REACTION PRODUCTS CONTAINING URETHANE GROUPS AND UREA GROUPS

Abstract

The present invention relates to reaction products containing urethane groups and urea groups, containing at least one species of general formula (I), to a method for producing said reaction products, to the use of said reaction products as wetting agents, dispersants, dispersion stabilizers, and/or adhesion promoters, and to compositions that contain the reaction products containing urethane groups and urea groups.

##STR00001##

Claims

1. A reaction product containing urethane and urea groups, comprising at least one species of the general formula (I) ##STR00013## where a+b+c=x, r+s=q1 p+y=w1 x is an integer from 2 to 10, a is an integer from 1 to 9, b is an integer from 1 to 9, c is an integer from 0 to 8, q is an integer from 1 to 5, r is an integer from 0 to 4, s is an integer from 0 to 4, w is an integer from 1 to 10, p is an integer from 0 to 9, y is an integer from 0 to 9, and R is the organic radical of a corresponding polyisocyanate R(NCO).sub.x, R is a branched or unbranched, saturated or unsaturated organic radical having 1 to 150 carbon atoms and does not contain any free isocyanate groups, the Y radical(s) is/are independently the organic radical(s) of a corresponding alcohol Y(OH).sub.q where q is an integer from 1 to 5 and Y is a branched or unbranched, saturated or unsaturated organic radical having 1 to 1000 carbon atoms, the X group(s) is/are independently O, NH and/or NZ.sup.2 and the XH group(s) is/are independently a hydroxyl group OH, a primary amino group NH.sub.2 and/or a secondary amino group NHZ.sup.2 where the Z.sup.2 radical(s) is/are independently a branched or unbranched, saturated or unsaturated organic radical G(XH).sub.j(XP).sub.i where i+j=k, k is an integer from 0 to 9, j is an integer from 0 to 9, i is an integer from 0 to 9, and the G radical is a branched or unbranched, saturated or unsaturated organic radical, and the A radical(s) is/are independently a radical of the general formula (II) ##STR00014## where the R.sup.1 radical is H or NH.sub.2 or a branched or unbranched, saturated or unsaturated organic radical having 1 to 25 carbon atoms or, if Z.sup.b is C and R.sup.2 is CHN, where the nitrogen atom of the R.sup.2 radical is bonded directly to Z.sup.b to form a 5-membered ring, R.sup.1 is OH, the Z.sup.a group is CH or N or CR.sup.3 where the R.sup.3 radical is a branched or unbranched, saturated or unsaturated organic radical having 1 to 18 carbon atoms, the Z.sup.b group is CH or N or, if R.sup.1 is OH, Z.sup.b is C, the R.sup.2 radical is H or, if R.sup.1 is OH, R.sup.2 is CHN, and the Z.sup.1 radical(s) is/are independently the organic radical of a corresponding species of the general formula (III)
(HX).sub.y-Z.sup.1(XH).sub.p+1(III) where Z.sup.1 is a branched or unbranched, saturated or unsaturated organic radical containing 1 to 150 carbon atoms, the P radical(s) is/are independently a radical of the general formula (IVa)
(CO)NHR-(Q).sub.x1(IVa) where the Q radical(s) is/are independently a radical
NH(CO)-A or
NH(CO)XZ.sup.1(XH).sub.y(XU).sub.p or
NH(CO)OY(OH).sub.r(OU).sub.s where the U radical(s) is/are independently a radical of the general formula (IVb)
(CO)NHR(V).sub.x1(IVb) where the V radical(s) is/are independently a radical
NH(CO)-A or
NH(CO)XZ.sup.1(XH).sub.y or
NH(CO)OY(OH).sub.r.

2. The reaction product containing urethane and urea groups as claimed in claim 1, containing at least 40% by weight of one or more species of the general formula (I).

3. The reaction product containing urethane and urea groups as claimed in claim 1, wherein x is an integer from 2 to 7, a is an integer from 1 to 6 and b is an integer from 1 to 6.

4. The reaction product containing urethane and urea groups as claimed in claim 3, wherein x is 2, a is 1 and b is 1.

5. The reaction product containing urethane and urea groups as claimed in claim 1, wherein the following conditions are applicable to the A radical(s) of the general formula (II): the R.sup.1 radical is H or a branched or unbranched, saturated or unsaturated organic radical having 1 to 25 carbon atoms, the Z.sup.a group is CH or N, the Z.sup.b group is CH or N, and the R.sup.2 radical is H.

6. The reaction product containing urethane and urea groups as claimed in claim 1, wherein p is an integer from 0 to 3, and s is an integer from 0 to 2.

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

8. A process for preparing a reaction product containing urethane and urea groups as claimed in claim 1, wherein i) b alcohols Y(OH), are reacted with at least one polyisocyanate R(NCO).sub.x to form at least one urethane of the general formula (V)
((HO).sub.q1YOCONH).sub.bR(NCO).sub.xb(V) where the urethane of the general formula (V) contains at least one free isocyanate group, and ii) at least one urethane of the general formula (V) is reacted with a species of the general formula (IIa) ##STR00015## iii) optionally with c components of the general formula (III)
(HX).sub.y-Z.sup.1(XH).sub.p+1(III), to give a reaction product containing urethane and urea groups, comprising at least one species of the general formula (I) ##STR00016##

9. A wetting agent and dispersant comprising a reaction product containing urethane and urea groups as claimed in claim 1.

10. An adhesion promoter comprising a reaction product containing urethane and urea groups as claimed in claim 1.

11. A composition comprising a reaction product containing urethane and urea groups as claimed in claim 1.

12. A reaction product containing urethane and urea groups as claimed in claim 1 as an additive, wetting agent, dispersant, dispersion stabilizer, adhesion promoter, viscosity reducer, or compatibilizer in coatings, varnishes, plastics, pigment pastes, sealants, cosmetics, ceramics, adhesives, potting compounds, spackling compounds, printing inks and other inks.

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

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

15. A reaction product containing urethane and urea groups, comprising one or more modification products of the species general formula (I) as claimed in claim 1, wherein one or more tertiary amino groups in the structural element 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 structural element of the general formula (I) have been reacted with carboxylic anhydrides.

Description

EXAMPLES

[0276] 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.

[0277] Unless stated otherwise, figures in parts are parts by weight and figures in percent are percent by weight.

Solids Content

[0278] 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

[0279] 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

[0280] 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

[0281] 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.

Starting Materials

[0282]

TABLE-US-00001 Desmodur HL BA isocyanurates based on HDI and TDI, 60% in butyl acetate, % NCO = 10.6; manufacturer: Bayer Material Science Desmodur N 100A biuret based on HDI, 100%, % NCO = 22.0; manufacturer: Bayer Material Science Desmodur N 3400 uretdione based on HDI, 100%, % NCO = 21.8; manufacturer: Bayer Material Science Desmodur IL BA isocyanurates based on TDI, 51% in butyl acetate, % NCO = 8.0; manufacturer: Bayer Material Science TDI tolyl 2,4-diisocyanate, % NCO = 48.3; manufacturer: Bayer Material Science HDI hexamethylene 1,6-diisocyanate, % NCO = 49.9; manufacturer: Bayer Material Science MPA methoxypropyl acetate (solvent), manufacturer: Dow Chemical Comp. DMSO dimethyl sulfoxide (solvent), supplier: Sigma- Aldrich NFM N-formylmorpholine (solvent), manufacturer: BASF DBTL dibutyltin dilaurate, manufacturer: Merck DMAPA N,N-dimethylaminopropylamine, manufacturer: Huntsman Corp. TEA triethanolamine, manufacturer: BASF DEEA N,N-diethylethanolamine, manufacturer: Dow Chemical Comp. MEA N-methylethanolamine, manufacturer: BASF DEA N,N-diethanolamine, manufacturer: BASF IPA 3-imidazolyl-1-propylamine, manufacturer: BASF 4MDETA N,N,N,N-tetramethyldiethylenetriamine = Jeffcat Z 130, manufacturer: Huntsman Corp. DMAE N,N-dimethylaminoethanol, manufacturer: BASF DEEA N,N-diethylethanolamine, manufacturer: BASF DMEA N,N-dimethylethanolamine, manufacturer: BASF GLY glycerol, manufacturer: Merck Jeffcat DPA N-(3-dimethylaminopropyl)-N,N-diisopropanol- 1-ylamine, manufacturer: Huntsman Corp. BGA benzoguanamine (2,4-diamino-6-phenyl-1,3,5- triazine), manufacturer: Nippon Shokubai AGA acetoguanamine (2,4-diamino-6-methyl-1,3,5- triazine), supplier: Sigma-Aldrich 2,6-DAP 2,6-diaminopyridine, supplier: Sigma-Aldrich melamine 2,4,6-triamino-1,3,5-triazine, supplier: Helm AG guanine 2-amino-6-oxopurine, supplier: Sigma-Aldrich Grilonit RV 1814 C.sub.13/C.sub.15-alkyl glycidyl ether, manufacturer: EMS- Chemie

General Preparation Method for Preparation of the Urethanes of the General Formula (V) (Table 1):

[0283] A four-neck flask provided with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube is initially charged with 430 g of a diisocyanate R(NCO).sub.2 Desmodur T100 (about 100% tolylene 2,4-diisocyanate, NCO content=48.8) and 7 g of benzoyl chloride, which are mixed thoroughly. X g of the alcohol Y(OH).sub.q 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%. The urethanes of the general formula (V) are identified by serial numbers preceded by M in the table below.

TABLE-US-00002 TABLE 1 Overview of the urethanes of the general formula (V) M1 to M49 Urethane of the formula Amount X (III) Alcohol Y-(OH).sub.q in [g] M1 Y1 butanol-started PO polyether Mn 800, OH number: 70 mg KOH/g 800 M2 Y2 MPEG 350, OH number: 162 mg KOH/g 350 M3 Y3 butanol-started EO/PO polyether (EO:PO 1:1) Mn 2240, OH number: 2240 25 mg KOH/g M4 Y4 polyester, OH number: 72 mg KOH/g (for preparation see below) 780 M5 Y5 hexadecanol-started monohydroxy-functional epsilon-caprolactone 600 polyester, Mn 600 M6 Y6 hexadecanol-started monohydroxy-functional epsilon-caprolactone 1200 polyester, Mn 1200 M7 Y7 MPEG 500 = methoxy polyethylene glycol, Mn 500 500 M8 Y8 butanol-started EO/PO polyether (EO:PO 1:1) Mn 1100 1100 M9 Y9 butanol-started EO/PO polyether (EO:PO 1:1) Mn 1700 1700 M10 Y10 butanol-started EO/PO polyether (EO:PO 1:1) Mn 2000 2000 M11 Y11 butanol-started EO/PO polyether (EO:PO 1:1) Mn 3100 3100 M12 Y12 butanol-started EO/PO polyether (EO:PO 1:1) Mn 4800 4800 M13 Y13 hydroxyethyl acrylate-started epsilon-caprolactone polyester; Mn 1200 1200 M14 Y14 monohydroxy-functional hydroxypropyl polydimethylsiloxane with 1200 butyl end group, Mn 1200 M15 Y15 methanol-started EO/PO polyether (EO:PO 3:1) Mn 1400 1400 M16 Y16 MPEG 500-started epsilon-caprolactone polyester; Mn 900 900 M17 Y17 isodecanol-started epsilon-caprolactone polyester Mn 700 700 M18 Y18 isodecanol-started epsilon-caprolactone polyester Mn 1000 1000 M19 Y19 monophenyl glycol-started epsilon-caprolactone polyester; Mn 1200 1200 M20 Y20 n-butanol-started epsilon-caprolactone polyester, Mn 600 600 M21 Y21 n-butanol-started epsilon-caprolactone polyester, Mn 1200 1200 M22 Y22 n-butanol-started PO polyether, Mn 1100 1100 M23 Y23 isodecanol-started polyester formed from epsilon-caprolactone and 2000 delta-valerolactone in a molar ratio of 3:1; Mn = 2000 M24 Y24 B11/50-started epsilon-caprolactone polyester; Mn = 2000 2000 M25 Y25 MPEG 350-started epsilon-caprolactone polyester; Mn 900 900 M26 Y26 MPEG 350-started polyester formed from epsilon-caprolactone and 950 delta-valerolactone in a molar ratio of 3:1; Mn 950 M27 Y27 MPEG 500-started polyester formed from epsilon-caprolactone and 1100 delta-valerolactone in a molar ratio of 3:1; Mn 1100 M28 Y28 MPEG 750-started polyester formed from epsilon-caprolactone and 1400 delta-valerolactone in a molar ratio of 3:1; Mn = 1400 M29 Y29 MPEG 750 750 M30 Y30 epsilon-caprolactone polyester Mn 1600, started with a methanol- 1600 started EO/PO polyether (EO:PO 3:1); Mn 1400 M31 Y31 butanol-started EO/PO polyether (EO:PO 1:1); Mn 3170 3170 M32 Y32 butanol-started EO/PO polyether (EO:PO 1:1); Mn 2540 2540 M33 Y33 n-butanol-started PO polyether; Mn 2240 2240 M34 Y34 n-butanol-started butylene oxide polyether; Mn 960 960 M35 Y35 alpha, omega-dihydroxy-functional hydroxypropyl- 1800 polydimethylsiloxane; Mn 1800 M36 Y36 dihydroxy-functional epsilon-caprolactone polyester Mn 2800, started 2800 with an alpha, omega-dihydroxy-functional hydroxypropyl- polydimethylsiloxane; Mn 900 M37 Y37 oleyl alcohol 268 M38 Y38 monophenyl glycol 138 M39 Y39 isotridecyl alcohol 200 M40 Y40 n-decanol 158 M41 Y41 isodecanol 158 M42 Y42 benzyl alcohol 108 M43 Y43 cyclohexanol 100 M44 Y44 isobutanol 74 M45 Y45 polyethylene glycol (dihydroxy-functional); Mn 600 300 M46 Y46 polyethylene glycol (dihydroxy-functional); Mn 1000 500 M47 Y47 dipropylene glycol monomethyl ether 148 M48 Y48 butyltriglycol 206 M49 Y49 isodecanol-started polyester formed from epsilon-caprolactone and 1400 delta-valerolactone in a molar ratio of 3:1; Mn 1400

Preparation of the Polyether-Polyester Y4; Mn 780

[0284] 350 g of MPEG 350 (methoxy polyethylene glycol, Mn 350), 434 g of epsilon-caprolactone and 1 g of DBTL (dibutyltin dilaurate) are reacted at 160 C. until a solids content of >95% has been attained.

[0285] The OH number of the reaction product is 72 mg KOH/g.

Preparation of a Siloxane-Containinq Epsilon-Caprolactone Polyester Y36, M.SUB.n .2800

[0286] 35 g of an alpha,omega-dihydroxyalkyl-functional dimethylpolysiloxane with M.sub.n about 900 g/mol are reacted with 75 g of epsilon-caprolactone. For this purpose, the mixture with addition of 0.035 g of DBTL is left to react at 160 C. in an N.sub.2 atmosphere for about 8 hours. The reaction has ended when there is a solids content of >98%. The alpha,omega-hydroxyalkyl-functional dimethylpolysiloxane as starter alcohol is obtained in a known manner, by addition of suitable unsaturated alcohols (for example the allyl alcohol used in this example) onto dimethylpolysiloxanes bearing terminal silane units.

General Method for Reaction of the Urethanes M of the General Formula (V) with Species of General Formula (IIa) to Give Reaction Products MA Containinq Urethane and Urea Groups, Comprising at Least One Species of the General Formula (I) (Table 2):

[0287] A four-neck flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube is initially charged with x g of urethane M of the formula (V) and heated to 80 C. while stirring under nitrogen. Subsequently, y.sup.1 g of a component of the general formula (IIa) or of the mixture of y.sup.1 g of a component of the general formula (IIa) and y.sup.2 g of a component of the general formula (III) are added and the reaction temperature is raised to 120 C. 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 to EN ISO 9369. A small amount y.sup.2 (in g) of an optional component of the general formula (III) can also be added after the main reaction, in order to fully convert residual amounts of isocyanate and to obtain particularly storage-stable products. Dilution with MPA is optionally possible during or after the reaction.

[0288] The reaction products containing urethane and urea groups, comprising at least one species of the general formula (I), are identified hereinafter by serial numbers preceded by MA.

TABLE-US-00003 TABLE 2 Overview of the products MA1 to MA60 Amount y.sup.2 of Amount x of Amount y.sup.1 of a an optional urethane of component of component of the general the general the general NCO Solids Example formula (V) formula (IIa) formula (III) MPA in g number in % MA1 90.1 g M1 10.50 g BGA 0.2 g TEA 0.01 99.2% MA2 90.0 g M8 7.65 g BGA 0.2 g TEA 0.01 99.8% MA3 90.2 g M9 4.96 g BGA 0.2 g TEA 0.01 99.8% MA4 90.2 g M4 10.48 g BGA 0.2 g TEA 64.2 g 0.01 .sup.60% MA5 90.1 g M6 7.04 g BGA 0.2 g TEA 63.8 g <0.01 .sup.61% MA6 90.0 g M27 7.63 g BGA 0.2 g TEA 64.0 g 0.01 .sup.60% MA7 90.3 g M33 3.75 g BGA 0.2 g TEA <0.01 99.1% MA8 89.5 g M19 7.03 g BGA 0.2 g TEA 64.7 g <0.01 .sup.60% MA9 91.2 g M1 6.10 g 2,6-DAP 0.2 g DEA 0.01 99.3% MA10 90.0 g M8 4.44 g 2,6-DAP 0.2 g DEA <0.01 98.1% MA11 90.5 g M9 2.85 g 2,6-DAP 0.2 g DEA 0.01 99.2% MA12 90.1 g M4 6.11 g 2,6-DAP 0.2 g DEA 0.01 99.8% MA13 90.2 g M6 4.08 g 2,6-DAP 0.2 g DEA 0.01 99.8% MA14 89.7 g M27 4.43 g 2,6-DAP 0.2 g DEA 0.01 99.3% MA15 90.1 g M33 2.18 g 2,6-DAP 0.2 g DEA <0.01 98.1% MA16 90.3 g M19 4.08 g 2,6-DAP 0.2 g DEA 0.01 99.2% MA17 89.8 g M1 20.91 g BGA 0.1 g MEA 0.01 99.8% MA18 90.3 g M8 14.72 g BGA 0.1 g MEA 0.01 99.8% MA19 90.0 g M9 9.88 g BGA 0.1 g TEA 0.01 99.3% MA20 90.1 g M4 20.94 g BGA 0.1 g DEEA <0.01 98.1% MA21 90.2 g M6 14.01 g BGA 0.1 g TEA 0.01 99.2% MA22 89.6 g M12 3.48 g BGA 0.1 g TEA 0.01 99.8% MA23 90.1 g M33 7.35 g BGA 0.2 g 4MDETA 0.01 99.8% MA24 90.0 g M19 14.06 g BGA 0.1 g DMAPA 0.01 99.3% MA25 90.1 g M1 6.10 g 2,6-DAP 0.2 g DEA <0.01 98.1% MA26 90.1 g M8 4.44 g 2,6-DAP 0.2 g DEEA 0.01 99.2% MA27 90.2 g M9 2.85 g 2,6-DAP 0.2 g DEA 0.01 99.8% MA28 89.7 g M4 6.11 g 2,6-DAP 0.2 g TEA 0.01 99.8% MA29 89.9 g M6 4.08 g 2,6-DAP 0.2 g MEA 0.01 99.3% MA30 90.3 g M27 4.43 g 2,6-DAP 0.2 g DEA <0.01 98.1% MA31 90.1 g M33 2.18 g 2,6-DAP 0.2 g DEA 0.01 99.2% MA32 89.6 g M19 4.08 g 2,6-DAP 0.2 g 4MDETA 0.01 99.8% MA33 90.0 g M1 12.09 g 2,6-DAP 0.1 g BzA 0.01 99.8% MA34 90.2 g M8 8.81 g 2,6-DAP 0.1 g IPA 0.01 99.3% MA35 90.1 g M9 5.62 g 2,6-DAP 0.1 g TEA <0.01 98.1% MA36 90.1 g M4 12.05 g 2,6-DAP 0.1 g TEA 0.01 99.2% MA37 90.2 g M6 8.04 g 2,6-DAP 0.1 g DMAPA 0.01 99.8% MA38 90.2 g M27 8.80 g 2,6-DAP 0.1 g DEA 0.01 99.8% MA39 90.0 g M33 4.35 g 2,6-DAP 0.1 g MEA 0.01 99.3% MA40 89.9 g M19 8.12 g 2,6-DAP 0.1 g DEA <0.01 98.1% MA41 90.3 g M8 5.10 g AGA 0.2 g DEA 95.6 g DMSO 0.01 50.2% MA42 90.0 g M9 3.30 g AGA 0.2 g DEA 91.6 g DMSO 0.01 50.8% MA43 90.1 g M4 7.02 g AGA 0.2 g DEA 95.1 g DMSO 0.01 49.8% MA44 90.2 g M6 4.68 g AGA 0.2 g DEA 93.6 g DMSO 0.01 50.3% MA45 90.0 g M27 5.09 g AGA 0.2 g DEEA 94.5 g DMSO <0.01 48.1% MA46 89.8 g M8 10.15 g AGA 0.1 g DEA 98.6 g DMSO 0.01 50.2% MA47 90.1 g M9 6.55 g AGA 0.1 g DEA 96.6 g DMSO 0.01 49.8% MA48 90.0 g M4 13.90 g AGA 0.1 g DEA 113.2 g DMSO <0.01 50.1% MA49 90.3 g M6 9.30 g AGA 0.1 g DEA 99.0 g DMSO <0.01 50.3% MA50 90.0 g M27 10.04 g AGA 0.1 g DEA 100.6 g DMSO <0.01 49.1% MA51 90.1 g M4 16.97 g guanine 0.1 g DEEA <0.01 99.2% MA52 90.0 g M6 11.31 g guanine 0.1 g DEA 0.01 99.8% MA53 90.4 g M27 12.34 g guanine 0.1 g DEA 0.01 99.8% MA54* 90.1 g M9 5.35 g DMAPA 0.1 g TEA <0.01 99.0% MA55* 90.2 g M9 6.55 g IPA 0.1 g TEA <0.01 99.3% MA56* 90.0 g M9 4.70 g DMAE 0.1 g TEA <0.01 99.0% MA57* 90.1 g M9 8.40 g 4MDETA <0.01 99.4% MA58* 90.1 g M9 7.92 g TEA <0.01 99.6% MA59 90.1 g M9 6.65 g melamine 9.6 g NFM 0.01 90.1% MA60 90.3 g M9 6.60 g melamine 0.1 g GLY 9.5 g NFM 0.01 91.1% *not in accordance with the invention
General Method for Preparation of a Reaction Product Containing Urethane and Urea Groups, Comprising at Least One Species of the General Formula (I), from R(NCO).sub.x and Y(OH).sub.q (Table 3):

[0289] A reaction vessel provided with a stirrer, thermometer, reflux condenser and nitrogen inlet tube is initially charged with x g of a polyisocyanate R(NCO).sub.x together with y.sup.3 g of an alcohol Y(OH).sub.q, which are heated at 50 C. while stirring under nitrogen. After the addition of 0.008 wt % of DBTL based on the amount of the polyisocyanate R(NCO).sub.x, the reaction temperature is increased to 70 C. Subsequently, y.sup.1 g of a species of the general formula (IIa) are added and the reaction temperature is raised to 95 C. The progress of the reaction is still followed by means of titrimetric determination of the NCO number to EN ISO 9369. The conversion of the polyisocyanate R(NCO).sub.x is completed or, if appropriate, further aminic bonding groups are introduced by adding to the mixturein the case of the presence of residual NCO groups after the reaction with the species of the general formula (IIa)y.sup.2 g of a component of the general formula (III). The reaction has ended when, by titrimetric determination of the NCO number to EN ISO 9369, an NCO value of <0.01 is determined. Dilution with MPA is optionally possible during or after the reaction.

TABLE-US-00004 TABLE 3 Overview of the products MA61 to MA85 Amount y.sup.2 of Amount y.sup.1 of a an optional component of component of Amount x of Amount y.sup.3 of the general the general NCO Solids Example R(NCO).sub.x Y-(OH).sub.q formula (IIa) formula (III) MPA in g number in % MA61 10.50 g 13.8 g Y1 1.75 g BGA 17.8 <0.01 50 Desmodur HL BA MA62 10.52 g 13.9 g Y1 1.15 g AGA 17.7 <0.01 50 Desmodur HL BA MA64 10.51 g 13.8 g Y1 1.00 g 2,6-DAP 17.9 <0.01 50 Desmodur HL BA MA65 17.45 g 61.1 g Y18 6.15 g BGA 1.06 g TEA 85.0 <0.01 50 TDI MA66 17.44 g 57.3 g Y18 4.85 g 2,6-DAP 84.8 <0.01 50 TDI MA67 17.41 g 60.85 g Y18 4.12 g AGA 1.08 g TEA 85.7 <0.01 50 TDI MA68 20.1 g 378.8 g Y12 3.75 g BGA 1.0 g DEEA 403.0 g <0.01 50 Desmodur N 100A MA69 20.0 g 377.5 g Y12 2.51 g AGA 1.0 g DEEA 401.7 g <0.01 50 Desmodur N 100A MA70 20.1 g 379.0 g Y12 3.02 g guanine 1.0 g DEEA 402.9 g <0.01 50 Desmodur N 100A MA71 20.2 g 378.0 g Y12 2.52 g melamine 402.1 g <0.01 50 Desmodur N 100A MA72 20.5 g 81.9 g Y18 3.74 g BGA 1.0 g DEEA 101.6 g <0.01 50 Desmodur N 3400 MA73 20.6 g 82.1 g Y18 2.18 g 2,6-DAP 1.0 g DEEA 102.2 g <0.01 50 Desmodur (0.08 mol) N 3400 MA74 20.5 g 82.0 g Y18 2.51 g melamine 1.0 g DEEA 101.8 g <0.01 50 Desmodur N 3400 MA75 20.4 g 82.4 g Y18 3.01 g guanine 1.0 g DEEA 102.0 g <0.01 50 Desmodur N 3400 MA76 24.15 g 30.37 g Y18 3.75 g BGA 34.1 <0.01 50 Desmodur IL BA MA77 24.20 g 30.40 g Y18 2.50 g AGA 33.6 <0.01 50 Desmodur IL BA MA78 24.15 g 30.41 g Y18 2.16 g 2,6-DAP 33.8 <0.01 50 Desmodur IL BA MA79 24.17 g 30.39 g Y18 2.50 g melamine 33.5 <0.01 50 Desmodur IL BA MA80 24.16 g 41.71 g Y18 1.86 g BGA 38.3 <0.01 50 Desmodur IL BA MA81 24.15 g 46.30 g Y18 0.92 g BGA 48.0 <0.01 50 Desmodur IL BA MA82 24.21 g 19.31 g Y18 3.72 g BGA 34.1 <0.01 50 Desmodur 7.02 g Y2 IL BA MA83 24.12 g 19.29 g Y18 3.75 g BGA 25.0 <0.01 50 Desmodur 1.52 g Y45 IL BA MA84 24.17 g 19.33 g Y18 3.74 g BGA 26.3 <0.01 50 Desmodur 2.89 g Y37 IL BA MA85* 17.71 g 61.23 g Y49 20.05 g Jeffcat 99.3 0.01 50 TDI DPA *not in accordance with the invention

General Method for Quaternization (Table 4):

[0290] 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 z.sup.1 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-00005 TABLE 4 Quaternization Example Starting compound z.sup.1 g of alkylating reagent MAQ1 798.2 g MA68 0.9 g benzyl chloride MAQ2 205.5 g MA73 1.8 g Grilonit 1814 0.8 g benzoic acid MAQ3 93.8 g MA32 0.3 g benzyl chloride MAQ4 45.4 g MA19 0.4 g Grilonit 1814 0.2 g benzoic acid MAQ5* 185.0 g MA85* 9.4 g benzyl chloride

General Method for Salt Formation (Table 5):

[0291] 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 and 35 g of butylglycol is stirred with z.sup.2 g of salt conversion reagent at 60 C. for 1 h.

TABLE-US-00006 TABLE 5 Salt formation Example Starting compound z.sup.2 g of salt conversion reagent MAS1 89.1 g MA3 2.6 g tall oil fatty acid MAS2 91.0 g MA3 1.0 g benzoic acid MAS3 87.2 g MA3 11.5 g MPEG500 monophosphate MAS4 89.8 g MA3 10.4 g MPEG500 monosuccinate MAS5 85.1 g MA3 0.5 g of lactic acid MAS6 95.1 g MA78 5.6 g tall oil fatty acid MAS7 94.8 g MA78 2.3 g benzoic acid MAS8 95.2 g MA78 11.2 g MPEG500 monophosphate MAS9 95.0 g MA78 12.3 g MPEG500 monosuccinate MAS10 95.6 g MA78 1.6 g of lactic acid

Performance Testing

[0292] Use of the inventive reaction products containing urethane and urea groups, comprising at least one species of the general formula (I), as wetting and dispersing additives for production of pigment concentrates and use thereof in paint systems.

Starting Materials

[0293]

TABLE-US-00007 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 70 polyamidoamine, manufacturer: Huntsman Joncryl 500 hydroxy-functional acrylic resin, manufacturer: BASF Laropal A 81 aldehyde resin, manufacturer: BASF Dynapol LH 830 (60%) polyester resin in solvent naphtha and butylglycol, manufacturer: Evonik Dynapol 1203 (50%) nonionic protected sulfonic acid catalyst, 50% in xylene, manufacturer: Evonik Cymel 303 amino crosslinker, manufacturer: Allnex Nacure 2500 p-toluenesulfonic acid, manufacturer: King Industries DIDP diisodecyl phthalate MAK methyl amyl ketone, manufacturer: Eastman Dowanol PMA propylene glycol methyl ether acetate, manufacturer: Dow Chemicals Dowanol PM propylene glycol methyl ether, manufacturer: Dow Chemicals Starsol (DBE) dibasic ester, manufacturer: DuPont butyldiglycol acetate butyldiglycol acetate, manufacturer: BASF Solvesso 150ND aromatic hydrocarbons, 180-193 C. fraction, manufacturer: ExxonMobil Aerosil R972 hydrophobized fumed silica, manufacturer: Evonik Raven 5000 Ultra III carbon black pigment for high jetness, manufacturer: Birla Carbon Paliogen Red L3880 HD perylene red pigment, manufacturer: BASF Hostaperm RL NF violet pigment, manufacturer: Clariant InkJet Margenta E02 pigment for inkjet inks, manufacturer: Clariant Novoperm Yellow P-M3R isoindoline pigment, manufacturer: Clariant Nipex 160 IQ gas black with primary particle size 20 nm, 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 Pink E quinacridone red (P.R. 122), manufacturer: Clariant Heliogen Green L8735 phthalocyanine-copper, halogenated (P.G. 7), manufacturer: BASF Colour Black FW 200 carbon black pigment (P. Bk. 7), manufacturer: Orion Special black 100 oxidized furnace black, manufacturer: Orion Engineered Carbons Tiona 696 TiO.sub.2 pigment, manufacturer: Cristal BYK 325 substrate wetting agent, manufacturer: BYK-Chemie BYK 310 substrate wetting agent, manufacturer: BYK-Chemie BYK 306 substrate wetting agent, manufacturer: BYK-Chemie BYK-358N leveling agent, manufacturer: BYK- Chemie BYK-057 defoamer additive, manufacturer: BYK- Chemie DISPERBYK 170 dispersant, manufacturer: BYK-Chemie

Procedures

Production of the TPA Pigment Dispersion

[0294] 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)

[0295]

TABLE-US-00008 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%/50%) 4.2/8.4 2.0/4.0 2.0/4.0 n-Butanol 5.0 5.0 5.0 PMA by solids content of the 11.0/9.0 14.0/12.0 dispersing additive (100%/50%) Butyl acetate by solids content of the 10.8/6.6 dispersing additive (100%/50%) Total pigment content (%) 12 16 10 Dispersant (% s.o.p.) 70 25 40

Grinding Conditions:

[0296] Equipment: Lau Disperser DAS 200

[0297] Dispersing time: 300 min, cooling power at level 3

[0298] Ratio of millbase to glass beads (diameter 1 mm): 1:1 (parts by weight)

Assessment of Millbase Viscosity of the TPA Dispersions

[0299] The millbase viscosity of the TPA dispersions was determined with a Rheological Stresstech Rheometer (plate/cone, 25 mm, 1) at 23 C.

Millbase Viscosities

[0300]

TABLE-US-00009 TPA 1 (black) TPA 2 (red) TPA 3 (violet) Viscosity in mPa * s 1/s 10/s 100/s 1/s 10/s 100/s 1/s 10/s 100/s MA56* 45.890 7.727 1.828 15.370 2.876 0.814 42.110 4.786 1.085 MA57* 48.380 7.022 1.663 15.440 2.879 0.864 38.460 4.680 1.005 MA58* 51.610 7.534 1.774 22.470 3.808 1.011 57.960 7.762 1.432 MA22 3.326 2.455 1.080 4.786 1.497 0.644 41.590 5.476 1.129 MA59 15.180 2.409 0.834 3.727 0.942 0.431 24.370 3.621 0.732 MA19 1.778 0.759 0.487 7.213 1.536 0.575 26.730 2.820 0.705 *not in accordance with the invention

[0301] The inventive dispersing additives MA19, MA22 and MA59 have a significant viscosity-reducing effect compared to the prior art MA56* to MA58* in TPA dispersions of 3 different pigments, which is manifested even at low shear rates.

Production of the TPA-Based Letdown System

[0302] 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)

[0303]

TABLE-US-00010 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

[0304] The TPA letdown system and the TPA-based pigment dispersion were weighed into a PE cup and mixed by 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)

[0305]

TABLE-US-00011 TPA-B1 TPA-B2 TPA letdown system 27.0 26.0 TPA 1 (red) 3.0 TPA 2 (violet) 4.0 Pigment content (%) 1.6 1.3

Application and Evaluation of the Pigmented TPA Letdown Systems

[0306] 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-00012 TPA-B1 (red) Masstone Masstone Masstone 100 m 100 m 100 m PE film Dispersing additive PE film PE film Transparency/ in the millbase Haze Gloss 20 color intensity MAQ5* 87 60 5 MA55* 47 67 4 MA58* 20 73 4 MA22 11 78 2 MA59 18 77 1-2 MA47 12 78 2 TPA-B2 (violet) Masstone Masstone Masstone 100 m 100 m 50 m PE film Dispersing additive PE film PE film Transparency/ in the millbase Haze Gloss 20 color intensity MAQ5* 131 52 5 MA55* 50 71 4 MA22 38 74 3 MA59 36 75 1-2 MA47 45 72 3 *not in accordance with the invention

[0307] The inventive dispersing additives MA22, MA59 and MA47 exhibit lower haze, better gloss values and higher transparency and color intensity compared to the prior art MAQ5*, MA55* and MA58* for TPA-based varnish systems.

Production of the Laropal A81 Pigment Dispersion

[0308] 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 g)

[0309]

TABLE-US-00013 LA 1 LA 2 LA 3 LA 4 (black) (pink) (blue) (red) Laropal A 81 (60% in PMA) 8.7 20.4 21.9 9.7 Color Black FW 200 4.0 Hostaperm Pink E 7.0 Heliogen Blue 7101F 7.5 Bayferrox Red 130M 25.0 Dispersing additive 2.8/5.6 1.8/3.6 1.9/3.8 2.5/5.0 (100%/50%) PMA 34.6 20.9 18.8 12.8 Total pigment content (%) 8 14 15 50 Dispersing additive 70 25 25 5 (% s.o.p.)

Grinding Conditions:

[0310] Equipment: Lau Disperser DAS 200

[0311] Grinding time: 300 min, cooling power at level 3

[0312] Ratio of millbase to glass beads (diameter 1 mm): 1:1 (parts by weight)

Assessment of the Millbase Viscosity and Turbidity of the Laropal A81 Dispersions

[0313] 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

[0314]

TABLE-US-00014 LA 1 (black) LA 2 (pink) LA 3 (blue) Viscosity in mPa * s Viscosity in mPa * s Viscosity in mPa * s 1/s 10/s 100/s 1/s 10/s 100/s 1/s 10/s 100/s MA54* 44 13 10 34870 3934 794 9457 1017 214 MA57* 185 86 34 28460 3656 939 10450 1474 228 MA58* 232 25 9 33660 3399 995 10720 815 247 MA22 27 19 15 20530 2716 491 5370 745 181 MA59 60 10 7 6238 962 230 3413 537 142 MA35 47 13 9 23100 2782 619 1345 379 96 *not in accordance with the invention

[0315] The inventive dispersing additives MA22, MA35 and MA59 have a significant viscosity-reducing effect compared to the prior art MA54*, MA57* and MA58* in Laropal A81 dispersions of 3 different pigments, which is manifested even at low shear rates.

Production of the Nitrocellulose-Based Clearcoat NC1

[0316] 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 Nitrocellulose-Based Clearcoat NC1 (Figures in g)

[0317]

TABLE-US-00015 Nitrocellulose-based Weight clearcoat NC1 in g Vialkyd AC 433 75% 167.0 NC chips E 510 122.0 DIBP 8.0 Ethyl acetate 154.0 Toluene 154.0 Isopropanol 86.0 Butyl acetate 267.0 Xylene 40.0 BYK-306 2.0

Production of the Baking Varnish JC1

[0318] 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)

[0319]

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 the 2-Component Epoxy Varnish 2KE1

[0320] The epoxy component and the amine component of the 2-component varnish are weighed out separately in a 2.5 L PE bucket and in an 800 mL PE beaker respectively, and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.

Composition of the 2-Component Epoxy Varnish 2KE1 (Figures in g)

[0321]

TABLE-US-00017 2-component epoxy varnish 2KE1 Weight in g Epoxy component Epikote 1001 75% 600.0 Xylene 170.0 Dowanol PM 128.0 Butanol 100.0 BYK-325 2.0 Amine component Aradur 115 X 70 355.0 Xylene 60.0 Dowanol PM 40.0 Butanol 45.0

Production of Various Varnishes Based on the Laropal A81 Pigment Dispersions

[0322] The Laropal A81-based pigment dispersions and the respective clearcoats were weighed into a PE cup and mixed by hand with a spatula. In the case of the 2-component epoxy varnish, the pigment dispersion was incorporated into the epoxy component prior to the amine component. Subsequently, all pigmented varnishes were homogenized in an ANDALOK shaker for 10 min.

Composition of the Pigmented NC1-B3 (Blue) Letdown System (Figures in g)

[0323]

TABLE-US-00018 NC1-B3 (blue) NC1 16.0 LA 3 (blue) 4.0 Pigment content 3.0 (%)

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

[0324]

TABLE-US-00019 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 (%)

Composition of the Pigmented 2KE1 Letdown Systems (Figures in g)

[0325]

TABLE-US-00020 2KE1-B1 2KE1-B4 (black) (red) 2KE1 epoxy 12.0 12.5 component LA 1 (black) 2.0 LA 4 (red) 1.2 2KE1 amine 6.0 6.3 component Pigment content (%) 0.8 3.0
Application and Evaluation of the Pigmented Nitrocellulose Varnish NC1-B3 (blue)

[0326] The pigmented nitrocellulose varnish NC1-B3 (blue) was bar-coated onto PE film (50 m) and dried at 22 C. for 24 h. Then the optical transparency and color intensity through the drawdowns onto PE film was assessed using grades 1 (excellent) to 5 (unacceptable). The colorimetric assessment of the drawdowns was conducted with a BYK-Gardner color guide D65/10 in the CIELab color space (L, a, b).

TABLE-US-00021 L 100 = white a = greenish b = bluish L 0 = black +a = reddish +b = yellowish

Comparison of the NC-Based Blue Drawdowns NC1-B3 (Blue)

[0327]

TABLE-US-00022 Transparency/ Synthesis name color intensity L a b MAQ5* 5 41.0 33.5 42.7 MA54* 2.5 37.4 30.0 42.3 MA56* 2.5 36.8 29.6 42.1 MA57* 3 36.8 29.6 42.0 MA58* 3 36.7 29.5 42.0 MA22 1.5 37.3 28.3 42.8 MA59 1 37.6 28.4 43.1 MA47 1.5 36.3 28.4 42.8

[0328] It should be particularly emphasized here that smaller a values in terms of magnitude indicate better dispersion of the blue pigment, and negative b values that are larger in terms of magnitude point to a deeper blue impression. This trend is shown by inventive examples MA22, MA59 and MA47 compared to the prior art.

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

[0329] 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)

[0330]

TABLE-US-00023 Synthesis Gloss Transparency/ name 20 Haze color intensity MAQ5* 105 14 3 MA54* 106 11 4 MA55* 106 12 2 MA56* 105 10 5 MA57* 103 24 3.5 MA22 106 10 1 MA59 105 14 1 MA19 106 10 1 MA47 106 10 1 MA35 106 10 1

[0331] Comparison of the Pink Baking Varnishes JC1-B2 (Pink)

TABLE-US-00024 Synthesis Gloss Transparency/ name 20 color intensity MAQ5* 111 5 MA55* 113 4 MA57* 113 4 MA58* 113 4 MA22 114 3 MA59 117 1.5 MA35 114 3

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

[0332]

TABLE-US-00025 Synthesis Gloss Transparency/ name 20 Haze color intensity MAQ5* 107 31 3.5 MA54* 115 21 4 MA56* 115 21 4 MA57* 112 38 3 MA58* 114 27 3.5 MA22 119 16 2 MA59 118 18 1 MA47 117 18 2

Application and Evaluation of the Pigmented 2-Component Epoxy Varnishes 2KE1-B1 (Black) and 2KE1-B4 (Red)

[0333] The pigmented 2-component epoxy varnish 2KE1-B1 was bar-coated onto PE film (50 m) and dried at 22 C. for 24 h. The formulation 2KE1-B4 was poured onto a PE film and then likewise dried at 22 C. for 24 h. 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 2-Component Epoxy Varnishes 2KE1-B1 (Black)

[0334]

TABLE-US-00026 Gloss Transparency/ Synthesis name 20 Haze color intensity MA54* 101 13.8 4 MA55* 102 10 3.5 MA56* 101 10.9 3 MA57* 100 12.6 3 MA58* 100 13 3 MA22 104 12.6 2 MA59 106 10 2 MA19 102 10 2

Comparison of the Red 2-Component Epoxy Varnishes 2KE1-B4 (Red)

[0335]

TABLE-US-00027 Gloss Transparency/ Synthesis name 20 Haze color intensity MAQ5* 101 15.2 3 MA54* 101 16.4 3.5 MA55* 101 11.9 4 MA57* 100 19.6 3 MA22 102 10 2.5 MA59 101 13.8 2.5 MA19 101 15.2 2 MA35 102 10 3
Use Example for the Dispersing Additives of the Invention in Polyester Baking Varnishes with Organic and Inorganic Pigments

Production of the Red Pigment Concentrates PKR1 to PKR5

[0336] The components of the pigment concentrates PKR1 to PKR5 based on the inorganic red pigment BAYFERROX red 130M were each weighed into a PE cup and dispersed by means of a Dispermat CV with a toothed disk at a peripheral speed of 18 m/s at 40 C. for 30 min.

Composition of the Red Pigment Concentrates

[0337]

TABLE-US-00028 PKR1 PKR2 PKR3 PKR4 PKR5 Dynapol LH 830 (60%) 20.0 20.0 20.0 20.0 20.0 Methoxypropyl acetate 3.5 7.2 7.2 7.2 7.2 DISPERBYK-170* (30%) 15.0 MAS6 (40%) 11.3 MAS8 (40%) 11.3 MAS9 (40%) 11.3 MAQ5* (40%) 11.3 Starsol (DBE) 1.0 1.0 1.0 1.0 1.0 Aerosil R972 0.5 0.5 0.5 0.5 0.5 Bayferrox red 130M 60.0 60.0 60.0 60.0 60.0 100.0 100.0 100.0 100.0 100.0

Production of the Green Pigment Concentrates PKG1 to PKG5

[0338] The components of the pigment concentrates PKG1 to PKG5 based on Heliogen Green L8735 were each weighed into a PE cup and dispersed by means of a Dispermat CV with a toothed disk at a peripheral speed of 23 m/s at 40 C. for 40 min.

Composition of the Green Pigment Concentrates

[0339]

TABLE-US-00029 PKG1 PKG2 PKG3 PKG4 PKG5 Dynapol LH 830 (60%) 56.0 56.0 56.0 56.0 56.0 Methoxypropyl acetate 5.0 7.6 7.6 7.6 7.6 DISPERBYK-170* (30%) 10.4 MAS6 (40%) 7.8 MAS8 (40%) 7.8 MAS9 (40%) 7.8 MAQ5* (40%) 7.8 Starsol (DBE) 13.0 13.0 13.0 13.0 13.0 Heliogen Green L8735 15.6 15.6 15.6 15.6 15.6 100.0 100.0 100.0 100.0 100.0
Production of the black pigment concentrates PKS1 to PKS5

[0340] The components of the pigment concentrates PKS1 to PKS5 based on Special black 100 were each weighed into a PE cup and dispersed by means of a Dispermat CV with a toothed disk at a peripheral speed of 23 m/s at 40 C. for 60 min. Subsequently, the black pigment dispersions were homogenized with 11.7 g of Dynapol LH 830 (60%) and 5.0 g of butyldiglycol acetate to give the finished pigment concentrates.

Composition of the Black Pigment Concentrates

[0341]

TABLE-US-00030 PKS1 PKS2 PKS3 PKS4 PKS5 Dynapol LH 830 (60%) 44.1 44.1 44.1 44.1 44.1 Methoxypropyl acetate 5.0 8.0 8.0 8.0 8.0 DISPERBYK-170* (30%) 12.0 MAS6 (40%) 9.0 MAS8 (40%) 9.0 MAS9 (40%) 9.0 MAQ5* (40%) 9.0 Starsol (DBE) 10.2 10.2 10.2 10.2 10.2 Special black 100 12.0 12.0 12.0 12.0 12.0 Dispersion: Dispermat CV, 23 m/s, 60 minutes, 40 C. Dynapol LH 830 (60%) 11.7 11.7 11.7 11.7 11.7 butyldiglycol acetate 5.0 5.0 5.0 5.0 5.0 100.0 100.0 100.0 100.0 100.0

Measurement of Viscosity of the Pigment Concentrates

[0342] The pigment concentrates were analyzed by means of a rotary viscometer (Stress Tech Instrument, cone-plate geometry, cone diameter 2.5 cm, cone angle 1, temperature 21 C.) at various shear rates (1 s.sup.1, 10 s.sup.1, 100 s.sup.1).

Measurement of Viscosity of Pigment Concentrates PKR1 to PKR5 Based on Bayferrox Red 130M

[0343]

TABLE-US-00031 Viscosity Viscosity Viscosity [Pa .Math. s] [Pa .Math. s] [Pa .Math. s] at 1 s.sup.1 at 10 s.sup.1 at 100 s.sup.1 PKR1 (DISPERBYK-170*) 21.02 4.98 3.86 PKR2 (MAS6) 15.77 4.21 3.22 PKR3 (MAS8) 10.70 3.11 1.68 PKR4 (MAS9) 11.81 3.61 2.13 PKR5 (MAQ5*) 19.39 4.77 3.71

Measurement of Viscosity of Pigment Concentrates PKG1 to PKG5 Based on Heliogen Green L8735

[0344]

TABLE-US-00032 Viscosity Viscosity Viscosity [Pa .Math. s] [Pa .Math. s] [Pa .Math. s] at 1 s.sup.1 at 10 s.sup.1 at 100 s.sup.1 PKG1 (DISPERBYK-170*) 14.72 3.03 1.21 PKG2 (MAS6) 9.23 2.47 1.11 PKG3 (MAS8) 7.65 2.19 0.97 PKG4 (MAS9) 11.54 2.89 1.19 PKG5 (MAQ5*) 18.21 4.84 1.76

Measurement of Viscosity of Pigment Concentrates PKS1 to PKS5 Based on Special Black 100

[0345]

TABLE-US-00033 Viscosity Viscosity Viscosity [Pa .Math. s] [Pa .Math. s] [Pa .Math. s] at 1 s.sup.1 at 10 s.sup.1 at 100 s.sup.1 PKS1 (DISPERBYK-170*) 1.36 0.74 0.59 PKS2 (MAS6) 1.08 0.54 0.46 PKS3 (MAS8) 0.71 0.51 0.42 PKS4 (MAS9) 0.88 0.52 0.45 PKS5 (MAQ5*) 1.29 0.73 0.60

Production of the White Drawdown Systems ASW1 to ASW5

[0346] For the letdown of the pigment concentrates PKR1 to PKR5, PKG1 to PKG5 and PKS1 to PKS5 produced, a formulation based on DYNAPOL LH 830 as white base pigmented with Tiona 696 was chosen.

[0347] The components of letdown system part 1 were each weighed into large PE beakers and dispersed by means of a Dispermat CV with a toothed disk at a peripheral speed of 18 m/s at 40 C. for 20 min. Subsequently, the white dispersions were homogenized with the part 2 components to give the finished letdown systems.

TABLE-US-00034 TABLE 1 Letdown system (DYNAPOL LH 830/CYMEL 303 white base) ASW1 ASW2 ASW3 ASW4 ASW5 Part 1 Dynapol LH 830 (60%) 132.0 132.0 132.0 132.0 132.0 Methoxypropyl acetate 18.8 20.3 20.3 20.3 20.3 DISPERBYK-170* (30%) 6.0 MAS6 (40%) 4.5 MAS8 (40%) 4.5 MAS9 (40%) 4.5 MAQ5* (40%) 4.5 Aerosil R972 1.2 1.2 1.2 1.2 1.2 Tiona 696 120.0 120.0 120.0 120.0 120.0 Dispersion: Dispermat CV, 18 m/s, 20 minutes, 40 C. Part 2 Dynapol LH 830 (60%) 68.0 68.0 68.0 68.0 68.0 Cymel 303 (>98%) 30.0 30.0 30.0 30.0 30.0 Dynapol 1203 (50%) 15.2 15.2 15.2 15.2 15.2 BYK-358N 2.0 2.0 2.0 2.0 2.0 BYK-057 0.8 0.8 0.8 0.8 0.8 Solvesso 150ND 6.0 6.0 6.0 6.0 6.0 400.0 400.0 400.0 400.0 400.0

Production of the Final Test Formulations Based on Dynapol LH 830

[0348] The pigment concentrates PKR1, PKG1 and PKS1 were each formulated with the corresponding white base ASW1 using the same dispersing additive. The final test systems TSRW1 (PKR1+ASW1), TSGW1 (PKG1+ASW1) and TSSW1 (PKS1+ASW1) contain, for example, DISPERBYK-170 only as prior art dispersing additive. The same applies analogously to the other inventive examples in the table below.

Naming of the Test Formulations Based on Dynapol LH 830

[0349]

TABLE-US-00035 Test system based on white base and pigment concentrate TSRW1 ASW1 PKR1 TSGW1 ASW1 PKG1 TSSW1 ASW1 PKS1 TSRW2 ASW2 PKR2 TSGW2 ASW2 PKG2 TSSW2 ASW2 PKS2 TSRW3 ASW3 PKR3 TSGW3 ASW3 PKG3 TSSW3 ASW3 PKS3 TSRW4 ASW4 PKR4 TSGW4 ASW4 PKG4 TSSW4 ASW4 PKS4 TSRW5 ASW5 PKR5 TSGW5 ASW5 PKG5 TSSW5 ASW5 PKS5

Formulation of the Test Systems Based on DISPERBYK 170 (Analogously for all Other Additives)

[0350]

TABLE-US-00036 TSRW1 TSGW1 TSSW1 ASW1 white base 50.0 54.2 53.0 PKR1 pigment concentrate 10.0 (based on Bayferrox red 130M) PKG1 pigment concentrate 5.8 (based on Heliogen Green L8735) PKS1 pigment concentrate 7.0 (based on Special black 100) 60.0 60.0 60.0

[0351] The final test systems are formulated by weighing white base and pigment concentrate in each case together into a sealable vessel. The mixture is homogenized in a Skandex shaker for ten minutes. Subsequently, the varnishes are applied to aluminum sheet by means of a spiral coating bar in a wet film layer thickness of 80 m. In a coil oven, the varnishes are baked at 320 C. for 33 seconds with peak metal temperature 232 C. A dry layer thickness of about 18 m is achieved.

[0352] A rubout test is also conducted in order to determine the difference in shade (E) between rubbed and unrubbed surface within the rub. For this purpose, a portion of the final test systems that have been homogenized on the Skandex shaker are applied again to aluminum sheet by means of a spiral coating bar in a wet film layer thickness of 80 m. Subsequently, a portion of the varnish applied is rubbed (sheared) in horizontal direction in each case using a finger. Subsequently, the varnishes are baked in a coil oven at 320 C. for 33 seconds with peak metal temperature 232 C. After cooling, the difference in shade (E) between rubbed (sheared) and unrubbed surface is measured by means of colorimetry with a BYK spectro-guide sphere. A small difference in shade AE indicates that both pigments (white and the respective shade) in each case are equally stabilized and no floating is observed.

Difference in Shade (E) of the Final Test Systems (Rubout Test)

[0353]

TABLE-US-00037 E TSRW1-5 E TSGW1-5 E TSSW1-5 Bayferrox red Heliogen Green Special black 130M L8735 100 DISPERBYK-170* 3.6 0.9 1.4 (30%) MAS6 (40%) 1.8 0.5 1.1 MAS8 (40%) 1.5 0.7 0.9 MAS9 (40%) 1.4 0.7 0.8 MAQ5* (40%) 4.0 0.9 2.5

Measurement of Gloss in the Final Test Systems

[0354] For the test systems that have been applied to aluminum sheets and baked under coil conditions, gloss is measured at an angle of 20 with a BYK micro haze plus.

Measurement of Gloss of the Final Test Systems at a 20 Angle

[0355]

TABLE-US-00038 TSRW1-5 TSGW1-5 TSSW1-5 Bayferrox red Heliogen Green Special black 130M L8735 100 DISPERBYK-170* 55 79 80 (30%) MAS6 (40%) 76 84 86 MAS8 (40%) 75 92 85 MAS9 (40%) 72 88 86 MAQ5* (40%) 65 66 80