COLOR-STABLE CURING AGENT COMPOSITIONS COMPRISING WATER-DISPERSIBLE POLYISOCYANATES

Abstract

A polyisocyanate composition comprising (A) at least one polyisocyanate obtainable by reacting (c) at least one diisocyanate or polyisocyanate, (d) at least one surfactant comprising a mixture of compounds based on the following formulae (I) and (II); in which R.sup.1 and R.sup.2 independently of one another are alkyl, cycloalkyl or aryl, it being possible for each of the stated radicals to be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles, said mixture of compounds of formulae (I) and (II) being characterised in that the molar ratio between compound (II), i.e. the monoester-type compound, and compound (I), i.e. the diester-type compound, is from 5:95 to 95:5, and (c) at least one monofunctional polyalkylene glycol, —and (B) at least one sterically hindered phenol.

##STR00001##

Claims

1.-16. (canceled)

17. A polyisocyanate composition comprising (A) at least one polyisocyanate obtained by reacting (a) at least one diisocyanate or polyisocyanate, (b) at least one surfactant comprising a mixture of compounds based on the following formulae (I) and (II): ##STR00009## in which R.sup.1 and R.sup.2 independently of one another are alkyl, cycloalkyl or aryl, it being possible for each of the stated radicals to be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles, said mixture of compounds of formulae (I) and (II) being characterised in that the molar ratio between compound (II), i.e. the monoester-type compound, and compound (I), i.e. the diester-type compound, is from 5:95 to 95:5, and (c) at least one monofunctional polyalkylene glycol, and (B) at least one sterically hindered phenol.

18. The polyisocyanate composition according to claim 17, wherein component (a) is a polyisocyanate synthesized from (cyclo)aliphatic isocyanates.

19. The polyisocyanate composition according to claim 17, wherein component (a) is a polyisocyanate containing allophanate and/or isocyanurate groups which is based on isophorone diisocyanate and/or 1,6-hexamethylene diisocyanate.

20. The polyisocyanate composition according to claim 17, wherein in component (b) R.sup.1 and R.sup.2 independently of one another are unsubstituted alkyl or unsubstituted aryl.

21. The polyisocyanate composition according to claim 20, wherein R.sup.1 and R.sup.2 independently of one another are selected from the group consisting of phenyl, methyl, ethyl, n-butyl, and 2-ethylhexyl.

22. The polyisocyanate composition according to claim 17, wherein the compound (b) is selected from the group consisting of mono methyl phosphate, di methyl phosphate, mono ethyl phosphate, di ethyl phosphate, mono n-butyl phosphate, di n-butyl phosphate, mono 2-ethylhexyl phosphate, di 2-ethylhexyl phosphate, and mixtures thereof.

23. The polyisocyanate composition according to claim 17, wherein the compound (c) fulfills the formula
R.sup.4—O—[—X.sub.i—].sub.k—H in which R.sup.4 is C.sub.1-C.sub.20 alkyl, C.sub.2-C.sub.20 alkyl uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or by one or more substituted or unsubstituted imino groups, or is C.sub.6-C.sub.12 aryl, C.sub.5-C.sub.12 cycloalkyl or a five- or six-membered heterocycle containing oxygen, nitrogen and/or sulfur atoms, it being possible for each of the stated radicals to be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocycles, k is an integer from 5 to 40, and each X.sub.i for i=1 to k can be selected independently from the group consisting of —CH.sub.2—CH.sub.2—O—, —CH.sub.2—CH(CH.sub.3)—O—, —CH(CH.sub.3)—CH.sub.2—O—, —CH.sub.2—C(CH.sub.3).sub.2—O—, —C(CH.sub.3).sub.2—CH.sub.2—O—, —CH.sub.2—CHVin-O—, —CHVin-CH.sub.2—O—, —CH.sub.2—CHPh-O—, and —CHPh-CH.sub.2 in which Ph is phenyl and Vin is vinyl.

24. The polyisocyanate composition according to claim 17, having the following construction of polyisocyanate (A), based on isocyanate groups in synthesis component (a): (b) 0.5 to 30 wt % of compounds of formula (I) and/or (II), and (c) at least 0.3 wt % up to 25 wt %, based on isocyanate-reactive groups in (c).

25. The polyisocyanate composition according to claim 17, wherein the phosphate groups in compound (b) have been at least partly neutralized.

26. The polyisocyanate composition according to claim 25, wherein the phosphate groups have been at least partly neutralized with tertiary amines (A1).

27. The polyisocyanate composition according to claim 17, wherein compound (B) is selected from the group consisting of 2,6-bis-tert-butyl-4-methylphenol (BHT), 3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionic ester, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 3,3′,3″,5,5′,5″-hexa-tert-butyl-a,a′,a″-(mesitylene-2,4,6-triyl)tri-p-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

28. A method of stabilizing a polyisocyanate composition comprising in addition to polyisocyanate (A) at least one sterically hindered phenol (B).

29. A process for preparing a polyurethane coating material, which comprises reacting a polyisocyanate composition according to claim 17 with at least one binder which comprises isocyanate-reactive groups.

30. A process for preparing a polyurethane coating material, which comprises reacting a polyisocyanate composition according to claim 17 with at least one binder selected from the group consisting of polyacrylate-polyol dispersions, polyester-polyol dispersions, polyether-polyol dispersions, polyurethane-polyol dispersions, polycarbonate-polyol dispersions, and their hybrids.

31. The use of a polyisocyanate composition according to claim 17 as a curing agent in a coating composition, in primers, surfacers, pigmented topcoat, basecoat, and clearcoat materials in the segment of refinish, in automotive refinish, large-vehicle coating, and wood coating, and also as a curing agent in coating materials, adhesives, and sealants.

32. The use of at least one sterically hindered phenol (B) for reducing the color number of mixtures comprising at least one polyisocyanate (A), obtained by reacting (a) at least one at diisocyanate or polyisocyanate, (b) at least one surfactant comprising an amine and a mixture of compounds based on the following formulae (I) and (II): ##STR00010## in which R.sup.1 and R.sup.2 independently of one another are alkyl, cycloalkyl or aryl, it being possible for each of the stated radicals to be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles, said mixture of compounds of formulae (I) and (II) being characterized in that the molar ratio between compound (II), i.e. the monoester-type compound, and compound (I), i.e. the diester-type compound, is from 5:95 to 95:5, and (c) at least one monofunctional polyalkylene glycol.

Description

EXAMPLES

[0287] Raw Materials:

[0288] Polyisocyanate A:

[0289] HDI-Isocyanurate with a NCO content of 22.0% and a viscosity of 3000 mPa*s at 23° C. (Basonat® HI 100 NG from BASF SE).

[0290] Polyether C:

[0291] Monofunctional poly(ethylene oxide), started with a methanol and using potassium hydroxide-based catalysis, with a OH content of 112 (DIN 53240) and an average molecular weight of 500 g/mol. The product was neutralized with acetic acid and the different remaining potassium salts removed.

[0292] Phosphate Salt D:

[0293] Mixture of 40.0 g Dibutyl/monobutylphosphate (molar ratio 0.8/1.0) and 19.0 g triethylamine

[0294] Polyisocyanate Crosslinker Synthesis:

[0295] Polyisocyanate 1:

[0296] 908.0 g Polyisocyanate A, 28.3 g Polyether C and 63.6 g Phoshphate Salt D are charged to a 1000 mL, 3-neck round bottom flask equipped with a thermometer (coupled with a temperature regulated oil-bath), mechanical stirring, a cold water condenser and nitrogen inlet. The reaction mixture is stirred and heated at 90° C. After 3 hours, the NCO content reached a value of 19.0%. The reaction mixture is cooled down to room temperature and the corresponding polyisocyanate presented a viscosity of 4200 mPa.Math.s at 23° C.

[0297] Storage Test:

TABLE-US-00001 Solvent/ Stabilizer/ Initial Final Hardener dilution quantities Storage color color PIC1 70 wt% No 21 Days 75 335 in PGDA Stabilizer @ 50° C. PIC1 70 wt% 500 ppm 21 Days 75 382 in PGDA Irgafos OPH @ 50° C. PIC1 70 wt% 500 ppm 21 Days 75 384 in PGDA DEHP @ 50° C. PIC1 70 wt% 500 ppm 21 Days 75  81 in PGDA BHT @ 50° C. PIC1 70 wt% 500 ppm 21 Days 75  97 in PGDA Irganox 1135 @ 50° C. PIC1 70 wt% No 21 Days 69 206 in MPA Stabilizer @ 50° C. PIC1 70 wt% 500 ppm 21 Days 69 242 in MPA Irgafos OPH @ 50° C. PIC1 70 wt% 500 ppm 21 Days 69 210 in MPA DEHP @ 50° C. PIC1 70 wt% 500 ppm 21 Days 69  69 in MPA BHT @ 50° C. PIC1 70 wt% 500 ppm 21 Days 69  95 in MPA Irganox 1135 @ 50° C. PIC1 100%-No No 14 Days 70 554 Solvent Stabilizer @ 50° C. PIC1 100%-No 100 ppm 14 Days 70  71 Solvent Irganox 1135 @ 50° C. PIC1 100%-No 250 ppm 14 Days 70  58 Solvent Irganox 1135 @ 50° C. PIC1 100%-No 500 ppm 14 Days 70  69 Solvent Irganox 1135 @ 50° C. PIC1 100%-No 500 ppm 14 Days 70 538 Solvent Irgafos OPH @ 50° C. PIC1 100%-No 500 ppm 14 Days 70 612 Solvent DEHP @ 50° C. PGDA: Propyleneglycoldiacetate MPA: 1-Methoxy-2-propylacetat Irgafos OPH: Di n-octylphosphonic acid DEHP: Di-2-ethylhexylphosphate BHT: Butylhydroxytoluol

##STR00007##

[0298] Irganox 1135: benzenepropanoic acid, 3,5-bis (1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl esters

##STR00008##