USE OF POLYAMINE- AND/OR POLYALKANOLAMINE-BASED CARBOXYLIC ACID DERIVATIVES IN AQUEOUS POLYURETHANE DISPERSIONS

Abstract

The use of polyamine- and/or polyalkanolamine-based carboxylic acid derivatives as additives in aqueous polymer dispersions for production of porous polymer coatings, preferably for production of porous polyurethane coatings, is described.

Claims

1-17. (canceled)

18. An aqueous polymer dispersion, comprising polyamine- and/or polyalkanolamine-based carboxylic acid derivatives obtainable by reacting polyamines and/or polyalkanolamines with at least one acyl group donor, wherein the solids content of the dispersion is in the range of 20-70% by weight based on the overall dispersion, and wherein the concentration of the polyamine- and/or polyalkanolamine-based carboxylic acid derivatives is in the range of 0.2-20% by weight based on the total weight of the aqueous polymer dispersion.

19. The aqueous polymer dispersion of claim 18, wherein the acyl group donor is a carboxylic acid, a carboxylic ester, a carbonyl halide or a carboxylic anhydride.

20. The aqueous polymer dispersion of claim 18, wherein the acyl group donor is a carboxylic acid of general formula R—C(O)OH, wherein R is a monovalent aliphatic saturated or unsaturated hydrocarbon radical having 3 to 39 carbon atoms.

21. The aqueous polymer dispersion of claim 18, wherein the acyl group donor is a carboxylic acid selected from the group consisting of: butyric acid (butanoic acid), caproic acid (hexanoic acid), caprylic acid (octanoic acid), pelargonic acid (nonanoic acid), capric acid (decanoic acid), lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachidic acid (eicosanoic acid), behenic acid (docosanoic acid), lignoceric acid (tetracosanoic acid), palmitoleic acid ((Z)-9-hexadecenoic acid), oleic acid ((Z)-9-octadecenoic acid), elaidic acid ((E)-9-octadecenoic acid), cis-vaccenic acid ((Z)-11-octadecenoic acid), linoleic acid ((9Z,12Z)-9,12-octadecadienoic acid), alpha-linolenic acid ((9Z,12Z,15Z)-9,12,15-octadecatrienoic acid), gamma-linolenic acid ((6Z,9Z,12Z)-6,9,12-octadecatrienoic acid), di-homo-gamma-linolenic acid ((8Z,11Z,14Z)-8,11,14-eicosatrienoic acid), arachidonic acid ((5Z,8Z,11Z,14Z)-5,8,11,14-eicosatetraenoic acid), erucic acid ((Z)-13-docosenoic acid), nervonic acid ((Z)-15-tetracosenoic acid), ricinoleic acid, hydroxystearic acid and/or undecylenic acid, and mixtures thereof.

22. The aqueous polymer dispersion of claim 18, wherein the acyl group donor is rapeseed oil acid, soya fatty acid, sunflower fatty acid, peanut fatty acid and/or tall oil fatty acid.

23. The aqueous polymer dispersion of claim 18, wherein the acyl group donor is palmitic acid, stearic acid, a mixture of palmitic acid and stearic acid; and/or an aliphatic, linear or branched di- and/or tricarboxylic acid having a chain length of 2 to 18 carbon atoms and/or dimer fatty acids obtained by catalytic dimerization of unsaturated fatty acids having 4 to 22 carbon atoms.

24. The aqueous polymer dispersion of claim 18, wherein the polyamine is selected from the group consisting of: diethylenetriamine, triethylenetetraamines, tetraethylenepentamines, pentaethyleneheptaamine, dipropylenetriamine, tripropylenetetraamine, tetraethylenepentamine, pentaethyleneheptaamine, spermine, spermidine, and N-alkylated, N-methylated derivatives of these compounds.

25. The aqueous polymer dispersion of claim 18, wherein the polyamine is selected from the group consisting of: polyethyleneimines, polypropyleneimines and/or amine group-bearing (co)polymers based on allylamine and/or vinylamine

26. The aqueous polymer dispersion of claim 18, wherein the polyalkanolamine is selected from the group consisting of: polydiethanolamine, polydipropanolamine, polydiisoproanolamine, polytriethanolamine, polytripropanolamine, polytriisopropanolamine, polyetheramines, and/or (co)polymers based on allyl alcohol, vinyl alcohol, allylamine and/or vinylamine, and mixtures of these substances.

27. The aqueous polymer dispersion of claim 18, wherein the polyamine-based carboxylic acid derivatives are reaction products of at least one polyethyleneimine with at least one carboxylic acid, wherein the polyethyleneimine has an average molar mass of less than 25 000 g/mol when determined by gel permeation chromatography (GPC).

28. The aqueous polymer dispersion of claim 18, wherein the polyalkanolamine is obtainable by condensation of a trialkanolamine of general formula 1: ##STR00006## wherein R.sup.1 to R.sup.3 radicals are independently identical or different 1,2-alkylene groups having 2 to 4 carbon atoms.

29. The aqueous polymer dispersion of claim 18, wherein the polyamine-based carboxylic acid derivatives are reaction products of (co)polymers bearing amine groups with at least one carboxylic acid, where the (co)polymers bearing amine groups have at least one repeat unit A of general formula 2: ##STR00007## and/or at least one repeat unit B of general formula 3: ##STR00008## wherein the R.sup.4 radicals are identical or different monovalent aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having 1 to 10 carbon atoms, or hydrogen.

30. The aqueous polymer dispersion of claim 18, wherein the polyalkanolamine-based carboxylic acid derivatives are reaction products of (co)polymers bearing amine and OH groups with at least one carboxylic acid, where the (co)polymers bearing amine and OH groups, as well as at least one of the repeat units A (of formula 2) and/or B (of formula 3), also have at least one repeat unit C of formula 4: ##STR00009## and/or at least one repeat unit D of general formula 5: ##STR00010##

31. The aqueous polymer dispersion of claim 18, wherein the preparation of polyamine- and/or polyalkanolamine-based carboxylic acid derivatives, polyamine and/or polyalkanolamine and carboxylic acids are reacted in such a way that the molar ratio of amine and OH functions reactive toward carboxylic acids to carboxylic acids is in the range of 5:1-1.5:1.

32. The aqueous polymer dispersion of claim 18, wherein the polyamine- and/or polyalkanolamine-based carboxylic acid derivatives are used in combination with at least one further cosurfactant, selected from the group consisting of: fatty alcohols, fatty acid amides, ethylene oxide-propylene oxide block copolymers, betaines, amine oxides, quaternary ammonium surfactants, amphoacetates, ammonium and/or alkali metal salts of fatty acids, alkyl sulfates, alkyl ether sulfates, alkylsulfonates, alkylbenzenesulfonates, alkyl phosphates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl sarcosinates and/or silicone-based cosurfactants and mixtures of these substances.

33. The aqueous polymer dispersion of claim 18, wherein the polyamine- and/or polyalkanolamine-based carboxylic acid derivatives are used in combination with at least one cosurfactant, wherein said cosurfactant is a free fatty alcohol having 12 to 40 carbon atoms, an alkyl sulfate having 12 to 40 carbon atoms, or a mixture of these substances.

34. The aqueous polymer dispersion of claim 18, wherein the aqueous polymer dispersion is selected from the group consisting of: an aqueous polystyrene dispersion; a polybutadiene dispersion, a poly(meth)acrylate dispersion, and a polyvinyl ester dispersion.

35. The aqueous polymer dispersion of claim 18, wherein the aqueous polymer dispersion is an aqueous polyurethane dispersion.

36. The aqueous polymer dispersion of claim 35, wherein the concentration of the polyamine- and/or polyalkanolamine-based carboxylic acid derivatives based on the total weight of the aqueous polymer dispersion is in the range of 0.5-10% by weight.

37. A process for producing a porous polymer coating, comprising the steps of: a) providing a mixture comprising at least one aqueous polymer dispersion, at least one polyamine- and/or a polyalkanolamine-based carboxylic acid derivative according to the claim 18; b) foaming the mixture to give a foam; c) optionally adding at least one thickener to adjust the viscosity of the wet foam; d) applying a coating of the foamed polymer dispersion, to a suitable carrier; e) drying the coating.

Description

EXAMPLES

Substances

[0072] IMPRANIL® DLU: aliphatic polycarbonate ester-polyether-polyurethane dispersion from Covestro.

[0073] REGEL® WX 151: aqueous polyurethane dispersion from Cromogenia.

[0074] CROMELASTIC® PC 287 PRG: aqueous polyurethane dispersion from Cromogenia.

[0075] STOKAL® STA: ammonium stearate (about 30% in H.sub.2O) from Bozetto.

[0076] STOKAL® SR: tallow fat-based sodium sulfosuccinamate (about 35% in H.sub.2O) from Bozetto.

[0077] ECO Pigment Black: aqueous pigment dispersion (black) from Cromogenia.

[0078] TEGOWET® 250: polyethersiloxane-based levelling additive from Evonik.

[0079] ORTEGOL® PV 301: polyurethane-based associative thickener from Evonik.

[0080] REGEL® TH 27: isocyanate-based crosslinking additive from Cromogenia.

Viscosity Measurements

[0081] All viscosity measurements were conducted with a Brookfield viscometer, LVTD, equipped with spindle #64, at a constant rotation speed of 12 rpm. For the viscosity measurements, the samples were transferred into a 100 ml jar into which the measurement spindle was immersed to a stipulated depth. The display of a constant viscometer measurement was always awaited.

Method of Determining Acid Value

[0082] Suitable methods of determining acid value are especially those according to DGF C-V 2, DIN EN ISO 2114, Ph. Eur. 2.5.1, ISO 3682 and ASTM D 974.

Method of Determining Amine Value

[0083] A suitable starting weight is dissolved in 50 ml of tetrahydrofuran and, after dissolution, 50 ml of acetic acid (anhydrous, 99-100%) are added. Thereafter, the sample is titrated in an automatic titrator against a 0.1 M solution of perchloric acid in dioxane.

Example 1: Synthesis of a Polyethyleneimine Palmitoylamide with 6.90 eq. of Palmitic Acid

[0084] A mixture of palmitic acid (108.5 g, 0.423 mol, 6.90 eq., C16≥99%) and polyethyleneimine (49.05 g, 0.0613 mol, 800 g/mol, 1.00 eq., Lupasol® FG from BASF) was heated to 170° C. while stirring and passing N.sub.2 through, in the course of which the water formed was continuously removed by distillation until an acid value of 3.2 mg KOH/g and an amine value of 226 mg KOH/g had been attained.

Example 2: Synthesis of a Polyethyleneimine Palmitoylamide with 8.30 eq. of Palmitic Acid

[0085] A mixture of palmitic acid (114.9 g, 0.448 mol, 8.30 eq., C16≥99%) and polyethyleneimine (43.2 g, 0.0540 mol, 800 g/mol, 1.00 eq., Lupasol® FG from BASF) was heated to 175° C. while stirring and passing N.sub.2 through, in the course of which the water formed was continuously removed by distillation until an acid value of 2.1 mg KOH/g and an amine value of 173 mg KOH/g had been attained.

Example 3: Synthesis of a Polyethyleneimine Palmitoylamide with 10.3 eq. of Palmitic Acid

[0086] A mixture of palmitic acid (121.9 g, 0.475 mol, 10.3 eq., C16≥99%) and polyethyleneimine (36.7 g, 0.0459 mol, 800 g/mol, 1.00 eq., Lupasol® FG from BASF) was heated to 175° C. while stirring and passing N.sub.2 through, in the course of which the water formed was continuously removed by distillation until an acid value of 14.2 mg KOH/g and an amine value of 158 mg KOH/g had been attained.

Example 4: Blending of the Surfactants According to the Invention

[0087] The surfactants according to the invention from Examples 1-3 were blended according to the compositions detailed in Table 1 and then homogenized at 80° C.:

TABLE-US-00001 TABLE 1 Composition of surfactant blends used hereinafter Surfactant 1 Surfactant 2 Surfactant 3 Polyethyleneimine 19.7 g — — palmitoylamide from Example 1 Polyethyleneimine — 19.7 g — palmitoylamide from Example 2 Polyethyleneimine — — 19.7 g palmitoylamide from Example 3 Cetearyl sulfate 1.6 g 1.6 1.6 Water 59.1 g 59.1 g 59.1 g Propylene glycol 6.25 g 6.25 g 6.25 g

[0088] 25

Example 5: Foaming Tests

[0089] To test the efficacy of the additive combination according to the invention, a series of foaming experiments was conducted. For this purpose, in a first step, the IMPRANIL® DLU polyurethane dispersion from Covestro was used. The foam stabilizers used were the inventive surfactant formulations 1-3 (see table 1) and a combination of the two surfactants Stokal® STA (ammonium stearate) and Stokal® SR (sodium sulfosuccinamate) as comparison. Table 2 gives an overview of the compositions of the respective experiments.

[0090] All foaming experiments were conducted manually. For this purpose, polyurethane dispersion and surfactant were first placed in a 500 ml plastic cup and homogenized with a dissolver equipped with a disperser disc (diameter=6 cm) at 1000 rpm for 3 min. For foaming of the mixtures, the speed was then increased to 2000 rpm, ensuring that the dissolver disc was always immersed into the dispersion to a sufficient degree that a proper vortex formed. At this speed, the mixtures were foamed to a volume of about 425 ml. The mixture was then sheared at 1000 rpm for a further 15 minutes. In this step, the dissolver disc was immersed sufficiently deeply into the mixtures that no further air was introduced into the system, but the complete volume was still in motion.

TABLE-US-00002 TABLE 2 Overview of foam formulations #1 #2 #3 #4 IMPRANIL ® DLU 150 g 150 g 150 g 150 g  Surfactant 1  5 g — — — Surfactant 2 —  5 g — — Surfactant 3 —  5 g Stokal ® STA — — 2 g Stokal ® SR — — 2 g Wet foam viscosity [mPa s] 9200 7600 8200 4000

[0091] In all cases, fine homogeneous foams were obtained at the end of this foaming operation. It was noticeable that the foams which had been produced with inventive surfactants 1-3 had a higher viscosity (see Table 2). The foams were coated onto a siliconized polyester film with the aid of a film applicator (AB3220 from TQC) equipped with an applicator frame (coat thickness=800 μm) and then dried at 60° C. for 5 min and at 120° C. for a further 5 min.

[0092] Compared to sample #4, the dried inventive samples #1-#3 featured a more homogeneous macroscopic appearance and a more velvety feel. In electron microscopy studies, moreover, it was possible to ascertain a finer pore structure.

Example 6: Migration Tests

[0093] To assess the surface migration of the surfactants according to the invention, imitation leather materials were produced by the method that follows. First of all, a topcoat coating was applied to a siliconized polyester film (layer thickness 100 μm). This was then dried at 100° C. for 3 minutes. Subsequently, a foam layer was coated onto the dried topcoat layer (layer thickness 800 μm) and dried at 60° C. for 5 minutes and at 120° C. for 5 minutes. In a last step, an aqueous adhesive layer (layer thickness 100 μm) was coated onto the dried foam layer, and then a textile carrier was laminated onto the still-moist adhesive layer. The finished laminate was dried again at 120° C. for 5 minutes and then detached from the polyester film.

[0094] All coating and drying operations were performed here with a Labcoater LTE-S from Mathis AG. Topcoat and adhesive layer were formulated here in accordance with the compositions listed in Table 3; the foam layers used were the foam formulations listed in Table 2, which were foamed by the method described in Example 5.

TABLE-US-00003 TABLE 3 Topcoat and adhesive formulation for production of imitation leather materials Topcoat Adhesive CROMELASTIC ® PC 287 PRG 100 g — REGEL ® WX 151 — 100 g ECO Pigment Black 10 g 5 g TEGOWET ® 250 0.2 g 0.2 g REGEL ® TH 27 6 g 6 g ORTEGOL ® PV 301 7 g 5 g

[0095] For assessment of surfactant migration, the imitation leather samples, after production, were placed into water at 100° C. for 30 minutes and then dried at room temperature overnight. After this treatment, the comparative sample produced with the Stokal® STA/SR surfactants (foam formulation #4, Table 2) had distinctly visible white spots on the surface of the imitation leather, whereas this surface discoloration was not observed in the case of the samples produced with the surfactants according to the invention (foam formulation #1-#3, Table 2).