WO2008116893A1 - Compositions de durcisseurs - Google Patents

Compositions de durcisseurs Download PDF

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Publication number
WO2008116893A1
WO2008116893A1 PCT/EP2008/053613 EP2008053613W WO2008116893A1 WO 2008116893 A1 WO2008116893 A1 WO 2008116893A1 EP 2008053613 W EP2008053613 W EP 2008053613W WO 2008116893 A1 WO2008116893 A1 WO 2008116893A1
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WIPO (PCT)
Prior art keywords
polyisocyanate
acid
optionally
groups
compositions according
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PCT/EP2008/053613
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German (de)
English (en)
Inventor
Harald Schäfer
Carl Jokisch
Horst Binder
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Basf Se
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Publication of WO2008116893A1 publication Critical patent/WO2008116893A1/fr

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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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret 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
    • C08G18/70—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'

Definitions

  • the present invention relates to color stable hardener compositions for polyurethane coatings.
  • WO 2005/089085 describes polyisocyanate compositions as curing agents for 2K polyurethane coatings which, in addition to a catalyst for the reaction between isocyanate groups and reactive groups, contain a stabilizer mixture selected from hindered phenols and secondary arylamines and organophosphites, in particular trialkyl phosphites.
  • tributyl phosphite is harmful to health in contact with the skin and corrosive.
  • Triphenyl phosphite is irritating to eyes and skin and very toxic to aquatic life.
  • phosphites are sensitive to moisture. Thus, at least before and during incorporation into polyisocyanate compositions, these compounds pose a health, occupational hygiene and processing problem. While the antioxidant activity of aromatic phosphites is lower compared to the aliphatic ones, the availability of the aliphatic phosphites is inferior.
  • EP 643042 B1 describes stabilizer mixtures for the stabilization of monomeric isocyanates, which have been obtained by a cleavage of the corresponding carbamic esters.
  • the monomeric isocyanates stabilized in this way are advantageously convertible to oligomeric isocyanates.
  • a disadvantage of the stabilizer systems disclosed therein is that they can be used only for phosgene-free monomeric isocyanates and that the resulting oligomeric isocyanates are not yet ready for the reaction in polyurethane coatings, since they lack the presence of a catalyst.
  • No. 4,065,362 describes the distillation of monomeric isocyanates in the presence of metal salts of benzothiazoles or dithiocarbamic acids and also phenols, thio-bisphenol or triaryl phosphite.
  • a disadvantage of the stabilizer systems disclosed therein is that the monomeric isocyanates obtained are not yet ready for reaction in polyurethane paints since they lack the presence of a catalyst for this purpose.
  • the object of the present invention was to provide further storage-stable polyisocyanate compositions which already contain a catalyst for the reaction between isocyanate groups and reactive groups and are color-stable, and their stabilizers of odor, toxicology and / or moisture sensitivity unproblematic Occupational and sanitary hygiene, and whose stabilizing effect is at least comparable to the state of the art.
  • the stabilizing effect should be independent of the origin of the monomeric isocyanate.
  • Such polyisocyanate compositions have good color stability in storage and can be reacted directly with components containing isocyanate-reactive groups in polyurethane paints.
  • the polyisocyanate compositions according to the invention after storage at 50 ° C. for 10 weeks, do not show more than 30% of the increase in color number (APHA color number according to DIN EN 1557) of a similar polyisocyanate composition of the prior art in which neither component (C) another component (D) is present on.
  • the monomeric isocyanates used can be aromatic, aliphatic or cycloaliphatic, preferably aliphatic or cycloaliphatic, which in this document is referred to briefly as (cyclo) aliphatic, particular preference is given to aliphatic isocyanates.
  • Aromatic isocyanates are those which contain at least one aromatic ring system, ie both purely aromatic and also araliphatic compounds.
  • Cycloaliphatic isocyanates are those which contain at least one cycloaliphatic ring system. Aliphatic isocyanates are those which contain exclusively straight or branched chains, ie acyclic compounds.
  • the monomeric isocyanates are preferably diisocyanates which carry exactly two isocyanate groups. In principle, however, it may also be monoisocyanates with an isocyanate group.
  • higher isocyanates having an average of more than 2 isocyanate groups are also considered.
  • triisocyanates such as triisocyanato-nano, 2'-isocyanatoethyl- (2,6-diisocyanatohexanoate), 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate or 2,4,4'-triisocyanatodiphenyl ether or the mixtures of di-, are suitable for this purpose.
  • Tri- and higher polyisocyanates obtained, for example, by phosgenation of corresponding aniline / formaldehyde condensates and represent methylene bridges containing polyphenyl polyisocyanates.
  • the monomeric isocyanates are preferably isocyanates having 4 to 20 C atoms.
  • customary diisocyanates are aliphatic diisocyanates, such as tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, (for example methyl or ethyl-2, 6-diisocyanatohexanoate), trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1, 4, 1, 3 or 1, 2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyan
  • isophorone diisocyanate 1, 6- Hexamethylene diisocyanate
  • 1,6-hexamethylene diisocyanate there may also be mixtures of said isocyanates.
  • Isophorone diisocyanate is usually present as a mixture, namely the cis and trans isomers, usually in the ratio of about 60:40 to 80:20 (w / w), preferably in the ratio of about 70:30 to 75 : 25 and most preferably in the ratio of about 75:25.
  • Dicyclohexylmethane-4,4'-diisocyanate may also be present as a mixture of the different cis and trans isomers.
  • (cyclo) aliphatic diisocyanates eg such as 1, 6-hexamethylene diisocyanate (HDI), isomeric aliphatic diisocyanates having 6 carbon atoms in the alkylene radical, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane and 1-isocyanato-S-isocyanato-methyl-S ⁇ - trimethylcyclohexane (isophorone diisocyanate or IPDI) are prepared by reacting the (cyclo) aliphatic diamines with, for example, urea and alcohols to (cyclo) aliphatic biscarbamic acid esters and their thermal cleavage into the corresponding diisocyanates and alcohols.
  • cyclo aliphatic diisocyanates eg such as 1, 6-hexamethylene diisocyanate (HDI), isomeric aliphatic diisocyanates having 6 carbon atoms in the alkylene radical,
  • diisocyanates generally have a very low or even non-measurable proportion of chlorinated compounds, which is advantageous, for example, in applications in the electronics industry.
  • the isocyanates used have a total hydrolyzable chlorine content of less than 200 ppm, preferably less than 120 ppm, more preferably less than 80 ppm, even more preferably less than 50 ppm, in particular less than 15 ppm and specifically less than 10 ppm. This can be measured, for example, by ASTM D4663-98. Of course, it is also possible to use monomeric isocyanates having a higher chlorine content, for example up to 500 ppm.
  • mixtures of such monomeric isocyanates which have been obtained by reacting the (cyclo) aliphatic diamines with, for example, urea and alcohols and cleavage of the obtained (cyclo) aliphatic biscarbamic, with such diisocyanates obtained by phosgenation of the corre sponding amines are to be used.
  • the polyisocyanates (A) to which the monomeric isocyanates can be oligomerized are generally characterized as follows:
  • the average NCO functionality of such compounds is generally at least 1.8, and may be up to 8, preferably 2 to 5 and more preferably 2.4 to 4.
  • the polyisocyanates (A) are preferably the following compounds:
  • isocyanurate polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate.
  • the isocyanurates present are, in particular, trisisocyanatoalkyl or trisisocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs having more than one isocyanurate ring.
  • the isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO functionality of 2.6 to 8.
  • polyisocyanates containing uretdione groups with aromatic, aliphatic and / or cycloaliphatic bonded isocyanate groups preferably aliphatically and / or cycloaliphatically bonded and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
  • the polyisocyanates containing uretdione groups are obtained in the context of this invention in a mixture with other polyisocyanates, in particular those mentioned under 1).
  • the diisocyanates can be reacted under reaction conditions under which both uretdione groups and the other polyisocyanates are formed, or first the uretdione groups are formed and these are subsequently reacted to the other polyisocyanates or the diisocyanates are first added to the other polyisocyanates and these brushedd to uretdione group-containing products are implemented.
  • biuret polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably cycloaliphatic or aliphatic bound isocyanate groups, in particular tris (6-isocyanatohexyl) biuret or its
  • biuret polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 2.8 to 6.
  • diisocyanate for example hexamethylene diisocyanate or isophorone diisocyanate
  • A monovalent or polyvalent Al knock
  • These urethane and / or allophanate-containing polyisocyanates generally have an NCO content of 12 to 24 wt .-% and an average NCO functionality of 2.5 to 4.5.
  • Such polyisocyanates containing urethane and / or allophanate groups can be used uncatalyzed or, preferably, in the presence of catalysts, such as, for example, ammonium carboxylates or hydroxides, or allophanatization catalysts, e.g. Zn (II) -
  • oxadiazinetrione-containing polyisocyanates preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetrione-containing polyisocyanates are accessible from diisocyanate and carbon dioxide.
  • polyisocyanates containing iminooxadiazinedione groups preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • iminooxadiazine-dione-containing polyisocyanates can be prepared from diisocyanates by means of special catalysts.
  • Hyperbranched polyisocyanates as are known, for example, from DE-A1 10013186 or DE-A1 10013187.
  • polyurethane-polyisocyanate prepolymers of di- and / or polyisocyanates with alcohols 1
  • polyurethane-polyisocyanate prepolymers 1
  • the polyisocyanates 1) -11), preferably 1), 3), 4) and 6) may according to their preparation in biuret or urethane / allophanate groups polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably ( cyclo) aliphatically bound isocyanate groups.
  • the formation of biuret groups takes place, for example, by addition of water or reaction with amines.
  • the formation of urethane and / or allophanate groups by reaction with mono-, di- or polyhydric, preferably monohydric alcohols, optionally in the presence of suitable catalysts.
  • These biuret or urethane / allophanate groups containing polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 2.8 to 6 on.
  • Hydrophilic modified polyisocyanates i. Polyisocyanates which contain, in addition to the groups described under 1-12, those which formally arise by addition of molecules with NCO-reactive groups and hydrophilicizing groups to the isocyanate groups of the above molecules.
  • the latter are non-ionic groups such as alkyl polyethylene oxide and / or ionic, which of
  • Phosphoric acid phosphonic acid, sulfuric acid or sulfonic acid, or their salts are derived.
  • Modified Polyisocyanates for Dual Cure Applications i. Polyisocyanates which, in addition to the groups described under 1-12, contain those which formally form by addition of molecules with NCO-reactive groups and groups which can be crosslinked by UV or actinic radiation to the isocyanate groups of the above molecules. These molecules are, for example, hydroxyalkyl (meth) acrylates and other hydroxy-vinyl compounds.
  • the diisocyanates or polyisocyanates listed above may also be present at least partially in blocked form.
  • classes of compounds used for blocking are phenols, imidazoles, triazoles, pyrazoles, oximes, N-hydroxyimides, hydroxybenzoic acid esters, secondary amines, lactams, CH-acidic cyclic ketones, malonic esters or alkyl acetoacetates.
  • the polyisocyanate (A) is selected from the group consisting of isocyanurates, biurets, urethanes and allophanates, preferably from the group consisting of isocyanurates, urethanes and allophanates, more preferably from the group consisting of isocyanurates and Allophanates, in particular is an isocyanurate group-containing polyisocyanate.
  • the polyisocyanate (A) is isocyanurate group-containing polyisocyanates of 1,6-hexamethylene diisocyanate.
  • the polyisocyanate (A) is a mixture of polyisocyanates containing isocyanurate groups of 1,6-hexamethylene diisocyanate and of isophorone diisocyanate.
  • the polyisocyanate (A) is a mixture comprising low-viscosity polyisocyanates, preferably polyisocyanates containing isocyanurate groups, having a viscosity of 600-1500 mPa * s, in particular less than 1200 mPa * s, low-viscosity urethanes and / or allophanates with a viscosity of 200-1600 mPa * s, in particular 600-1500 mPa * s, and / or iminooxadiazine dione group-containing polyisocyanates.
  • low-viscosity polyisocyanates preferably polyisocyanates containing isocyanurate groups, having a viscosity of 600-1500 mPa * s, in particular less than 1200 mPa * s, low-viscosity urethanes and / or allophanates with a viscosity of 200-1600 mPa * s, in particular 600-1
  • reaction can be stopped, for example, as described there from page 31, line 19 to page 31, line 31 and the workup carried out as described there from page 31, line 33 to page 32, line 40, which hereby incorporated by reference in each of the present Registration is.
  • the reaction can also be stopped, as described in WO 2005/087828 from page 11, line 12 to page 12, line 5, which is hereby incorporated by reference in the present application.
  • thermally labile catalysts it is also possible to stop the reaction by heating the reaction mixture to a temperature above at least 80 ° C., preferably at least 100 ° C., more preferably at least 120 ° C. The heating of the reaction mixture usually suffices , as required for the separation of the unreacted isocyanate by distillation in the workup.
  • Suitable deactivators are, for example, hydrogen chloride, phosphoric acid, organic phosphates, such as dibutyl phosphate or diethylhexyl phosphate, carbamates, such as hydroxyalkyl carbamate or organic carboxylic acids.
  • Compounds (B) which are capable of accelerating the reaction of isocyanate groups with isocyanate-reactive groups are those compounds which, owing to their presence in a starting material mixture, lead to a higher proportion of urethane group-containing reaction products than the same starting material mixture in their absence under the same reaction conditions ,
  • Lewis acidic organic metal compounds e.g. Tin compounds in
  • tin (II) salts of organic carboxylic acids e.g. Tin (II) diacetate, tin (II) dioctoate, tin (II) bis (ethylhexanoate) and tin (II) dilaurate
  • dialkyltin (IV) salts of organic carboxylic acids e.g.
  • zinc (II) salts can be used, such as zinc (II) dioctoate.
  • carboxylic acids e.g. in octoate
  • carboxylic acids are branched and / or unbranched isomers, preferably unbranched.
  • Metal complexes such as acetylacetonates of iron, titanium, aluminum, zirconium, manganese, nickel, zinc and cobalt are also possible.
  • Other metal catalysts are described by Blank et al. in Progress in Organic Coatings, 1999, Vol. 35, pages 19-29.
  • Zirconium, bismuth and aluminum compounds used. These are e.g. Zirconium tetraacetylacetonate (e.g., K-KAT® 4205 from King Industries); Zirconium dionates (e.g., K-KAT® XC-9213; XC-A 209 and XC-6212 from King Industries); Bismuth compounds, in particular tricarboxylates (for example K-KAT® 348, XC-B221, XC-C227, XC 8203 from King Industries); Aluminum dionate (e.g., K-KAT® 5218 from King Industries). Tin and zinc free catalysts are otherwise used e.g. also available under the trade name Borchi® Kat from Borchers, TK from Goldschmidt, BICAT® from Shepherd, Lausanne.
  • Tin and zinc free catalysts are otherwise used e.g. also available under the trade name Borchi® Kat from Borchers, TK from Goldschmidt,
  • catalysts are suitable for solvent, water-based and / or blocked systems.
  • Molybdenum, wofram and vanadium catalysts are described in particular for the conversion of blocked polyisocyanates under WO 2004/076519 and WO 2004/076520.
  • Cesium salts can also be used as catalysts. Suitable cesium salts are those compounds in which the following anions are used: F, Ch, CIO “ , CIO 3 , CIO 4 , Br, J, JO 3 , CN, OCN, NO 2 - , NO 3 -, HCO 3 -, CO 3 2 -, S 2 -, SH-, HSO 3 -, SO 3 2 " , HSO 4 " , SO 4 2 " , S 2 O 2 2” , S 2 O 4 2 “ , S 2 O 5 2” , S 2 O 6 2 “ , S 2 O 7 2” , S 2 O 8 2 " , H 2 PO 2 -, H 2 PO 4 -, HPO 4 2 -, PO 4 3 -, P 2 O 7 4 " , (OC n H 2n + i) -, (C n H 2n - 3 O 2 ) - as well as (Cn + iH 2n - 2 O 4 ) 2 -
  • Cesium carboxylates are preferred in which the anion conforms to the formulas (C n H 2n -iO 2 ) - and (C n + iH 2n - 2 O 4 ) 2 - where n is 1 to 20.
  • Particularly preferred cesium salts have as anions monocarboxylates of the general formula (C n H 2n -i0 2 ) -, where n is the numbers 1 to 20.
  • Preferred Lewis acidic organic metal compounds are dimethyltin diacetate, dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, dioctyltin dilaurate, zinc (II) dioctoate, zirconium acetylacetonate and zirconium-2, 2,6,6-tetramethyl-3,5-heptanedionate.
  • Compounds (C) are those which contain at least one thioether group, ie a sulfur atom which is substituted by two identical or different organic substituents.
  • Preferred compounds (C) are thioethers of the formula
  • R 1 and R 2 independently of one another are C 1 -C 6 -alkyl, C 2 -C -alkyl which is optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, C 2 -C 6 -alkenyl, C 6 -C 12 Aryl, C 5 -C 12 -cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle, where the radicals mentioned may each be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, could be.
  • Ci - cis-alkyl for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl , 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl, 1, 1, 3,3-tetramethylbutyl, benzyl, 1-phenylethyl , 2-phenylethyl, ⁇ , ⁇ -
  • the number of oxygen and / or sulfur atoms and / or imino groups is not limited. As a rule, it is not more than 5 in the radical, preferably not more than 4, and very particularly preferably not more than 3.
  • At least one carbon atom preferably at least two, is usually present between two heteroatoms.
  • Substituted and unsubstituted imino groups may be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino.
  • C2-cis-alkenyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example vinyl, 1-propenyl, allyl, methallyl, 1,1-dimethylallyl, 2-butenyl, 2-hexenyl, octenyl, Undecenyl, dodecenyl, octadecenyl, 2- Phenylvinyl, 2-methoxyvinyl, 2-ethoxyvinyl, 2-methoxyallyl, 3-methoxyallyl, 2-ethoxyallyl, 3-ethoxyallyl or 1- or 2-chlorovinyl,
  • Ci2-aryl example phenyl, ToIyI, XyIyI, ⁇ -naphthyl, ß-
  • aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Cs - Ci2-cycloalkyl for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, Dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as Norbornyl or norbornenyl, and
  • a five- to six-membered heterocycle having oxygen, nitrogen and / or sulfur atoms for example furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, Difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
  • Preferred thioethers which may be mentioned are: 2-methyl-1-propenyl-tert-dodecylthioether, cyclohexylidenemethyl-n-dodecylthioether, 3-cyclohexene- (1) -ylidenemethyl-n-octadecylthioether, 3-cyclohexen- (1) -ylidenemethyl-n dodecyl thioether, 3-cyclohexene (1) -ylidenemethyl-n-octyl thioether 3-cyclohexeno (1) -ylidenemethyl-cyclohexyl thioether, 3-methyl- (3) -cyclohexene (1) -ylidenemethyl-n-dodecyl thioether, 3 Cyclohexene (1) -ylidene-methyl-p-tolylthioether, 3-cyclohexeno (1) -ylidenemethylbenzylthioether, and
  • Particularly preferred compounds (C) are those of the formula
  • R 3 and R 5 independently of one another are C 1 -C 20 -alkyl, C 2 -Cis-alkyl, C 6 -C 12 -aryl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups C5 - C-12-cycloalkyl, where the radicals mentioned may each be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, and
  • R 4 is C 2 -C 20 -alkylene, C 5 -C 12 -cyclocyclic or by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups and / or by one or more cycloalkyl, - (CO) - , -0 (CO) O-, - (NH) (CO) O-, -O (CO) (NH) -, -O (CO) - or - (CO) O- groups interrupted C 2 -C 20 - Alkylene, where the radicals mentioned in each case by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles may be substituted.
  • C 1 -C 20 -alkylene denotes linear or branched alkylene, for example methylene, 1,2-ethylene, 1,2- or 1,3-propylene, 1, 2, 1, 3 or 1, 4-butylene, 1 , 1-dimethyl-1, 2-ethylene or 1, 2-dimethyl-1, 2-ethylene, 1, 6-hexylene, 1, 8-octylene, 1, 10-decylene, 1, 12-dodecylene and 1, 20 -Ecoosylene, and
  • Ci2 cycloalkylene looctylen for example cyclopropylene, cyclopentylene, cyclohexylene, Cyc- and cyclododecylene.
  • the radical R 3 is optionally substituted C ⁇ - Ci 2 aryl or Ci - C 20 - alkyl, more preferably optionally substituted Ci - C 20 alkyl, most preferably unsubstituted Ci - C 20 alkyl.
  • the radical R 5 is preferably optionally substituted C 1 -C 20 -alkyl, particularly preferably unsubstituted C 1 -C 20 -alkyl.
  • the radical R 4 is preferably methylene, 1,2-ethylene or 1,2-propylene, more preferably 1,2-ethylene.
  • Very particularly preferred compounds (C) are those in which at least one of the radicals R 1 and R 2 , preferably both, are identical or different C 1 -C 20 -alkyl-oxycarbonylalkyl, preferably C 1 -C 20 -alkyl-oxycarbonylethyl groups.
  • R 4 and R 5 have the meanings given above.
  • the compounds (C) contain further functional groups which, if appropriate, improve the antioxidant activity and / or the solubility of the compound (C) in the polyisocyanate preparation.
  • Preferred compounds (C) are thiodipropionic acid esters, for example dimethyl 3,3'-thiodipropionate [4131-74-2], 3,3'-thiodipropionic acid ditetradecyl ester [16545-54-3], 3,3'-thiodipropionic acid dioctadecyl ester [693-36-7].
  • 3,3'-thiodipropionic acid ditridecyl esters [10595-72-9] (e.g.
  • 3,3'-Thiodipropion Acid-ditridecylester is liquid and thus particularly well suited for paint components and its dosage.
  • 3,3'-thiodipropionic acid dodecyl ester and 3,3'-thiodipropionic acid ditetradecyl ester are also well suited because of their low melting points.
  • didodecyl 3,3'-thiodipropionate (and dioctadecyl 3,3'-thiodipropionate) are very well studied toxicologically and harmless to humans. They are only slightly hazardous to water.
  • the thioethers in particular the 3,3'-thiodipropionic acid esters, are generally resistant to hydrolysis.
  • Particularly preferred compounds (C) are those which are liquid at 23 ° C. or have a melting point below 50 ° C.
  • the thioethers (C) function primarily as a secondary antioxidant in this invention. These are usually understood by the skilled person as compounds which prevent the formation of radicals, in particular intercept and / or decompose peroxides.
  • At least one phenol (D) may be present, preferably at least one, more preferably exactly one phenol (D) is present.
  • Phenols have in mind the invention the function of a primary antioxidant. This is usually understood by the person skilled in the art as meaning compounds which scavenge radicals.
  • phenols are alkylphenols, for example o-, m- or p-cresol (methylphenol), 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2, 6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4- tert-butyl-2,6-dimethylphenol, or 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 4,4'-oxydiphenyl, 3,4-methylenedioxydiphenol (sesamol), 3,4-dimethylphenol, hydroquinone, catechol (1, 2-dihydroxybenzene), 2- (1'-methylcyclohex-1'-yl) -4,6-dimethylphenol, 2- or 4- (1'-phenyl-ethane) 1 '-yl) -
  • Methyl catechol 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, 3-methylcatechol, 4-methylcatechol, tert-butylhydroquinone, 4-ethoxyphenol, 4-butoxyphenol, hydroquinone monobenzyl ether, p-phenoxyphenol, 2-methylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, and 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycoumaran), 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox®), gallic acid, ferulic acid, cinnamic acid and their derivatives.
  • Trolox® 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid
  • Sterically hindered phenols are those which have exactly one phenolic hydroxyl group and have a tert-butyl group in at least one, preferably both ortho positions based on the functional OH group.
  • Such phenols may also be components of a polyphenolic system having a plurality of phenolic groups, such as pentaerythritol tetrakis- [ ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate] (eg Irganox® 1010), Irganox® 1330, 1, 3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (eg Irganox® 3114), all products of Ciba Specialty Chemicals.
  • phenolic groups such as pentaerythritol tetrakis- [ ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate] (eg Irganox® 1010), Irganox® 1330, 1, 3,5-tris (3,5-d
  • Corresponding products are e.g. available under the trade names Irganox® (Ciba Specialty Chemicals), Sumilizer® from Sumitomo, Lowinox® from Great Lakes, Cyanox® from Cytec.
  • compound (C) can additionally combine phenolic groups in one molecule, for example thiodiethylene bis [3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionate] (Irganox® 1035) and 6 , 6'-di-tert-butyl-2,2'-thiodi-p-cresol (for example Irganox® 1081), in each case products of Ciba Specialty Chemicals.
  • a solvent or solvent mixture (E) may be present.
  • Useful solvents are those which have no groups reactive toward isocyanate groups or blocked isocyanate groups and in which the polyisocyanates are at least 10% by weight, preferably at least 25, more preferably at least 50, most preferably at least 75, in particular at least 90 and especially at least 95 wt% are soluble.
  • solvents examples include aromatic (including alkylated benzenes and naphthalenes) and / or (cyclo) aliphatic hydrocarbons and mixtures thereof, chlorinated hydrocarbons, ketones, esters, alkoxylated Alkanklarealkylester, ethers, respectively mixtures of solvents.
  • aromatic hydrocarbons (cyclo) aliphatic hydrocarbons, alkanoic acid alkyl esters, alkoxylated alkanoic acid alkyl esters and mixtures thereof.
  • Preferred aromatic hydrocarbon mixtures are those which comprise predominantly aromatic C 7 - to C 20 -hydrocarbons and may have a boiling range of from 10 to 300 ° C., particular preference is given to toluene, o-, m- or p-
  • Solvesso® brands from ExxonMobil Chemical, Particularly Solvesso® 100 (CAS No. 64742-95-6, predominantly C9 and Cio aromatics, boiling range about 154 -. 178 0 C), 150 (boiling range about 182 -. 207 0 C) and 200 (CAS No. 64742-94-5), and the Shellsol TM grades from Shell, Caromax® (eg Caromax® 18) from Petrochem Carless and hydrosol from DHC (eg as Hydrosol® A 170). Hydrocarbon mixtures of paraffins, cycloparaffins and aromatics are also available under the designations crystal oil (for example, crystal oil 30, boiling range about 158-198 0 C or crystal oil. 60: CAS No.
  • hydrocarbon mixtures are generally more than 90% by weight, preferably more than 95, more preferably more than 98, and very preferably more than 99% by weight. It may be useful to use hydrocarbon mixtures with a particularly reduced content of naphthalene.
  • Examples of (cyclo) aliphatic hydrocarbons include decalin, alkylated decalin and isomer mixtures of straight-chain or branched alkanes and / or cycloalkanes.
  • the content of aliphatic hydrocarbons is generally less than 5, preferably less than 2.5 and more preferably less than 1% by weight.
  • Esters include, for example, n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2 and 2-methoxyethyl acetate.
  • Ethers are, for example, THF, dioxane and the dimethyl, ethyl or n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.
  • ketones are acetone, diethyl ketone, ethyl methyl ketone, isobutyl methyl ketone, methyl amyl ketone and tert-butyl methyl ketone.
  • Patentful Polyisocyanatzu- compositions containing ketones or aromatic mixtures are particularly critical in terms of color formation on storage.
  • esters, ethers, and individual aromatics such as XyIoI or its isomer mixtures are less problematic.
  • xylenes also carry benzylic hydrogen atoms analogously to the aromatic mixtures, which could be involved in color formation.
  • solvent naphtha mixtures depending on the source of supply and storage times, can have significantly different effects on the color number drift when used in the polyisocyanate compositions.
  • At least one, preferably exactly one acidic, stabilizer (F) is added as a further stabilizing compound.
  • These are Bransted acids.
  • Suitable organic monocarboxylic acids and / or organic polycarboxylic acids for example linear or branched, aliphatic monocarboxylic acids having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, optionally with halogen atoms, preferably chlorine atoms and / or alkoxy groups with 1 to 12 C atoms, preferably 1 to 6 C atoms, in particular methoxy and / or ethoxy groups may be substituted, such as formic acid, acetic acid, propionic acid, 2,2-dimethylpropionic acid, butyric acid, isobutyric acid, 2-methoxybutyric acid, n-valeric acid, Chloroacetic acid, caproic acid, 2-ethylhexanoic acid, n-heptanoic acid, n-octylic acid, caprylic acid and perboronic acid, aromatic monocarboxylic acids having 6 to 12 C atoms, such as, for example, benzoic acid
  • aliphatic polycarboxylic acid having 2 to 12 C atoms, preferably 4 to 6 C atoms, such as oxalic acid, succinic acid, maleic acid, fumaric acid, 2-ethyl-succinic acid, glutaric acid, 2-methylglutaric acid, adipic acid, 2-methyl-, 2,2-dimethyl-adipic acid, 1, 8-octanoic acid, 1, 10-decanoic acid and 1, 12-dodecanoic acid, aromatic dicarboxylic acids having 8 to 12 carbon atoms, such as phthalic acid, terephthalic acid and isophthalic acid, carboxylic acid chlorides
  • aliphatic and aromatic monocarboxylic acid, Carbonklado- and dichlorides of aliphatic and aromatic polycarboxylic acids preferably dicarboxylic acids, inorganic acids such as phosphoric acid, phosphorous acid and hydrochloric acid and diesters such
  • Preferably used as acidic stabilizers use aliphatic monocarboxylic acids having 1 to 8 carbon atoms, such as. Formic acid, acetic acid, aliphatic dicarboxylic acids having 2 to 6 C atoms, such as e.g. Oxalic acid and in particular 2-ethylhexanoic acid, chloropropionic acid and / or methoxyacetic acid.
  • typical additives can be used for example: other antioxidants such as phosphites of the type P (OR a ) (OR b ) (OR C ) with R a , R b , R c as the same or different aliphatic or aromatic radicals (which can also form cyclic or spiro structures), UV stabilizers such as UV absorbers and suitable radical scavengers (in particular HALS compounds, hindered amine light stabilizers), activators (accelerators), drying agents, fillers, pigments, dyes, antistatic agents, Flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents. Preference is given to UV stabilizers.
  • other antioxidants such as phosphites of the type P (OR a ) (OR b ) (OR C ) with R a , R b , R c as the same or different aliphatic or aromatic radicals (which can also form cycl
  • Suitable UV absorbers include oxanilides, triazines and benzotriazole (the latter being available, for example, as Tinuvin® grades from Ciba Specialty Chemicals) and benzophenones (e.g., Chimassorb® 81 from Ciba Specialty Chemicals). Preferred are e.g.
  • radical scavengers for example sterically hindered amines (often also referred to as HALS or HAS compounds; hindered amines (Light) Stabilizers) such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert - butylpiperidine or its derivatives, e.g. For example, bis (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate can be used. These are available, for example, as Tinuvin® and Chi- massorb® grades from Ciba Specialty Chemicals.
  • suitable radical scavengers for example sterically hindered amines (often also referred to as HALS or HAS compounds; hindered amines (Light) Stabilizers) such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert - butylpiperidine or its derivatives, e.g.
  • hindered amines which are N-alkylated, for example bis (1, 2,2,6,6-pentamethyl-4-piperidinyl) - [[3,5-bis (1 , 1-dimethylethyl) -4-hydroxyphenyl] methyl] -butyl malonate (eg Tinuvin® 144 from Ciba Specialty Chemicals); a mixture of bis (1, 2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl (1, 2,2,6,6-pentamethyl-4-piperidinyl) sebacate (eg Tinuvin® 292 from Ciba Specialty Chemicals ); or the N- (O-alkylated), such as decanoic acid, bis (2, 2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, reaction products with 1, 1-
  • Dimethyl ethyl hydroperoxide and octane e.g., Tinuvin® 123 from Ciba Specialty Chemicals.
  • UV stabilizers are usually used in amounts of 0.1 to 5.0 wt .-%, based on the solid components contained in the preparation.
  • chelating agents e.g. Ethylenediaminetic acid and its salts and ß-di-ketones are used.
  • fillers, dyes and / or pigments may also be present as component (H).
  • practically insoluble means a solubility at 25 ° C. of less than 1 g / 1000 g of application medium, preferably less than 0.5, more preferably less than 0.25, very preferably less than 0.1 and in particular less than 0.05 g / 1000 g of application medium.
  • pigments in the true sense include any systems of absorption and / or effect pigments, preferably absorption pigments.
  • Number and selection of the pigment components are not subject to any restrictions. They can be adapted to the particular requirements, for example the desired color impression, as desired, for example as described in step a).
  • all the pigment components of a standardized mixed-paint system can be based.
  • Effect pigments are to be understood as meaning all pigments which have a platelet-like structure and impart special decorative color effects to a surface coating.
  • the effect pigments are, for example, all effect pigments which can usually be used in vehicle and industrial coating.
  • effect pigments are pure metal pigments; such as aluminum, iron or copper pigments; Interference pigments such as titanium dioxide coated mica, iron oxide coated mica, mixed oxide coated mica (eg with titanium dioxide and Fe2O3 or titanium dioxide and O2O3), metal oxide coated aluminum, or liquid crystal pigments.
  • the coloring absorption pigments are, for example, customary organic or inorganic absorption pigments which can be used in the coatings industry.
  • organic absorption pigments are azo pigments, phthalocyanine, quinacridone and pyrrolopyrrole pigments.
  • inorganic absorption pigments are iron oxide pigments, titanium dioxide and carbon black.
  • Dyes are also colorants and differ from the pigments by their solubility in the application medium, ie they have at 25 0 C, a solubility above 1 g / 1000 g in the application medium.
  • dyes examples include azo, azine, anthraquinone, acridine, cyanine, oxazine, polymethine, thiazine, triarylmethane dyes. These dyes may find application as basic or cationic dyes, mordant, direct, disperse, development, vat, metal complex, reactive, acid, sulfur, coupling or substantive dyes.
  • Coloriferous inert fillers are understood as meaning all substances / compounds which on the one hand are coloristically inactive; i.e. which show low intrinsic absorption and whose refractive index is similar to the refractive index of the coating medium and which, on the other hand, are capable of controlling the orientation (parallel alignment) of the effect pigments in the surface coating, i. in the applied paint film to influence, further properties of the coating or the coating materials, such as hardness or rheology.
  • examples of usable inert substances / compounds are mentioned, but without limiting the term coloristically inert topology-influencing fillers to these examples.
  • Suitable inert fillers as defined may be, for example, transparent or semi-transparent fillers or pigments, e.g. Silica gels, blancfixe, diatomaceous earth, talc, calcium carbonates, kaolin, barium sulfate, magnesium silicate, aluminum silicate, crystalline silica, amorphous silica, alumina, microspheres or hollow microspheres, e.g. of glass,
  • transparent or semi-transparent fillers or pigments e.g. Silica gels, blancfixe, diatomaceous earth, talc, calcium carbonates, kaolin, barium sulfate, magnesium silicate, aluminum silicate, crystalline silica, amorphous silica, alumina, microspheres or hollow microspheres, e.g. of glass,
  • any solid inert organic particles such as, for example, urea-forming aldehyde condensation products, micronized polyolefin wax and micronized amide wax.
  • the inert fillers can also be used in each case in a mixture. Preferably, however, only one filler is used in each case.
  • Preferred fillers include silicates, e.g. Example by hydrolysis of silicon tetrachloride available silicates such as Aerosil® the Fa. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonate, etc.
  • silicates e.g. Example by hydrolysis of silicon tetrachloride available silicates such as Aerosil® the Fa. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonate, etc.
  • the content of polyisocyanate is usually more than 50%, in particular 65-99.99% by weight.
  • These mixtures are then converted in a second step by adding optionally further of components (B) to (G), and optionally (H), into the polyisocyanate compositions according to the invention.
  • Preferred solvents for premixes of this first step are n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2, 2-methoxyethyl acetate, and mixtures thereof, in particular with the abovementioned aromatic hydrocarbon mixtures.
  • Such mixtures can be prepared in a volume ratio of 5: 1 to 1: 5, preferably in a volume ratio of 4: 1 to 1: 4, more preferably in a volume ratio of 3: 1 to 1: 3 and most preferably in a volume ratio of 2: 1 to 1: 2
  • Preferred examples are butyl acetate / xylene, methoxypropyl acetate / xylene 1: 1, butyl acetate / solvent naphtha 100 1: 1, butyl acetate / Solvesso® 100 1: 2 and crystal oil 30 / Shellsol® A 3: 1.
  • polyisocyanate compositions according to the invention are composed, for example, as follows:
  • (D) 0 to 5000 ppm by weight, preferably 10 to 2000, particularly preferably 20 to 600 and very particularly preferably 50 to 200 ppm by weight, and
  • components (H) are present, they are not included in the composition of components (A) to (G).
  • polyisocyanate compositions according to the invention can be used with advantage as hardener components in addition to at least one binder in polyurethane paints.
  • the reaction with binders can take place after a long period of time which requires appropriate storage of the polyisocyanate composition.
  • the storage of polyisocyanate preferably takes place at room temperature, but can also be carried out at higher temperatures. In practice, heating of such Polyisocyanatzusammen applicant at 40 0 C, 60 0 C, even up to 80 0 C quite possible.
  • the binders may be, for example, polyacrylate polyols, polyester polyols, polyether polyols, polyurethane polyols; polyurea; Polyester polyacrylate latpolyols; polyester polyurethane polyols; Polyurethane polyacrylate polyols, polyurethane modified alkyd resins; Fatty acid-modified polyester polyurethane polyols, copolymers with allyl ethers, graft polymers of the substance groups mentioned with e.g. different glass transition temperatures, as well as mixtures of said binders act. Preference is given to polyacrylate polyols, polyester polyols and polyether polyols.
  • Preferred OH numbers measured according to DIN 53240-2, are 40-350 mg KOH / g solid resin for polyester, preferably 80-180 mg KOH / g solid resin, and 15-250 mg KOH / g solid resin for polyacrylatols, preferably 80-160 mg KOH / g.
  • the binders may have an acid number according to DIN EN ISO 3682 up to 200 mg KOH / g, preferably up to 150 and particularly preferably up to 100 mg KOH / g.
  • Polyacrylate polyols preferably have a molecular weight M n of at least 1000, particularly preferably at least 2000 and very particularly preferably at least 5000 g / mol.
  • the molecular weight M n may in principle be infinite upwards, preferably up to 200,000, more preferably up to 100,000 and in particular up to 50,000 g / mol.
  • the latter can be, for example, monoesters of ⁇ , ⁇ -unsaturated carboxylic acids, such as acrylic acid, methacrylic acid (referred to in this document as "(meth) acrylic acid”), with diols or polyols which preferably have 2 to 20 C atoms and at least two hydroxypolyols.
  • monoesters of ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, methacrylic acid (referred to in this document as "(meth) acrylic acid”
  • diols or polyols which preferably have 2 to 20 C atoms and at least two hydroxypolyols.
  • xy jury such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 1-dimethyl-1, 2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,6-hexanediol, 2-Methyl-1, 5-pentanediol, 2-ethyl-1,4-butanediol, 2-ethyl-1,3-hexanediol, 2,
  • the hydroxy-group-containing monomers are used in the copolymerization in admixture with other polymerizable, preferably free-radically polymerizable monomers, preferably those containing more than 50% by weight of C 1 -C 20, preferably C 1 -C 4 -alkyl (meth) acrylate, (Meth ) acrylic acid, vinyl aromatics having up to 20 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl halides, non-aromatic hydrocarbons having 4 to 8 carbon atoms and 1 or 2 double bonds, unsaturated nitriles and mixtures thereof.
  • Particular preference is given to the polymers which consist of more than 60% by weight of C 1 -C 10 -alkyl (meth) acrylates, styrene and its derivatives, vinylimidazole or mixtures thereof.
  • the polymers may contain hydroxy-functional monomers corresponding to the above hydroxy group content and optionally other monomers, e.g. (Meth) acrylic acid glycidyl epoxyesters, ethylenically unsaturated acids, in particular carboxylic acids, acid anhydrides or acid amides.
  • monomers e.g. (Meth) acrylic acid glycidyl epoxyesters, ethylenically unsaturated acids, in particular carboxylic acids, acid anhydrides or acid amides.
  • polyesterols as are obtainable by condensation of polycarboxylic acids, in particular dicarboxylic acids, with polyols, in particular diols.
  • polycarboxylic acids in particular dicarboxylic acids
  • polyols in particular diols.
  • triols, tetrols, etc., as well as triacids, etc. are also used in some cases.
  • Polyesterpolyols are known, for example, from Ullmanns Encyklopadie der ischen Chemie, 4th Edition, Volume 19, pages 62 to 65. Preference is given to using polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids.
  • polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic or heterocyclic and may optionally be substituted, for example by halogen atoms, and / or unsaturated. Examples include:
  • anhydrides or dialkyl esters for example C 1 -C 4 -alkyl esters, preferably methyl, ethyl or n-but
  • dicarboxylic acids of the general formula HOOC- (CH 2) y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, particularly preferably succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.
  • polyesterols 1, 2-propanediol, ethylene glycol, 2,2-dimethyl-1, 2-ethanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 3-methylpentane-1, 5-diol, 2-ethylhexane-1,3-diol, 2,4-diethyloctane-1,3-diol, 1,6-hexanediol, poly-THF having a molecular weight between 162 and 4500, preferably 250 to 2000, poly-1,3-propanediol having a molecular weight between 134 and 1 178, poly-1,2-propanediol having a molecular weight between 134 and 898, polyethylene glycol having a molecular weight between 106 and 458, Neopentyl glycol, hydroxypiva
  • Alcohols of the general formula HO- (CH 2) X -OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20.
  • Preferred are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol.
  • Further preferred is neopentyl glycol.
  • polycarbonate diols as can be obtained, for example, by reacting phosgene with an excess of the low molecular weight alcohols mentioned as synthesis components for the polyester polyols.
  • lactone-based polyesterdiols which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules.
  • Suitable lactones are preferably those which are derived from compounds of the general formula HO- (CH 2) ⁇ -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit by a C 1 to C 4 alkyl radical may be substituted.
  • Examples are ⁇ -caprolactone, ⁇ -propiolactone, gamma-butyrolactone and / or methyl- ⁇ -caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivolactone, and mixtures thereof.
  • Suitable starter components are e.g. the low molecular weight dihydric alcohols mentioned above as the synthesis component for the polyesterpolyols.
  • the corresponding polymers of ⁇ -caprolactone are particularly preferred.
  • Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers.
  • polyetherols which are prepared by addition of ethylene oxide, propylene oxide or butylene oxide to H-active components.
  • polycondensates of butanediol are suitable.
  • hydroxy-functional carboxylic acids for example dimethylolpropionic acid or dimethylolbutanoic acid.
  • the polymers may of course also be compounds with primary secondary amino groups.
  • the polyisocyanate composition and binder in a molar ratio of isocyanate groups to isocyanate-reactive groups of 0.1: 1 to 10: 1, preferably 0.2: 1 to 5: 1, particularly preferably 0.3: 1 to 3: 1, completely particularly preferably 0.5: 1 to 2: 1, in particular 0.8: 1 to 1, 2: 1 and especially 0.9: 1 to 1, 1: 1 mixed with each other, it being possible, where appropriate, to admix further typical constituents of the paint, and applied to the substrate.
  • ambient temperature to 140 0 C, preferably 20 to 80 0 C, more preferably cured to 60 0 C, the paint mixture.
  • this usually requires no more than 12 hours, preferably up to 8 hours, more preferably up to 6, very preferably up to 4 and in particular up to 3 hours.
  • the substrates are coated by customary methods known to the person skilled in the art, at least one coating composition being applied to the substrate to be coated in the desired thickness and the volatile constituents of the coating composition, if appropriate with heating, being removed. If desired, this process can be repeated one or more times.
  • the application to the substrate can in a known manner, for. B. by spraying,
  • the thickness of such a layer to be hardened may range from 0.1 ⁇ m to several mm, preferably from 1 to 2,000 ⁇ m, particularly preferably 5 to 200 ⁇ m, very particularly preferably from 5 to 60 ⁇ m (based on the lacquer in the state in FIG the solvent is removed from the paint).
  • substrates coated with a multilayer coating according to the invention are also the subject of the present invention.
  • the resulting two-component coating compositions and paint formulations are suitable for coating substrates such as wood, wood veneer, paper, cardboard, textile, film, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials such as cement blocks and fiber cement boards or metals, the each optionally optionally precoated or pretreated.
  • Such coating compositions are suitable as or in inner or outer coatings, ie applications that are exposed to daylight, preferably of building parts, coatings on (large) vehicles and aircraft and industrial applications, commercial vehicles in the agricultural and construction sector, decoupling - bridges, buildings, electricity pylons, tanks, containers, pipelines, power plants, chemical plants, ships, cranes, piles, sheetpings, fittings, pipes, fittings, flanges, couplings, halls, roofs and structural steel, furniture, windows, doors, Parquet, Can-Coating and Coil-Coating, for floor coverings, as for parking decks or in hospitals in automotive lacquers as OEM and refinish application.
  • Such coating compositions are preferably at temperatures between ambient temperature to 80 0 C, preferably 0 to 60 C, particularly preferably 0 to 40 C.
  • these are those items that can not be cured at high temperatures, such as large machines, airplanes, open space vehicles, and refinish applications.
  • the coating compositions of the invention are used as clearcoats, basecoats and topcoats, primers and fillers.
  • Such polyisocyanate compositions can be used as curing agents in paints, adhesives and sealants.
  • the polyisocyanate A-1 was prepared as follows:
  • 1, 6-hexamethylene diisocyanate from a phosgene process was stirred in the presence of 0.7% by weight of 2-ethylhexanol at a temperature of 95 0 C for 90 min. Subsequently, 65 ppm by weight of (2-hydroxypropyl) -N, N, N-trimethylammonium 2-ethylhexanoate was added as a catalyst for the trimerization and allowed to react at 65 0 C.
  • the reaction was stopped by adding 150 ppm by weight of 2-hydroxyethyl carbamate. The excess monomeric isocyanate was removed by vacuum distillation at 145 ° C.
  • Biuret group-containing polyisocyanate based on hexamethylene diisocyanate (Basonat® HB 100 from BASF AG)
  • Catalyst B-1 dibutyltin dilaurate (DBTL, DBTDL)
  • Thioether C-2 3,3'-thiodipropionic acid dodecyl ester (Irganox® PS 800 from Ciba Specialty Chemicals).
  • Phenols D Phenol D-1 Benzenepropionic acid, 3,5-bis (1,1-dimethyl-ethyl) -4-hydroxy-C7-C9 branched alkyl ester (e.g., Irganox® 1 135 from Ciba Specialty Chemicals)
  • Solvent E-1 Solvent naphtha (boiling range about 170-180 0 C)
  • Solvent E-2 n-Butyl acetate
  • the polyisocyanates A were in about 50 wt .-% with the specified in the experiments concentrations of catalysts (B), thioether (C), phenols (D), in each case 10 wt .-% - ig in butyl acetate, and about 50 wt % Solvent (E) in tightly sealed screw-top containers, usually stored to exclude air under nitrogen. Traces of air are not excluded. The percentages by weight are based on 100% total weight.
  • concentrations of the compounds (B), (C), (D) in ppm in each case undiluted state of the compounds (B) to (D) refer to the total amount of polyisocyanate (A).
  • the storage is carried out in each case at 50 0 C in a convection oven.
  • the color numbers are measured directly (immediately before the start of storage), after storage over different periods of time.
  • the color number measurement is carried out in APHA according to DIN EN 1557 on a Lico 300 from Lange in a 5 cm measuring cuvette with a volume of 5 mL.
  • the error tolerances for the setpoint value are 20 Hz (+/- 5, actual value 18 Hz); Setpoint 102 Hz (+/- 10, actual value 99 Hz); Reference value 202 Hz (+/- 20, actual value 197 Hz).
  • test results show that the antioxidative stabilization by stabilization with the compounds C-1 and D-1 in Solvent Naphtha is particularly preferred.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne des compositions de durcisseurs stables au niveau de la couleur et destinées à des vernis polyuréthanne.
PCT/EP2008/053613 2007-03-27 2008-03-27 Compositions de durcisseurs WO2008116893A1 (fr)

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WO2011061314A1 (fr) 2009-11-23 2011-05-26 Basf Se Catalyseurs pour des masses de revêtement à base de polyuréthane
US8373004B2 (en) 2007-03-27 2013-02-12 Basf Se Method for producing colorless isocyanurates of diisocyanates
WO2013060614A1 (fr) 2011-10-28 2013-05-02 Basf Se Compositions de durcisseurs de couleur stable contenant des polyisocyanates de diisocyanates (cyclo)aliphatiques
WO2013060809A2 (fr) 2011-10-28 2013-05-02 Basf Se Procédé de production de polyisocyanates de diisocyanates (cyclo)aliphatiques résistants à la floculation dans les solvants
US9617402B2 (en) 2011-10-28 2017-04-11 Basf Se Process for preparing polyisocyanates which are flocculation-stable in solvents from (cyclo)aliphatic diisocyanates
EP3305863A1 (fr) 2016-10-07 2018-04-11 Basf Se Procédé de production de polyisocyanates de diisocyanates (cyclo)aliphatiques résistants à la floculation dans les solvants
EP3305824A1 (fr) 2016-10-07 2018-04-11 Basf Se Compositions de durcisseur de couleur stable comprenant du polyisocyanate de diisocyanates (cyclo)aliphatiques
US9963538B2 (en) 2013-01-07 2018-05-08 Basf Se Catalysts for polyurethane coating compounds
EP3336118A1 (fr) 2017-09-20 2018-06-20 Basf Se Compositions d'agents de durcissement de couleur stable comprenant du polyisocyanate d'isocyanates (cyclo)aliphatiques
EP3336117A1 (fr) 2017-09-20 2018-06-20 Basf Se Procédé de fabrication de polyisocyanates de diisocyanates (cyclo)aliphatiques résistants à la floculation dans les solvants
EP3431521A1 (fr) 2017-07-20 2019-01-23 Basf Se Compositions d'agents de durcissement de couleur stable comprenant du polyisocyanate d'isocyanates (cyclo)aliphatiques
WO2021151774A1 (fr) 2020-01-30 2021-08-05 Basf Se Compositions d'agent de durcissement à couleur stable comprenant des polyisocyanates hydrodispersables
CN113396133A (zh) * 2019-02-12 2021-09-14 建筑研究和技术有限公司 用于制造聚氨酯/脲水泥混合体系的多组分组合物
WO2022128925A1 (fr) 2020-12-18 2022-06-23 Basf Se Compositions de durcisseur de couleur stable contenant des polyisocyanates de diisocyanates (cyclo)aliphatiques
WO2023280648A1 (fr) 2021-07-08 2023-01-12 Basf Se Formulations contenant un polyisocyanate
WO2023117989A1 (fr) 2021-12-21 2023-06-29 Basf Se Attributs environnementaux pour additifs de formulation

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EP2644270A1 (fr) * 2012-03-29 2013-10-02 Huntsman International Llc Composition de catalyseur de trimérisation de polyisocyanate
CN106554293B (zh) * 2015-09-24 2018-04-20 万华化学集团股份有限公司 一种制备无色或浅色多异氰酸酯的方法
CN112111044B (zh) * 2019-06-21 2021-06-29 万华化学集团股份有限公司 一种聚异氰酸酯组合物及其制备方法和应用
CN111704709B (zh) * 2020-06-29 2022-01-28 上海华峰新材料研发科技有限公司 一种合成革用低模量无溶剂聚氨酯树脂及其制备方法

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US3555072A (en) * 1968-09-20 1971-01-12 Olin Corp Stabilization of tolylene diisocyanate
GB1289689A (fr) * 1968-12-18 1972-09-20
US3772218A (en) * 1971-10-12 1973-11-13 Scott Paper Co Flexible,open-cell,non-discoloring polyurethane foam
DE2231069A1 (de) * 1972-06-24 1974-01-03 Bayer Ag Oxidationsstabilisatoren enthaltende polyurethane
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EP0381125A2 (fr) * 1989-02-03 1990-08-08 Ppg Industries, Inc. Compositions de polymère ayant une stabilité oxydative modifiée
US5205916A (en) * 1991-12-11 1993-04-27 E. I. Du Pont De Nemours And Company Cathodic electrodeposition coatings containing an antioxidant additive
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Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8373004B2 (en) 2007-03-27 2013-02-12 Basf Se Method for producing colorless isocyanurates of diisocyanates
US8709544B2 (en) 2009-11-23 2014-04-29 Basf Se Catalysts for polyurethane coating compounds
WO2011061314A1 (fr) 2009-11-23 2011-05-26 Basf Se Catalyseurs pour des masses de revêtement à base de polyuréthane
WO2013060614A1 (fr) 2011-10-28 2013-05-02 Basf Se Compositions de durcisseurs de couleur stable contenant des polyisocyanates de diisocyanates (cyclo)aliphatiques
WO2013060809A2 (fr) 2011-10-28 2013-05-02 Basf Se Procédé de production de polyisocyanates de diisocyanates (cyclo)aliphatiques résistants à la floculation dans les solvants
US9617402B2 (en) 2011-10-28 2017-04-11 Basf Se Process for preparing polyisocyanates which are flocculation-stable in solvents from (cyclo)aliphatic diisocyanates
US9963538B2 (en) 2013-01-07 2018-05-08 Basf Se Catalysts for polyurethane coating compounds
EP3305863A1 (fr) 2016-10-07 2018-04-11 Basf Se Procédé de production de polyisocyanates de diisocyanates (cyclo)aliphatiques résistants à la floculation dans les solvants
WO2018065343A1 (fr) 2016-10-07 2018-04-12 Basf Se Procédé de production de polyisocyanates de diisocyanates (cyclo)aliphatiques résistants à la floculation dans les solvants.
WO2018065344A1 (fr) 2016-10-07 2018-04-12 Basf Se Compositions de durcisseurs de couleur stable contenant des polyisocyanates de diisocyanates (cyclo)aliphatiques
EP3305824A1 (fr) 2016-10-07 2018-04-11 Basf Se Compositions de durcisseur de couleur stable comprenant du polyisocyanate de diisocyanates (cyclo)aliphatiques
US11807709B2 (en) 2016-10-07 2023-11-07 Basf Se Method for producing polyisocyanates of (cyclo)aliphatic diisocyanates which are flocculation-stable in solvents
US11001730B2 (en) 2016-10-07 2021-05-11 Basf Se Colour-stable curing compositions containing polyisocyanates of (cyclo)aliphatic diisocyanates
WO2019016097A1 (fr) 2017-07-20 2019-01-24 Basf Se Compositions de durcisseurs de couleur stable contenant des polyisocyanates de diisocyanates (cyclo)aliphatiques
CN110914327A (zh) * 2017-07-20 2020-03-24 巴斯夫欧洲公司 包含脂(环)族二异氰酸酯的多异氰酸酯的颜色稳定的固化组合物
EP3431521A1 (fr) 2017-07-20 2019-01-23 Basf Se Compositions d'agents de durcissement de couleur stable comprenant du polyisocyanate d'isocyanates (cyclo)aliphatiques
CN110914327B (zh) * 2017-07-20 2023-08-22 巴斯夫欧洲公司 包含脂(环)族二异氰酸酯的多异氰酸酯的颜色稳定的固化组合物
US11624003B2 (en) 2017-09-20 2023-04-11 Basf Se Colour-stable curing compositions containing polyisocyanates of (cyclo)aliphatic diisocyanates
WO2019057539A1 (fr) 2017-09-20 2019-03-28 Basf Se Compositions de durcisseurs de couleur stable contenant des polyisocyanates de diisocyanates (cyclo)aliphatiques
WO2019057540A1 (fr) 2017-09-20 2019-03-28 Basf Se Procédé de production de polyisocyanates de diisocyanates (cyclo)aliphatiques résistants à la floculation dans les solvants
EP3336117A1 (fr) 2017-09-20 2018-06-20 Basf Se Procédé de fabrication de polyisocyanates de diisocyanates (cyclo)aliphatiques résistants à la floculation dans les solvants
EP3336118A1 (fr) 2017-09-20 2018-06-20 Basf Se Compositions d'agents de durcissement de couleur stable comprenant du polyisocyanate d'isocyanates (cyclo)aliphatiques
US11542356B2 (en) 2017-09-20 2023-01-03 Basf Se Method for producing polyisocyanates of (cyclo)aliphatic diisocyanates which are flocculation-stable in solvents
CN113396133A (zh) * 2019-02-12 2021-09-14 建筑研究和技术有限公司 用于制造聚氨酯/脲水泥混合体系的多组分组合物
CN113396133B (zh) * 2019-02-12 2023-09-22 Sika技术股份公司 用于制造聚氨酯/脲水泥混合体系的多组分组合物
WO2021151774A1 (fr) 2020-01-30 2021-08-05 Basf Se Compositions d'agent de durcissement à couleur stable comprenant des polyisocyanates hydrodispersables
WO2022128925A1 (fr) 2020-12-18 2022-06-23 Basf Se Compositions de durcisseur de couleur stable contenant des polyisocyanates de diisocyanates (cyclo)aliphatiques
WO2023280648A1 (fr) 2021-07-08 2023-01-12 Basf Se Formulations contenant un polyisocyanate
WO2023117989A1 (fr) 2021-12-21 2023-06-29 Basf Se Attributs environnementaux pour additifs de formulation

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