EPOXY/AMINE ADDUCTS FOR DISPERSING SOLIDS

Abstract

The invention relates to comb copolymers, which can be produced from at least one diglycidyl ether (A) of general formula (I), at least one polyether monoamine (B) of the general formula R.sup.t—[OEt].sub.n[OPr].sub.m[OBu].sub.s—NH.sub.2, at least one amine (C) of the general formula Z—R.sup.1—NH.sub.2, and optionally at least one secondary amine (D) that is free of primary amino groups and is of the general formula NHTV, wherein R stands for a residue free of epoxy groups, selected from aliphatic residues, aromatic residues, and araliphatic residues; R.sup.t stands for a residue selected from alkyl residues having 1 to 6 carbon atoms; OEt stands for an ethylene oxide residue, OPr stands for a propylene oxide residue, and OBu stands for a butylene oxide residue; n stands for a number from 0 to 100, m stands for a number from 3 to 50, and s stands for a number from 0 to 20, and n+m+s=3 to 103; R.sup.1 stands for an aliphatic, aromatic, or araliphatic hydrocarbon residue having 1 to 12 carbon atoms; Z stands for a residue free of primary and secondary amino groups and having at least one basic nitrogen atom, T and V do not contain any secondary amino groups and stand, independently of each other, for aliphatic residues having 1 to 12 carbon atoms, aromatic residues having 6 to 12 carbon atoms, or araliphatic residues having 7 to 12 carbon atoms, wherein the molar number of the sum of the primary amino groups of the polyether monoamines (B) and primary amino groups of the amines (C) divided by the molar number of the epoxy groups of the diglycidyl ethers (A) equals a value of ⅓ to ¾. The invention further relates to the production of the comb copolymers, dispersions, particulate preparations, wetting agents, and dispersants that contain the comb copolymers, to particles coated with the comb copolymers, and to the use of the comb copolymers as wetting agents and dispersants, in particular for increasing the jetness.

Claims

1. A comb copolymer prepared from at least one diglycidyl ether (A) of the general formula (I) ##STR00005## at least one polyether monoamine (B) of the general formula (II)
R.sup.t—[OEt].sub.n[OPr].sub.m[OBu].sub.s—NH.sub.2   (II), at least one amine (C) of the general formula (III)
Z—R.sup.1—NH.sub.2   (III) and optionally at least one secondary amine (D) which is free of primary amino groups and is of the general formula (IV)
NHTV (IV) where R is a radical free of epoxy groups, selected from aliphatic radicals, aromatic radicals and araliphatic radicals, R.sup.t is a radical selected from alkyl radicals having 1 to 6 carbon atoms, OEt is an ethylene oxide radical, OPr is a propylene oxide radical and OBu is a butylene oxide radical, n is a number from 0 to 100, m is a number from 3 to 50 and s is a number from 0 to 20 and n+m+s=3 to 103, R.sup.1 is an aliphatic, aromatic or araliphatic hydrocarbyl radical having 1 to 12 carbon atoms, Z is a radical which is free of primary and secondary amino groups and has at least one basic nitrogen atom, T and V do not contain any secondary amino groups and are independently aliphatic radicals having 1 to 12 carbon atoms, aromatic radicals having 6 to 12 carbon atoms or araliphatic radicals having 7 to 12 carbon atoms, characterized in that the molar number of the sum total of the primary amino groups of the polyether monoamines (B) and primary amino groups of the amines (C), divided by the molar number of epoxy groups of the diglycidyl ethers (A), gives a value of ⅓ to ¾.

2. The comb copolymer as claimed in claim 1, which has a structure of the general formula (V) ##STR00006## in which the w+1 R radicals may be selected independently of one another, one of the Y and X radicals is OH and the other radical is NHQ or NTV, one of the Y′ and X′ radicals is OH and the other radical is NHQ or NTV, and Q radicals are independently Q.sup.1=R.sup.t—[OEt].sub.n[OPr].sub.m[OBu].sub.s or Q.sup.2=Z—R.sup.1, and w is a number from 1 to 20, with the proviso that the formula (V) contains at least one Q.sup.1 radical and at least one Q.sup.2 radical.

3. A comb copolymer obtained by salt conversion, quaternization and/or amidation of the comb copolymer as claimed in claim 1.

4. A process for preparing the comb copolymer of claim 1, wherein at least one diglycidyl ether (A) of the general formula (I) is reacted with at least one polyether monoamine (B) of the general formula (II) and at least one amine (C) of the general formula (III) and optionally a secondary amine (D) of the general formula (IV) at a temperature between 25° C. and 300° C., and wherein the molar number of the sum total of the primary amino groups of the polyether monoamine (B) and primary amino groups of the amines (C), divided by the molar number of epoxy groups of the diglycidyl ethers (A), gives a value of ⅓ to ¾.

5. A dispersion comprising at least one dispersion medium, at least one kind of dispersed particulate solid and at least one comb copolymer as claimed in claims 1.

6. The dispersion as claimed in claim 5, wherein the comb copolymers are present in an amount of 0.1% to 10% by weight, based on the total weight of the dispersion.

7. The dispersion as claimed in claim 5, characterized in that the dispersion is an ink or a coating composition.

8. A particulate solid, characterized in that it has been coated with a comb copolymer as claimed in claim 1.

9. A particle formulation containing 5.0% to 99.9% by weight of one or more particulate solids, characterized in that the formulation it contains 0.1% to 95.0% by weight of the comb copolymers as claimed in claim 1, based on the total weight of the particle formulation.

10. The particle formulation as claimed in claim 9, comprising powder, chips, granules, color concentrates, pigment paste, full tone pastes, shading or tinting pastes or pigment pastes.

11. A wetting agent and dispersant, characterized in that it comprises at least one comb copolymer as claimed in claim 1.

12. A method comprising utilizing the comb copolymers as claimed in claim 1 as wetting agents and dispersants in the processing or production of products that contain particulate solids.

13. The method use as claimed in claim 12, characterized in that the wetting agents and dispersants serve for dispersion of carbon blacks and/or organic black pigments.

14. The method use as claimed in claim 13, wherein the wetting agent and dispersant serves to increase jetness.

Description

EXAMPLES

[0103] Test methods

[0104] Amine number

[0105] The amine number (AN) is understood to mean the amount of KOH in mg corresponding to the amine content of 1 g of substance. The amine number is determined according to DIN 16945 by a neutralization reaction with 0.1 N perchloric acid in acetic acid as titrant:

R—NH.sub.2+HClO.sub.4.fwdarw.R—NH.sub.3.sup.⊕CIO.sub.4.sup.⊖

[0106] The additions of inert solvents, such as cyclohexane, dioxane, chlorobenzene, acetone, methyl ethyl ketone, can improve the titration of very weak bases.

[0107] Epoxy Equivalent

[0108] The epoxy equivalent weight is understood to mean that amount of epoxy resin in g containing 16 g of epoxy-bonded oxygen (epoxide oxygen). The epoxy groups in epoxy resins can be determined by addition of HBr onto the epoxide ring. The equivalent amount of HBr is released by titration with HClO.sub.4 in the presence of cetyltrimethylammonium bromide (N,N,N-trimethyl-1-hexadecanaminium bromide; CTABr).

[0109] Since the amine is simultaneously also protonated in the titration with perchloric acid, this amount of perchloric acid has to be subtracted to calculate the epoxy equivalent. It is therefore necessary to determine the amine number before the determination of the epoxy equivalent.

##STR00004##

[00001]$\mathrm{Epoxy}.Math..Math.\mathrm{equivalent}=\frac{\mathrm{starting}.Math..Math.\mathrm{weight}.Math..Math.\left(g\right)*100}{\left(\mathrm{consumption}.Math..Math.\left(\mathrm{ml}\right)*n*f\right)-\left(\mathrm{amine}.Math..Math.\mathrm{number}/56.1\right)}$$.Math.n=\mathrm{normality}.Math..Math.\mathrm{of}.Math..Math.\mathrm{the}.Math..Math.\mathrm{titrant}$$.Math.f=\mathrm{factor}.Math..Math.\mathrm{of}.Math..Math.\mathrm{the}.Math..Math.\mathrm{titrant}$

[0110] Acid Number

[0111] The acid number is determined according to DIN EN ISO 2114 by a neutralization reaction with 0.1 N KOH in ethanol as titrant:

R—COOH+KOH.fwdarw.R—COOK+H.sub.2O

Comparative Examples

[0112] Polymer 1

[0113] 82 g of Epikote 828 (0.07 mol; undiluted difunctional bisphenol A/epichlorohydrin reaction product, manufacturer: Momentive) are reacted with 528 g of Surfonamine L 207 (0.085 mol; methanol-started polyether monoamine with a terminal primary amino group, about 10 OPr and 31 OEt units; amine number=27 mg KOH/g; manufacturer: Huntsman) at 140° C. for 27 h.

[0114] Amine number: 19.6 mg KOH/g

[0115] Epoxy equivalent: infinite

[0116] Polymer 2

[0117] 82 g of Epikote 828 (0.22 mol) are reacted with 359 g of Surfonamine L 207 (0.177 mol) and 8.6 g of dimethylaminopropylamine (0.08 mol) at 140° C. for 7 h. Subsequently, 145 g of a polyether/tolylene diisocyanate adduct (for preparation see below) are added and the mixture is left to react at 65° C. for a further 5 h.

[0118] Amine number: 21.7 mg KOH/g

[0119] Epoxy equivalent: infinite

[0120] Isocyanate content: 0.05% [0121] Preparation of the polyether/tolylene diisocyanate adduct: [0122] A four-neck flask provided with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube is charged with 43 g of Desmodur T 100 (about 100% tolylene 2,4-diisocyanate, NCO content=48.8) and 0.7 g of benzoyl chloride, which are mixed thoroughly. 200 g of MPEG 2000, which is anhydrous and alkali-free in the case of polyethers, are metered in gradually, such that the temperature does not exceed 55° C. After the metered addition, the mixture is stirred at 55° C. for a further 3 hours. The excess TDI is removed from the reaction mixture by means of a thin-film evaporator at 150° C. The residual TDI content is<1%.

[0123] Polymer 3

[0124] 82 g (0.22 mol) of Epikote 828 are reacted with 323 g of Surfonamine L 207 (0.16 mol), 8.6 g of dimethylaminopropylamine (0.08 mol) and 36 g of polysiloxane monoamine (example 2 from WO 2012/049186) at 140° C. for 7 h.

[0125] Amine number: 40.7 mg KOH/g

[0126] Epoxy equivalent: infinite

Inventive Examples

[0127] Polymer 4

[0128] 82 g (0.22 mol) of Epikote 828 are reacted with 359 g of Surfonamine L 207 (0.177 mol) and 8.5 g of dimethylaminopropylamine (0.08 mol) at 140° C. for 7 h.

[0129] Amine number: 40.9 mg KOH/g

[0130] Epoxy equivalent: infinite

[0131] Polymer 5

[0132] 82 g (0.22 mol) of Epikote 828 are reacted with 363 g of Surfonamine L 200 (0.177 mol; methanol-started polyether monoamine with a terminal primary amino group, about 4 OPr and 41 OEt units; amine number=25 mg KOH/g, manufacturer: Huntsman) and 8.5 g of dimethylaminopropylamine (0.08 mol) at 140° C. for 7 h.

[0133] Amine number: 40.1 mg KOH/g

[0134] Epoxy equivalent: infinite

[0135] Polymer 6

[0136] 41 g (0.11 mol) of Epikote 828 and 25.3 g of hexamethylene diglycidyl ether (0.11 mol) are reacted with 359 g of Surfonamine L 207 (0.177 mol) and 8.5 g of dimethylaminopropylamine (0.08 mol) at 140° C. for 7 h.

[0137] Amine number: 39.2 mg KOH/g

[0138] Epoxy equivalent: infinite

[0139] Polymer 7

[0140] 449.5 g of polymer 4 are reacted with 9 g of benzoyl chloride (0.08 mol) in 305 g of water at 100° C. for 4 h.

[0141] Amine number: 13.4 mg KOH/g

[0142] Polymer 8

[0143] 449.5 g of polymer 4 are reacted with 9.8 g of benzoic acid at 50° C. for 4 h.

[0144] Amine number: 40.0 mg KOH/g

[0145] Acid number: 19.8 mg KOH/g

[0146] Polymer 9

[0147] 82 g of Epikote 828 (0.22 mol) are reacted with 359 g of Surfonamine L 207 (0.177 mol), 6.4 g of dimethylaminopropylamine (0.06 mol) and 2.6 g of dibutylamine (0.02 mol) at 140° C. for 7 h.

[0148] Amine number: 39.1 mg KOH/g

[0149] Epoxy equivalent: infinite

[0150] Performance Testing

[0151] Use of the polymers of the invention as wetting agents and dispersants for production of pigment concentrates and use thereof in paint systems.

[0152] Starting Materials

TABLE-US-00001 BYK-011 silicone-free defoamer from BYK- Chemie AMP 95 2-amino-2-methyl-1-propanol from Angus Chemicals Setalux 6801 AQ-24 aqueous acrylate binder from Nuplex Resins Setalux 6802 AQ-24 aqueous acrylate binder from Nuplex Resins BYK-347 silicone-containing surface additive from BYK-Chemie BYK-348 silicone-containing surface additive from BYK-Chemie BYK-425 rheology control agent from BYK- Chemie PPG 600 difunctional polypropylene glycol from BASF FF99-0364 Pro Gloss 2K polyurethane binder from BASF topcoat Glossodur isocyanate hardener from BASF Carbon Black FW 200 carbon black pigment from Orion Carbon Black XPB 255 carbon black pigment from Orion Raven 5000 Ultra III carbon black pigment from Birla Carbon Heliogen blue L7101F phthalocyanine pigment from BASF Hostaperm Pink E quinacridone pigment from Clariant Laropal A 81 aldehyde resin from BASF Macrynal SM 510 hydroxy-functional acrylate binder from Allnex Shellsol A aromatic hydrocarbon mixture from Shell BYK-066N silicone-containing defoamer from BYK-Chemie BYK-306 silicone-containing surface additive from BYK-Chemie Desmodur N 3390 BA aliphatic polyisocyanate from Bayer Material Science Synthalat E405 aldehyde resin from Synthopol NC Chips E510 ESO nitrocellulose from Dow Wolff Cellulosics BYK-052 silicone-free defoamer from BYK- Chemie PMA methoxypropyl acetate

[0153] Production and Testing of Pigmented Aqueous Paints with Carbon Black Pigments

TABLE-US-00002 Pigment concentrate Water 64 Wetting agent and dispersant 10.5 Byk-011 0.5 AMP 95 10 Pigment 15 100.00

[0154] The dispersion was effected with a Lau Paint Shaker DAS H[/A]200-K. The ratio of grinding material to glass beads (diameter 1 mm) was 1:2 (parts by weight), 300 min, cooling level 3, normal speed.

TABLE-US-00003 Paint Setalux 6801 AQ-24 240 Setalux 6802 AQ-24 450 Byk-028 6 Dimethylaminoethanol, 10% in 28 water Water 255 BYK-347 6 BYK-348 5 BYK-425/PPG600/water 2:1:7 10 1000.00

TABLE-US-00004 Letdown Pigment concentrate 10 Paint 100 110.00

[0155] The pigment concentrate is shaken with the paint for 5 min.

[0156] The pigmented letdown was applied to contrast card with a 120 μm spiral coating bar and the paint was flashed off and then subjected to intermediate drying at 80° C. for 15 min.

[0157] Subsequently, the FF99-0364 Pro Gloss topcoat, mixed 100:33 with the Glossodur hardener, was applied with a 120 μm spiral coating bar, flashed off and then subjected to through-drying at 100° C. for 15 min.

[0158] The viscosity measurements were conducted with the Stresstech instrument from Reologica Instruments AB. This was done using the CC 25 cylinder measurement system. The balancing time before the measurement commenced was 5 s. 12 measurement points were recorded at a shear rate of 100 1/s with a total measurement time of 48 s at a measurement temperature of 25° C. The viscosity value reported is the mean of the last 10 measurement points.

[0159] As a measure of the “jetness”, the XYZ values were measured by means of a 45°/0° Color Guide with D65/10° illuminant. These are the converted to Mc, My and dM values by the following formula:

[00002]$\mathrm{My}=100.Math..Math.\log \left[\frac{1}{Y}\right];$$\mathrm{Mc}=100.Math.\left\{\log \left[\frac{\mathrm{Xn}}{X}\right]-\log \left[\frac{\mathrm{Zn}}{Z}\right]+\log \left[\frac{\mathrm{Yn}}{Y}\right]\right\};$$\mathrm{dM}=\mathrm{Mc}-\mathrm{My}$

[0160] Good jetness is identified by a high Mc value. In addition, a high blue level is desired, which is characterized by a high dM value.

[0161] Results for Carbon Black/Water

[0162] Carbon Black FW 200

TABLE-US-00005 Wetting agent Viscosity Viscosity and dispersant immediate 7 d/40° C. Mc dM Polymer 1 61 mPas 62 mPas 288 13 Polymer 2 54 mPas 70 mPas 282 12 Polymer 3 62 mPas 68 mPas 292 13 Polymer 4 51 mPas 61 mPas 293 15

[0163] Carbon Black XPB 255

TABLE-US-00006 Wetting agent Viscosity Viscosity and dispersant immediate 7 d/40° C. Mc dM Polymer 1 51 mPas 58 mPas 308 19 Polymer 2 65 mPas 56 mPas 316 20 Polymer 3 48 mPas 57 mPas 209 14 Polymer 4 40 mPas 47 mPas 318 22

[0164] Raven 5000 Ultra III

TABLE-US-00007 Wetting agent Viscosity Viscosity and dispersant immediate 7 d/40° C. Mc dM Polymer 1 38 mPas 56 mPas 318 22 Polymer 2 41 mPas 47 mPas 324 22 Polymer 3 31 mPas 42 mPas 322 20 Polymer 4 31 mPas 38 mPas 327 22

[0165] For all three aqueous paints containing different carbon black pigments, it was shown that the polymer 4 of the invention gives the best jetness (highest value for Mc) and simultaneously a high blue level (highest value for dM).

[0166] Production and Testing of Pigmented Aqueous Paints with Organic Pigments

TABLE-US-00008 Pigment concentrate Water 62 Wetting agent and dispersant 7.5 Byk-011 0.5 Pigment 30 100.00

[0167] Dispersion with Lau Paint Shaker DAS H[/A]200-K: ratio of grinding material to glass beads (diameter 1 mm): 1:2 (parts by weight), 300 min, cooling level 3, normal speed.

TABLE-US-00009 Paint Setalux 6801 AQ-24 240 Setalux 6802 AQ-24 450 Byk-028 6 Dimethylethanolamine, 10% in 28 water Water 255 BYK-347 6 BYK-348 5 BYK-425/PPG600/water 2:1:7 10 1000.00

TABLE-US-00010 Letdown Pigment concentrate 10 Paint 100 110.00

[0168] The pigment concentrate is shaken with the paint for 5 min.

[0169] The pigmented letdown is applied to a polyethylene film with a 50 gm spiral coating bar. The paint was flashed off and then dried at room temperature for 16 h.

[0170] Gloss measurement:

[0171] Instrument: Micro-TRI-Gloss, BYK Gardner

[0172] Angle: 20°

[0173] Number of measurements: n=3

[0174] Transparency is assessed visually: 1=good, 5=poor. Transparency is transmittance of light and, in the case of coatings which have been applied to transparent films, can be assessed via the visual sharpness of objects which are behind the film from the viewer's point of view.

[0175] Results for Organic Pigments/Water

[0176] Heliogen Blue L7101F

TABLE-US-00011 Wetting agent Viscosity Viscosity Gloss Trans- and dispersant immediate 7 d/40° C. 20° parency Polymer 1 68 mPas 64 mPas 55.1 1-2 Polymer 2 68 mPas 110 mPas 53.8 1-2 Polymer 3 64 mPas 62 mPas 37.3 3 Polymer 4 55 mPas 55 mPas 56.6 1

[0177] Hostanerm Pink E

TABLE-US-00012 Wetting agent Viscosity Viscosity Gloss Trans- and dispersant immediate 7 d/40° C. 20° parency Polymer 1 122 mPas 147 mPas 43.7 1-2 Polymer 2 65 mPas 56 mPas 43.6 2 Polymer 3 411 mPas 491 mPas 45.6 3 Polymer 4 263 mPas 293 mPas 46.1 1-2

[0178] Production and Testing of Pigmented Solventborne Paints with Carbon Black Pigments

TABLE-US-00013 Pigment concentrate Laropal A 81 27.8 PMA 50 Wetting agent and dispersant 9.2 Pigment 13 100.00

[0179] Dispersion with Lau Paint Shaker DAS H[/A]200-K: ratio of grinding material to glass beads (diameter 1 mm): 1:2 (parts by weight), 300 min, cooling level 3, normal speed.

TABLE-US-00014 Paint Macrynal SM 510 (70% in 750 butyl acetate) PMA 50 Shellsol A 50 Xylene 66 Butyl acetate 80 BYK-066N 3 BYK-306 1 1000.00

TABLE-US-00015 Hardener Desmodur N 3390 BA 50 Butyl acetate 35 Xylene 10 100.00

TABLE-US-00016 Letdown Pigment concentrate 6 Paint 20 Hardener 10 36

[0180] The pigment concentrate is shaken with the paint and the hardener for 5 min.

[0181] The pigmented letdown is applied to contrast card with a 120 μm spiral coating bar. Drying: 16 h at room temperature.

[0182] Results for Carbon Black/Solvent

[0183] Carbon Black FW 200

TABLE-US-00017 Wetting agent Viscosity Viscosity and dispersant immediate 7 d/40° C. Mc dM Polymer 1 109 mPas 183 mPas 313 8 Polymer 2 101 mPas 156 mPas 313 8 Polymer 3 93 mPas 157 mPas 317 10 Polymer 4 83 mPas 156 mPas 320 12

[0184] Carbon Black XPB 255

TABLE-US-00018 Wetting agent Viscosity Viscosity and dispersant immediate 7 d/40° C. Mc dM Polymer 1 75 mPas 2500 mPas 324 1 Polymer 2 72 mPas 10 200 mPas 323 7 Polymer 3 112 mPas 23 400 mPas 316 0 Polymer 4 7 mPas 86 mPas 331 9

[0185] Raven 5000 Ultra III

TABLE-US-00019 Wetting agent Viscosity Viscosity and dispersant immediate 7 d/40° C. Mc dM Polymer 1 78 mPas 131 mPas 342 10 Polymer 2 73 mPas 7100 mPas 329 7 Polymer 3 70 mPas 156 mPas 323 7 Polymer 4 65 mPas 142 mPas 352 12

[0186] For all three solvent-based paints containing different carbon black pigments, it was shown that the polymer 4 of the invention gives the best jetness (highest value for Mc) and simultaneously a high blue level (highest value for dM).

[0187] Production and Testing of Pigmented Solventborne Paints with Organic Pigments

TABLE-US-00020 Pigment concentrate Laropal A 81 17 PMA 62.4 Wetting agent and dispersant 5.4 Pigment 15.2 100.00

[0188] Dispersion with Lau Paint Shaker DAS H[/A]200-K: ratio of grinding material to glass beads (diameter 1 mm): 1:2 (parts by weight), 300 min, cooling level 3, normal speed.

TABLE-US-00021 Paint Synthalat E405, 60% in xylene 260 NC Chips E510 ESO 120 Ethyl acetate 196 Xylene 185 Butyl acetate 236 BYK-052 2 BYK-306 1 1000.00

TABLE-US-00022 Letdown Pigment concentrate 25 Paint 100 125.00

[0189] The pigment concentrate is shaken with the paint for 5 min.

[0190] The pigmented letdown is applied to a polyethylene film with a 50 μm spiral coating bar. Drying: 16 h at room temperature.

[0191] Results for Organic Pigments/Solvents

[0192] Heliogen Blue L7101F

TABLE-US-00023 Wetting agent Viscosity Viscosity Gloss Trans- and dispersant immediate 7 d/40° C. 20° parency Polymer 1 19 Pas 11 Pas 99.1 2 Polymer 2 19 Pas 11 Pas 97.4 1 Polymer 3 20 Pas 14 Pas 22.3 2 Polymer 4 18 Pas 11 Pas 100.0 1

[0193] Hostanerm Pink E

TABLE-US-00024 Wetting agent Viscosity Viscosity Gloss Trans- and dispersant immediate 7 d/40° C. 20° parency Polymer 1 52 Pas 36 Pas 75.3 2 Polymer 2 32 Pas 29 Pas 78.8 2 Polymer 3 38 Pas 41 Pas 74.1 3 Polymer 4 31 Pas 24 Pas 79.5 1