An Amine Functional Compound Having A Urethane Group

Abstract

An amine functional compound is provided comprising: i. at least one segment consisting of at least one ether unit and at least one ester unit, wherein the ether units and ester units are connected by an ether link or an ester link, and wherein the sum of the number of ether units and ester units is at least three, and wherein the ether units and ester units are arranged in random order, and ii. at least one amine group ii. selected from a tertiary amine group, a salt of a tertiary amine group and a quaternary ammonium group, and wherein each segment i. is covalently linked to the at least one amine group ii. via a linkage comprising an urethane group and another group selected from an urethane group, an urea group, a biuret group and an allophanate group.

Claims

1. An amine functional compound comprising: at least one segment comprising at least one ether unit and at least one ester unit, wherein the at least one ether unit and the at least one ester unit are connected by an ether link or an ester link, the sum of the number of the at least one ether unit and the at least one ester unit is at least three, and the at least one ether unit and the at least one ester unit are arranged in random order, and at least one amine group, selected from a tertiary amine group, a salt of a tertiary amine group, and a quaternary ammonium group, wherein the at least one segment is covalently linked to the at least one amine group via a linkage comprising a urethane group and another group selected from a urethane group, a urea group, a biuret group, and an allophanate group.

2. The amine functional compound according to claim 1, wherein the at least one segment comprises the largest portion between two ester links, and the at least one segment comprises an average number of ether links L between two adjacent ether units and an average number of ether units E, and a ratio R is defined according to formula (I): L/(E−1), wherein E is larger than 1.0, and R is smaller than 1.0.

3. The amine functional compound according to claim 2, wherein the ratio R is smaller than 0.9.

4. The amine functional compound according to claim 2, wherein the ratio R is substantially equal to 0.5.

5. The amine functional compound according to claim 2, wherein the ratio R is substantially equal to 0.0.

6. The amine functional compound according to claim 1, wherein the at least one segment has a molar ratio of the the at least one ester unit to the at least one ether unit in the range 19:1 to 1:1.

7. The amine functional compound according to claim 1, wherein the at least one ether unit has the formula (IV) —[CR.sup.30.sub.2].sub.n—O—, wherein n is an integer of 2 or 3, and each R.sup.30 independently represents an organic group having 1 to 25 carbon atoms or a hydrogen atom.

8. The amine functional compound according to claim 7, wherein when n is equal to 2, at least one R.sup.30 represents an ether group having the formula —R.sup.31—O—R.sup.32, wherein R.sup.31 and R.sup.32 each independently represent organic groups having 1 to 30 carbon atoms.

9-10. (canceled)

11. A composition comprising particles and the amine functional compound according to claim 1.

12. A method for producing an amine functional compound comprising: at least one segment comprising at least one ether unit and at least one ester unit, wherein the at least one ether unit and the at least one ester unit are connected by an ether link or an ester link, the sum of the number of the at least one ether unit and the at least one ester unit is at least three, and the at least one ether unit and the at least one ester unit are arranged in random order, and at least one amine group selected from a tertiary amine group, a salt of a tertiary amine group, and a quaternary ammonium group, wherein the at least one segment is covalently linked to the at least one amine group via a linkage comprising a urethane group and another group selected from a urethane group, a urea group, a biuret group and an allophanate group, the method comprising: preparing a segment by reacting a cyclic ester and a cyclic ether together in a ring-opening polymerization reaction, wherein the ring-opening polymerization reaction is started by a polymerization starter compound comprising at least one functional group selected from a hydroxyl group, a primary amine group, and a secondary amine group, and converting the segment with a coupling agent to covalently link at least one amine group to the segment.

13. The method according to claim 12, wherein the coupling agent includes one or more polyfunctional isocyanates containing an uretdione group, and converting the segment comprises step reacting the one or more polyfunctional isocyanates with the segment and reacting the segment with an amine compound comprising the at least one amine group to covalently link the at least one amine group to the segment, the amine compound comprising at least one tertiary amine group.

14. The method according to claim 13, wherein the amine compound further comprises at least one reactive group selected from a primary amine group and a secondary amine group.

15. The method according to claim 13, wherein reacting the one or more polyfunctional isocyanates with the segment is performed before reacting the segment with the amine compound, and reacting the segment with the amine compound comprises coupling the amine compound to the product of reacting the one or more polyfunctional isocyanates with the segment.

16. The method according to claim 12, wherein preparing the segment comprises substantially simultaneously adding the cyclic ester and the cyclic ether into a reaction mixture maintained in reaction conditions.

17. The method according to claim 12, wherein preparing the segment comprises adding the polymerization starter compound to a reaction mixture containing the cyclic ester and the cyclic ether, and maintained in reaction conditions.

18. The amine functional compound according to claim 2, wherein the ratio R is smaller than 0.8.

19. The amine functional compound according to claim 2, wherein the ratio R is smaller than 0.7.

Description

APPLICATION EXAMPLES

[0129] The amine functional compound of the invention is used in particular in known fields of use of dispersants, as for example in the production or processing of paints and varnishes, of printing inks, of paper coating, of leather colors and textile colors, of pastes, of pigment concentrates, of ceramics or of cosmetic preparations, and especially when these products include solids, such as pigments and/or fillers.

[0130] The amine functional compound of the invention can also be used in the production or processing of casting compounds and/or molding compounds based on synthetic, semisynthetic or natural macromolecular substances, such as polyvinyl chloride, saturated or unsaturated polyesters, polyurethanes, polystyrene, polyacrylate, polyamide, epoxy resins, polyolefins, such as polyethylene or polypropylene. Corresponding polymers can be used, for example, for producing casting compounds, PVC plastisols, gelcoats, polymer concrete, printed circuit boards, industrial paints, wood and furniture varnishes, vehicle finishes, marine paints, anticorrosion paints, can coatings and coil coatings, decorating paints, and architectural paints. Examples of customary binders are resins based on polyurethane, cellulose nitrate, cellulose acetobutyrate, alkyd, melamine, polyester, chlorinated rubber, epoxide, and acrylate. Examples of water-based coatings are cathodic or anodic electrodeposition coating systems for automobile bodies, for example. Further examples are renders, silicate paints, emulsion paints, waterborne paints based on water-thinnable alkyds, alkyd emulsions, hybrid systems, 2-component systems, polyurethane dispersions and acrylate dispersions.

[0131] The amine functional compounds of the invention are especially suitable also as dispersants for producing solids concentrates, such as pigment concentrates. For this purpose, for example, the amine functional compounds are introduced in a carrier medium, such as organic solvents, plasticizers and/or water, and the solids for dispersal are added with stirring. These concentrates may additionally comprise binders and/or other auxiliaries. With the amine functional compound of the invention, however, it is possible in particular to produce stable, binder-free pigment concentrates. It is also possible with the polymers to produce flowable solids concentrates from pigment presscakes. In this case, the polymers of the invention are admixed to the presscake, which may still comprise organic solvents, plasticizers and/or water, and the resulting mixture is dispersed. The solids concentrates produced in various ways can then be incorporated into a variety of substrates, such as alkyd resins, polyester resins, acrylate resins, polyurethane resins or epoxy resins, for example. Pigments, however, can also be dispersed solventlessly without a solvent directly into the amine functional compound of the invention and are then suitable especially for pigmenting thermoplastic and thermoset plastic formulations.

[0132] The amine functional compound of the invention can also be used advantageously in the production of inks for “non impact” printing processes such as “themal inkjet” and the “bubble jet process”. These inks may be, for example, aqueous ink formulations, solvent-based ink formulations, solvent-free or low-solvent inks for UV applications and waxlike inks. The amine functional compound of the invention may also be used advantageously in the production of color filters for liquid-crystal displays. liquid-crystal screens, color resolution devices, sensors, plasma screens, displays based on SED (Surface conduction Electron emitter Display) and for MLCC (Multi Layer Ceramic Compounds). In this case the liquid color filter varnish, also called color resist, can be applied by any of a wide variety of application processes such as spin coating, knife coating, combination of the two or via “non-impact” printing processes such as inkjet processes, for example. The MLCC technology is used in the production of microchips and printed circuit boards.

[0133] The amine functional compound of the invention can also be used for producing cosmetic preparations such as, for example, makeup, powder, lipsticks, hair colorants, creams, nail varnishes, and sun protection products. These products may be present in the usual forms, such as W/O or O/W emulsions, solutions, gels, creams, lotions or sprays, for example. The polymers of the invention can be used advantageously in dispersions that are used for producing these preparations. These dispersions may comprise the carrier media that are customary in cosmetology for these purposes, such as water, castor oils or silicone oils and solids, examples being organic and inorganic pigments, such as titanium dioxide or iron oxide.

[0134] A dispersant of this kind may also be used, lastly, for producing a pigmented coating on a substrate, in which case the pigmented paint is applied to the substrate and the pigmented paint applied to the substrate is dried, baked or cured, or crosslinked.

[0135] The amine functional compound of the invention can be used alone or together with customary binders. In the case of use in polyolefins, it may be advantageous, for example, to use corresponding low molecular weight polyolefins as carrier materials together with an amine functional compound.

[0136] Another possible use of the amine functional compound of the invention lies in the production of dispersible solids in powder particle and/or fiber particle form, more particularly of dispersible pigments or polymeric fillers, in which case the particles are coated with an amine functional compound. Coatings of this kind of organic and inorganic solids are performed in a known way. The solvent or emulsion medium in this case may either be removed or may remain in the mixture, to form pastes. These pastes are customary commercial products and may additionally comprise binder fractions and also further auxiliaries and adjuvants. Especially in the case of pigments, the coating of the pigment surface may take place during or after the synthesis of the pigments, by addition of an amine functional compound the pigment suspension, for example, or during or after pigment conditioning. The pigments pretreated in this way are notable for greater ease of incorporation and for improved characteristics with respect to viscosity, flocculation, and gloss, and for greater color strength by comparison with untreated pigments.

[0137] Examples of pigments are mono-, di-, tri- and polyazo pigments, oxazine, dioxazine and thiazine pigments, diketopyrrolopyrroles, phthalocyanines, ultramarine and other metal complex pigments, indigoid pigments, diphenylmethane, triarylmethane, xanthenes, acridine, quinacridone, methine pigments, anthraquinone, pyranthrone, perylene and other polycyclic carbonyl pigments. Further examples of organic pigments are found in the following monograph: W. Herbst, K. Hunger “Industrial Organic Pigments”, 1997 (publisher: Wiley-VCH, ISBN: 3-527-288368). Examples of inorganic pigments are pigments based on carbon black, graphite, zinc, titanium dioxide, zinc oxide, zinc sulfide, zinc phosphate, barium sulfate, lithopone, iron oxide, ultramarine, manganese phosphate, cobalt aluminate, cobalt stannate, cobalt zincate, antimony oxide, antimony sulfide, chromium oxide, zinc chromate, mixed metal oxides based on nickel, bismuth, vanadium, molybdenum, cadmium, titanium, zinc, manganese, cobalt, iron, chromium, antimony, magnesium, aluminum (examples being nickel titanium yellow, bismuth vanadate molybdate yellow, or chromium titanium yellow). Further examples are cited in the following monograph: G. Buxbaum, “Industrial Inorganic Pigments”, 1998 (publisher: Wiley-VCH, ISBN: 3-527-28878-3). Inorganic pigments may also be magnetic pigments based on pure iron, iron oxides and chromium oxides or mixed oxides, metallic effect pigments composed of aluminum, zinc, copper or brass and pearlescent pigments, fluorescent and phosphorescent luminous pigments. Further examples are nanoscale organic or inorganic solids with particle sizes of below 100 nm, such as particular types of carbon black or particles consisting of a metal or a semimetal oxide and/or hydroxide and also particles which consist of mixed metal and/or semimetal oxides and/or hydroxides. For example, the oxides and/or oxide hydroxides of aluminum, of silicon, of zinc, of titanium, etc., can be employed for producing extremely finely divided solids of this kind. The process by which these oxidic and/or hydroxidic and/or oxide-hydroxidic particles are produced may take place via any of a wide variety of methods such as, for example, ion exchange operations, plasma operations, sol-gel processes, precipitation, comminution (by grinding, for example) or flame hydrolysis, etc. These nanoscale solids may also be what are called hybrid particles, consisting of an inorganic core and an organic shell or vice versa. Examples of fillers in powder or fiber form are, for example, those, which are constructed from particles in powder or fiber form of aluminum oxide, aluminum hydroxide, silicon dioxide, kieselguhr, siliceous earth, quartz. silica gel, talc, kaolin, mica, perlite, feldspar, finely ground slate calcium sulfate, barium sulfate, calcium carbonate, calcite, dolomite, glass, polyvinylidene fluoride (PVDF) or carbon. Further examples of pigments or fillers are found, for example, in EP-A-0 270 126. Flame retardants as well, such as aluminum or magnesium hydroxide, and matting agents such as silicas, for example, are likewise amenable to effective dispersal and stabilization.

[0138] The amine functional compound of the invention, moreover, can also be used as emulsifier, phase mediator (liquid/liquid compatibilizer) or adhesion promoter.

[0139] The invention is elucidated in more detail below by means of working examples.

EXAMPLES

General Remarks

[0140] In the case of substances without molecular uniformity the stated molecular weights—below as already in the foregoing description—represent average values of the numerical mean. The molecular weights or number-average molecular weights Mn, are determined, when titratable hydroxyl or amino groups are present, by end-group determination via the determination of the OH number or amine number, respectively. In the case of compounds to which an end-group determination cannot be applied, the number-average molecular weight is determined by means of gel permeation chromatography against a polystyrene standard. Unless otherwise remarked percentages are percentages by weight.

Measurement of Non-Volatile Components

[0141] The sample (2.0±0.1 g of the tested substance) was weighed in a previously dried aluminum crucible and dried in furnace for 20 minutes at 150° C., cooled in a desiccator and then reweighed. The residue corresponds to the solids content in the sample (ISO 3251).

Measurement of Acid Numbers

[0142] The acid number is the KOH quantity in mg that is required for neutralizing 1 g of substance under the defined conditions. The acid numbers were determined by a neutralization reaction with a 0.1 N KOH in Ethanol according to DIN EN ISO 2114.

##STR00003##

Measurement of Hydroxyl Numbers

[0143] The alcoholic hydroxyl groups were reacted by acetylation with an excess of acetic anhydride. The excess acetic anhydride was cracked into acetic acid by adding water and titrated back using ethanolic KOH. The hydroxyl number was understood to be the KOH quantity in mg, which is equivalent to the acetic acid quantity bound when acetylating 1 g of substance (according to DIN ISO 4629)

Measurement of Amine Numbers

[0144] Perchloric acid (HC104) in acetic acid has proved to be a suitable titration agent for organic bases containing nitrogen as well as primary, secondary and tertiary amine groups. Acid solvents such as acetic acid have stood the test in determining weak organic bases (good dissolving properties, proton-donating acid solvent). Additions of inert solvents such as cyclohexane, dioxane, chlorobenzene, acetone and methyl ethyl ketone can improve the titration of very weak bases (according to DIN 16945).

R—NH.sub.2+HClO.sub.4.fwdarw.R—NH.sub.3.sup.++ClO.sub.4.sup.−

Measurement of NCO Values

[0145] The free NCO content of the polyisocyanates employed and also the course of the NCO addition reactions, are determined in accordance with EN ISO 9369 by reaction with dibutylamine and subsequent titration of the amine excess.

NMR Measurements

[0146] The NMR measurements were carried out on a Bruker DPX 300 at 300 MHZ (.sup.1H) or 75 MHZ (.sup.13C). Solvents used were deuterated chloroform (CDCl.sub.3) and deuterated dimethyl sulfoxide (DMSO-d.sub.6).

Preparation of the Intermediate Products: First Step

[0147] Preparation Method 1

[0148] A clean dry four-necked flask (500 ml) equipped with a condenser, KPG-stirrer thermostat and a nitrogen line was charged with a chain starter (which was dried in rotary evaporator at 100° C. for 2 hours) and the catalyst and heated up to 80° C. Additionally a mixture of the lactone and the epoxide was added so that the temperature did not exceed 85° C. After complete addition the reaction mixture was stirred at that temperature until the epoxide was completely reacted (controlled by the means of NMR) and the content of non-volatile components was >98% (measurement of non-volatile components according to ISO 3251). After complete reaction the catalyst was neutralized with dibutylethanolamine (with 10 mol % excess of amine).

TABLE-US-00001 TABLE 1 Intermediate products prepared according to the method 1 Example chain starter wt. % lactone wt. % epoxide wt. % catalyst wt. % M1 hexadecanol 20.43 CAPA 47.9 EHGE 31.56 TFMSS 0.05 M2 MPEG 350 45.53 CAPA 29.83 EHGE 24.57 TFMSS 0.03 M3 MPEG 500 45.74 CAPA 20.47 EHGE 33.72 TFMSS 0.03 M4 1-decanol 7.59 CAPA 65.38 EHGE 26.92 TFMSS 0.05 CAPA = ε-Caprolactone, 2-EHGE = 2-ethylhexyl glycidyl ether, TFMSS = trifluormethansulfonic acid MPEG 350 = Methoxypolyethylene glycol, Mw = 350 g/mol, MPEG 500 = Methoxypolyethylene glycol, Mw = 500 g/mol

Preparation of Comparative Intermediate Products: First Step

[0149] Preparation Method 2

[0150] A clean dry four-necked flask (500 ml) equipped with a condenser, KPG-stirrer, thermostat and a nitrogen line was charged with a chain starter (which was dried in rotary evaporator at 100° C. for 2 hours), the lactone and the catalyst and heated up to 160° C. The reaction mixture was stirred at this temperature until the content of non-volatile components was >98% (measurement of non-volatile components according to ISO 3251).

TABLE-US-00002 TABLE 2 Intermediate products prepared according to the method 2 Example Chain starter wt. % lactone wt. % lactone wt. % catalyst wt. % N1* hexadecanol 21.04 CAPA 78.92 — — DBTL 0.004 N2* MPEG 350 50.42 CAPA 49.54 — — DBTL 0.004 N3* MPEG 500 59.81 CAPA 40.15 — — DBTL 0.004 N4* 1-decanol 8.24 CAPA 70.97 VALERO 20.75 DBTL 0.004 CAPA = ε-Caprolactone, MPEG 350 = Methoxypolyethylene glycol, Mw = 350 g/mol, MPEG 500 = Methoxypolyethylene glycol, Mw = 500 g/mol, DBTL = dibutyl tin dilaurate, VALERO = δ-Valerolacton

Preparation of the Products: Second Step

[0151] Preparation Method 3

[0152] A clean dry four-necked flask (500 mL) equipped with condenser, KPG-stirrer, thermostat and a nitrogen line was charged with the isocyanate P3, the intermediate product (Example N2,

[0153] N3, M2 or M3) and the (molten) polyether and homogenized. Then the catalyst (DBTL) was added and the mixture was heated up to 80° C. The mixture was stirred at this temperature until the NCO value reached <0.1% NCO (DIN EN ISO 9369). Then the amine compound was added and the mixture was heated up to 100° C. and stirred at this temperature until completed reaction of uretdione, which was controlled by the means of NMR.

TABLE-US-00003 TABLE 3 Products prepared according to the method 3 Example isocyanate wt. % Intermediate wt. % polyether wt. % catalyst wt. % amine wt. % K3* P3 20.56 N2* 34.49 MPEG 39.55 DBTL 0.004 PEI 5.35 750 300 K4 P3 19.67 M2 34.31 MPEG 40.86 DBTL 0.004 PEI 5.12 750 300 K5* P3 17.75 N3* 40.72 MPEG 36.87 DBTL 0.004 PEI 4.62 750 300 K6 P3 18.62 M3 37.82 MPEG 38.68 DBTL 0.004 PEI 4.85 750 300 P3 = aliphatic hexamethylene diisocyanate (HDI)-Uretdione with a free NCO-value of 21.8% e.g. Desmodur.sup. ® N3400 Covestro, PEI (number) = polyethyleneimine (molecular weight, MPEG 750 = Methoxypolyethylene glycol, Mw = 750 g/mol, DBTL = dibutyl tin dilaurate

[0154] Preparation Method 4

[0155] A clean dry four-necked flask (500 mL) equipped with condenser, KPG-stirrer, thermostat and a nitrogen line was charged with the isocyanate P4 and the stabilizer and heated up to 80° C. Then the intermediate product (N4 or M4) was slowly added to the mixture. After complete addition, the reaction mixture was stirred until the NCO reaches the nominal value (DIN EN ISO 9369).

[0156] Then the amine was slowly added (exothermic) and the mixture was stirred at 80° C. until the NCO value reached <0.1% NCO (DIN EN ISO 9369).

TABLE-US-00004 TABLE 4 Products prepared according to the method 4 Example isocyanate wt. % Intermediate wt. % Stabilizer wt. % amine wt. % K7* P4 8.23 N4* 87.16 benzoyl 0.048 DMAPA 4.57 chloride K8 P4 9.51 M4 84.15 benzoyl 0.048 DMAPA 6.29 chloride P4 = Toluene dissocyanate (TDI), DMAPA = Dimethylaminopropylamine

Application Examples

[0157] Samples marked with (*) are comparative examples.

APPLICATION EXAMPLE 1

[0158] During the application test additive K4 was compared with K3* and additive K6 with K5*. Samples prepared according to the invention (K4 and K6) are flowable, easy to handle and less crystalline as comparative examples (K3* and K5*), which showed high tendency to crystallization.

WORKING METHOD 1

System

[0159] Dispersion a solution of an universal grinding resin

[0160] Pigmented coating composition based on a clearcoat based on Thermoplastic Acrylate (TPA)

Raw Material Used for the Application Tests

[0161] Laropal A81: (60% in Methoxy propyl acetate (PMA))—Aldehyde grinding resin from BASF Paraloid B66: Thermoplastic Acrylate (TPA) from Dow Chemicals

[0162] Novoperm F3RK70: Very opaque organic pigment from Clariant

Preparation of Millbase

[0163] Variation of parameters such as pigment/binder-ratio and additive dosage in the millbase formulation has a tremendous influence on the quality of the pigment dispersion and stabilization. The amount of resin may have an influence on flow behavior/viscosity, pigment wetting, storage stability of millbase and final paint for example. Only if there is an optimal amount of wetting & dispersing-additive available in the grinding phase the best pigment dispersion can be achieved. Consequently, for test purpose the system is adjusted by variation of W&D additives (see table 5).

TABLE-US-00005 TABLE 5 Formulation of the millbase Mill base K3* K4 K5* K6 (solids) (100%) (100%) (100%) (100%) Laropal A81 (60%) 13.5 13.5 13.5 13.5 PMA 12.4 12.4 12.4 12.4 W&D-additive 6.3 6.3 6.3 6.3 Novoperm Red F3RK70 18.0 18.0 18.0 18.0 50 g 50 g 50 g 50 g Additive dosage (sop) 35% 35% 35% 35% Pigment content 36% 36% 36% 36% Pigment/binder ratio 1/0.8 1/0.8 1/0.8 1/0.8

[0164] For the preparation of the millbase a binder, a wetting and dispersing additive (K3*, K4, K5* or K6) and a solvent were filled in a glass bottle (100 ml) and homogenized with a spatula. After this procedure the pigment and glass beads (1 mm) were added to the mixture and dispersed by high speed shaker (Disperser DAS A 200-K with cooling system—SYSTEM LAU) for 180 minutes at a maximum energy input. After that, the glass beads were removed by filtration (using 240 μm paper filter).

TABLE-US-00006 TABLE 6 Formulation of clearcoat Clearcoat based on TPA Paraloid B-66 (50% in Xylene) 70.0 DIDP 2.0 Xylene 21.8 PMA 6.0 BYK-306 0.2 100.0

[0165] For the preparation of clearcoat Paraloid B-66 was dissolved in xylene. Then solvents (xylene, PMA), DIDP (Diisodecyl phthalate) and BYK-306 were slowly added to the mixture and mixed with dissolver (firma Getzmann) for 20 min.

[0166] A pigmented coating composition using a clearcoat based on thermoplastic acrylate (TPA) was formulated for each mill base (K3*, K4, K5* or K6) using the composition according to the table 7. Samples were applied on contrast charts using 100 μm spiralrackel.

TABLE-US-00007 TABLE 7 Pigmented coating composition based on millbases and TPA-clearcoat Pigmented coating composition TPA-Clearcoat 15.0 Millbase of Novoperm F3RK70 in Laropal A81(36% pigment) 3.0 18.0 For pour-out diluted 1:1.5 with Xylene

Gloss Measurement

[0167] Gloss (table 9) was measured with micro haze plus device from BYK.

Evaluation of Millbases in a TPA Topcoat

Color Comparison of Paints with and Without Wetting and Dispersing Additive

[0168] The state of dispersion of pigments (opaque and also transparent one's) can be judged by the color shift. The sample to be tested should be applied with low shear forces (pouring or draw down) and needs to be compared against a standard. A better dispersed pigment will change it's color “counter-clock-wise” based on the ClElab color space compared to the control. The CIELAB color space (also known as CIE L*a*b* or sometimes abbreviated as simply “Lab” color space) is a color space defined by the International Commission on Illumination (CIE) in 1976.In a case of a red pigment this would be reflected by a positive shift along the b*-axis.

[0169] This test method works for all colored pigments, but not for white and black. The color measurement (L*, a*, b*-values) was done with a spectro-guide sphere (45/0)—BYK-Gardner. In the known CIElab color space, L* is always positive and represents brightness, a*>0 represents red component, a*<0 represents green component, b*>0 represents yellow component, b*<0 represents blue component.

Results

[0170] K4 and K6 improve the pigment dispersion and lead to better pigment stabilization in the TPA-system. This is reflected by the desired color shift. Compared to the comparative samples K3* and K5* the additives K4 and K6 led to a positive shift along the b*-axis (see Table 7) Furthermore the additives K4 and K6 show significantly improvement of gloss values and better surface appearance, see table 9.

TABLE-US-00008 TABLE 8 Meassurement of b* values. b* K3* 60.53 K4 63.86 K5* 60.69 K6 63.47

[0171] Comparative examples K3* and K5* showed significantly lower b* values.

TABLE-US-00009 TABLE 9 Measurement of gloss (in units) angle (in°) K3* K4 K5* K6 20 3.2 27.3 3.5 14.7 60 29.5 73.9 29.1 66.1 85 79.5 90.9 72.9 92.0

APPLICATION EXAMPLE 2

[0172] Samples marked with (*) are comparative samples.

WORKING METHOD 2

[0173] During the application test additive K8 was compared with additive K7*

System

[0174] Solventborne TPA Topcoat

Raw Material used for the Application Tests

[0175] Paraloid B66 (50% in Xylene): thermoplastic acrylate from Dow Chemicals Company CAB 551.01: Cellulose acetate butyrate from Eastman

[0176] Paliogen Maroon L3920: transparent organic pigment PR 179 (perylene) from BASF

Preparation of Millbase

[0177] For the preparation of the millbase according to table 10 a binder, a wetting and dispersing additive and a solvent were filled in a glass bottle (100 ml) and homogenized with a spatula. After this procedure the pigment and glass beads (1 mm) were added to the mixture and dispersed by high speed shaker (Disperser DAS A 200-K with cooling system—SYSTEM LAU) for 180 minutes at a maximum energy input. Subsequently the glass beads (1 mm) were removed by filtration (using 240 μm paper filter).

TABLE-US-00010 TABLE 10 Formulation of millbase Millbase (solids) K7* (100%) K8 (100%) Paraloid B66 (50% in Xylene) 15.5 15.5 n-Butanol 5.0 5.0 Butyl acetate/Xylene (1:1) 22.0 22.0 W&D-additive 1.5 1.5 Paliogen Marron L3920 6.0 6.0 50 g 50 g Additive dosage (sop) 25% 25% Pigment content 12% 12% Pigment/binder ratio 1/2.5 1/2.5

Millbase Viscosity

[0178] TPA systems are very fast drying systems, which lead to an enormous increase of viscosity of the millbase. As the dispersion process is the most expensive step during the paint manufacture, millbase viscosity is a decisive parameter for saving cost and energy. The better the dispersion of the pigments, the lower the attractive forces between the particles and consequently the lower the mill base viscosity and the more Newtonian is the flow behavior.

[0179] The viscosity was measured with Stresstech Rheometer, Reologica (1/10/100/500 1/s, cone/plate, 23° C.).

Results

[0180] The measurement showed that the viscosity of the mill base prepared with additive K8 is much lower than the one prepared with the comparative sample K7*. The effect is clearly visible at low shear rate which reflects the reduced attraction between the particles due to the successful stabilization of the pigment by additive K8 (see Table 11).

TABLE-US-00011 TABLE 11 The viscosity of the mill base formulated using additives K8 and K7* share rate in [1/s] K7* K8 1 3309 196 10 1650 134 100 302 78 500 64 8