Use of rhamnolipids and/or sophorolipids in coating compositions for obtaining a homogeneous colour appearance of the dry coating film and/or for increasing occupational safety in the production of coating compositions

Abstract

Rhamnolipids and/or sophorolipids can be used in coating compositions for improvement of the speed of wetting of pulverulent formulation constituents in such compositions, which leads to a reduction in dust nuisance during incorporation thereof and to the increase in occupational safety in the production of coating compositions. Rhamnolipids and/or sophorolipids can also be used in coating compositions for obtaining improved homogeneous colour appearance of the dry paint film with regard to difference in hue, ascertained from the delta E and visual assessment.

Claims

1. A method of improving the speed of wetting of pulverulent formulation constituents in a coating composition and of obtaining improved homogeneous colour appearance of a dry paint film hue, the method comprising: mixing at least one rhamnolipid (RL) and/or at least one sophorolipid into a coating composition.

2. The method according to claim 1, wherein the coating composition is a paint or coating material selected from the group consisting of an interior wall paint, an exterior paint, an architectural paint, a floor coating, a wood paint, an industrial paint, an automotive OEM or refinishing paint, a primer, a primer-surfacer, a basecoat, and a topcoat.

3. The method according to claim 1, wherein the coating composition is mixed with an additive composition that comprises the at least one rhamnolipid and/or the at least one sophorolipid, wherein the additive composition is a pigment concentrate, a colour paste, a pigment paste, or a millbase.

4. The method according to claim 1, wherein the coating composition includes at least one solid selected from the group consisting of a filler, a pigment, a dye, an optical brightener, a ceramic material, and a magnetic material.

5. The method according to claim 1, wherein the coating composition comprises at least one further additive.

6. The method according to claim 1, wherein the at least one rhamnolipid is a compound of the general formula (I) or a salt thereof: ##STR00005## wherein m=2, 1 or 0, n=1 or 0, R.sup.6 and R.sup.7=independently an identical or different organic radical having 2 to 24 carbon atoms.

7. The method according to claim 1, wherein the at least one rhamnolipid is a mixed composition with >90% diRL.

8. The method according to claim 1, wherein the at least one rhamnolipid is a mixed composition comprising rhamnolipids, wherein the mixed composition contains: 51% by weight to 95% by weight of diRL-C10C10, and 0.5% by weight to 9% by weight of monoRL-C10C10, wherein percentages by weight are based on a sum total of all rhamnolipids present, and with the proviso that a weight ratio of di-rhamnolipids to mono-rhamnolipids is greater than 91:9.

9. The method according to claim 1 wherein the at least one rhamnolipid is a mixed composition comprising rhamnolipids, wherein the mixed composition contains 0.5% by weight to 15% by weight of diRL-C10C12:1, wherein percentages by weight are based on a sum total of all rhamnolipids present.

10. The method according to claim 1, wherein the at least sophorolipid is a compound of the formula (II) or (IIa): ##STR00006## wherein R.sup.1 and R.sup.2 are independently either H or an acetyl group, R.sup.3 is H, a methyl, ethyl, or hexyl group, R.sup.4 is independently a saturated or unsaturated divalent branched or unbranched organic group, R.sup.5 is H or a methyl group, and with the proviso that a total number of carbon atoms in the groups R.sup.4 and R.sup.5 do not exceed 29.

11. The method according to claim 1, wherein the at least one rhamnolipid and/or the at least one sophorolipid is present within a range from 0.01% by weight to 10.0% by weight, based on the coating composition.

12. The method according to claim 5, wherein the at least one further additive is selected from the group consisting of a wetting agent, a dispersing additive, a rheology additive, a levelling aid, and a defoamer.

13. The method according to claim 6, wherein in the Formula (I), R.sup.6 and R.sup.7 are independently an optionally branched, optionally substituted, optionally unsaturated alkyl radical having 2 to 24 carbon atoms.

14. The method according to claim 6, wherein in the Formula (I), R.sup.6 and R.sup.7 are independently selected from the group consisting of pentenyl, heptenyl, nonenyl, undecenyl, tridecenyl, and (CH.sub.2).sub.x—CH.sub.3 with x=1 to 23.

15. The method according to claim 8, wherein the weight ratio of di-rhamnolipids to mono-rhamnolipids is greater than 98:2.

16. The method according to claim 11, wherein the at least one rhamnolipid and/or the at least one sophorolipid is present within a range from 0.1% by weight to 5.0% by weight, based on the coating composition.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0042] FIG. 1 shows a diagram of a colour model with colour loci based on a coordinate system.

[0043] FIG. 2 shows a photograph of 3 different samples in a test of pigment wetting characteristics.

DETAILED DESCRIPTION OF THE INVENTION

[0044] The coating compositions are preferably preparations for various fields of application that are applied to the substrate to be coated by application methods such as, for example, spraying, dipping, rolling or painting application, and various printing methods.

[0045] Examples of coating materials in the context of the present invention are paints, coating materials, printing inks and other coating materials, such as solventborne or aqueous coatings and solvent-free coatings, powder coatings, UV-curable coatings, low-solids, medium-solids and high-solids, automotive coatings, wood coatings, baked coatings, 2-component coatings, metal coating materials, toner compositions. Further examples of coating materials are given in “Bodo Müller, Ulrich Poth, Lackformulierung und Lackrezeptur, Lehrbuch für Ausbildung und Praxis [Coating Formulation and Coating Composition, Textbook for Training and Practice], Vincentz Verlag, Hanover (2003), 73-1996” and “P. G. Garrat, Strahlenhärtung [Radiative Curing], Vincent Verlag, Hanover (1996)”.

[0046] The paints and coating materials are interior wall paints, exterior paints, architectural paints, floor coatings, wood paints, industrial paints, paints for automotive OEM (original equipment manufacturer) or refinishing, primers, primer-services, basecoats and topcoats.

[0047] Examples of printing inks and/or printing varnishes in the context of the present invention are solvent-based or aqueous printing inks, flexographic printing inks, intaglio printing inks, letterpress or relief printing inks, offset printing inks, lithographic printing inks, printing inks for printing of packaging, screenprinting inks, printing inks such as printing inks for inkjet printers, inkjet ink, printing varnishes such as overprint varnishes. Further printing ink and/or printing varnish formulations are given in “E. W. Flick, Printing Ink and Overprint Varnish Formulations—Recent Developments, Noyes Publications, Park Ridge, N.J., (1990)” and subsequent editions.

[0048] The coating compositions preferably include solids selected from the group of the fillers, pigments, dyes, optical brighteners, ceramic materials, magnetic materials.

[0049] Examples of pigments are those from the group of inorganic pigments, such as carbon blacks, titanium dioxides, zinc oxides. Prussian blue, iron oxides, cadmium sulfides, chromium pigments, for example chromates, molybdates and mixed chromates and sulfates of lead, zinc, barium, calcium and mixtures thereof. Further examples of inorganic pigments are specified in the book “H. Endriss, Aktuelle anorganische Bunt-Pigmente [Inorganic Colour Pigments Today], Vincentz Verlag, Hannover (1997)”.

[0050] Examples of organic pigments are those from the group of the azo, diazo, condensed azo, naphthol, metal complex, thioindigo, indanthrone, isoindanthrone, anthanthrone, anthraquinone, isodibenzanthrone, triphendioxazine, quinacridone, perylene, diketopyrrolopyrrole and phthalocyanine pigments. Further examples of organic pigments are specified in the book “W. Herbst, K. Hunger, Industrial Organic Pigments, VCH, Weinheim (1993)”.

[0051] Examples of fillers are those from the groups of talc, kaolin, silicas, barytes and lime; ceramic materials, for example aluminium oxides, silicates, zirconium oxides, titanium oxides, boron nitrides, silicon nitrides, boron carbides, mixed silicon aluminium nitrides and metal titanates; magnetic materials, for example magnetic oxides of transition metals, such as iron oxides, cobalt-doped iron oxides and ferrites; metals, for example iron, nickel, cobalt and alloys thereof.

[0052] The person skilled in the art will be aware that such coating compositions may include further ingredients. As liquid medium, they may contain organic solvents (e.g. acetates such as butyl or ethyl acetate, hydrocarbons such as petroleum spirits of various boiling ranges, alcohols, ethers, glycols and glycol ethers) and/or water, as known as prior art depending on the binders used.

[0053] It is possible to use customary binders. It is possible with preference to use alkyd, acrylate, styrene-acrylate, epoxy, polyvinylacetate, polyester or polyurethane binders. Any kind of curing is possible, for example by oxidative drying, physical drying, self-crosslinking, UV or electron beam curing or crosslinking by baking.

[0054] It is conceivable that the coating composition comprises further additives, for example preferably wetting agents, dispersing additives, rheology additives, levelling aids or defoamers.

[0055] The person skilled in the art is aware that the production of coating compositions comprising particles can be effected, for example, by the use of pigment concentrates, colour paste, pigment pastes or liquid formulations of the particles. However, it is also possible to produce a millbase in order to use it in a timely manner for the production of coating compositions.

[0056] The invention therefore preferably also provides for use of rhamnolipids and/or sophorolipids in pigment concentrates, colour paste, pigment paste or liquid formulations of the particles or millbases.

[0057] Rhamnolipids and sophorolipids are surfactants which can be prepared by means of fermentation.

[0058] Rhamnolipids are composed of one to two rhamnose units and one to three, mostly β-hydroxy fatty acids. The fatty acids can be saturated or unsaturated.

[0059] The variation in the chain length and number (congener) of the fatty acid portions has been described in a number of publications (Howe et al., FEBS J. 2006; 273(22):5101-12; Abdel-Mawgoud et al., Appl Microbiol Biotechnol, 86, 2010; p. 1323-1336).

[0060] Miao et al., Journal of Surfactants and Detergents, 17 (6), 2014; 1069-1080, describes the synthesis of di-rhamnolipid ethyl esters by esterification with ethanol and also the suitability of the esters as nonionic surfactant.

[0061] WO2001010447 and EP1889623 disclose the pharmaceutical and cosmetic applications of rhamnolipids and short-chain rhamnolipid esters (C1-C6; methyl to hexyl esters, linear or branched), in particular in wound healing.

[0062] The rhamnolipids are preferably compounds of the general formula (I) or salts thereof

##STR00003##

where [0063] m=2. 1 or 0, in particular 1 or 0, [0064] n=1 or 0, in particular 1, [0065] R.sup.6 and R.sup.7=independently an identical or different organic radical having 2 to 24, preferably 5 to 13, carbon atoms, especially optionally branched, optionally substituted, especially hydroxy-substituted, optionally unsaturated, especially optionally mono-, di- or triunsaturated, alkyl radical, preferably those selected from the group consisting of pentenyl, heptenyl, nonenyl, undecenyl and tridecenyl and (CH2).sub.x—CH3 with x=1 to 23, preferably 4 to 12.

[0066] Preference is given to a mixed composition of rhamnolipids containing >90% diRL.

[0067] Preference is given to a mixed composition of rhamnolipids containing [0068] 51% by weight to 95% by weight of diRL-C10C10 and [0069] 0.5% by weight to 9% by weight of monoRL-C10C10, where the percentages by weight are based on the sum total of all rhamnolipids present, with the proviso that the weight ratio of di-rhamnolipids to mono-rhamnolipids is greater than 91:9, preferably greater than 97:3, more preferably greater than 98:2.

[0070] For the use according to the invention, preference is given to using a rhamnolipid mixture containing 0.5% by weight to 15% by weight of diRL-C10C12:1, where the percentages by weight are based on the sum total of all rhamnolipids present.

[0071] The sophorolipids are preferably compounds of the formula (II) or (IIa)

##STR00004## [0072] where [0073] R.sup.1 and R.sup.2 are independently either H or an acetyl group, [0074] R.sup.3 is H, a methyl, ethyl or hexyl group, [0075] R.sup.4 is independently a saturated or unsaturated divalent branched or unbranched organic group, [0076] R.sup.5 is H or a methyl group, [0077] with the proviso that the total number of the carbon atoms in the groups R.sup.4 and R.sup.5 do not exceed the number 29.

[0078] Rhamnolipids are available under the Natsurfact name from Stepan (Northfield, Ill., USA) and RHEANCE® One from Evonik Operations GmbH.

[0079] Sophorolipids are available under the HoneySurf name from Holiferm Limited (Manchester, UK) and REWOFERM® SL ONE from Evonik Operations GmbH.

[0080] Preference is given to using rhamnolipids and/or sophorolipids within a range from 0.01% by weight to 10.0% by weight, more preferably 0.1% by weight to 5.0% by weight, based on the overall coating composition.

[0081] Preference is given to using the rharnnolipids and sophorolipids of the general formulae (I), (II) and (IIa) for accelerating the wetting of pulverulent formulation constituents in coating compositions.

[0082] Preference is given to using the rhamnolipids and sophorolipids of the general formulae (I), (II) and (IIa) for optimizing the process regime in the production of coating compositions of pigment concentrates, colour pastes, pigment pastes or millbases.

[0083] The invention is to be elucidated in detail hereinafter by working examples.

Methods

[0084] Rub-Out Test (Delta E) and Visual Assessment

[0085] For the rub-out test, the coating compositions were applied with a 150 μm applicator from Leneta to a test base or test substrate. After the drying time of 5 minutes, the rub-out test was conducted, which involves mixing the paint applied by circular movements with a grinding body, for example a gloved finger, with moderate contact pressure. There should be no occurrence here either of complete pushing of the coating away from the substrate or of tearing of the paint film.

[0086] After the paint films have been dried at room temperature for seven days, the colour values are determined in the area where the rub-out test was done and on an adjacent area not subjected to the rub-out test. The two values are used to calculate the ΔE (delta E). This difference in the colour loci is a measurement of the quality of pigment stabilization.

[0087] The colour values and the Delta E value were determined with an X-Rite Model SP 62 spectrometer. As is well known, the L*a*b* colour space describes all perceivable colours. It uses a three-dimensional colour space in which the brightness value L*stands vertical on the colour plane (a*, b*). The colour model is standardized in EN ISO 11664-4 “Colorimetry—Part 4: CIE 1976 L*a*b* Colour space”. Typically, the measuring instrument measures the values L*, a* and b*. These values then result in a colour locus in a coordinate system, where L* indicates the brightness (0=black; 100 =white), a* the red/green value (−green/+red) and b* the blue/yellow value (−blue/+yellow). (see FIG. 1)

[0088] The visual assessment of the dried films with regard to spottiness and the differences in hue of the rubbed area compared to the unrubbed area was made in a colour inspection cabin with D65 daylight illumination using the following assessment scale: [0089] 0=homogeneous, no spots, no differences in colour [0090] 1=very slight spots, very slight differences in hue [0091] 2=slight spots, slight differences in hue [0092] 3=significant spots, significant differences in hue [0093] 4=very significant spots, very significant differences in hue

EXAMPLES

[0094] 1. Production of the Pigment Concentrates

[0095] Pigment concentrates were first produced according to the figures from the respective tables, Tables 1.2-1.4. For production of these pigment concentrates, the liquid constituents were first weighed out and then the pigments were added. After addition of grinding bodies (glass beads of diameter 2-3 mm, same volume as the pigment concentrate), dispersion was effected for one hour (inorganic pigments) or two hours (organic pigments and carbon black) in an agitator (FAS 500 from Lau GmbH) with air cooling. The grinding bodies were sieved off. The resultant filtrate is the pigment concentrate.

[0096] The comparative examples were produced analogously with Tego® Dispers 755.

TABLE-US-00001 TABLE 1.1 Materials used Trade name Description Manufacturer Water, delonized Evonik Operations GmbH Bayferrox 130 M Pigment Lanxess AG Heliogen Blue L7101F Pigment BASF AG Special Black 4 Pigment, carbon Orion Engineered black Carbons GmbH Tego ® Dispers 755 Copolymer Evonik Operations GmbH Rewoferm ® SL One Sophorolipid Evonik Operations GmbH RHEANCE ® One Rhamnolipid Evonik Operations GmbH Tego ® Foamex 830 Defoamer Evonik Operations GmbH Tego ® Foarnex 810 Defoamer Evonik Operations GmbH Aerosil ® 200 Filler Evonik Operations GmbH

TABLE-US-00002 TABLE 1.2 Pigment concentrates comprising Bayferrox 130M CBay Bay1 Bay2 Product Amount in g Amount in g Amount in g Water, deionized 47.4 47.4 47.4 Tego ® Dispers 755 30.0 Rewoferm ® SL One 30.0 RHEANCE ® One 30.0 Tego ® Foamex 830 2.0 2.0 2.0 Aerosil ® 200 0.6 0.6 0.6 Bayferrox ® 130 M 120.0 120.0 120.0

TABLE-US-00003 TABLE 1.3 Pigment concentrates comprising Heliogen Blue L7101F CBlue Blue1 Blue2 Product Amount in g Amount in g Amount in g Water, delonized 42.1 42.1 42.1 Tegoe ® Dispers 755 21.9 Rewoferm ® SL One 21.9 RHEANCE ® One 21.9 Tego ® Foamex 810 1.0 1.0 1.0 Heliogen Blue L7101F 35.0 35.0 35.0

TABLE-US-00004 TABLE 1.4 Pigment concentrates comprising Special Black 4 CBlack Black1 Black2 Product Amount in g Amount in g Amount in g Water, deionzed 42.8 42.8 42.8 Additive 1 31.2 Additive 2 31.2 Additive 3 31.2 Tego ® Foamex 810 1.0 1.0 1.0 Special Black 4 25.0 25.0 25.0

[0097] 2. Determination of Delta E Value

[0098] For performance testing, the respective pigment concentrates from Example 1 were converted to an aqueous coating composition:

[0099] 0.73 g of pigment concentrate and 19.27 g of a polyurethane-based paint of the ContiPur Satin brand from Kluthe were weighed out in a 50 ml cosmetics pot and homogenized with the aid of a Speed Mixer DAC 150 FVZ (from Hauschild) at 2000 rpm for 1 min.

[0100] Thereafter, a rub-out test was conducted in each case. The following results were obtained:

TABLE-US-00005 TABLE 2 L* a* b* Rubout ΔE CBay 66.58 19.30 6.60 1.08 Bay1 67.58 18.73 6.04 0.61 Bay2 67.48 18.04 4.57 0.85 CBlue 65.14 −21.95 −34.39 1.07 Blue1 68.09 −21.67 −31.85 1.04 Blue2 65.73 −21.77 −34.07 0.58 CBlack 49.05 −0.80 −3.35 1.01 Black1 49.19 −0.83 −3.63 0.74 Black2 49.59 −0.81 −3.67 0.68

[0101] On the basis of the low delta E values, the dry paint films obtained by virtue of the use according to the invention have less significant floating effects than the comparative examples. This permits the conclusion that the dried paint film has a homogeneous (colour) appearance.

TABLE-US-00006 TABLE 2a Visual assessment Visual assessment CBay 4 Bay1 2 Bay2 3 CBlue 4 Blue1 3 Blue2 2 CBlack 4 Black1 2 Black2 2

[0102] The visual assessment shows that the dry paint films obtained through the use according to the invention have much smaller differences in hue and distinctly lower spottiness than the comparative examples.

[0103] 3. Testing of Pigment Wetting Characteristics

[0104] The wetting characteristics of pigments were tested by introducing 50 g of demineralized water in each case into a 100 ml wide-neck glass bottle. Then the appropriate amount of the rhamnolipids and phospholipids according to Table 3.1 was added and the mixture was homogenized by upturning the bottle for 30 seconds to obtain a lipid-water mixture. Thereafter, 0.1 g of the pigment Heliogen Blue L7101F was applied to the surface of the lipid-water mixture, and the wetting and settling behaviour of the pigment was observed.

[0105] For the comparative example (CWetting), commercially available TEGO Dispels 755 W was used.

[0106] is The following results were obtained:

TABLE-US-00007 TABLE 3.1 Pigment wetting characteristics CWetting Wetting1 Wetting2 A B C Amount in g Amount in g Amount in g Demineralized water 50.0 50.0 50.0 TEGO Dispers 755 W 0.1 Rewoferm SL ONE 0.1 RHEANCE ® One 0.1 Heliogen Blau L7101F 0.1 0.1 0.1 Time until complete >>60:00 01:43 00:48 wetting [min]

[0107] It was found that the pigments can be wetted more quickly on account of the use according to the invention. In the comparative example, the wetting operation took more than 60 minutes.

[0108] FIG. 2 shows a photograph of the 100 ml wide-neck glass bottles after 2 minutes. it is clearly.sup., apparent that the pigments are lying on the surface of the TEGO Dispers/water mixture (CWetting). Whereas, in the inventive examples, the pigments are wetted and distributed in the lipid-water mixture.