WO2019121079A1 - Composition de revêtement comprenant l'isocyanurate d'un diisocyanate cycloaliphatique - Google Patents

Composition de revêtement comprenant l'isocyanurate d'un diisocyanate cycloaliphatique Download PDF

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Publication number
WO2019121079A1
WO2019121079A1 PCT/EP2018/084083 EP2018084083W WO2019121079A1 WO 2019121079 A1 WO2019121079 A1 WO 2019121079A1 EP 2018084083 W EP2018084083 W EP 2018084083W WO 2019121079 A1 WO2019121079 A1 WO 2019121079A1
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Prior art keywords
coating composition
diisocyanate
compounds
weight
diisocyanates
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PCT/EP2018/084083
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English (en)
Inventor
Frederic Lucas
Alexander Panchenko
Harald Schaefer
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BASF SE
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BASF SE
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Classifications

    • 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
    • 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
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups
    • 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
    • C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
    • 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
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
    • 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
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G2115/00—Oligomerisation
    • C08G2115/02—Oligomerisation to isocyanurate groups

Definitions

  • Coating composition comprising the isocyanurate of a cycloaliphatic diisocyanate
  • the present invention relates to a coating composition
  • a coating composition comprising a trimerization product of diisocyanates, wherein at least 50 % by weight of the diisocyanates are a cycloaliphatic diisocy- anate selected from a diisocyanate of formula I
  • Coating compositions comprising compounds with isocyanate groups and compounds that are reactive with isocyanate groups, such as hydroxy or amino compounds are well-known.
  • diisocyanates Compounds with two isocyanate groups - hereinafter referred to as diisocyanates - often have a volatility which is not low enough to be useful in coating applications. Therefore, low molecular diisocyanates may be reacted to compounds of higher molecular weight which have less volatil- ity, such as dimers or trimers of the diisocyanate.
  • a suitable dimer of diisocyanates are uretdi- ones, a suitable trimer of diisocyanates are isocyanurates.
  • the higher molecular weight is ad- vantageous in respect to toxicology and functionality as well.
  • coating compositions usually are two-compo- nent coating compositions.
  • a first component comprises the compounds with isocyanate groups and the second component comprises the compounds that are reactive with isocyanate, such as compounds with hydroxy or amino groups.
  • the isocyanate groups react with the hydroxy or amino groups and form the polyurethane or polyurea coating. It is desired that the obtained mixture remains usable when mixed, at least for a certain time. The time during which the mixture remains usable is known as pot life.
  • EP-A 2289963 discloses two component coating compositions comprising isocyanurates of iso- phorone diisocyanate.
  • EP-A 0761670 discloses polycyclic imino-oxa-diazindiones obtained from linear or cyclic diiso- cyanates and their use in coating compositions.
  • the cyclic diisocyanates include 1 ,3-diisocya- nato-2-methylcyclohexane, 1 ,3-diisocyanato-4-methylcyclohexane and mixtures thereof.
  • An improved process for the preparation of cyclic diisocyanates including 1 ,3-diisocyanato-2- methylcyclohexane, 1 ,3-diisocyanato-4-methylcyclohexane and mixtures thereof is known from WO 17/013154.
  • An improved process for the preparation of isocyanurates of cyclic diisocya- nates is subject of the EP patent application with application number 16200079.8 (INV 15001 1 ).
  • the coating composition comprises a trimerization product of diisocyanates, wherein at least 50 % by weight of the diisocyanates are a cycloaliphatic diisocyanate selected from a diisocya- nate of formula I
  • the cycloaliphatic diisocyanate is a mixture of the diisocyanates of formula I and II. More preferably, the cycloaliphatic diisocyanate is a mixture of 50 to 95 % by weight of the diisocyanate of formula I and 5 to 50 % by weight of the diisocyanate of formula II.
  • the cycloaliphatic diisocyanate is a mixture of 70 to 90 % by weight of the diisocyanate of formula I and 10 to 30 % by weight of the diisocya- nate of formula II.
  • the weight percent relate to the total weight of the diisocyanates of formula I and II.
  • the two isocyanate groups in formula I and II may be in cis or trans position to the cyclohexane ring.
  • Cis position means that both isocyanate groups are on the same side of the cyclohexane ring.
  • Trans position means that the two isocyanate groups are on opposite sides of the cyclo- hexane ring.
  • the isocyanate groups are in trans position to the cyclohexane ring in more than 70 mol% of the cycloaliphatic diisocyanate, notably in more than 90 mol% of the cycloaliphatic diisocyanate.
  • the cycloaliphatic diisocyanate and the synthesis thereof are known.
  • the synthesis is de- scribed, for example, in WO 17/013154.
  • Starting material are the corresponding toluene dia mines which are hydrogenated to obtain 1 ,3-diamino-2-methylcyclohexane, 1 ,3-diamine-4- methylcyclohexane or mixtures thereof.
  • the amino groups are transferred into isocyanate groups by reacting with phosgene before or after the hydrogenation, preferably thereafter.
  • the proportion of isocyanate groups that are in trans or cis position depends from the diamino- methyl cyclohexane used as starting material. If the diamino-methyl cyclohexane comprises too much amino groups which are in cis transition, the corresponding isomers of the diamino-methyl cyclohexane may be separated, for example according to the process disclosed in WO
  • the trimerization product of the diisocyanates is preferably a mixture comprising an isocyanu- rate formed from three diisocyanates and compounds of higher molecular weight resulting from further trimerization reactions of the isocyanate groups of the isocyanurate.
  • Such compounds with higher molecular weight are, for example, the trimerization product composed of five diiso cyanates and comprising two isocyanurate ring systems or the trimerization product composed of seven diisocyanates and comprising three isocyanaruate ring systems.
  • trimerization product is obtained by cyclo-trimerization of the diisocyanates in the presence of a trimerization catalyst.
  • a preferred trimerization process for cycloaliphatic diisocyanates is disclosed in EP patent appli cation with application number 16200079.8 (INV 150011 ).
  • the trimerization products consists to at least 40 % by weight, notably to at least 50 % by weight of the isocyanurate formed from three diisocyanates.
  • the trimerization product may be formed from the cycloaliphatic diisocyanates of formula I and II, only.
  • a mixture of cycloaliphatic diisocyanates of formula I and II and other diisocyanates may be used as starting materials for the trimerization.
  • the obtained trimer comprises the cycloaliphatic diisocyanates of formula I and II in an amount corresponding to the composition of the mixture.
  • the trimerization product is a trimerization product of diisocyanates, wherein at least 70 % by weight, notably to at least 95 % by weight of the diisocyanates are a cycloaliphatic diisocyanate selected from a diisocyanate of formula I, of formula II or mixtures thereof.
  • the trimerization product is a trimerization product of diisocyanates, wherein 100% by weight of the diisocyanates are a cycloaliphatic diisocyanate selected from a diisocyanate of formula I, of formula II or mixtures thereof.
  • the coating composition comprises the above trimer and compounds that react with isocyanate groups.
  • the coating composition comprises the trimer, further compounds with at least one isocyanate group and compounds that react with isocyanate groups.
  • Further compounds with at least one isocyanate group are compounds with one isocyanate group - hereinafter referred to as monoisocyanate, compounds with two isocyanate groups - hereinafter referred to as diisocyanates and compounds with at least three isocyanate groups - hereinafter referred to as polyisocyanates.
  • monoisocyanates are used to limit the molecular weight of the obtained polymer. Hence, monoi- socyanates are used only optionally and - if used - they are used in low amounts, only.
  • Preferred diisocyanates are diisocyanates of formula X(NCO)2, where X is an aliphatic hydro- carbon radical having 4 to 12 carbon atoms, a cycloaliphatic or aromatic hydrocarbon radical having 6 to 15 carbon atoms, or an araliphatic hydrocarbon radical having 7 to 15 carbon at- oms.
  • diisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocy- anate (HDI), dodecamethylene diisocyanate, 1 ,4-diisocyanatocyclohexane, 1-isocyanato-3,5,5- trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,2-bis(4-isocyanatocyclohexyl)-propane, tri- methylhexane diisocyanate, 1 ,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocya- natotoluene (TDI), 4,4’-diisocyanato-diphenylmethane, 2,4’-diisocyanatodiphenylmethane (MDI), p-xylylene diisocyanate, tetramethylxylylene
  • Diisocyanates include dimers of the compounds listed above, notably uretdiones or allophan- ates.
  • Polyisocyanates are, in particular, compounds with three isocyanate groups such as isocyanu- rates obtained by trimerization of diisocyanates or biurets obtained from diisocyanates.
  • the coating composition comprises the above tri merization product of the diisocyanates and, in addition, further compounds with at least one isocyanate group.
  • the coating composition comprises
  • the coating composition comprises
  • the further polyisocyanate is an aliphatic polyisocyanate. More preferably the further polyisocyanate is an aliphatic isocyanurate.
  • the further polyisocyanate is selected from the isocyanurate of HDI, the isocy- anurate of IPDI, the isocyanurate of PDI and mixtures thereof.
  • At least 60 % by weight of all compounds with at least one isocya- nate group are the above trimerization product and further polyisocyanates.
  • At least 90%, notably at least 95% by weight of all compounds with at least one isocyanate group are the above trimerization product and further polyisocyanates.
  • Compounds that react with isocyanate groups are, in particular, compounds with at least one functional group selected from hydroxy groups, primary or secondary amino groups or mercap- tane groups.
  • compounds that react with isocyanate groups are selected from compounds with at least two hydroxy groups and compounds with at least two primary or secondary amino groups.
  • At least 50 mol%, in particular at least 80 mol %, most preferably at least 95 mol % of all compounds that react with isocyanates are compounds with at least two hydroxy groups.
  • the obtained polymer is a polyurethane.
  • Compounds with at least two hydroxy groups are preferably polyetherpolyols, polyesterpolyols or polymers with at least two hydroxy groups which are obtainable by radical polymerization of ethylenically unsaturated compounds herein referred to as monomers.
  • Preferred polyesterpolyols have two to eight, preferably two to five hydroxy groups, more prefer- ably two or three, in particular two hydroxy groups and are obtainable by reacting polyols, which include notably diols, with polycarboxylic acids which include notably dicarboxylic acids.
  • the polycarboxylic acids can be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and can if appropriate be substituted, by halogen atoms for example, and/or unsaturated.
  • Ex- amples thereof include the following: suberic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic an- hydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric an- hydride, maleic acid, maleic anhydride, fumaric acid, and dimeric fatty acids.
  • Preferred dicarbox- ylic acids are those of the formula HOOC-(CH2) y -COOH, where y is a number from 1 to 20, pref- erably an even number from 2 to 20, examples being succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid.
  • suitable polyols include ethylene glycol, propane-1 ,2- diol, propane-1 ,3-diol, bu- tane-1 ,3-diol, butene-1 ,4-diol, pentane-1 ,5-diol, neopentyl glycol, bis (hydroxymethyl)cyclohex- anes such as 1 ,4-bis(hydroxymethyl)cyclohexane, 2-methylpropane-1 ,3-diol, methylpentanedi- ols, and diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropyl ene glycol, polypropylene glycol, and dibutylene glycol and polybutylene glycols.
  • Preferred poly- ols are those of the formula HO-(CH2)x-OH, where x is a number from 1 to 20, preferably an even number from 2 to 20. Examples of such include ethylene glycol, butane-1 ,4-diol, hexane-
  • the number-average molecular weight Mn of the polyesterpolyol is preferably at least 500 g/mol, more preferably at least 700 g/mol.
  • the upper limit of the molecular weight M n is preferably 30 000 g/mol, more preferably 10 000 g/mol, very preferably 4000 g/mol.
  • the polyesterpolyol has a molecular weight M n being from 500 to 4000, more particularly from 700 to 2000 g/mol.
  • the polydispersity M w /M n is preferably 1.1 - 50, more preferably less than or equal to 5, more particularly less than 3.5.
  • Preferred polyetherpolyols have two to eight hydroxy groups, preferably two to five hydroxy groups, most preferably two hydroxy groups and are obtainable in particular by polymerizing ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohy- drin with itself, in the presence of a catalyst, which is, for example, BF3 and a starter component containing reactive hydrogen atoms, such as alcohols or amines, examples being water, eth- ylene glycol, propane-1 ,2-diol, propane-1 ,3-diol, 1 ,2-bis(4-hydroxydiphenyl)propane, and ani- line.
  • a preferred polyetherpolyol is polytetrahydrofuran with a molecular weight of from 240 to 5000, and notably of from 500 to 4500.
  • a preferred polymer with at least two hydroxy groups is a polymer obtained by polymerization of acrylic or methacrylic compounds (herein referred to as (meth)acrylics) and optionally further monomers as e.g. styrene, whereby at least 50 mol %, more preferably at least 80 mol % of all monomers are (meth)acrylics.
  • Such a polymer is hereinafter referred to as poly(meth)acrylate - polyol.
  • Poly(meth)acrylate - polyols are usually copolymers of (meth)acrylic esters, examples being Ci- C20 alkyl (meth)acrylates, with hydroxyalkyl (meth)acrylates, examples being the
  • 1.6-hexanediol and optionally other monomers such as vinylaromatic monomers, in particular styrene, vinyl ester, in particular vinyl acetate, ethylenically unsaturated nitriles, aliphatic hydrocarbons having 2 to 8 C atoms and 1 or 2 double bonds, vinyl ethers, aliphatic hydrocarbons having 2 to 8 C atoms and 1 or 2 double bonds and a,b-unsaturated carboxylic acids and their anhydrides which includes, for example (meth)acrylic acid, maleic acid and maleic anhydride.
  • vinylaromatic monomers in particular styrene, vinyl ester, in particular vinyl acetate, ethylenically unsaturated nitriles, aliphatic hydrocarbons having 2 to 8 C atoms and 1 or 2 double bonds, vinyl ethers, aliphatic hydrocarbons having 2 to 8 C atoms and 1 or 2 double bonds and a,b-unsaturated
  • the poly(meth)acrylate - polyols preferably have a molecular weight M n (number average), as determinable by gel permeation chromatography, of 500 to 50 000 D, more particularly 500 to 10 000 D or 500 to 5000 D. In one preferred embodiment, they have a molecular weight M n of 800-2000 D. Such poly(meth)acrylate polyols are usually used for coating materials with low solids contents.
  • Preferred poly(meth)acrylate - polyols have OH numbers, measured according to DIN 53240-2:2007-1 1 , of 15-250 mg KOH/g resin solids, preferably 60-180 mg KOH/g, more preferably 80-160 mg KOH/g.
  • the poly(meth)acrylate - polyols may additionally have an acid number to BS EN ISO 3682/BS 6782-3 of less than 100 mg KOH/g, preferably less than 30, and more preferably less than 20 mg KOH/g.
  • the coating composition comprises a poly(meth)acrylate - polyol as compound that reacts with isocyanate.
  • At least 50 % by weight, more preferably at least 70 % by weight and most preferably at least 90% by weight of all compounds that react with isocyanate are poly(meth)acrylates - polyols.
  • the coating composition comprises compounds with isocyanate groups and compound that are reactive with isocyanate preferably in an amount that the molar ratio of isocyanate groups to isocyanate-reactive groups is of from 0.5:1 to 2:1 , preferably 0.7:1 to 1.3:1 , more preferably 0.8:1 to 1.2:1 , and especially 0.9:1 to 1.1 :1.
  • the coating composition preferably is a two-component coating composition with a first compo- nent comprising the trimer and any further compounds with isocyanate groups and the second component comprises all compounds that are reactive with isocyanate groups.
  • Both compo- nents are usually mixed short before the application thereof; the compounds react and the coat- ing which is preferably a polyurethane coating is formed.
  • the coating composition may comprise further compounds besides isocyanate compounds and isocyanate-reactive compounds.
  • Such further compounds are, in particular, solvents, catalysts, in particular, catalysts for the urethanization and additives such as UV stabilizers, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents, fillers, dyes and pigments, drying agents, antistatic agents, antioxidants or flame retardants.
  • the further compounds may form part of either of both components or of both components.
  • the coating compositions preferably is a liquid coating composition.
  • a solvent is required.
  • the above trimerization product and other polyi socyanates are usually solid at room temperature.
  • they are solved in a solvent.
  • the solvent may be a reactive solvent, such as a diisocyanate or a non-reactive solvent such as usual organic solvents. Water is preferably not used as solvent.
  • the coating composition comprises no water or water in small, residual amounts, for example in amounts of preferably less than 2 % by weight, more preferably less than 0.5 % by weight and most preferably less than 0.05 % by weight based on the total weight of the coating composition.
  • the organic solvent preferably is an aprotic solvent or mixture of aprotic solvents. The solvent should not comprise any group that is reactive with isocyanate.
  • Suitable organic solvents are notably aromatic compounds including alkylated benzenes and naphthalenes, (cyclo)aliphatic hydrocarbons and mixtures thereof, chlorinated hydrocarbons, ketones, esters, alkoxylated alkyl alkanoates, ethers, and mixtures thereof.
  • Preferred solvents are n-butyl acetate, ethyl acetate, 1 -methoxyprop-2-yl acetate, 2-methoxy- ethyl acetate, xylene and Solvesso® 100.
  • the coating composition further comprises an urethanization catalyst or mixture of urethanization catalysts.
  • Urethanization catalysts are compounds with the capacity to accelerate the reaction of isocyanate groups with groups that are reactive toward isocyanate.
  • the urethanization catalyst is preferably a Lewis base and preferably has a pKa of more than 8, determined in water.
  • the Lewis base is an organic amine.
  • the urethanization catalysts may, for example, be tertiary aliphatic, cycloaliphatic, aromatic amines, amidines, guanidines or ionic liquids containing amine groups.
  • the urethanization catalyst may as well be a metal based Lewis acid derived from e.g. tin, zinc, bismuth, titanium or zirconium.
  • the urethanization catalyst is preferably used in amounts of 0.1 to 2 parts by weight per 100 parts by weight of compounds with at least one hydroxy group.
  • UV stabilizers are, in particular, UV absorbers and radical scavengers (especially HALS corn- pounds, hindered amine light stabilizers).
  • the coating composition of this invention is preferably used for the preparation of coatings.
  • the two components are preferably mixed short before the application.
  • the coating composition may be applied to substrates of all kind.
  • the coating composition is suitable for coating substrates such as wood, wood veneer, paper, cardboard, paperboard, textile, film, leather, nonwoven, plastics surfaces, glass, ceramic, min- eral building materials, such as molded cement blocks and fiber-cement slabs, or metals, which in each case may optionally have been precoated or pretreated. Preference is given to wood, metals and plastics, which may optionally have been precoated or pretreated. Particularly pre- ferred are metals and plastics.
  • the coating composition is suitable as or in interior or exterior coatings, i.e., in those
  • ACE agricultural, construction and earthmoving equipment
  • wind turbines bridges, power masts, tanks, containers, pipelines, power stations, chemical plants, ships, cranes, halls, roofs, furniture, windows, doors, wood flooring, paper, board, for floor coverings, such as in parking levels or in hospitals and in particular in automotive paints as refinish.
  • refinish plastics, and industrial applications, ACE for example.
  • the coating composition of the invention is used in coatings applications as clear- coat, basecoat, topcoat, primer or surfacer materials, especially as clearcoat or topcoat materi- als.
  • the substrates may be coated by typical methods known to the skilled person, for example by spraying, troweling, knife coating, brushing, rolling, roller coating, pouring, laminating, injection- back molding or coextruding.
  • the thickness of a film of this kind for curing may be from 0.1 pm up to several mm, preferably from 1 to 2000 pm, more preferably 5 to 200 pm, very preferably from 5 to 60 pm.
  • the applied coating compositions may be cured by any method known to the skilled person. Preferably curing occurs at room temperature or by heating to elevated temperatures, notably to temperatures of up to 80°C.
  • Curing may also take place with and/or be assisted by infrared radiation.
  • the coating compositions are especially suitable for applications requiring particularly high ap- plication reliability, exterior weathering resistance, optical qualities, solvent resistance, chemical resistance and water resistance.
  • the coating composition of the invention has an extended pot life. After mixing the two compo- nents of the two-component coating composition the obtained mixture usable for a longer time.
  • the obtained coatings have high performance and have very good mechanical properties and chemical resistance. Examples:
  • Isocyanurate of hexamethylene-diisocyanate (HDI-lsocyanurate), 2800 mPa * s, 22.0% by weight of NCO, Basonat® HI 100 of BASF
  • Isocyanurate of isophorone-diisocyanate (IPDI-lsocyanurate), solved in in Solvesso 100, 1 1.7 % by weight of NCO, solid content 70% by weight, Vestanat 1890® of Evonik SE.
  • the coating compositions were coated using a four-way bar coater (doc- tor blade) in a dry film thickness of 35-45 mhh; the wet film thickness was 150 mhh.
  • the obtained coatings were cured at 23 ⁇ 2°C and 50 ⁇ 10% humidity for determination of the pendulum hardness.
  • the obtained coatings were first kept at room temperature for 10-15 minutes. Thereafter they were kept at 60°C for 30 minutes. The curing was followed by conditioning at 23 ⁇ 2°C and 50 ⁇ 10% humidity and for 24 hours unless explicitly stated otherwise.
  • Viscosities are reported at 23°C in accordance with DIN EN ISO 3219/A.3 in a cone/plate system with a shear rate of 1000 s -1 .
  • the liquid coating was prepared as described above and was directly after its preparation introduced into a test tube (20 mm x 180 mm) with a copper pad (about 5 mm x 5 mm) attached adhesively at the bottom end.
  • the fill level of the test tube was at least 60%.
  • the test tube was placed into a slot in the gel time apparatus. Here, a contact was closed between copper pad and gel time apparatus. A metal spoke with a bent tip was clamped into the spoke holder at a length of 22 cm. The spoke holder was then inserted into the apparatus. This caused the spoke to be immersed in the liquid paint.
  • the opening of the test tube was closed with a perforated lid. The spoke was guided through the hole in the lid.
  • a counter was initiated. Furthermore, the assembly moved the spoke in the sample up and down until the sample became solid or gelled.
  • the test tube was subsequently lifted, the contact of the copper pad was lost, and the counter of the apparatus was halted automatically.
  • the gel time listed in the table is the time when the contact of the copper pad was lost. A long gel time corresponds to a long pot life.
  • the coating was applied to a glass plate at room temperature and the paint surface was contacted with a cotton pad at intervals of time.
  • the coating is con- sidered dust dry when cotton no longer remains sticking to the surface. Measurement took place at ambient temperature. The time until the cotton did not stick any more to the surface is listed in table 2.
  • the pendulum hardness was determined by the method of Koenig on glass plates (DIN EN ISO 1522). Cross-cut
  • the cross-cut was determined in accordance with DIN EN ISO 2409 on a Bonder panel.
  • the obtained coatings were first kept at room temperature for 10-15 minutes. Thereafter they were kept at 60°C for 30 minutes. The curing was followed by conditioning at 23 ⁇ 2°C and 50 ⁇ 10% humidity for one day (1 d) or seven days (7d). The adhesion of the coating to the panel was judged pursuant to a scale of 0 to 5 with 0 standing for“no detachment of the coating layer observed” and 5 standing for“full detachment”.
  • the gloss of the paint was determined by means of a Mikro TRI-Gloss instrument at an angle of 20 and 60° and at a temperature of 60°C.
  • a coated, deep-drawn metal panel was ther- mally conditioned at 130°C, respectively at 60°C for 30 minutes and for 7 d (examples E1 , C1 ) respectively 5 d (examples E2, C2) at 23 ⁇ 2°C and 50 ⁇ 10% humidity.
  • the panel has been treated with sulfuric acid (1 % strength; 25 pi).
  • the panel was then placed into the gradient oven (from BYK Gardner) and thermally condi- tioned at 30-75°C for 30 minutes. After the end of this operation, the panel was cleaned to re- move the sulfuric acid, using fully demineralized water. Then, the panel was washed off thor- oughly but gently using cold water, and the remaining drops of water were removed using a soft paper towel. After 24 hours of conditioning at 23 ⁇ 2°C and 50 ⁇ 10% humidity, evaluation took place.
  • the temperature in the table is the temperature at which the first attack on the coating is perceptible under artificial light with the eyes.

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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)

Abstract

La composition de revêtement comprend un produit de trimérisation de diisocyanates, au moins 50 % en poids des diisocyanates étant un diisocyanate cycloaliphatique choisi parmi un diisocyanate de formule (I), un diisocyanate de formule (II) ou un mélange de ceux-ci.
PCT/EP2018/084083 2017-12-19 2018-12-10 Composition de revêtement comprenant l'isocyanurate d'un diisocyanate cycloaliphatique Ceased WO2019121079A1 (fr)

Applications Claiming Priority (2)

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EP17208340 2017-12-19
EP17208340.4 2017-12-19

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WO2019121079A1 true WO2019121079A1 (fr) 2019-06-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114262302A (zh) * 2022-01-04 2022-04-01 山东新和成维生素有限公司 一种合成二异氰酸酯三聚体的方法、催化剂及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB966338A (en) * 1961-10-26 1964-08-12 Ici Ltd Polyurethane surface coatings
EP0761670A2 (fr) 1995-08-31 1997-03-12 Bayer Ag Luminoxadiazindiones, leur préparation et utilisation
US20010027243A1 (en) * 2000-03-30 2001-10-04 Degussa Ag Iisocyanato-2,2,6-trimethylcyclohexane polyisocyanates containing
EP2289963A2 (fr) 2009-08-27 2011-03-02 Basf Se Masses de revêtement dotées de polyisocyanates contenant des groupes allophanate
WO2016083210A1 (fr) 2014-11-25 2016-06-02 Basf Se Procédé de préparation de mdach cis- et trans-enrichi
WO2017013154A1 (fr) 2015-07-21 2017-01-26 Basf Se Procédé pour la préparation d'un isocyanate cyclique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB966338A (en) * 1961-10-26 1964-08-12 Ici Ltd Polyurethane surface coatings
EP0761670A2 (fr) 1995-08-31 1997-03-12 Bayer Ag Luminoxadiazindiones, leur préparation et utilisation
US20010027243A1 (en) * 2000-03-30 2001-10-04 Degussa Ag Iisocyanato-2,2,6-trimethylcyclohexane polyisocyanates containing
EP2289963A2 (fr) 2009-08-27 2011-03-02 Basf Se Masses de revêtement dotées de polyisocyanates contenant des groupes allophanate
WO2016083210A1 (fr) 2014-11-25 2016-06-02 Basf Se Procédé de préparation de mdach cis- et trans-enrichi
WO2017013154A1 (fr) 2015-07-21 2017-01-26 Basf Se Procédé pour la préparation d'un isocyanate cyclique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114262302A (zh) * 2022-01-04 2022-04-01 山东新和成维生素有限公司 一种合成二异氰酸酯三聚体的方法、催化剂及其制备方法
CN114262302B (zh) * 2022-01-04 2023-09-29 山东新和成维生素有限公司 一种合成二异氰酸酯三聚体的方法、催化剂及其制备方法

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