URETHANE-GROUP-CONTAINING REACTION PRODUCTS

Abstract

A reaction product containing urethane groups, comprising one or more species of the general formula (I)

(R.sup.1X).sub.pZ.sup.1(XH).sub.y(I) where p+y=w and w is an integer from 2 to 10, p is an integer from 2 to 10, y is an integer from 0 to 8, and X is independently O, NH and/or NZ.sup.2 and XH is independently a hydroxyl group OH, a primary amino group NH.sub.2 and/or a secondary amino group NHZ.sup.2 where Z.sup.2 is independently a branched or unbranched, saturated or unsaturated organic radical G(U).sub.a where U is independently a hydroxyl group, a primary amino group or a secondary amino group and a is an integer from 0 to 8, where w+a10, G is a branched or unbranched, saturated or unsaturated organic radical, the p R.sup.1 radicals are independently a radical of the general formula (II)

YOCONHR.sup.2NHCO(II)

in which the p Y radicals are independently a branched or unbranched, saturated or unsaturated organic radical which has 1 to 1000 carbon atoms and does not contain any hydroxyl groups, any primary amino groups or any secondary amino groups, the p R.sup.2 radicals are independently a branched or unbranched, saturated or unsaturated organic radical having 6 to 20 carbon atoms, and Z.sup.1 is a branched or unbranched, saturated or unsaturated organic radical which contains at least one tertiary nitrogen group and is free of XH groups.

Claims

1. A reaction product containing urethane groups, comprising at least 40% by weight one or more species of the general formula (I)
(R.sup.1X).sub.pZ.sup.1(XH).sub.y(I), where p+y=w and w is an integer from 2 to 10, p is an integer from 2 to 10, y is an integer from 0 to 8, and X is independently O, NH and/or NZ.sup.2 and XH is independently a hydroxyl group OH, a primary amino group NH.sub.2 and/or a secondary amino group NHZ.sup.2 where Z.sup.2 is independently a branched or unbranched, saturated or unsaturated organic radical G(U).sub.a where U is independently a hydroxyl group, a primary amino group or a secondary amino group and a is an integer from 0 to 8, where w+a10, and the p R radicals are independently a radical of the general formula (II)
YOCONHR.sup.2NHCO(II) in which the p Y radicals are independently a branched or unbranched, saturated or unsaturated organic radical which has 1 to 1000 carbon atoms and does not contain any hydroxyl groups, any primary amino groups or any secondary amino groups, the p R.sup.2 radicals are independently a branched or unbranched, saturated or unsaturated organic radical having 6 to 20 carbon atoms, Z.sup.1 is a branched or unbranched, saturated or unsaturated organic radical which contains at least one tertiary nitrogen group and is free of XH groups.

2. The reaction product containing urethane groups as claimed in claim 1, wherein the at least one tertiary nitrogen group is a tertiary amino group.

3. The reaction product containing urethane groups as claimed in claim 1, containing at least 60% by weight of one or more species of the general formula (I).

4. The reaction product containing urethane groups as claimed in claim 1, wherein the diisocyanate R.sup.2(NCO).sub.2 corresponding to the R.sup.2 radical has two isocyanate groups of different reactivity.

5. The reaction product containing urethane groups as claimed in claim 1, wherein Y contains at least one polyether radical, polyester radical, hydrocarbyl radical and/or polysiloxane radical.

6. A process for preparing the reaction product containing urethane groups as claimed in claim 1, wherein i) at least one diisocyanate R.sup.2(NCO).sub.2 is reacted with at least one monoalcohol YOH to form a urethane of the general formula (III)
YOCONHR.sup.2NCO(III) ii) p urethanes of the general formula (III) are reacted with at least one component of the formula (IV)
(HX).sub.pZ.sup.1(HX).sub.y(IV) to give a reaction product containing urethane groups, comprising one or more species of the general formula (I)
(R.sup.1X).sub.pZ.sup.1(XH).sub.y(I).

7. The process as claimed in claim 6, wherein the diisocyanate R.sup.2(NCO).sub.2 is used in step i) relative to the monoalcohol YOH in a molar ratio of at least 1.1:1.0 and the diisocyanate R.sup.2(NCO).sub.2 that has not been converted to the urethane of the general formula (III) in step i) is removed from the reaction mixture, optionally by distillation, prior to the performance of step ii).

8. The process as claimed in claim 6, wherein the diisocyanate R.sup.2(NCO).sub.2 corresponding to the R.sup.2 radical has two isocyanate groups of different reactivity.

9. The process as claimed in claim 8, wherein the diisocyanate R.sup.2(NCO).sub.2 is selected from the group consisting of toluene 2,4-diisocyanate and isophorone diisocyanate.

10. The process as claimed in claim 6, wherein one or more species of the general formula (IV) are obtained by modification of amino alcohols, amines or polyamines containing primary and secondary amino groups with a modifying component MZ containing epoxy and/or acrylic ester groups.

11. A wetting agent and dispersant comprising the reaction product containing urethane groups, as claimed in claim 1.

12. A composition comprising the reaction product containing urethane groups, as claimed in claim 1.

13. A method of utilizing the reaction product containing urethane groups as claimed in claim 1 comprising adding the reaction product as a wetting agent or dispersant or dispersion stabilizer or viscosity reducer or compatibilizer in coatings, varnishes, plastics, pigment pastes, sealants, cosmetics, ceramics, adhesives, potting compounds, spackling compounds, printing inks or other inks.

14. A reaction product containing urethane groups which is one species of the general formula (I) of the reaction product as claimed in claim 1.

15. A reaction product containing urethane groups, comprising one or more salt(s) and/or one or more quaternization product(s) of the species of the general formula (I) of the reaction product as claimed in claim 1.

16. A reaction product containing urethane groups, comprising one or more modification products of the species of the general formula (I) of the reaction product as claimed in claim 1, wherein one or more tertiary amino groups of the general formula (I) have been converted to amine oxides with oxygen and/or peroxo compounds and or XH groups still present in the general formula (I) have been reacted with carboxylic anhydrides.

17. The reaction product containing urethane groups as claimed in claim 1, containing at least 90% by weight of one or more species of the general formula (I).

18. A wetting agent and dispersant comprising the reaction product containing urethane groups, prepared by the process as claimed in claim 6.

19. A composition comprising the reaction product containing urethane groups, prepared by the process as claimed in claim 6.

20. A method of utilizing the reaction product containing urethane groups prepared by the process as claimed in claim 6 comprising adding the reaction product as a wetting agent or dispersant or dispersion stabilizer or viscosity reducer or compatibilizer in coatings, varnishes, plastics, pigment pastes, sealants, cosmetics, ceramics, adhesives, potting compounds, spackling compounds, printing inks or other inks.

Description

EXAMPLES

[0167] In the case of molecularly inhomogeneous substances, the stated molecular weights are number-average values. The molecular weights or number-average molecular weights M.sub.n, in the event that titratable hydroxyl or amino groups are present, are determined by end group determination via the finding of the OH number or the amine number. In the case of compounds to which end group determination is not applicable, the number-average molecular weight is determined by means of gel permeation chromatography against a polystyrene standard.

[0168] Unless stated otherwise, figures in parts are

parts by weight and figures in percent are percent by weight.

Solids Content

[0169] The sample (2.00.1 g of test substance) is weighed into an aluminum dish that has been dried beforehand and dried in a drying cabinet at 150 C. for 10 minutes, cooled down in a desiccator, and then re-weighed. The residue corresponds to the solids content.

NCO Number

[0170] The free NCO content of the polyisocyanates being used and the course of reaction of the NCO additions is determined according to EN ISO 9369 by reaction with butylamine and subsequent titration of the excess of amine. These methods are also described in Saul Patai The Chemistry of Cyanates and their Thioderivates, Part 1, Chapter 5, 1977.

OH Number

[0171] The OH number is determined according to DIN ISO 4629 by acetylation with an excess of acetic anhydride. Subsequently, the excess acetic anhydride is hydrolyzed to acetic acid by addition of water and back-titrated with ethanolic KOH solution. The OH number indicates the amount of KOH in mg equivalent to the amount of acetic acid bound in the acetylation of 1 g of substance.

Amine Number

[0172] 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 potentiometric titration with 0.1 N perchloric acid in acetic acid.

Preparation of the Polyether-Polyester YOH 1, Mn 780

[0173] 350 g of MPEG 350 (methoxy polyethylene glycol, Mn 350), 434 g of -caprolactone and 1 g of DBTL (dibutyltin dilaurate) are reacted at 160 C. until a solids content of >95% has been attained. The OH number of the reaction product is 72 mg KOH/g. The further monohydroxy-functional polyesters used as YOH are prepared in an analogous manner.

General Preparation Method for the Monoadducts M of the General Formula (III) (Table 1):

[0174] A four-neck flask provided with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube is initially charged with 430 g of Desmodur T100 (about 100% toluene 2,4-diisocyanate, NCO content=48.8) and 7 g of benzoyl chloride, and mixed thoroughly. X g of the alcohol component 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 h. 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%.

TABLE-US-00001 TABLE 1 Overview of the monoadducts M of the general formula (III) Mono- Amount X adduct Alcohol component Y-OH in [g] M1 Butanol-started PO polyether Mn 800, OH number: 70 mg 800 KOH/g M2 MPEG 350, OH number: 162 mg KOH/g 350 M3 Butanol-started EO/PO polyether (EO:PO 1:1) Mn 2240, OH 2240 number: 25 mg KOH/g M4 Polyester Y-OH 1, OH number: 72 mg KOH/g 780 M5 Hexadecanol-started monohydroxy-functional - 600 caprolactone polyester, Mn 600 M6 Hexadecanol-started monohydroxy-functional - 1200 caprolactone polyester, Mn 1200 M7 MPEG 500 = methoxy polyethylene glycol, Mn 500 500 M8 Butanol-started EO/PO polyether (EO:PO 1:1) Mn 1100 1100 M9 Butanol-started EO/PO polyether (EO:PO 1:1) Mn 1300 1300 M10 Butanol-started EO/PO polyether (EO:PO 1:1) Mn 2000 2000 M11 Butanol-started EO/PO polyether (EO:PO 1:1) Mn 3100 3100 M12 Butanol-started EO/PO polyether (EO:PO 1:1) Mn 4800 4800 M13 Hydroxyethyl acrylate-started -caprolactone polyester, Mn 1200 1200 M14 Monohydroxy-functional hydroxypropyl polydimethylsiloxane 1200 with butyl end group, Mn 1200 M15 Methanol-started EO/PO polyether (EO:PO 3:1), Mn 1400 1400 M16 MPEG 500-started -caprolactone polyester Mn 900 900 M17 Isodecanol-started -caprolactone polyester Mn 700 700 M18 Isodecanol-started -caprolactone polyester Mn 1000 1000 M19 Monophenyl glycol-started -caprolactone polyester Mn = 1200 1200 M20 n-Butanol-started -caprolactone polyester, Mn = 600 600 M21 n-Butanol-started -caprolactone polyester, Mn = 1200 1200 M22 Butanol-started PO polyether, Mn 1100 1100 M23 Isodecanol-started polyester formed from -caprolactone 1400 and -valerolactone in a molar ratio of 9:2, Mn = 1400 M24 -caprolactone polyester, started with a butanol-started 2000 EO/PO polyether (EO:PO 1:1) Mn 1300, mean molecular weight Mn = 2000 M25 MPEG 350-started -caprolactone polyester Mn 900 900 M26 MPEG 350-started polyester formed from -caprolactone 950 and -valerolactone in a molar ratio of 3:1, Mn = 950 M27 MPEG 500-started polyester formed from -caprolactone 1100 and -valerolactone in a molar ratio of 3:1, Mn = 1100 M28 MPEG 750-started polyester formed from -caprolactone 1400 and -valerolactone in a molar ratio of 3:1, Mn = 1400 M29 MPEG 750 750 M30 -caprolactone polyester Mn 1600, started with a methanol- 1600 started EO/PO polyether (EO:PO 3:1), Mn 1400 M31 Butanol-started EO/PO polyether (EO:PO 1:1) Mn 3170 3170 M32 Butanol-started EO/PO polyether (EO:PO 1:1) Mn 2540 2540 M33 Butanol-started PO polyether, Mn 2240 2240 M34 Butanol-started butylene oxide polyether, Mn 960 960 M35 Butanol-started PO polyether, Mn 2000 2000 M36 MPEG 2000 2000 M37 Isotridecyl alcohol 200 M38 n-Decanol 158 M39 Isodecanol 158 M40 Benzyl alcohol 108 M41 Cyclohexanol 100 M42 Isobutanol 74 M43 Dipropylene glycol monomethyl ether 148 M44 Butyltriglycol 206

[0175] The compounds used as component of the formula (IV) (HX).sub.pZ.sup.1(HX).sub.y are listed in the table which follows. If no modifying component MZ is listed, the amines specified are used as they are.

General Method for Reaction of Amines with Modifying Components MZ to Give Components of the Formula (IV) (Table 2):

[0176] A four-neck flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube is initially charged with x g of amine or amine mixture and heated to 80 C. Subsequently, while stirring, y g of modifying component MZ are added dropwise at a sufficiently slow rate that the reaction temperature does not exceed 90 C. in the case of acrylate components and 120 C. in the case of epoxide components. Subsequently, stirring is continued at this temperature until conversion of MZ is complete. The progress of the reaction can be monitored via NMR measurements. Dilution with MPA is optionally possible during or after the reaction.

TABLE-US-00002 TABLE 2 Components of the general formula (IV) and reaction of amines with modifying component MZ to give components of the general formula (IV) Amount Amount of Component of amine Modifying component MZ (IV) Amine x [g] MZ y [g] A1 API 376 TMPTA 296 A2 API 250 TMPTA 296 DMAPA 102 A3 API 250 DPGDA 242 A4 API 250 TPGDA 300 A5 DMAPA 307 TMPTA 296 A6 DMAPA 204 DPGDA 242 A7 DMAPA 204 TPGDA 300 A8 EA 122 DPGDA 242 A9 DEA 210 DPGDA 242 A10 EA 61 HEA 232 A11 DEA 105 HEA 116 A12 DEA 105 EHA 184 A13 DEA 105 PEGA-320 320 A14 DMAPA 102 HEA 232 A15 API 125 DPGDA 242 DMAPA 102 A16 API 125 HEA 232 A17 DMAPA 102 Grilonit RV 1814 540 A18 DMAPA 204 BDGE 202 A19 DEA 210 BDGE 202 A20 DMAPA 102 CGE 164 A21 TEA A22 MDEA A23 THPEDA A24 DMADPA A25 BAPMA A26* DMAE *not in accordance with the invention DMAPA = N,N-dimethylaminopropylamine; API = N-(3-aminopropyl)imidazole, TEA = triethanolamine; DEA = diethanolamine, EA = monoethanolamine, MDEA = N-methyldiethanolamine, THPEDA = tetra(2-hydroxypropyl)ethylenediamine, DMADPA = dimethylaminopropyldiisopropanolamine, BAPMA = N,N-bis(3-aminopropyl)methylamine, DMAE = dimethylaminoethanol TMPTA = trimethylolpropane triacrylate, DPGDA = dipropylene glycol diacrylate, TPGDA = tripropylene glycol diacrylate, HEA = 2-hydroxyethyl acrylate, EHA = 2-ethylhexyl acrylate, PEGA-320 = polyethylene glycol monoacrylate Mn 320, Grilonit RV 1814 = C.sub.13/C.sub.15-alkyl glycidyl ether, EMS-Chemie, CGE = cresyl glycidyl ether, BDGE = butane-1,4-diol diglycidyl ether, MPA = methoxypropyl acetate (solvent);
General Method for Reaction of the Monoadducts M of the General Formula (III) with Components of the General Formula (IV) to Give Reaction Products Containing Urethane Groups, Comprising One or More Species of the General Formula (I) (Table 3):

[0177] A four-neck flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube is initially charged with y g of component of the formula (IV) and heated to 70 C. while stirring under nitrogen. Subsequently, x1 g of monoadduct M1 are added gradually, such that the reaction temperature does not exceed 80 C. Subsequently, the reaction mixture is stirred at 80 C. until the isocyanate has reacted to completion. Turbidity may arise, which dissolves in the course of the reaction. The progress of the reaction is followed by means of titrimetric determination of the NCO number. In the same way, if stated, x2 g of monoadduct M2 are added and reacted to completion in a second reaction stage. Dilution with MPA is optionally possible during or after the reaction.

[0178] If component (IV) contains hydroxyl groups that are to be converted, the urethane formation can be accelerated by addition of 200 ppm of dibutyltin dilaurate.

TABLE-US-00003 TABLE 3 Reaction of monoadducts M with components of the formula (IV) Mono- Mono- adduct Amount adduct Amount Component Amount Example M1 x1 [g] M2 x2 [g] (IV) y [g] B1 M23 3150 A24 218 B2 M9 2948 A21 149 B3 M9 4422 A21 149 B4 M9 2948 A22 119 B5 M22 2748 M12 6174 A1 672 B6 M01 1748 M12 6174 A1 672 B7 M22 2748 M12 6174 A2 649 B8 M35 5348 M12 6174 A1 672 B9 M01 1748 M09 1474 A1 672 B10 M01 1748 M10 1774 A1 672 B11 M22 2748 A3 493 B12 M12 12348 A3 493 B13 M12 12348 A4 551 B14 M12 18522 A1 676 B15 M12 6174 M22 1374 A4 551 B16 M12 6174 M22 1374 A3 493 B17 M12 12348 M22 1374 A1 672 B18 M12 6174 M22 2748 A1 672 B19 M12 18522 A5 603 B20 M22 4122 A5 603 B21 M22 2748 A4 551 B22 M22 4122 A1 672 B23 M12 12348 A6 447 B24 M12 12348 A6 447 B25 M12 6174 M22 1374 A7 505 B26 M12 12348 A7 505 B27 M22 2748 A6 447 B28 M12 6174 M22 1374 A6 447 B29 M12 12348 M22 1374 A5 603 B30 M12 6174 M22 2748 A5 603 B31 M22 1374 A7 505 B32 M2 1050 A21 149 B33 M3 2415 M20 775 A21 149 B34 M4 950 M21 1375 A21 149 B35 M5 775 M23 1574 A21 149 B36 M6 1375 M24 2175 A22 119 B37 M7 675 M25 1075 A23 292 B38 M8 2550 M26 1125 A23 292 B39 M11 3274 M27 3820 A23 292 B40 M13 1375 M28 1574 A22 119 B41 M14 1375 M39 332 A21 149 B42 M15 1575 M29 924 A24 218 B43 M16 1074 M30 1775 A25 145 B44 M17 875 M31 3345 A25 145 B45 M18 1175 M32 2715 A21 149 B46 M19 1375 M34 1134 A21 149 B47 M12 6174 M35 2674 A6 447 B48 M12 6174 M35 2674 A3 493 B49 M12 6174 M35 2674 A15 470 B50 M35 5348 A3 493 B51 M33 7348 A3 493 B52 M09 2948 A3 493 B53 M12 6174 M09 1474 A3 493 B54 M09 1474 M35 1674 A3 493 B55 M12 6174 M35 1674 A3 493 B56 M36 4350 A21 149 B57 M9 1474 M37 375 A21 149 B58 M9 1474 M38 330 A21 149 B59 M40 282 M43 320 A21 149 B60 M41 274 M44 380 A21 149 B61 M9 1474 M42 250 A21 149 BX1* M9 1475 A26 89 BX2* M9 1475 A21 149 BX3* M9 1475 DMAPA 102 *noninventive comparative examples

General Method for Quaternization (Table 4):

[0179] In a four-neck flask provided with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube, the starting compound in 40 g of MPA (methoxypropyl acetate) and 40 g of butylglycol and x g of alkylating reagent are reacted at 120 C. for 4 h. The solids content is adjusted to 40% with a 1:1 mixture of MPA and butylglycol.

TABLE-US-00004 TABLE 4 Quaternization Example Starting compound Alkylating reagent Q1 120 g B1 3.9 g of benzyl chloride Q2 335 g B58 12.7 g of benzyl chloride Q3 329 g B59 12.7 g of benzyl chloride Q4 335 g B58 26.2 g of Grilonit 1814 11.4 g of benzoic acid Q5 329 g B59 15.7 g of CGE 11.4 g of benzoic acid Grilonit RV 1814 = C.sub.13/C.sub.15-alkyl glycidyl ether, EMS-Chemie

General Method for Salt Formation (Table 5):

[0180] In a four-neck flask provided with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube, the compound to be converted to a salt in 40 g of MPA and 40 g of butylglycol is stirred with x g of salt conversion reagent at 60 C. for 1 h.

TABLE-US-00005 TABLE 5 Salt formation Example Compound used Salt conversion reagent S1 3100 g B2 146 g of adipic acid S2 3100 g B2 6.4 g of benzoic acid S3 3100 g B2 7.3 g of benzoic acid S4 3100 g B2 73 g of adipic acid S5 3100 g B2 282 g of oleic acid S6 3100 g B2 200 g of lauric acid S7 3100 g B2 298 g of ricinoleic acid S8 3100 g B2 60 g of acetic acid

c) Performance Testing

[0181] Use of the polymers of the invention as wetting agents and dispersants for production of pigment concentrates and use thereof in varnish systems

Starting Materials

[0182]

TABLE-US-00006 Paraloid B-66 thermoplastic acrylate resin, manufacturer: DOW Chemicals Vinnol E 15/45 copolymer resin based on vinyl chloride and vinyl acetate, manufacturer: Wacker Chemie NC E 510 nitrocellulose, manufacturer: Dow Wolff Cellulosics GmbH Vialkyd AC 433 75% alkyd resin, manufacturer: Allnex Epikote 1001 75% epoxy resin based on bisphenol A, manufacturer: Hexion Aradur 115 X 70 polyamidoamine, manufacturer: Huntsman Joncryl 500 hydroxy-functional acrylic resin, manufacturer: BASF Laropal A 81 aldehyde resin, manufacturer: BASF Cymel 303 amino crosslinker, manufacturer: Allnex MAK methyl amyl ketone, manufacturer: Eastman DIDP diisodecyl phthalate Nacure 2500 p-toluenesulfonic acid, manufacturer: King Industries Dowanol PMA propylene glycol methyl ether acetate, manufacturer: Dow Chemicals Dowanol PM propylene glycol methyl ether, manufacturer: Dow Chemicals Raven 5000 Ultra III carbon black pigment for high jetness, manufacturer Paliogen Red L3880 HD perylene red pigment, manufacturer Hostaperm RL NF violet pigment, manufacturer InkJet Margenta E02 pigment for inkjet inks, manufacturer Novoperm Yellow P-M3R isoindoline pigment, manufacturer Nipex 160 IQ gas black with primary particle size 20 mm, manufacturer: Degussa Bayferrox Red 130M iron oxide red (P.R. 101), manufacturer: Lanxess Heliogen Blue L7101F phthalocyanine blue (P.B. 15:4), manufacturer: BASF Hostaperm Rosa E quinacridone red (P.R. 122), manufacturer: Clariant Colour Black FW 200 carbon black pigment (P. Bk. 7), manufacturer: Orion BYK 325 substrate wetting agent, manufacturer: BYK-Chemie BYK 310 substrate wetting agent, manufacturer: BYK-Chemie BYK 306 substrate wetting agent, manufacturer: BYK-Chemie

Procedures

Production of the TPA Pigment Dispersion

[0183] The Paraloid B-66 dispersion resin, solvent, dispersing additive and pigment were weighed into 100 mL glass bottles so as to obtain 50 g of millbase. Subsequently, 50 g of glass beads (1 mm) were weighed in.

Composition of the TPA Pigment Concentrates (Figures in g)

[0184]

TABLE-US-00007 TPA 1 TPA 2 TPA 3 (black) (red) (violet) Paraloid B-66 (50% in xylene) 24.0 24.0 24.0 Raven Ultra 5000 III 6.0 Paliogen Red L 3880 HD 8.0 Hostaperm RL-NF 5.0 Dispersant (100%) 4.2 2.0 2.0 n-Butanol 5.0 5.0 5.0 PMA (100%) 11.0 14.0 Butyl acetate (100%) 10.8 Total pigment content (%) 12 16 10 Dispersant (% s.o.p.) 70 25 40

Grinding Conditions:

[0185] Equipment: Lau Disperser DAS 200, dispersing time: 300 min, cooling power at level 3

[0186] Ratio of millbase to glass beads (diameter 1 mm):1:1 (parts by weight)

Assessment of Millbase Viscosity of the TPA Dispersions

[0187] The millbase viscosity of the TPA dispersions was determined with a Rheological Stresstech Rheometer (plate/cone, 25 mm, 1) at 23 C.

Millbase Viscosities

[0188]

TABLE-US-00008 TPA 1 (black) TPA 2 (red) TPA 3 (violet) Raven 5000 Ultra III Paliogen Red L3880 HD Hostaperm RL-NF Viscosity in Pa * s 1/s 10/s 100/s 1/s 10/s 100/s 1/s 10/s 100/s BX1* 45.890 7.727 1.828 15.370 2.876 0.814 42.110 4.786 1.085 BX2* 51.610 7.534 1.774 22.470 3.808 1.011 57.960 7.762 1.432 Q1 11.780 2.340 0.839 11.120 1.917 0.579 41.550 4.480 1.056 B2 34.090 6.209 1.632 13.210 2.672 0.732 40.290 4.187 1.020 B3 37.300 6.136 1.496 9.812 2.068 0.730 40.920 4.500 1.061 B4 33.340 6.088 1.598 13.720 2.611 0.733 41.920 4.532 1.062

[0189] The inventive dispersing additives have a significant viscosity-reducing effect compared to the prior art BX1* and BX2* in TPA dispersions of 3 different pigments, which is manifested even at low shear rates.

Production of the TPA-Based Letdown System

[0190] Paraloid B-66, solvent and leveling additive were weighed into a 2.5 L PE bucket and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.

Composition of the TPA Letdown System (Figures in g)

[0191]

TABLE-US-00009 TPA clearcoat Weight in g Paraloid B-66 (50% in xylene) 700 DIDP 20 Xylene 218 PMA 60 BYK-306 2

Production of the Pigmented TPA Letdown Systems

[0192] The TPA letdown system and the TPA-based pigment dispersion were weighed into a PE cup and mixed with a spatula. Subsequently, all the final TPA letdown systems were homogenized in an ANDALOK shaker for 10 min.

Composition of the Pigmented TPA Letdown Systems (Figures in g)

[0193]

TABLE-US-00010 TPA-B1 TPA-B2 TPA-B3 TPA letdown system 28.0 27.0 26.0 TPA 1 (black) 2.0 TPA 2 (red) 3.0 TPA 3 (violet) 4.0 Pigment content (%) 0.8 1.6 1.3

Application and Evaluation of the Pigmented TPA Letdown Systems

[0194] The pigmented TPA letdown systems were bar-coated onto PE film (50 m or 100 m) and dried at 22 C. for 24 h. Subsequently, the haze and gloss were measured with a BYK micro haze plus instrument at an angle of 20. In each case, low values for haze and high values for gloss are considered to be positive results. In addition, the optical color intensity and transparency through the drawdowns onto PE film was assessed using grades 1 (excellent) to 5 (unacceptable).

TABLE-US-00011 TPA B1 (black) Raven 5000 Ultra III Dispersing additive in the millbase Masstone Masstone Masstone 100 m PE film 100 m PE film 100 m PE film Transparency/ Haze Gloss 20 color intensity BX1* 11 79 2-3 BX2* 12 79 3 B2 9 82 2 B3 10 83 1-2 B4 9 82 1

TABLE-US-00012 TPA B2 (red) Paliogen Red L3880 HD Dispersing additive in the millbase Masstone Masstone Masstone 50 m PE film 100 m PE film 100 m PE film Transparency/ Haze Gloss 20 color intensity BX1* 13 75 4 BX2* 20 73 4-5 B2 12 78 3 B3 12 78 3 B4 9 79 3

TABLE-US-00013 TPA B3 (violet) Hostaperm RL-NF Dispersing additive in the millbase Masstone Masstone Masstone 50 m PE film 50 m PE film 50 m PE film Transparency/ Haze Gloss 20 color intensity BX1* 45 69 4 BX2* 47 69 4-5 Q1 42 72 3 B2 41 72 3 B3 38 72 2-3 B4 40 72 3

[0195] The dispersing additives of the invention exhibit lower haze, better gloss values and higher transparency and color intensity compared to the prior art BX1* and BX2* for TPA-based varnish systems.

Production of the Laropal A81 Pigment Dispersion

[0196] The Laropal A81 dispersion resin (60 parts) was weighed into a 2.5 L PE bucket together with PMA (40 parts) and homogenized by means of a Dispermat CV (65 mm toothed disk) at 2000 rpm for 30 min. Subsequently, the solution of the dispersion resin, solvent, dispersing additive and pigment was weighed into 100 mL glass bottles so as to obtain 50 g of millbase. Subsequently, 50 g of glass beads (1 mm) were weighed in.

Composition of the Laropal A81 Pigment Concentrates (Figures in q)

[0197]

TABLE-US-00014 LA 1 LA 2 LA 3 (black) (pink) (blue) Laropal A 81 (60% in PMA) 8.7 20.4 21.9 Colour Black FW 200 4.0 Hostaperm Rosa E 7.0 Heliogen Blau 7101F 7.5 Dispersing additive (100%) 2.8 1.8 1.9 PMA 34.5 20.8 18.7 Total pigment content (%) 8 14 15 Dispersant (% s.o.p.) 70 25 25

Grinding Conditions:

[0198] Equipment: Lau Disperser DAS 200, grinding time: 300 min, cooling power at level 3 Ratio of millbase to glass beads (diameter 1 mm):1:1 (parts by weight)

Assessment of the Millbase Viscosity and the Laropal A81 Dispersions

[0199] The millbase viscosity of the Laropal A81 dispersions was determined with a Rheological Stresstech Rheometer (plate/cone, 25 mm, 1) at 23 C.

Millbase Viscosities

[0200]

TABLE-US-00015 LA 1 (black) LA 2 (pink) LA 3 (blue) Viscosity Viscosity Viscosity in mPa * s in mPa * s in mPa * s 1/ 10/ 100/ 1/ 10/ 100/ 1/ 10/ 100/ s s s s s s s s s BX3* 64 23 16 34870 3934 894 9757 1017 274 BX2* 232 25 19 33660 3399 995 10720 915 297 Q1 17 5 6 19260 1860 323 6991 791 141 B2 42 14 12 31930 3179 682 9734 697 180 B3 24 17 13 27900 3027 734 8718 568 165 B4 44 16 12 28850 3284 811 9083 710 182

Production of a Baking Varnish JC1

[0201] Binder, solvent and substrate wetting agent were weighed into a 2.5 L PE bucket and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.

Composition of the Baking Varnish JC1 (Figures in g)

[0202]

TABLE-US-00016 Baking varnish JC1 Weight in g Joncryl 500 576.0 Cymel 303 198.0 Butanol 80.0 MAK 130.0 BYK-310 3.0 Nacure 2500 13.0

Production of Various Varnishes Based on the Laropal A81 Pigment Dispersions

[0203] The Laropal A81-based pigment dispersions and the baking varnish JC1 were weighed into a PE cup and mixed by hand with a spatula. Subsequently, the pigmented varnishes were homogenized in an ANDALOK shaker for 10 min.

Composition of the Pigmented JC1 Letdown Systems (Figures in g)

[0204]

TABLE-US-00017 JC1-B1 JC1-B2 JC1-B3 (black) (pink) (blue) JC1 18.0 17.9 16.0 LA 1 (black) 2.0 LA 2 (pink) 2.1 LA 3 (blue) 4.0 Pigment content (%) 0.8 1.5 3.0

Application and Evaluation of the Pigmented Baking Varnishes JC1-B1 to JC1-B3

[0205] The pigmented baking varnishes JC1-B1 to JC1-B3 were bar-coated onto PE film (50 m), flashed off at 22 C. for 15 min and baked at 150 C. for 20 min. Subsequently, haze and gloss were measured with a BYK micro haze plus instrument at an angle of 20. In each case, low values for haze and high values for gloss are considered to be positive results. In addition, the optical transparency and color intensity through the drawdowns onto PE film was assessed using grades 1 (excellent) to 5 (unacceptable).

Comparison of the Black Baking Varnishes JC1-B1 (Black)

[0206]

TABLE-US-00018 Transparency/ Synthesis name Gloss 20 Haze color intensity BX3* 99 18 4-5 BX2* 101 21 3-4 Q1 106 10 2-3 B2 106 10 1-2 B3 104 15 1 B4 106 11 2-3

Comparison of the Pink Baking Varnishes JC1-B2 (Pink)

[0207]

TABLE-US-00019 Transparency/ Gloss 20 Haze color intensity BX3* 109 33 4-5 BX2* 108 28 5 Q1 116 14 3 B2 115 17 3 B3 115 19 3 B4 114 23 3

Comparison of the Blue Baking Varnishes JC1-B3 (Blue)

[0208]

TABLE-US-00020 Transparency/ Synthesis name Gloss 20 Haze color intensity BX3* 110 35 4-5 BX2* 109 38 4 Q1 116 24 3 B2 117 20 3 B3 116 20 2-3 B4 116 23 3

[0209] The dispersing additives of the invention exhibit lower haze, better gloss values and higher transparency and color intensity compared to the prior art BX3 and BX2 for pigment concentrates based on Laropal A81 used in an acid-catalyzed baking varnish.