=37909706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800430277A Expired - Fee Related CN101541846B (en) | 2006-11-20 | 2007-10-03 | Coating composition |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101541846B (en) |
| BR (1) | BRPI0719116A2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101831892B1 (en) * | 2016-06-30 | 2018-02-26 | 에스케이씨 주식회사 | Polymerizable composition used in the preparation of a polythiourethane-based optical material |
| EP3336115A1 (en) * | 2016-12-19 | 2018-06-20 | Covestro Deutschland AG | Process for the reduction of emissions in polyurethane foams |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4617286A (en) * | 1983-09-08 | 1986-10-14 | Toyo Soda Manufacturing Co., Ltd. | Catalyst for polyurethane having delay property |
| CN1430634A (en) * | 2000-05-26 | 2003-07-16 | 阿克佐诺贝尔股份有限公司 | Sprayable coating composition |
| WO2006030029A1 (en) * | 2004-09-17 | 2006-03-23 | Akzo Nobel Coatings International B.V. | Coating composition based on thiol-nco curing |
-
2007
- 2007-10-03 CN CN2007800430277A patent/CN101541846B/en not_active Expired - Fee Related
- 2007-10-03 BR BRPI0719116-2A patent/BRPI0719116A2/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4617286A (en) * | 1983-09-08 | 1986-10-14 | Toyo Soda Manufacturing Co., Ltd. | Catalyst for polyurethane having delay property |
| CN1430634A (en) * | 2000-05-26 | 2003-07-16 | 阿克佐诺贝尔股份有限公司 | Sprayable coating composition |
| WO2006030029A1 (en) * | 2004-09-17 | 2006-03-23 | Akzo Nobel Coatings International B.V. | Coating composition based on thiol-nco curing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101541846A (en) | 2009-09-23 |
| BRPI0719116A2 (en) | 2013-12-10 |
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