WATER-EMULSIFIABLE ISOCYANATES WITH IMPROVED PROPERTIES

Abstract

Mixture comprising a) at least one polyisocyanate, b) at least one reaction product of at least one polyisocyanate b1) with at least one compound b2) having at least one hydrophilic group which is not reactive toward isocyanate (group A) and precisely one group which is reactive toward isocyanate (group B) and c) dioxolane.

Claims

1: A mixture comprising a) at least one polyisocyanate, b) at least one reaction product of at least one polyisocyanate b1) with at least one compound b2) having at least one hydrophilic group which is not reactive toward isocyanate (group A) and precisely one group which is reactive toward isocyanate (group B) and c) dioxolane.

2: The mixture according to claim 1, wherein the group (A) is an ionic group and/or a group which can be converted into an ionic group.

3: The mixture according to claim 2, wherein the content of the group (A) is from 0.1 to 3 mol per kg of the components a) and b).

4: The mixture according to claim 1, wherein the group (A) is a nonionic group.

5: The mixture according to claim 4, wherein the group (A) is a polyalkylene ether group.

6: The mixture according to claim 4, wherein the group (A) is a polyethylene ether group.

7: The mixture according to claim 4, wherein the content of the group (A) is from 0.1 to 30% by weight, based on the components a) and b).

8: The mixture according to claim 1, wherein the polyisocyanate (a) is an aliphatic polyisocyanate.

9: The mixture according to claim 1, wherein the polyisocyanate (a) has a functionality of more than 2.

10: The mixture according to claim 1, wherein the reactive group is a hydroxy, mercapto or primary or secondary amino group.

11: The mixture according to claim 1, comprising from 2 to 40% by weight of dioxolane based on the sum of the components a) to c).

12: An aqueous polymer dispersion, comprising a mixture according to claim 1 as an additive.

13: A two-component coating composition obtained by addition of a mixture comprising a) at least one polyisocyanate, b) at least one reaction product of a polyisocyanate b1) with at least one compound b2) having at least one hydrophilic group (group A) and precisely one group which is reactive toward isocyanate (group B) and c) dioxolane to an aqueous polymer dispersion.

14: The two-component coating composition according to claim 13, wherein the polymers dispersed in the aqueous polymer dispersion are selected from the group consisting of polyacrylate polyols, polyester polyols and polyurethane polyols.

15: A coated substrate obtained with a two-component coating composition according to claim 13.

Description

EXAMPLES

[0145] Water-Dispersible Polyisocyanate 1:

[0146] 100 g of HDI isocyanurate having an NCO content of 22.2% and a viscosity of 2800 mPa*s at 23 C. (commercially available as Basonat HI 100 from BASF SE, Ludwigshafen) were mixed with 15 g of a methanol-initiated monofunctional polyethylene oxide which had been prepared using potassium hydroxide catalysis and had an OH number of 112 (in accordance with DIN 53240) and a molecular weight of 500 g/mol, heated and reacted with one another. After 3 hours at 90 C., the reaction was stopped on reaching the indicated NCO content, which corresponds to complete formation of the urethane. The corresponding product had a viscosity at 23 C. of 2600 mPa*s and an NCO content of 17.9%.

[0147] Water-Dispersible Polyisocyanate 2:

[0148] As described in the document WO 200188006, 237.5 g of HDI isocyanurate having an NCO content of 22.2% and a viscosity of 2800 mPa*s at 23 C. (commercially available as Basonat HI 100 from BASF SE, Ludwigshafen), 5.8 g of dimethylcyclohexylamines (BASF SE) and 10 g of 3-(cyclohexylamino)-1-propanesulfonic acid were mixed. After 3 hours at 80 C., the reaction was stopped on reaching the indicated NCO content, which corresponds to complete formation of the urea. The corresponding product had a viscosity at 23 C. of 13 300 mPa*s and an NCO content of 19.3%.

Use Examples

[0149] The water-dispersible polyisocyanates 1 and 2 were diluted further in various solvents (90%, 80% and 70%) and the viscosity of the corresponding solutions was measured.

[0150] 0.1 g of solution was in each case shaken with 10 g of water until everything was emulsified. After 24 hours, the average particle size was measured.

[0151] The viscosity was measured at 23 C. in accordance with DIN EN ISO 3219/A.3 in a cone-plate system at a shear rate of 1000 s.sup.1.

[0152] The weight average particle diameters were measured by light scattering measurements using an Autosizer 2c from Malvern.

Comparative Example 1

[0153] a) 90 g of the water-emulsifiable polyisocyanate 1 was mixed with 10 g of dipropylene glycol dimethyl ether [0154] b) 80 g of the water-emulsifiable polyisocyanate 1 was mixed with 20 g of dipropylene glycol dimethyl ether [0155] c) 70 g of the water-emulsifiable polyisocyanate 1 was mixed with 30 g of dipropylene glycol dimethyl ether

Comparative Example 2

[0156] a) 90 g of the water-emulsifiable polyisocyanate 1 was mixed with 10 g of methoxypropyl acetate [0157] b) 80 g of the water-emulsifiable polyisocyanate 1 was mixed with 20 g of methoxypropyl acetate [0158] c) 70 g of the water-emulsifiable polyisocyanate 1 was mixed with 30 g of methoxypropyl acetate

Comparative Example 3

[0159] a) 90 g of the water-emulsifiable polyisocyanate 1 was mixed with 10 g of butyl glycol acetate [0160] b) 80 g of the water-emulsifiable polyisocyanate 1 was mixed with 20 g of butyl glycol acetate [0161] c) 70 g of the water-emulsifiable polyisocyanate 1 was mixed with 30 g of butyl glycol acetate

Comparative Example 4

[0162] a) 90 g of the water-emulsifiable polyisocyanate 1 was mixed with 10 g of propylene carbonate [0163] b) 80 g of the water-emulsifiable polyisocyanate 1 was mixed with 20 g of propylene carbonate [0164] c) 70 g of the water-emulsifiable polyisocyanate 1 was mixed with 30 g of propylene carbonate

Comparative Example 5

[0165] a) 90 g of the water-emulsifiable polyisocyanate 1 was mixed with 10 g of TME 1,1,2,2-tetramethoxyethane [0166] b) 80 g of the water-emulsifiable polyisocyanate 1 was mixed with 20 g of TME 1,1,2,2-tetramethoxyethane [0167] c) 70 g of the water-emulsifiable polyisocyanate 1 was mixed with 30 g of TME 1,1,2,2-tetramethoxyethane

Comparative Example 6

[0168] a) 90 g of the water-emulsifiable polyisocyanate 1 was mixed with 10 g of dioxane [0169] b) 80 g of the water-emulsifiable polyisocyanate 1 was mixed with 20 g of dioxane [0170] c) 70 g of the water-emulsifiable polyisocyanate 1 was mixed with 30 g of dioxane

Example 1

[0171] a) 90 g of the water-emulsifiable polyisocyanate 1 was mixed with 10 g of dioxolane [0172] b) 80 g of the water-emulsifiable polyisocyanate 1 was mixed with 20 g of dioxolane [0173] c) 70 g of the water-emulsifiable polyisocyanate 1 was mixed with 30 g of dioxolane

[0174] Water-Dispersible Polyisocyanate 1:

[0175] The water-dispersible polyisocyanate 1 has a viscosity at 23 C. of 2600 mPa*s.

TABLE-US-00001 Viscosity Average @ 23 C. particle Solvent Dilution (mPa * s) size (nm) Comparative example 1a) Dipropylene glycol 90% 600 140 1b) dimethyl ether 80% 210 194 1c) 70% 80 282 2a) Methoxypropyl 90% 650 130 2b) acetate 80% 200 175 2c) 70% 60 241 3a) Butyl glycol acetate 90% 2740 179 3b) 80% 550 205 3c) 70% 180 306 4a) Propylene 90% 900 92 4b) carbonate 80% 420 94 4c) 70% 200 168 5a) TME 1,1,2,2- 90% 950 107 5b) tetramethoxyethane 80% 310 146 5c) 70% 170 353 6a) Dioxane 90% 700 115 6b) 80% 250 142 6c) 70% 100 204 Example 1a) Dioxolane 90% 450 112 1b) 80% 160 143 1c) 70% 50 203

Comparative Example 7

[0176] a) 90 g of the water-emulsifiable polyisocyanate 2 was mixed with 10 g of dipropylene glycol dimethyl ether [0177] b) 80 g of the water-emulsifiable polyisocyanate 2 was mixed with 20 g of dipropylene glycol dimethyl ether [0178] c) 70 g of the water-emulsifiable polyisocyanate 2 was mixed with 30 g of dipropylene glycol dimethyl ether

Comparative Example 8

[0179] a) 90 g of the water-emulsifiable polyisocyanate 2 was mixed with 10 g of methoxypropyl acetate [0180] b) 80 g of the water-emulsifiable polyisocyanate 2 was mixed with 20 g of methoxypropyl acetate [0181] c) 70 g of the water-emulsifiable polyisocyanate 2 was mixed with 30 g of methoxypropyl acetate

Comparative Example 9

[0182] a) 90 g of the water-emulsifiable polyisocyanate 2 was mixed with 10 g of butyl glycol acetate [0183] b) 80 g of the water-emulsifiable polyisocyanate 2 was mixed with 20 g of butyl glycol acetate [0184] c) 70 g of the water-emulsifiable polyisocyanate 2 was mixed with 30 g of butyl glycol acetate

Comparative Example 10

[0185] a) 90 g of the water-emulsifiable polyisocyanate 2 was mixed with 10 g of propylene carbonate [0186] b) 80 g of the water-emulsifiable polyisocyanate 2 was mixed with 20 g of propylene carbonate [0187] c) 70 g of the water-emulsifiable polyisocyanate 2 was mixed with 30 g of propylene carbonate

Comparative Example 11

[0188] a) 90 g of the water-emulsifiable polyisocyanate 2 was mixed with 10 g of TME 1,1,2,2-tetramethoxyethane [0189] b) 80 g of the water-emulsifiable polyisocyanate 2 was mixed with 20 g of TME 1,1,2,2-tetramethoxyethane [0190] c) 70 g of the water-emulsifiable polyisocyanate 2 was mixed with 30 g of TME 1,1,2,2-tetramethoxyethane

Comparative Example 12

[0191] a) 90 g of the water-emulsifiable polyisocyanate 2 was mixed with 10 g of dioxane [0192] b) 80 g of the water-emulsifiable polyisocyanate 2 was mixed with 20 g of dioxane [0193] c) 70 g of the water-emulsifiable polyisocyanate 2 was mixed with 30 g of dioxane

Example 2

[0194] a) 90 g of the water-emulsifiable polyisocyanate 2 was mixed with 10 g of dioxolane [0195] b) 80 g of the water-emulsifiable polyisocyanate 2 was mixed with 20 g of dioxolane [0196] c) 70 g of the water-emulsifiable polyisocyanate 2 was mixed with 30 g of dioxolane

[0197] Water-Dispersible Polyisocyanate 2:

[0198] The water-dispersible polyisocyanate 2 has a viscosity at 23 C. of 3300 mPa*s.

TABLE-US-00002 Viscosity Average @ 23 C. particle size Solvent Dilution (mPa * s) (nm) Comparative example 7a) Dipropylene glycol 90% 2500 3350 dimethyl 7b) ether 80% 520 1550 7c) 70% 150 195 8a) Methoxypropyl acetate 90% 2300 3657 8b) 80% 540 1817 8c) 70% 170 1249 9a) Butyl glycol acetate 90% 2740 3146 9b) 80% 550 3172 9c) 70% 180 3793 10a) Propylene carbonate 90% 900 2741 10b) 80% 420 4122 10c) 70% 200 1378 11a) TME 1,1,2,2- 90% 3100 2935 tetramethoxyethane 11b) 80% 880 2635 11c) 70% 360 523 12a) Dioxane 90% 2000 2568 12b) 80% 620 526 12c) 70% 40 249 Example 2a) Dioxolane 90% 1300 2385 2b) 80% 270 493 2c) 70% 80 138