Use of rhamnolipids and/or sophorolipids for increasing coverage and/or for maintaining application properties in the course of storage of coating compositions

Abstract

Rhamnolipids and/or sophorolibids can be used for increasing coverage and/or for maintaining application properties in the course of storage of coating compositions.

Claims

1. A method of increasing coverage and/or maintaining application properties of a coating composition during storage, 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 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.

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

5. 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 rn =2, 1, or 0, n =1 or 0, and R.sup.6 and R.sup.7 =independently an identical or different organic radical having 2 to 24 carbon atoms.

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

7. 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-C10010, 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.

8. 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.

9. The method according to Claim , wherein the at least one sophorolipid is a compound of the formula (II) or (Ha); ##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.

10. 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.

11. The method according to claim 4, 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.

12. The method according to claim 5, 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.

13. The method according to claim 5, 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.

14. The method according to claim 7, wherein the weight ratio of di-rharnnoiipids to mono-rhamnolipids is greater than 98:2.

15. The method according to claim 10, 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

DETAILED DESCRIPTION OF THE INVENTION

[0031] This variance of the rheology profile is quantified by measurement of the viscosity of a coating composition at particular shear rates before and after storage. In the paints industry, viscosity values before (for example one day after production of the coating composition) and after storage (for example one week after production of the coating composition) at the shear rates of 1/sec. 100/sec and 1000/sec are typically employed in order to make a statement as to the application properties of the coating composition. The greater the numerical value of the viscosity ratio established, the greater the variance from the desired theology profile established as well.

[0032] 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, pouring or painting application, and various printing methods.

[0033] Examples of coating materials in the context of the present invention are paints, coating materials, printing inks and other coating materials, such as soiventborne or aqueous coatings and solvent-free coatings, powder coatings. UV-curable coatings, low-soiids, 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, Lackformuiierung 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, Strählenhartung [Radiative Curing], Vincent Verlag, Hanover (1996)”.

[0034] Coating materials and coating compositions are used as synonyms.

[0035] The paints and coating matenals 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.

[0036] 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.

[0037] The coating compositions preferably include solids selected from the group of the fillers, pigments, dyes, optical bnghteners, ceramic materials, magnetic materials.

[0038] 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 Veriag, Hannover (1997)”.

[0039] 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)”.

[0040] 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.

[0041] 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 methyl or ethyl acetate, hydrocarbons such as petroleum spirits of vanous boiling ranges, alcohols, ethers, glycols and glycol ethers) and/or water, as known as prior art depending on the binders used.

[0042] It is possible to use customary binders. It is possible with preference to use aikyd. acrylate, styrene-acryiate, 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.

[0043] It is conceivable that the coating composition comprises further additives, for example preferably wetting agents, dispersing additives, rheology additives, levelling aids or defoamers.

[0044] Rhamnolipids and sophorolipids are surfactants which can be prepared by means of fermentation.

[0045] Rhamnolipids are composed of one to two rhamnose units and one to three, mostly 62 -hydroxy fatty acids. The fatty acids can be saturated or unsaturated.

[0046] 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).

[0047] 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

[0048] WO 2001 010447 and EP1 889 623 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.

[0049] The rhamnolipids are preferably compounds of the general formula (I) or salts thereof

##STR00003## [0050] where [0051] m=2.1 or 0, especially 1 or 0, [0052] n=1 or 0, especially 1, [0053] 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 tridecenyi and (CH2).sub.x-CH3 with x=1 to 23, preferably 4 to 12.

[0054] Preference is given to a mixed composition of rhamnolipids containing >90% diRL.

[0055] Preference is given to a mixed composition of rhamnolipids containing

51% by weight to 95% by weight of diRL-C10C10 and
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-rhamnoiipids to mono-rhamnolipids is greater than 91:9, preferably greater than 97:3, more preferably greater than 98:2.

[0056] 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.

[0057] The sophorolipids are preferably compounds of the formula (II) or (IIa)

##STR00004## [0058] where [0059] R.sup.1 and R.sup.2 are independently either H or an acetyl group, [0060] R.sup.3 is H, a methyl, ethyl or hexyl group. [0061] R.sup.4 is independently a saturated or unsaturated divalent branched or unbranched organic group, [0062] R.sup.5 is H or a methyl group. [0063] 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.

[0064] Rharnnolipids are available under the Natsurfact name from Stepan (Northfield, Ill., USA) and RHEANCE® One from Evonik Operations GmbH.

[0065] Sophorolipids are available under the HoneySurf name from Holiferm Limited (Manchester. UK) and REWOFERM® SL ONE from Evonik Operations GmbH.

[0066] Preference is given to using rharnnolipids 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.

[0067] Preference is given to using the rharnnolipids and sophorolipids of the general formulae (I), (II) and (IIa) for increasing the storage stability of coating compositions.

[0068] Preference is given to using the rhamnolipids and sophorolipids of the general formulae (I), (II) and (IIa) for reducing the amount of coating compositions used.

[0069] The invention is to be elucidated in detail hereinafter by working examples.

Methods

Determination of rheology profile and viscosity ratio

[0070] The rheology profile of the coating compositions is determined with the aid of a rotary viscometer (Euro Physics. Rheo 2000 RC20). The measurement system used was a plate/cone system (45 mm. angle 1°, measurement temperature 25′C). The following shear rates and residence times were chosen:

0.1 to 10 s.sup.−1 in 60 s

10 to 90 S.SUP.−1 .in 30 s

[0071] 100 to 1000 s.sup.−1 in 40 s
1000 to 10 000 s.sup.−1 in 40 s

[0072] Variance was assessed using the viscosity values of the coating compositions shown in the rheology profile before and after storage at shear rates of 1, 100 and 1000 s.sup.−1. The viscosity ratio in % can be calculated as follows:

[0073] Viscosity ratio in %=(viscosity, 1 week after production at 50° C./viscosity one day after production)*100

[0074] The greater the numerical value of the viscosity ratio, the greater the variance of the rheology profile after storage from the desired rheology profile established.

Coverage

[0075] The coverage of a coating composition is defined in the “Richtlinie zur Bestimmung des Deckvermögens”. VdL-RL 09 from the Verfcand der deutschen Lackindustrie e. V., July 2002 edition.

[0076] A substrate with a standardized surface having black and white fields (Form 2A from Leneta) was weighed. The paint was applied to the substrates with the aid of a film applicator in wet film thicknesses of 150, 200 and 240 μm. The freshly coated substrates were weighed again and then dried at 23° C. and 50% air humidity for 24 hours. Thereafter, the contrast ratio of ail drawdowns was measured with a Byk Gardner spectrophotometer with a gloss trap For this purpose, measurement was effected at five measurement points, in each case in three black fields (Ys values) and in each case in three white fields (Yw values).

[0077] The contrast ratio was ascertained by forming the quotient Ys/Yw * 100 [%] of the average values Yw and Ys. Coverage was then ascertained in m.sup.2/l at 99.5% contrast ratio, taking account of the specific density of the paint and the amount of paint applied in each case.

EXAMPLES

1. Production of a Coating Composition

[0078] For the performance assessment, coating compositions CE1. E2 and E3 were produced according to the figures from Table 1. Comparative example CE1 was produced with the commercial dispersant Tego Dispers 747 W.

[0079] First of all, positions 1 to 5 were initially charged and homogenized with a Dispermat (Dispermat CA from VMA-Getzmann GmbH) at 800 rpm for five minutes, then position 6 was added while stirring at 800 rpm and the mixture was stirred for 2 minutes. Positions 7 to 11 were then added at 2500 rpm and the mixture was stirred for 30 minutes. Subsequently, the formulation was cooled down by stirring at 500 rpm for 15 minutes. Positions 12 to 14 were added while stirring at 2500 rpm.

TABLE-US-00001 TABLE 1 CE1 E2 E3 Amount Amount Amount Product in g in g in g Manufacturer Description  1 Deionized water 20.7 20.7 20.7 Evonik Operations GmbH  2 Calgon N 0.1 0.1 0.1 BK Giulini Polyphosphate  3 Additive 1: Tego Dispers 747 0.2 Evonik Operations GmbH Copolymer Additive 2: Rewoferm SL One 0.2 Evonik Operations GmbH Sophorolipid Additive 3: RHEANCE ® One 0.2 Evonik Operations GmbH Rhamnolipid  4 Acticid MBS 0.2 0.2 0.2 Thor GmbH Biocide  5 Tylose H 30.000 YP 2 0.4 0.4 0.4 SE Tylose GmbH & Co. KG Rheology additive  6 Aqueous ammonium 0.1 0.1 0.1 AUG. HEDINGER Adjustment to hydroxide solution (25%) GmbH & Co. KG pH of 6.5-9.0  7 Tioxide R-TC 90 12 12 12 Huntsman Corporation Pigment  8 Omyacarb Extra CL 5 5 5 Omya GmbH Filler  9 Talkum OOC 5 5 5 Imerys Performance Additives Filler 10 Omyacarb 2 GU 10 10 10 Omya GmbH Filler 11 Omyacarb 10 GU 14 14 14 Omya GmbH Filler 12 Tego Foamex 26 0.3 0.3 0.3 Evonik Operations GmbH Defoamer 13 Mowilith 1871 30 30 30 Celanese Corporation Binder 14 Texanol 2 2 2 Eastman Corporation Film-forming aid

2. Technical Testing

[0080] For performance testing, coating compositions CE1, E2 and E3 from Example 1 were examined with regard to Theological characteristics before and after storage, and coverage was determined.

2.1 Coverage

[0081] Table 2 shows the coverage results. It is found that the coating compositions, by virtue of the inventive use of Rewoferm(r) SL ONE or RHEANCE° One, achieved higher coverage at a contrast ratio of 99.5% (class 1) than with conventional TEGO® Dispers 747 W.

TABLE-US-00002 TABLE 2 Coverage Coating Coverage in (m.sup.2/l) compositions at contrast ratio 99.5% CE1 3.67 E2 5.25 E3 4.17

2.2 Viscosity Ratio

[0082] Table 3 shows the measured viscosities of the respective coating composition before and after storage, and their viscosity ratios.

[0083] It is found that the coating compositions, by virtue of the inventive use of Rewoferm(r) SL ONE or RHEANCE® One, have a lower viscosity ratio at the shear rates (1/sec, 100/sec, 1000/sec) than with conventional TEGO® Dispers 747 W. It is thus possible to draw the conclusion that the coating compositions according to the invention better retain application properties in the course of storage than the comparative examples.

TABLE-US-00003 TABLE 3 Shear Viscosity in mPas Viscosity in mPas Viscosity rate 1 day after 1 week after ratio Examples (1/sec) production production at 50° C. in % CE1 1 75700 207000 274% 100 2010 5230 260% 1000 449 414  92% E2 1 67000 97000 145% 100 1990 2570 129% 1000 501 466  93% E3 1 70500 85800 122% 100 2070 2310 112% 1000 484 432  89%