Solid amine adducts

Abstract

The invention relates to a process for preparing an amine adduct, in which a polyamine component (A), a polyester component (B) and a hydrocarbon component (C) are reacted. The amine adduct is of particularly good suitability as a wetting agent and dispersant, especially for coatings and plastics applications.

Claims

1. A process for preparing an amine adduct, in which a polyamine component (A), a polyester component (B) and a hydrocarbon component (C) are reacted in weight ratios of (A):(B)=1:1000 to 1:1 (A):(C)=1:100 to 100:1 and (B):(C)=2:1 to 50:1 in that according to reaction variant i) first a reaction intermediate (A-B) is produced from the polyamine component (A) and the polyester component (B), which is subsequently reacted with the hydrocarbon component (C) or according to reaction variant ii) first a reaction intermediate (A-C) is formed from the polyamine component (A) and the hydrocarbon component (C) and this is subsequently reacted with the polyester component (B) or according to reaction variant iii) the polyamine component (A) is reacted simultaneously with the polyester component (B) and the hydrocarbon component (C) wherein the polyamine component (A) is present in the form of at least one organic polyamine compound (A), which in each case has at least three amino groups (A+) selected from primary and secondary amino groups, in each case reactive with both the polyester component (B) and the hydrocarbon component (C), the polyester component (B) is present in the form of at least one polyester compound (B), which in each case contains no primary amino groups and no secondary amino groups, in each case has at least three ester groups, and in each case contains a coupling group (B+) present as a carboxyl group or carboxylic acid anhydride group, reactive with primary and/or secondary amino groups, and the hydrocarbon component (C) is present in the form of at least one branched or unbranched, saturated or unsaturated hydrocarbon compound (C) each having a linking group (C+), in each case (C) having no primary amino groups, in each case having no secondary amino groups, in each case having no carboxyl groups and in each case having no carboxylic acid anhydride groups, and in each case (C) having an overall ratio of carbon atoms to hetero atoms of at least 2:1, wherein the hetero atoms are selected from the group of elements consisting of at least one of O, N, P, S, and Si, wherein the linking groups (C+) in each case have the characteristic of reacting with primary amino groups with formation of secondary amino groups and/or with secondary amino groups with formation of tertiary amino groups, and also in each case are present in the form of an epoxy function of formula (I) ##STR00002## with R.sup.1, R.sup.2, and R.sup.3 in each case the same or different and each independently of one another is represented by H or by a saturated, branched or unbranched C.sub.1-C.sub.12 hydrocarbon moiety, wherein the amine adduct is obtained in solid form at room temperature in each case and has a melting range of 30 to 200 C. and the reaction of the polyamine component (A), the polyester component (B) and the hydrocarbon component (C) takes place in that for each weight unit of polyester component (B), a maximum of 0.8 weight units of other components that do not belong to any of the components (A), (B) or (C) are optionally present.

2. The process according to claim 1, wherein the reaction of (A), (B) and (C) is performed in weight ratios of (A):(B)=1:100 to 1:4 and (A):(C)=1:10 to 10:1.

3. The process according to claim 1, wherein the reaction of the polyamine component (A), the polyester component (B) and the hydrocarbon component (C) takes place in such a manner that for each weight unit of polyester component (B), a maximum of 0.2 units by weight of other components are optionally present, which do not belong to any of the components (A), (B) or (C).

4. The process according to claim 1, wherein the reaction of the polyamine component (A), the polyester component (B) and the hydrocarbon component (C) takes place in the absence of organic solvents.

5. The process according to claim 1, wherein at least 50% by weight of the polyester compounds (B) used is present in the form of linear, monocarboxy-functional caprolactone polyesters.

6. The process according to claim 5, wherein the at least 50% by weight of the polyester compounds (B) used is present in the form of linear, monocarboxy-functional caprolactone polyesters, which in each case have a weight-average molecular weight of 500 to 10,000.

7. The process according to claim 1, wherein the hydrocarbon component (C) contains at least 30% by weight of unsaturated C.sub.6-C.sub.50 hydrocarbon compounds (C), which in each case contain at least one aryl and/or one alkylaryl group.

8. The process according to claim 1, wherein the hydrocarbon component (C) contains at least 30% by weight of C.sub.10-C.sub.70 hydrocarbon compounds (C), which in each case contain at least one branched alkyl and/or one branched alkenyl moiety.

9. The process according to claim 1, wherein components (A), (B) and (C) are used respectively in stoichiometric ratios such that altogether at least 50 mol % of the totality of the reactive amino groups (A+) of the polyamine compounds (A) used are reacted with the polyester compounds (B) and/or with the hydrocarbon compounds (C).

10. The process according to claim 1, wherein the polyester component (B) and the hydrocarbon component (C) do not react with one another under the reaction conditions of the reaction.

11. The process according to claim 1, wherein the reaction of (A), (B) and (C) is performed in weight ratios of (A):(B)=1:25 to 1:7 and (A):(C)=1:2 to 2:1.

12. The process according to claim 1, wherein 70 to 100% by weight of the polyester compounds (B) used is present in the form of linear, monocarboxy-functional caprolactone polyesters.

13. The process according to claim 12, wherein the 70 to 100% by weight of the polyester compounds (B) used is present in the form of linear, monocarboxy-functional caprolactone polyesters, which in each case have a weight-average molecular weight of 500 to 10,000.

14. The process according to claim 1, wherein the hydrocarbon component (C) contains 50 to 100% by weight of unsaturated C.sub.6-C.sub.50 hydrocarbon compounds (C), which in each case contain at least one aryl and/or one alkylaryl group.

15. The process according to claim 1, wherein the hydrocarbon component (C) contains 50 to 100% by weight of C.sub.10-C.sub.70 hydrocarbon compounds (C), which in each case contain at least one branched alkyl and/or one branched alkenyl moiety.

16. The process according to claim 1, wherein components (A), (B) and (C) are used respectively in stoichiometric ratios such that altogether 70 to 100 mol % of the totality of the reactive amino groups (A+) of the polyamine compounds (A) used are reacted with the polyester compounds (B) and/or with the hydrocarbon compounds (C).

Description

PREPARATION PROCEDURES

(1) a) General Instructions for Producing Polyester Components from Lactones:

(2) In a four-necked flask with agitator, thermometer, reflux cooler and nitrogen inlet tube, substances R1a) to T1c) are placed and heated to 100 C. with agitation under N2 gas. Then the catalyst is added and heating under N2 gas is continued to T1. Agitation is continued at this temperature until the FK>99% is achieved.

(3) b) General Instructions for Producing Polyester Components from Hydroxycarboxylic Acids:

(4) In a four-necked flask equipped with agitator, thermometer, reflux cooler and nitrogen inlet tube, substances R1a) to R1c) are placed and heated to 100 C. with agitation under N2 gas.

(5) At 100 C. the catalyst is added and a distillation trap is attached.

(6) Heating is continued, and the water released is removed by the distillation trap.

(7) The reaction temperature is adapted to the water released and goes to T1.

(8) When no further water is released, the reaction is complete.

(9) c) General Instructions for Producing Polyester Components from Diols and Dicarboxylic Acids:

(10) In a four-necked flask equipped with agitator, thermometer, reflux cooler, distillation trap and nitrogen inlet tube, substances R1a) to R1c) are weighed in together with the catalyst and heated under N2 gas. The water of reaction produced is collected via the distillation trap.

(11) The reaction temperature is adapted to the water released and goes to T1. When no further water is released, the reaction is complete.

(12) d) General Instructions for Producing Intermediates:

(13) Reaction of Polyesters with Amines with Splitting Off of Water:

(14) In a four-necked flask equipped with agitator, thermometer, reflux cooler, distillation trap and nitrogen inlet tube, substances R2a) and R2b) are placed and heated under N2 gas. The water of reaction produced is collected via the distillation trap. The reaction temperature is adapted to the water released and goes to T1. When no further water is released, the reaction is complete.

(15) e) General Instructions for Producing Intermediates:

(16) Reaction of Polyesters with Amines with Splitting Off of Water:

(17) In a four-necked flask equipped with agitator, thermometer, reflux cooler and nitrogen inlet tube, reaction component R2a) is placed and heated under N2 gas to reaction temperature T1. Reaction component R2b) is added during the preset time X1. The consecutive reaction period is 1 h at T1.

(18) f) General Production Instructions According to Reaction Variant i):

(19) In a four-necked flask equipped with agitator, thermometer, reflux cooler and nitrogen inlet tube, reaction component R3a) is placed and heated under N2 gas to T2. The consecutive reaction period is over time X2 at T2.

(20) Then reaction component 3b) is added. Agitation is performed for time X1 at T1. Then reaction component 3c) is added and heating is performed under N2 gas to T2. The consecutive reaction period is over period X2 at T2. In the case of a further reaction with a raw material 3d), this is added 1 h after 3c) and the consecutive reaction period is added appropriately.

(21) g) General Production Instructions According to Reaction Variant i) with Intermediate Product:

(22) In a four-necked flask equipped with agitator, thermometer, reflux cooler and nitrogen inlet tube, reaction component 3a) is placed and heated to 100 C. with agitation under N2 gas.

(23) Then reaction component 3b) is added at 100 C., then heating to T1 and agitation for time X1 is performed.

(24) h) General Production Instructions According to Reaction Variant ii):

(25) In a four-necked flask equipped with agitator, thermometer, reflux cooler and nitrogen inlet tube, reaction component 3a) is placed and heated to T1. Component 3b) is added in X1. After addition, 0.5 h of consecutive reaction takes place at T1. Then reaction component 3c) is added, and heating is performed under N2 gas to T2. This is followed by a consecutive reaction time X2 at T2.

(26) i) General Production Instructions According to Reaction Variant (ii) with Intermediate Product:

(27) In a four-necked flask equipped with agitator, thermometer, reflux cooler and nitrogen inlet tube, reaction component 3a) is placed and heated to T1. Component 3b) is added in time period X1. Then heating to T2 is performed under N2 gas. The consecutive reaction time at T2 is then X2.

(28) j) General Production Instructions According to Reaction Variant iii):

(29) In a four-necked flask equipped with agitator, thermometer, reflux cooler and nitrogen inlet tube, reaction component 3a) is placed and heated to T1 under N2 gas. Then reaction components 3b) and 3c) are added separately each in X1. Then heating to T2 is performed and the mixture is heated at T2 for the time period X2.

(30) k) General Production Instructions According to Reaction Variant iv):

(31) In a four-necked flask equipped with agitator, thermometer, reflux cooler and nitrogen inlet tube, reaction components 3a) and b) are placed and heated to T1 under N2 gas.

(32) Component 3c) is added in X1. Then 0.5 h of consecutive reaction takes place at T1. Then reaction component 3d) is added and heating under N2 gas is continued further to T2. Then consecutive reaction X2 is performed at T2 under N2 gas.

(33) Preparation of a Comparison Example EX1 not According to the Invention:

(34) In a four-necked flask equipped with an agitator, thermometer, reflux cooler and inlet tube, 4.4 parts of hydroxyethylacrylate with 66.00 parts caprolactone and 28.3 parts valerolactone with 0.01% monobutyltin oxide and 0.1% hydroquinone are heated under an air atmosphere and agitation to 120 C. to obtain a polyester with Mn 2100. After 12 h at 120 C., cooling to 65 C. is performed. Then 6.91 parts polyethyleneimine, MW 2000, are added. The reactants are then agitated for 2 h at 65 C.

(35) Preparation of a Comparison Example EX2 not According to the Invention, Comparable to E14, but without Component C:

(36) In a four-necked flask equipped with an agitator, thermometer, reflux cooler and inlet tube, 94.3 parts of polyester B10 are placed, heated to 100 C., and 5.7 parts of a polyethyleneimine with MW 2000 are added. Then heating is performed to 140 C. and agitation continued for 2 h at this temperature.

(37) TABLE-US-00001 Table of polyester components Bsp HV R 1a) % R1a) R 1b) % R1b) R 1c) % R1c) Kat % T1 MG B1 a) LS 20.05 CAPA 79.80 ZB 0.15 190.00 1000 B2 a) HSS 22.40 CAPA 77.50 ZB 0.10 190.00 1500 B3 a) LS 14.90 CAPA 85.00 ZB 0.10 190.00 1300 B4 a) RFS 19.90 CAPA 79.80 ZB 0.30 190.00 1500 B5 a) RFS 15.40 CAPA 84.30 ZB 0.30 190.00 2000 B6 a) LS 11.30 CAPA 77.30 VAL 11.30 IPT 0.50 190.00 1770 B7 a) LS 14.00 CAPA 71.70 VAL 14.00 IPT 0.30 190.00 1400 B8 a) LS 19.90 CAPA 59.80 VAL 19.90 IPT 0.40 190.00 1000 B9 a) HSS 32.40 CAPA 67.30 ZB 0.30 190.00 1000 B10 a) LS 9.88 CAPA 90.10 ZB 0.02 190.00 2000 B11 a) LS 13.70 CAPA 85.80 IPT 0.50 190.00 1500 B12 b) RFS 99.00 PTS 1.00 170.00 1500 B13 b) HSS 99.00 PTS 1.00 170.00 1200 B14 b) RFS 49.50 HSS 49.50 PTS 1.00 170.00 3000 B15 c) LS 22.00 BDO 29.50 ADS 48.20 DBS 0.30 160.00 900 B16 c) ADS 62.80 BDO 36.20 PTS 1.00 160.00 3500 B17 c) PSA 66.40 BDO 33.40 DBS 0.20 160.00 1300 B18 a) LS 8.7 Capa 73.8 VAL 17.3 IPT 0.2 160.0 2100 B19 a) LS 11.3 CAPA 88.7 IPT 0.5 190 1770 B20 a) LS 14 CAPA 85.7 IPT 0.3 190 1400 B21 a) LS 19.9 CAPA 79.7 IPT 0.4 190 1000 B22 a) LS 8.7 CAPA 91.1 IPT 0.2 190 2100 Bsp = example; HV = production instructions; KAT = catalyst; T(number) temperature as described in the HV; LS = lauric acid; HSS = hydroxystearic acid, RFS = castor oil fatty acid; CAPA = epsilon-caprolactone; VAL = delta-valerolactone; BDO = butanediol; ADS = adipic acid; ZB = zirconium butylate; PT = isopropyl titanate; PTS = p-toluenesulfonic acid

(38) TABLE-US-00002 Table of intermediate products Bsp HV R 2a) % R2a R 2b % R2b T1 X1 Z1 d) BT2 94.00 TEPA 6.00 160 C. 180 Z2 d) BT2 93.50 DETA 6.50 160 C. 150 Z3 d) BT2 93.90 PEI 300 6.10 160 C. 150 Z4 d) BT3 94.70 TETA 5.30 160 C. 180 Z5 e) PEI 62.30 PGE 37.70 100 150 1200 Z6 e) DETA 28.60 EPN 71.40 100 120 Z7 e) TETA 44.20 EPN 55.80 100 120 Z8 e) PEI 300 61.70 PGE 38.30 100 150 Z9 e) TEPA 60.00 EPN 40.00 100 150 X (number) = reaction time described in the HV; TETA = triethylenetetramine; TEPA = tetraethylenepentamine; DETA = diethylenetetramine; PEI (number) = polyethyleneimine (MW); IPA = n-3-aminopropylimidiazole; EPN = epoxypropylneodecanoate; PGE = phenylglycidyl ether; BA = butyl acrylate.

(39) TABLE-US-00003 Table of end products T1 X1 T2 X2 Bsp HV R 3a) % 3a) R 3b) % 3b) Rc) % R3c) Rd) % R3d) [ C.] [min] [ C.] [min] E1 i) B1 81.70 Z6 18.30 100 20 140 120 E2 i) B2 90.60 Z8 9.40 100 20 140 120 E3 i) B2 94.80 Z7 5.20 100 20 140 120 E4 f) B2 84.50 PEI 1200 7.70 EPN 7.80 100 30 140 180 E5 h) PEI 8.70 EPN 8.90 B3 82.40 100 120 140 180 2000 E6 h) PEI 7.70 EHA 7.80 B4 84.50 100 120 140 120 1200 E7 i) B4 87.00 Z9 13.00 100 20 130 180 E8 i) B5 91.70 Z5 8.30 100 20 130 180 E9 i) B6 88.80 Z9 11.20 100 20 140 120 E10 i) B7 84.60 Z9 15.40 100 20 140 120 E11 h) PEI 8.70 EPN 8.80 B7 82.50 100 120 120 180 1200 E12 h) PEI 6.80 PC 3.4 B8 86.40 CGE 3.4 100 120 140 180 800 E13 i) B9 81.70 Z9 18.30 100 20 140 120 E14 k) B10 60.00 PEI 2000 9.80 PGE 11.60 B10 18.60 100 60 120 180 E15 i) B11 87.00 Z9 13.00 100 20 140 180 E16 h) PEI 5.70 PGE 3.00 B11 91.30 100 120 140 180 2000 E17 i) Z1 92.40 EHA 7.60 80 60 E18 i) Z2 86.00 LA 14.00 80 60 E19 i) Z3 93.30 EPN 6.70 80 60 E20 i) Z4 95.80 MSA 4.20 80 60 E21 j) B10 85.00 DMDPTA 8.10 PGE 6.90 60 60 120 240 E22 f) B14 93.60 PEI 300 3.2 PC 2.0 CGE 1.2 100 30 140 180 E23 f) B16 95.60 DETA 1.7 EHA 2.70 100 30 120 240 E24 f) B17 88.50 DETA 3.9 LA 7.60 100 30 120 240 E25 j) B1 65.80 TETA 9.70 EHA 25.50 100 60 120 240 E26 k) B15 90.30 PEI 300 6.5 EHA 2.30 MSA 1.20 100 30 120 120 E27 f) B18 78.6 PEI 2000 9.7 EHA 11.7 100 30 140 120 i) B19 88.8 Z9 11.2 100 20 140 120 E29 i) B20 84.6 Z9 15.4 100 20 140 120 E30 h) PEI1200 8.7 EPN 8.8 B20 82.5 100 120 120 180 E31 h) PEI800 6.8 PC 3.4 B21 86.4 CGE 3.4 100 120 140 180 E32 f) B22 78.6 PEI2000 9.7 EHA 11.7 100 30 140 120 E33 h) PEI1200 7.70 CGE 7.8 B4 84.50 100 120 140 120 MSA = maleic anhydride; EHA = ethylhexyl acrylate; LA = lauryl acrylate; PC = propylene carbonate, DMDPTA = dirnethyldipropylenetriamine, CGE = o-cresylglycidyl ether All end products listed in the table are solvent-free and solid at 30 C.

(40) Applications Technology Testing

(41) The relevant amine adducts (polymers) are used, among other things, as wetting and dispersing agents for producing pigment concentrates, paint systems and ink jet systems.

(42) Applications Technology Testing in Ink Jet Systems:

(43) Operating Equipment:

(44) Shaker: LAU Paint Shaker DAS H [/A]200-K

(45) Luster/haze measurement: Trigloss, (Byk Gardner) Measurement angle 20

(46) Substances for applications technology testing: Vinnol solution: 75% butylglycol acetate+2-% cyclohexanone+5% Vinnol 15/45; Vinnol 15/45: Copolymer of approx. 85% by weight vinyl chloride and approx. 15% by weight vinyl acetate; manufacturer: Wacker Novoperm P-M3R: P.Y. 139 InkJet Magenta E02: P.R. 122 Type A Irgalite Blue P.B. 15:4, Type B NiPex 90 p.Bk-7, pH=9.0

(47) Method of Operation: For producing the pigment concentrates: weigh items 1-4 into a 100 ml glass flask and mix. Then add 100 g zirconium beads (0.4-0.5 mm). Disperse premixed pigment concentrates for 960 minutes in a vibrating shaker at cooling level 3 Screen pigment concentrate into 50 ml glass bottles. After storage overnight and after storage for one week at 40 C., determine the viscosities using the Stress Tech instrument. The concentrates are applied to PU film with 25 m wet film layer thickness. The color intensity and transparency are evaluated visually on the film; for the luster and haze measurement, the films are placed on black cardboard and measured.

(48) Formulation 1Pigment concentrate based on Novoperm Yellow P-M3R

(49) TABLE-US-00004 Item No. Raw material [g] 1 VINNOL solution 15.0 2 Butylglycol acetate 25.9 3 Additive 2.1 4 Novoperm Yellow P-M3R 7.0 50.0 Additive addition rate [% s.o.p.] 30.0

(50) Formulation 2Pigment concentrate based on Ink Jet Magenta E 02

(51) TABLE-US-00005 Item No. Raw material [g] 1 VINNOL Solution 15.0 2 Butylglycol acetate 25.9 3 Additive 2.1 4 Ink Jet Magenta P-M3R 7.0 50.0 Additive addition rate [% s.o.p.] 30.0

(52) Formulation 3Pigment concentrate based on Irgalite Blue GLVO

(53) TABLE-US-00006 Item No. Raw material [g] 1 VINNOL solution 15.0 2 Butylglycol acetate 27.2 3 Additive 1.8 4 Irgalite Blue GLVO 6.0 50.0 Additive addition rate [% s.o.p.] 30.0

(54) Formulation 4Pigment concentrate based on NiPex 90

(55) TABLE-US-00007 Item No. Raw material [g] 1 VINNOL solution 15.0 2 Butylglycol acetate 26.0 3 Additive 3.0 4 NiPex 90 6.0 50.0 Additive addition rate [% s.o.p.] 50.0

(56) Results:

(57) Color intensity+transparency: 1-5 (1=good, 5=poor)

(58) TABLE-US-00008 Novoperm P-M3R Ink Jet Magenta E02 Visco 1 Visco 1 W W Addi- Visco 40 C. Color = Trans = Visco 40 C. Color = Trans = tive (mPas) (mPas) Luster Haze intensity parency (mPas) (mPas Luster Haze intensity parency EX1* 19 29 89 5 4 418 489 91 4 4 E4 11 14 95 1 1 309 386 97 2 2 E7 16 18 92 2 1 323 396 92 2 2 E19 13 15 95 1 2 311 401 93 2 2 Addi- Visco Visco 1 Color Trans = Visco Visco 1 Color Trans = tive (mPas) W Luster Haze intensity parenz (mPas) W Luster Haze intensity parency EX1* 164 167 92 3 3 525 885 93 31 3 E4 103 135 98 1 1 31 94 99 9 1 E7 142 148 97 1 2 174 324 96 21 2 E19 136 153 98 2 2 145 214 99 99 1 *Not according to invention Visco = viscosity

(59) Conclusion of Tests in Ink-Let Systems:

(60) The particularly good quality of the polymers according to the invention is demonstrated by their low viscosity, color intensity, transparency and good luster.

(61) An additional particular advantage of the polymers consists of the particularly good incorporation in the binder solution.

(62) Applications Technology Testing in Pigment Concentrates:

(63) Working Equipment:

(64) Dispermat CV

(65) Trigloss, (Byk Gardner)

(66) Scandex Vibrating Shaker

(67) Substances for Applications Technology Testing:

(68) TABLE-US-00009 Lamp black FW 200 .fwdarw. PB 7 Laropoal A81 .fwdarw. Aldehyde resin, manufacturer BASF Paraloid DM 66 .fwdarw. Thermoplastic acrylate resin TPA): manufacturer DOW Macrynal SM 510 .fwdarw. Acrylate resin 70% in; manufacturer Cytec Desmodur N75 .fwdarw. Aliphatic isocyanate, 75% in methoxypropyl acetate; manufacturer Bayer Setalux 1756 V V65 .fwdarw. Acrylate resin 65%% in solvent naphtha; manufacturer Nuplex Setamine US 138 0 .fwdarw. Melamine resin 70% in n-butanol, manufacturer Nuplex Epikote 1001 .fwdarw. Epoxy resin 75% in xylene, manufacturer Brenntag Aradur 115 .fwdarw. Polyamidoamine; manufacturer Huntsman Dowanol PMA .fwdarw. Methoxypropyl acetate, manufacturer DOW Dowanol PM .fwdarw. Methoxypropanol, manufacturer DOW Solvesso 100 .fwdarw. Aromatic solvent from Exxon BYK 306/310/325 .fwdarw. Leveler additive, manufacturer BYK

(69) Method of Operation:

(70) Preparation of the Pigment Concentrates: Weigh in the lacquer constituents in the indicated order (stir briefly manually after each addition) Dispermat CV/60 minutes/10,000 rpm (23 m/s) at 40 C. material to be ground/glass beads (0.8-1.2 mm) 1:1 ratio (by weight) Screen out the glass beads after dispersing Visually evaluate the viscosity (after preparation, after 1 day)

(71) Preparation of the Lacquer: Incorporate the pigment concentrates into the different lacquer systems with a Scandex vibrating shaker for 5 min Pour the diluted lacquer onto PE film Make an overall visual evaluation of transparency and optical properties-1-5; (1=good, 5=poor) Measure luster with Trigloss

(72) Formulation of Pigment Concentrate

(73) 12.5% carbon black with 80% additive solid on pigment

(74) TABLE-US-00010 Raw material [g] Laropal A81 60% in methoxypropyl acetate 54.1 Dowanol PMA 23.4 Additive 100% 10.0 Lamp black FW 200 12.5 (pigment/binder ratio 1/3.5) 100.0

(75) Formulation of Pigment Concentrate

(76) 15% carbon black with 60% additive solid on pigment

(77) TABLE-US-00011 Raw material [g] Laropal A81 60% in methoxypropyl acetate 53.1 Dowanol PMA 22.9 Additive 100% 9.0 Lamp black FW 200 15.0 (pigment/binder ratio 1/3.5) 100.0

(78) Formulations of clear lacquer with finalization of the pigment concentrate in clear lacquer

(79) TPA

(80) TABLE-US-00012 Paraloid B66 Paraloid B66 (50% in xylene) 70.0 Diisodecyl phthalate 2.0 Xylene 21.8 Dowanol PMA 6.0 BYK-306 0.2 100.0 Clear lacquer (Paraloid B66) 27.5 Pigment concentrate 2.5 30.0 Incorporation of pigment concentrate on vibrating shaker Xylene 30.0

(81) 2K-PUR

(82) TABLE-US-00013 Macrynal SM 510/Desmodur N Macrynal SM 510 (70% in butyl acetate) 75.0 Dowanol PMA 5.0 Solvesso 100 5.0 Xylene 6.9 Butyl acetate 8.0 BYK-306 0.1 100.0 Hardener solution 2:1 (weight) Desmodur N75 50.0 Butyl acetate 17.5 Solvesso 100 17.5 Dowanol PMA 5.0 Xylene 10.0 BYK-306 0.1 100.0 Clear lacquer (Macrynal SM 510/Desmodur N 20.0 Pigment concentrate 2.0 22.0 Incorporation of pigment concentrate on vibrating shaker Hardener solution 10.0
Acrylate/Melamine System

(83) TABLE-US-00014 Setalux 1756/Setamine US 138 Setalux 1756 VV 65 60.0 Setamine US 138 24.0 Solvesso 100 8.0 Xylene 7.8 BYK-310 0.2 100.0 Clear lacquer (Setalux 1756/Setamine US 138) 25.0 Pigment concentrate 2.0 27.0 Incorporation of pigment concentrate on vibrating shaker Solvesso 100 3.0

(84) After 15 [min] flash-off time, the applied lacquer is baked on for 20 min at 130 C.

(85) 2K Epoxide

(86) TABLE-US-00015 Epikote 1001/Aradur 115 x 70 Epikote 1001 (75% in xylene) 60.0 Xylene 17.0 Dowanol PM 12.8 n-Butanol 10.0 BYK-325 0.2 100.0 Hardener solution 2:1 (weight) Aradur 115 x 70 35.5 Xylene 6.0 Dowanol PM 4.0 n-Butanol 4.5 50.0 Clear lacquer (Epikote 1001/Aradur 115 x 70) 20.0 Pigment concentrate 2.0 22.0 Incorporation of pigment concentrate on vibrating shaker Hardener solution 10.0

(87) Results:

(88) Appearance in lacquer system: 1-5 (1=good, 5-poor)

(89) Viscosity: hv=high-viscosity; mv=medium-viscosity; lv=low viscosity Appear.=appearance

(90) Pigment pastes with 12.5% carbon black and 80% additive solid on pigment

(91) TABLE-US-00016 Visco. Visco. . of of paste on paste disper- after 1 Baking lacquer/ Baking lacquer/ 2K-PUR. SM 2K-PUR/Set. Addi- sion, day, acrylate alkyd 510 1573 2K-epoxy tive visual visual Appear. Luster Appear. Luster Appear. Luster Appear. Luster Appear. Luster EX1* hv very hv 4 78 3 85 5 79 4 84 5 85 floccu- lated EX2* hv hv 4 81 4 83 4 85 3 85 4 82 E2 mv mv 2 89 2 94 1 90 2 91 2 88 E4 mv lv 1 86 1 94 1 89 1 92 2 94 E5 mv mv 1 96 2 89 1 91 2 92 2 98 E8 lv lv 1 92 2 91 1 94 1 89 1 92 E14 very lv lv 1 94 1 95 1 92 1 93 2 89 E27 very lv very lv 1 98 1 96 1 95 1 98 1 95

(92) Pigment pastes with 15% carbon black and 60% additive solid on pigment

(93) TABLE-US-00017 Visco. Visco. of of paste on paste disper- after 1 Baking lacquer/ Baking lacquer/ 2K-PUR. SM 2K-PUR/Set. Addi- sion, day, acrylate alkyd 510 1573 2K-epoxy tive visual visual Appear. Luster Appear. Luster Appear. Luster Appear. Luster Appear. Luster EX1* cannot be cannot be made made EX2* cannot be cannot be made made E2 mv hv 2 87 3 89 3 84 2 90 3 88 E4 lv mv 3 82 2 93 2 87 1 87 2 90 E5 mv mv 2 89 2 91 3 89 2 86 3 86 E8 mv mv 2 86 3 89 2 91 2 89 2 89 E14 lv lv 1 94 2 87 1 92 2 91 3 85 E27 very lv lv 1 96 1 95 1 94 1 94 1 91 *Not according to invention

(94) Conclusions from Tests on Pigment Concentrates for Different Lacquer Systems:

(95) The relevant amine adducts are characterized by particularly good compatibility in the various lacquer systems. Corresponding pigment pastes have low viscosities and can be incorporated excellently. It is possible without further effort to produce pigment pastes with higher pigment contents. The outstandingly good luster and the excellent shelf life of the pigment concentrates are particularly noteworthy.