A composition and method for controlling the wettability of surfaces
Abstract
The present invention relates to a composition comprising hedge-hog shaped particles, at least one binder, and at least one hydrophobizing agent and/or at least one hydrophilizing agent, a method for controlling the wettability of substrate surfaces using these compositions, as well as a material comprising these compositions.
Term
5.4 yearsto projected expiry
Projected expiry 9 February 2032, counted from filing; an application has no term until it is granted.
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1 claim: 1 independent, 0 dependent
- 1Claims Zastrzeżenia patentowe 1. A composition containing 1. Kompozycja zawieraj ąca - cząstki w kształcie jeża, - hedge shaped particles, - at least one adhesive and - co najmniej jedno spoiwo oraz - at least one hydrophobizing agent and / or at least one hydrophilizing agent, wherein the hedge-shaped particles consist of a material selected from a material comprising calcium carbonate, satin white and mixtures thereof. - co najmniej jeden środek hydrofobizuj ący i/lub co najmniej jeden środek hydrofilizujący, przy czym cząstki w kształcie jeża składają się z materiału wybranego spośród materiału zawierającego węglan wapnia, bieli satynowej i ich mieszanin. 2. Kompozycja według zastrzeżenia 1, znamienna tym, że spoiwo działa jako co najmniej jeden środek hydrofobizuj ący i/lub co najmniej jeden środek hydrofilizuj ący. A composition according to claim 1, characterized in that the binder acts as at least one hydrophobizing agent and / or at least one hydrophilizing agent. 3. A composition according to any one of claims 1 or 2, characterized in that the material comprising calcium carbonate is selected from precipitated calcium carbonate, a natural material containing calcium carbonate and mixtures thereof. 3. Kompozycja według któregokolwiek z zastrzeżeń 1 albo 2, znamienna tym, że materiał zawieraj ący węglan wapnia jest wybrany spośród strącanego węglanu wapnia, naturalnego materiału zawieraj ącego węglan wapnia i ich mieszanin. 4. Kompozycja według któregokolwiek z poprzednich zastrzeżeń, znamienna tym, że cząstki w kształcie jeża składaj ą się z materiału obejmuj ącego aragonitowy, kalcytowy, waterytowy strącany węglan wapnia lub ich mieszaniny. Composition according to any one of the preceding claims, characterized in that the hedge-shaped particles consist of a material comprising aragonite, calcite, vater precipitated calcium carbonate or mixtures thereof. 5. Kompozycja według któregokolwiek z poprzednich zastrzeżeń, znamienna tym, że cząstki w kształcie jeża składaj ą się z materiału obejmuj ącego skupiska i/lub agregaty strącanego węglanu wapnia w postaci kryształów klasy skalenoedrycznej lub podwójnej piramidy rombowej. The composition according to any one of the preceding claims, characterized in that the hedge-shaped particles consist of a material comprising aggregates and / or aggregates of precipitated calcium carbonate in the form of scalenohedral crystals or a double rhombic pyramid. 6. A composition according to any one of the preceding claims, characterized in that the hedge-shaped particles have a BET specific surface area of 1 to 50 m.2/ g, preferably 2 to 40 m2/ g, more preferably 11 to 35 m2/ g, most preferably 15 to 20 m2/ g, measured using nitrogen using the BET method according to ISO 9277. 6. Kompozycja według któregokolwiek z poprzednich zastrzeżeń, znamienna tym, że cząstki w kształcie jeża maj ą powierzchnię właściwą BET od 1 do 50 m2/g, korzystnie 2 do 40 m2/g, korzystniej 11 do 35 m2/g, najkorzystniej 15 do 20 m2/g, mierzoną z użyciem azotu metodą BET zgodnie z ISO 9277. 7. Composition according to any one of the preceding claims, characterized in that the hedge-shaped particles have a weight median d50 particle diameter from 1 μm to 50 gm, preferably 2 μm to 40 gm, more preferably 3 μm to 30 μm. 7. Kompozycja według któregokolwiek z poprzednich zastrzeżeń, znamienna tym, że cząstki w kształcie jeża maj ą ważoną medianę średnicy cząstek d50 od 1 μm do 50 gm, korzystnie 2 μm do 40 gm, korzystniej 3 μm do 30 μm. 8. A composition according to any one of the preceding claims, characterized in that the hydrophobizing agent is selected from the group consisting of fatty acids, such as stearic acid, palmitic acid and their salts; alkyl ketene dimer; polyacrylamide resins; silicone resins, polysiloxanes, preferably polysiloxane modified with functional silicone resin and mixtures thereof. 8. Kompozycja według któregokolwiek z poprzednich zastrzeżeń, znamienna tym, że środek hydrofobizuj ący jest wybrany z grupy obejmuj ącej kwasy tłuszczowe, takie jak kwas stearynowy, kwas palmitynowy i ich sole; dimer alkiloketenu; żywice poliakryloamidowe; żywice silikonowe, polisiloksany, korzystnie polisiloksan modyfikowany żywicą silikonową z grupami funkcyjnymi oraz ich mieszaniny. 9. A composition according to any one of the preceding claims, characterized in that the hydrophilizing agent is selected from the group consisting of polyacrylic acids, salts of 1-hydroxyethane-1,1-diphosphonic acid, preferably its alkali metal salts, more preferably its potassium salts; and 1-hydroxyethane-1,1-diphosphonic acid chelates, preferably its chelates with aluminum hydroxide, more preferably aluminum hydroxide / 1-hydroxyethane-1,1-diphosphonic acid with a weight ratio of 1:5, and mixtures thereof. 9. Kompozycja według któregokolwiek z poprzednich zastrzeżeń, znamienna tym, że środek hydrofilizujący jest wybrany z grupy obejmującej polikwasy akrylowe, sole kwasu 1-hydroksyetano-1,1-difosfonowego, korzystnie jego sole z metalami alkalicznymi, korzystniej jego sole potasowe;oraz chelaty kwasu 1-hydroksyetano-1,1-difosfonowego, korzystnie jego chelaty z wodorotlenkiem glinu, korzyst23 niej chelaty wodorotlenek glinu/kwas 1-hydroksyetano-1,1-difosfonowy o stosunku wagowym 1:5, oraz ich mieszaniny. 10. A composition according to any one of the preceding claims, characterized in that at least one hydrophobizing agent or at least one hydrophilizing agent or mixture thereof is present in an amount of from 0.1 to 10% by weight, preferably 0.2 to 5% wt., more preferably 0.3 to 2.4 wt.%, most preferably 0.4 to 1.9 wt.%, especially 0.5 to 1.5 wt.%, based on the weight of the hedge-shaped particles. 10. Kompozycja według któregokolwiek z poprzednich zastrzeżeń, znamienna tym, że co najmniej jeden środek hydrofobizuj ący lub co najmniej jeden środek hydrofilizujący lub ich mieszanina, są obecne w ilości od 0,1 do 10% wag., korzystnie 0,2 do 5% wag., korzystniej 0,3 do 2,4% wag., najkorzystniej 0,4 do 1,9% wag., zwłaszcza 0,5 do 1,5% wag., w przeliczeniu na masę cząstek w kształcie jeża. 11. A composition according to any one of the preceding claims, characterized in that the binder is selected from the group consisting of latex binder, hybrid binder systems, preferably homopolymers or copolymers of acrylic and / or methacrylic acid, itaconic acid;and acid esters, such as e.g. ethyl acrylate, butyl acrylate;styrene, unsubstituted or substituted vinyl chloride, vinyl acetate, ethylene, butadiene, acrylamides and acrylonitrile;silicone resins, alkyd resins diluted with water, combinations of acrylic / alkyd resin, polyvinyl alcohol, natural oils, preferably linseed oil, and mixtures thereof. 11. Kompozycja według któregokolwiek z poprzednich zastrzeżeń, znamienna tym, że spoiwo jest wybrane z grupy obejmuj ącej spoiwa lateksowe, hybrydowe układy spoiw, korzystnie homopolimery lub kopolimery kwasu akrylowego i/lub metakrylowego, kwasu itakonowego;oraz estrów kwasów, takich jak np. akrylan etylu, akrylan butylu;styrenu, niepodstawionego lub podstawionego chlorku winylu, octanu winylu, etylenu, butadienu, akryloamidów i akrylonitryli;żywice silikonowe, żywice alkidowe rozcieńczalne wodą, połączenia żywica akrylowa/alkidowa, polialkohol winylowy, naturalne oleje, korzystnie olej lniany, oraz ich mieszaniny. 12. A composition according to any one of the preceding claims, characterized in that the binder is present in an amount up to 250% by weight, preferably up to 200% by weight, more preferably up to 150% by weight, most preferably up to 120% by weight. and it is particularly preferably present in an amount of from 1 to 50 wt.%, preferably from 3 to 25 wt.%, more preferably from 5 to 20 wt.%, particularly preferably from 10 to 15 wt.%, based on the weight of the particles in the shape hedgehog. 12. Kompozycja według któregokolwiek z poprzednich zastrzeżeń, znamienna tym, że spoiwo jest obecne w ilości do 250% wag., korzystnie do 200% wag., korzystniej do 150% wag., najkorzystniej do 120% wag. i szczególnie korzystnie jest obecne w ilości od 1 do 50% wag., korzystnie od 3 do 25% wag., korzystniej od 5 do 20% wag., szczególnie korzystnie od 10 do 15% wag., w przeliczeniu na masę cząstek w kształcie jeża. 13. A composition according to any one of the preceding claims, characterized in that the hedge-shaped particles are connected to at least one hydrophobicizing agent and / or at least one hydrophilizing agent and to at least one binder. 13. Kompozycja według któregokolwiek z poprzednich zastrzeżeń, znamienna tym, że cząstki w kształcie jeża są połączone z co najmniej jednym środkiem hydrofobizuj ącym i/lub co najmniej jednym środkiem hydrofilizuj ącym oraz z co najmniej jednym spoiwem. 14. A composition according to any one of the preceding claims, characterized in that the hedge-shaped particles are pre-treated with at least one hydrophobicizing agent and / or at least one hydrophilizing agent, and at least one binder is added to the hollow-shaped particles undergoes. pre-treatment with at least one hydrophobizing agent and / or at least one hydrophilizing agent or mixtures thereof. 14. Kompozycja według któregokolwiek z poprzednich zastrzeżeń, znamienna tym, że cząstki w kształcie jeża są poddawane wstępnej obróbce co najmniej jednym środkiem hydrofobizuj ącym i/lub co najmniej jednym środkiem hydrofilizuj ącym, oraz co najmniej jedno spoiwo dodaje się do cząstek w kształcie jeża poddanych wstępnej obróbce co najmniej jednym środkiem hydrofobizuj ącym i/lub co najmniej jednym środkiem hydrofilizuj ącym albo ich mieszaninami. 15. A composition according to claim 14, characterized in that further another at least one hydrophobicizing agent and / or at least one hydrophilizing agent is additionally additionally added, which may be the same or different than the means used in the pre-treatment. 15. Kompozycja według zastrzeżenia 14, znamienna tym, że ponadto dodatkowo dodaje się kolejny co najmniej jeden środek hydrofobizuj ący i/lub co najmniej jeden środek hydrofilizuj ący, które mogą być takie same lub inne niż środki stosowane w obróbce wstępnej. 16. A composition according to any one of claims 1 to 13, characterized in that the hedge-shaped particles are first mixed with the binder and then combined with at least one hydrophobicizing agent and / or at least one hydrophilizing agent. 16. Kompozycja według któregokolwiek z zastrzeżeń 1 do 13, znamienna tym, że cząstki w kształcie jeża najpierw miesza się ze spoiwem, a następnie łączy się z co najmniej jednym środkiem hydrofobizuj ącym i/lub co najmniej jednym środkiem hydrofilizuj ącym. 17. A composition according to any one of the preceding claims, characterized in that it is in the form of a coating formulation. 17. Kompozycja według któregokolwiek z poprzednich zastrzeżeń, znamienna tym, że jest w postaci preparatu powłokowego. 18. A composition according to claim 17, characterized in that it is provided in the form of a solution or dispersion in a suitable liquid medium, preferably in a medium selected from the group consisting of water, alcohol ethers, alcohols, aliphatic hydrocarbons, esters and mixtures thereof. 18. Kompozycja według zastrzeżenia 17, znamienna tym, że jest dostarczana w postaci roztworu lub dyspersji w odpowiednim ciekłym ośrodku, korzystnie w ośrodku wybranym z grupy obejmuj ącej wodę, etery alkoholi, alkohole, alifatyczne węglowodory, estry i ich mieszaniny. 19. A composition according to any one of claims 17 or 18, characterized in that it further comprises additives such as dispersing agents, silicone agents, thickeners, rheology modifiers, anti-settling agents, defoamers, antioxidants, coloring agents. , surfactants, cross-linking agents, flame retardants, catalysts, pI buffers, fillers, dyes, pigments, optical brighteners, waxes, coalescing agents, biocides and mixtures thereof. 19. Kompozycja według któregokolwiek z zastrzeżeń 17 albo 18, znamienna tym, że ponadto zawiera dodatki, takie jak środki dysperguj ące, środki silikonizuj ące, środki zagęszczaj ące, modyfikatory właściwości reologicznych, środki zapobiegaj ące osiadaniu, środki przeciwpieniące, przeciwutleniacze, środki farbkuj ące, środki powierzchniowo czynne, środki sieciuj ące, środki zmniejszaj ące palność, katalizatory, bufory pI, wypełniacze, barwniki, pigmenty, wybielacze optyczne, woski, środki wywołuj ące koalescencj ę, środki biobójcze i ich mieszaniny. 20. A method for adjusting the wettability of a substrate surface by coating a substrate with a composition according to any one of claims 1 to 19. 20. Sposób regulacji zwilżalności powierzchni podłoża przez powlekanie podłoża kompozycj ą według któregokolwiek z zastrzeżeń 1 do 19. 21. Sposób według zastrzeżenia 20, znamienny tym, że podłoże powleka się preparatem powłokowym z kompozycji zawieraj ącej cząstki w kształcie jeża, co najmniej jedno spoiwo i co najmniej jeden środek hydrofobizuj ący i/lub co najmniej jeden środek hydrofilizuj ący. 21. The method according to claim 20, characterized in that the substrate is coated with a coating formulation from a composition comprising hedge-shaped particles, at least one adhesive and at least one hydrophobizing agent and / or at least one hydrophilizing agent. 22. A method according to any one of claims 20 or 21, characterized in that the substrate is coated with a coating formulation from a composition comprising hedge shaped particles pre-treated with at least one hydrophobicizing agent and / or at least one hydrophilizing agent and mixed with at least one binder, wherein, optionally, a further at least one hydrophobizing agent and / or at least one hydrophilizing agent may be additionally added, which may be the same or different than the pre-treatment agents, before applying the coating formulation to the substrate . 22. Sposób według któregokolwiek z zastrzeżeń 20 albo 21, znamienny tym, że podłoże powleka się preparatem powłokowym z kompozycji zawieraj ącej cząstki w kształcie jeża, poddane wstępnej obróbce co najmniej jednym środkiem hydrofobizuj ącym i/lub co najmniej jednym środkiem hydrofilizuj ącym oraz zmieszane z co najmniej jednym spoiwem, przy czym, ewentualnie, dodatkowo można dodać kolejny co najmniej jeden środek hydrofobizuj ący i/lub co najmniej jeden środek hydrofilizuj ący, które mogą być takie same lub inne niż środki stosowane w obróbce wstępnej, przed naniesieniem preparatu powłokowego na podłoże. 23. A method according to any one of claims 20 or 21, characterized in that the substrate is first coated with a coating composition of a composition comprising hedge-shaped particles and at least one adhesive, followed by one or more successive layers of at least one hydrophobizing agent and / or at least one hydrophilizing agent on the top of the hollow particle and adhesive coating. 23. Sposób według któregokolwiek z zastrzeżeń 20 albo 21, znamienny tym, że podłoże powleka się najpierw preparatem powłokowym z kompozycji zawieraj ącej cząstki w kształcie jeża i co najmniej jedno spoiwo, następnie jedną lub większą liczbą warstw następczych z co najmniej jednego środka hydrofobizującego i/lub co najmniej jednego środka hydrofilizuj ącego na wierzchu powłoki z cząstek w kształcie jeża i spoiwa. 24. Sposób według któregokolwiek z zastrzeżeń 20 do 23, znamienny tym, że podłoże dodatkowo powleka się jedną lub większą liczbą warstw następczych z co najmniej jednego środka hydrofobizuj ącego i/lub co najmniej jednego środka hydrofilizuj ącego. 24. The method according to any one of claims 20 to 23, characterized in that the substrate is additionally coated with one or more sequential layers of at least one hydrophobizing agent and / or at least one hydrophilizing agent. 25. Sposób według któregokolwiek z zastrzeżeń 20 do 24, znamienny tym, że podłoże dodatkowo powleka się jedną lub większą liczbą warstw następczych z dodatkowych składników i dodatków, korzystnie materiałów wybranych z grupy obejmuj ącej żywice, silikony, związki tetrafluorowe. Method according to any of claims 20 to 24, characterized in that the substrate is additionally coated with one or more successive layers of additional components and additives, preferably materials selected from the group consisting of resins, silicones, tetrafluoro compounds. 26. Sposób według któregokolwiek z zastrzeżeń 20 do 25, znamienny tym, że podłoże jest wybrane z grupy obejmuj ącej papier, płytę, tapetę, drewno, kompozyty drzewne, takie jak płyta wiórowa, tworzywa sztuczne, folię, beton, powlekaną lub niepowlekaną obrzutkę, tynk, metale, ceramikę, kamień, cegłę i szkło. 26. The method according to any one of claims 20 to 25, characterized in that the substrate is selected from the group consisting of paper, board, wallpaper, wood, wood composites, such as particle board, plastics, foil, concrete, coated or uncoated rending, plaster, metals, ceramics, stone, brick and glass. 27. Use of a composition according to any of claims 1 to 19 as a coating formulation. 27. Zastosowanie kompozycji według któregokolwiek z zastrzeżeń 1 do 19, jako preparatu powłokowego. 28. A material comprising a composition according to any one of claims 1 to 19, which material is preferably selected from the group consisting of paper, sheet, wallpaper, wood, wood composites, such as particle board, plastics, foil, concrete, coated or uncoated coat, plaster, metals, ceramics, stone, brick and glass. 28. Materiał zawieraj ący kompozycj ę według któregokolwiek z zastrzeżeń 1 do 19, który to materiał korzystnie jest wybrany z grupy obejmuj ącej papier, płytę, tapetę, drewno, kompozyty drzewne, takie jak płyta wiórowa, tworzywa sztuczne, folię, beton, powlekaną lub niepowlekaną obrzutkę, tynk, metale, ceramikę, kamień, cegłę i szkło. Authorized by: Omya International AG Uprawniony: Omya International AG Pełnomocnik: Proxy: MSc. Agnieszka Marszałek Patent attorney mgr inż. Agnieszka Marszałek Rzecznik patentowy Fig. La Fig. la Fig * 2a Fig* 2a Fig. 3a Fig. 3a Fig. 4 Fig. 4 Measurements of the contact angle Pomiary kąta zwilżania - Próbki 1 do 4 - - Samples 1 to 4 - Fig. 5 Fig. 5 Fig. 6 Fig. 6 Measurements of the contact angle Pomiary kąta zwilżania - Próbki 5 do 8 - - Samples 5 to 8 - Kąta zwilżania [°] Kąta zwilżania [°] Wetting angle [°] Wetting angle [°] Fig. 7 Fig. 7 Measurements of the contact angle - Samples 9 to 12 - Pomiary kąta zwilżania - Próbki 9 do 12 - Fig. 8 Fig. 8 Measurements of the contact angle Pomiary kąta zwilżania - Próbki 13 do 16 Kąta zwilżania [°J - Samples 13 to 16 Wetting angle [° J Fig. 9 Fig. 9 Fig. 10 Fig. 10 Measurements of the contact angle Pomiary kąta zwilżania - Próbki 17 do 21 Kąta zwilżania [°] Kąta zwilżania [°] - Samples 17 to 21 Wetting angle [°] Wetting angle [°] Fig. 11 Fig. 11 Measurements of the contact angle Pomiary kąta zwilżania 28SA 28SA Fig. 16 Fig. 16 160 160 140 140 120 120 100 - 80 100 — 80 27SA 27SA Measurements of the contact angle - Samples 23 to 26 26A2 Pomiary kąta zwilżania - Próbki 23 do 26 26ŚA2 26SA1 26SA1 Fig. 17 Fig. 17 Measurements of the contact angle - Samples 27 to 29 - Pomiary kąta zwilżania - Próbki 27 do 29 -
387 paragraphs, as filed
The present invention relates to compositions for the regulation of surface wettability, coating compositions containing them, a method of regulating surface wettability using such a composition or a suitable coating formulation and their uses.
[0002] There is a constant interest in providing materials with tailor-made properties by adjusting the properties of their surface structure. One well-known example is the lotus effect relating to the very high water repellency (superhydrophobicity) of the leaves of certain plants on which dirt particles are captured by water droplets due to the complex micro- and nanoscopic surface architecture, which minimizes adhesion.
[0003] Due to their high surface tension, water droplets tend to minimize their surface in an attempt to achieve a spherical shape. In contact with the surface of adhesive force, they cause the surface to wet.
[0004] In nature, self-purifying properties are due to the hydrophobic, water-repellent double leaf surface structure, composed of a characteristic epidermis and covering waxes. The lotus plant epidermis has warts 10 to 20 μm high and 10 to 15 μm wide, on which so-called epicuticular waxes deposit. Such applied waxes are hydrophobic and form a second layer of the double structure, which causes the contact surface and adhesive strength between the surface and the droplet to be significantly reduced, which results in a self-cleaning process.
[0005] The free energy of the wax surface is relatively small and the contact angle of the water drop on the smooth surface of such a wax material should be> 90 ° but probably <120 °. The structure's effect comes from the exposed tips and margins of the warts, which minimize the surface contact of the solid / liquid, which causes the cohesion forces of the liquid drop to attempt to take a spherical shape (Cassie and Baxter, Trans Faraday Soc. 1944, 40, 546 ). As a result, complete non-wettability can be observed with a contact angle of 180 ° and rolling of the droplets from the surface without leaving a trace. An opposite phenomenon is also known when the internal contact angle is relatively small, e.g. <45 °. Designed textured surface can work so that it increases wetting,
[0006] In particular, the lotus effect has been extensively studied from a theoretical point of view (see, e.g., Narhe et al., Water Condensation on a super-hydrophobic spike surface, Europhys. Lett. 2006, 75 (1), 98 - 104; Wier i in , Langmuir 2006, 22, 2433 - 2436, Gao et al., Langmuir 2007, 23, 3762 - 3765), as well as its practical use in technical applications such as treatments, coatings, paints, tiles, fabrics and other surfaces that can stay dry and clean themselves in the same way as a lotus leaf.
[0007] In this aspect, the required surface structure has been obtained rather by complicated surface modification techniques, e.g. by using excimer laser KrF 248 nm laser in vacuum on PET films (Heitz et al., Dendritic Surface Structures on Excimer- Laser Irradiated PET Foils; Phys. A 1993, 56, 329 - 333), plasma polymerization on substrates, argon plasma pickling, silicon wafer silanization, etc. (Chen et al., Ultrahydrophobic and Ultralyophobic Surfaces:
Some Comments and Examples; Langmuir 1999, 15, 3395-3399; Oner et al., Ultrahydrophobic surfaces. Effects of Topography Length Scales on Wettability, Langmuir 2000, 16, 7777 - 7782); production of complex and oriented ZnO nanostructures using controlled seed growth and citrate anions that are selectively adsorbed on the basic ZnO planes as a structuring agent (Tian et al., Complex and oriented ZnO nanostructures, nature materials 2003, 2, 821 - 826).
[0008] However, in industrial applications, problems arise due to mechanical instability, since artificial surfaces, as opposed to plant structures, are not self-renewing and there is still a need for an innovative material that provides the ability to regulate the surface properties of different materials. In addition, there is a need for easy-to-use formulations, e.g. formulations that can be applied directly to the surface of the substrate in an easy to make and available manner.
[0009] In this aspect, there have been some approaches to obtaining a lotus effect on substrates by coating formulations. For example, EP 1144332 B1 discloses coating formulations consisting of a binder dispersion comprising at least one hydrophobic resin, a resinous material and / or a wax, a filler and optionally conventional additives, the filler being a part of at least a bimodal decomposition. particle size, wherein one particle size region (A) has an average particle diameter of at least 5 μm and the second particle size region (B) has a particle diameter of no more than 3 gm, wherein the weight ratio of the particles of the first particle size region (A) to particles of the last particle size region (B) is 0.01: 1 to 12: 1, and wherein the hydrophilic characteristics of the dispersion components are chosen in such a way,
[0010] In Hu, Z. et al., Colloids and Surfaces A: Physicochem. Eng. Aspcts 351 (2009), 70-70, describes the production of superhydrophobic cellulosic or semi-superhydrophobic papers in which commercial PCC particles, hydrophobic stearic acid and polymer latex particles are used for surface roughness adjustment, respectively, as a hydrophobic surface modifying agent and a polymeric binder. A simple method of coating or dipping was used to produce papers with a high contact angle and high water resistance. It has been found that the pre-treatment of PCC surface with a fatty acid salt before mixing with a polymer binder plays an important role in improving the water contact angle (WCA). The combination of treatment by surface coating with dipping further increases the water contact angle and water resistance of the paper (see abstract).
[0011] In Wang C. et al., Powder Technology 200 (2010), 84-86, a synthetic method for the production of super hydrophobic plaque vaterite is described in which crystallization of vaterite was carried out by reacting sodium carbonate with calcium chloride in the presence of oleic acid and heptadecafluorodecyltrimethoxysilane. (FAS-17), which leads to modification of the surface properties of CaCO3 in situ, the conversion of a naturally hydrophilic material to a hydrophobic and finally a super-hydrophobic one.
However, none of the technical solutions concerning the lotus effect mentioned above concerned the method of regulating the wettability of certain formulations, i.e. for the regulation of wettability on a scale from super hydrophobicity to super-wettability, as needed.
[0013] We have now found that the hedge-shaped particles can be conveniently used in surface modification applications by depositing them in the coating layer using adhesives in such a way that the surface under the SEM microscope still exhibits exposed spikes and tips. If the combination of such hedge-shaped particles and coating formulation, hydrophobizing and / or hydrophilizing agent is added and / or applied on top in a thin layer (from monolayer to multilayer), wettability can be accurately controlled from extremely hydrophobic to extremely hydrophilic.
[0014] It has also been found that mixtures of pre-hydrophobized and pre-hydrophilized hollow-shaped particles can be conveniently used. When the amount of hydrophobized particles exceeds the percolation threshold, the system may exhibit lotus-like downward rolldown while still maintaining hydrophilic centers that collect water by adsorption and allow droplets to grow to a given size at which gravity exceeds strength of adhesion force.
[0015] Accordingly, the present invention relates to a composition comprising
- hedgehog-shaped particles,
- at least one adhesive and
at least one hydrophobizing agent and / or at least one hydrophilizing agent, wherein the hedge-shaped particles consist of a material selected from a material comprising calcium carbonate, satin white and mixtures thereof.
[0016] "Hedge-shaped particles" in the context of the present invention means particles having the shape of a hedgehog, meaning that the particles are shaped such that the spikes and / or tips essentially project radially from the core. This shape may be due to an appropriate crystal growth or may be achieved by particle forming or stenciling techniques known to those skilled in the art.
[0017] It is also possible that the shape of the hedgehog is caused by agglomeration or the formation of clusters of needle-like crystals to form a shape similar to a hedgehog.
[0018] In a preferred embodiment, the calcium carbonate-containing material is selected from precipitated calcium carbonate, a material comprising natural calcium carbonate and mixtures thereof. [0019] If the hedge-shaped particles consist of precipitated calcium carbonate (PCC), it is particularly preferred that the hedge shaped particles consist of a material comprising aragonite, calcite, vater precipitated calcium carbonate or mixtures thereof.
[0020] Particularly useful according to the present invention are hedge shaped particles composed of a material comprising clusters and / or aggregates of precipitated calcium carbonate in the form of scalenohedral crystals or a double rhombic pyramid.
[0021] PCC, which may be particularly useful in the present invention, is prepared by the method described in the unpublished European patent application 10188840.2, in which low grade carbonates can be converted into very pure precipitated calcium carbonates with excellent brightness and a defined structure.
[0022] This is achieved by
a) providing and calcining calcium carbonate containing material;
b) quenching the reaction product obtained in step a) with an aqueous solution of ammonium chloride;
c) separating the components insoluble from the calcium chloride solution obtained in step b);
d) carbonation of the calcium chloride solution obtained in step c);
e) separating the precipitated calcium carbonate obtained in step d).
A special feature of this process for the production of PCC is the combination of the calcium oxide obtained in step a) with an aqueous solution of ammonium chloride in step b), leading to the formation of a highly soluble calcium chloride, while the undesirable impurities originally contained in the raw material containing calcium carbonate remain insoluble or are at least less soluble than calcium chloride in the resulting ammoniacal alkaline environment, allowing them to be separated.
[0024] Furthermore, due to the use of seeding crystals or other structure-modifying chemicals to the calcium chloride solution obtained in step c) before precipitation, crystallization of the precipitated products with a certain shape and size range can be provided.
[0025] Furthermore, PCC, which may conveniently be used in the composition of the present invention, can be obtained by the method described in EP 2371766, more particularly by the method of producing a precipitated calcium carbonate product, comprising the steps of:
(a) forming an aqueous suspension of grains of precipitated calcium carbonate by carbonating a suspension of Ca (OH) 2 in the presence of 0.005 to 0.030 moles of strontium in the form of Sr (OH) 2 per mole of Ca (OH) 2 before or during carbonation;
and (b) forming an aqueous suspension of the precipitated calcium carbonate product by carbonating the Ca (OH) 2 suspension in the presence of 0.5 to 5% by weight of the dry matter of the precipitated calcium carbonate seed material, wherein the seeding material of precipitated calcium carbonate has a d 50, which is less than d50 of the precipitated calcium carbonate product and the seeding material of the precipitated calcium carbonate comprises an aragonite polymorph in an amount greater than or equal to the product amount in the form of precipitated calcium carbonate.
[0026] There are, however, also other techniques for producing hedge shaped PCC particles useful in the present invention, which are well known in the art, e.g. from L. Zhu et al., Journal of Solid State Chemistry 179 (2006), 1247-1252 .
[0027] The hedge shaped particles used in the present invention preferably have a BET specific surface area of 1 to 50 m<sup>2</sup>/ g, particularly preferably 2 to 40 m<sup>2</sup>/ g, more preferably 11 to 35 m<sup>2</sup>/ g, most preferably 15 to 20 m<sup>2</sup>/ g, measured using nitrogen using the BET method according to ISO 9277.
[0028] In a preferred embodiment, the hedge-shaped particles have a median weight median d50 of from 1 μm to 50 μm, preferably from 2 μm to 40 gm, more preferably from 3 μm to 30 μm, determined by sedimentation using the Sedigraph ™ 5100 device from the company Micromeritics, USA. The measurement was carried out in an aqueous solution of Na-P 2 O 7 at a concentration of 0.1% by weight. The samples were dispersed using a high-speed stirrer and ultrasound. [0029] Hydrophobizing agents as well as hydrophilizing agents that may be conveniently used in the context of the present invention are those well known in the field of coatings, paints, etc.
[0030] In a particularly preferred embodiment, the hydrophobizing agent is selected from the group consisting of fatty acids, such as stearic acid, palmitic acid and their salts; alkyl ketene dimer; polyacrylamide resins; silicone resins, polysiloxanes, preferably polysiloxane modified with functional silicone resin, and mixtures thereof. [0031] Particularly preferred hydrophilizing agents are selected from the group consisting of polyacrylic acids, salts of 1-hydroxyethane-1,1-diphosphonic acid, preferably its alkali metal salts, more preferably its potassium salts; and 1-hydroxyethane-1,1-diphosphonic acid chelates, preferably its chelates with aluminum hydroxide, more preferably chelates, aluminum hydroxide / 1-hydroxyethane-1,1-diphosphonic acid with a weight ratio of 1: 5, and mixtures thereof.
[0032] The amounts of at least one hydrophobizing agent and / or at least one hydrophilizing agent also depend on the degree of wettability desired and will be readily determined by suitable tests with the specific agents used.
Typically, the total amount of the at least one hydrophobizing agent and / or at least one hydrophilizing agent will be from 0.1 to 10% by weight, preferably 0.2 to 5% by weight, more preferably 0.3 to 2.4% by weight. wt., most preferably 0.4 to 1.9 wt.%, especially 0.5 to 1.5 wt.%, based on the weight of the hedge-shaped particles.
[0034] The binder used in the present invention may be any conventional binder used in the field of paper and board coating, paint and coating as well as in impregnation. It is preferably selected from the group consisting of latex binders, hybrid binder systems, preferably homopolymers or copolymers of acrylic and / or methacrylic acid, itaconic acid; and acid esters, such as e.g. ethyl acrylate, butyl acrylate; styrene, unsubstituted or substituted vinyl chloride, vinyl acetate, ethylene, butadiene, acrylamides and acrylonitrile; silicone resins, alkyd resins diluted with water, combinations of acrylic / alkyd resin, polyvinyl alcohol, natural oils, preferably linseed oil, and mixtures thereof.
[0035] If binders having hydrophobic and / or hydrophilic properties are used, the binders may act as at least one hydrophobizing agent and / or at least one hydrophilizing agent, i.e. a binder and at least one hydrophobicizing agent and / or at least one hydrophilizing agent. they are identical compounds.
[0036] Depending on the substrate and nature of the gel-like shape, and also hydrophobicizing and / or hydrophilizing agents, the amount of binder that provides for binding of the various components to each other is appropriate. the coated substrate with the composition without affecting their properties.
Typically, the binder is present in an amount of up to 250 wt%, preferably up to 200 wt%, more preferably up to 150 wt%, most preferably up to 120 wt%, and is particularly preferably present in an amount of from 1 to 50 wt%. preferably from 3 to 25 wt.%, more preferably from 5 to 20 wt.%, particularly preferably from 10 to 15 wt.%, based on the weight of the hedge-shaped particles.
[0038] The composition may be provided in various forms.
[0039] In one embodiment of the invention, the hedge-shaped particles are connected to at least one hydrophobizing agent and / or at least one hydrophilizing agent and a binder.
[0040] In another preferred embodiment, the hedge shaped particles are pre-treated with at least one hydrophobizing agent and / or at least one hydrophilizing agent. Thereafter, the hedge-shaped particles treated with at least one hydrophobicizing agent and / or at least one hydrophilizing agent or mixtures thereof are mixed with the binder, wherein, optionally, in addition a further at least one hydrophobizing agent and / or at least one agent can be additionally added. hydrophilizing agents, which may be the same or different from the one used for pre-treatment.
[0041] The composition also includes embodiments in which the hedge-shaped particles are first mixed with the binder and then combined with at least one hydrophobizing agent and / or at least one hydrophilizing agent.
[0042] The composition of the present invention may be provided in the form of a coating formulation, wherein the composition may be dissolved or dispersed in a suitable medium, e.g. in a medium selected from the group consisting of water, alcohol ethers, alcohols, aliphatic hydrocarbons, esters and mixtures thereof.
[0043] In some embodiments, it may be convenient to use solvent mixtures, such as mixtures of water with other solvents, such as e.g. those mentioned above, optionally in combination with conventional additives, such as coalescing agents, e.g.<sup>®</sup>; anti-aging agents, preferably mineral oil and / or silicone based defoamers; rheology modifiers, preferably cellulose ethers, layered silicates, associative and non-associative acrylic polymers or polyurethanes.
[0044] However, it is also possible to use the composition as such, especially if one or more of the ingredients are liquids and they are present in an amount sufficient to evenly distribute it on the surface of the substrate, e.g. linseed oil is used as a binder.
In addition, the coating formulation containing the composition of the invention may contain conventional additives such as dispersing agents, silicone agents, thickeners, rheology modifiers, anti-settling agents, defoamers, antioxidants, dyes, surfactants, cross-linking agents, agents flame retardants, catalysts, pH buffers, fillers, dyes, pigments, optical brighteners, waxes, coalescence agents, biocides etc. in free or encapsulated form, e.g. in the form of slow release formulations, such as those described in EP 2168572 or unpublished patent application no
11188597.6 and mixtures thereof.
[0046] Because the compositions of the invention allow for the regulation of surface wettability, a suitable method for regulating surface wettability is a further aspect of the present invention.
[0047] This is achieved by coating the substrate with the above-described compositions of the invention.
To this end, the composition of the present invention is preferably provided in the form of a coating formulation as described above.
[0049] Thus, the substrate may be coated with a coating composition of a composition comprising hedge-shaped particles, at least one adhesive and at least one hydrophobizing agent and / or at least one hydrophilizing agent.
[0050] The substrate may also be coated with a coating composition of a composition comprising a hedge-shaped particles pretreated with at least one hydrophobicizing agent and / or at least one hydrophilizing agent and mixed with at least one binder, optionally, in addition, further at least one hydrophobizing agent and / or at least one hydrophilizing agent may be added, which may be the same or different from the pre-treatment agent, before applying the coating formulation to the substrate.
[0051] In a further embodiment, the composition may be applied in the form of a coating formulation comprising hedge-shaped particles and a binder which is first applied as a coating to the substrate, while at least one hydrophobicizing and / or hydrophilizing agent is applied to the top of the coating of particles in the shape of a hedgehog and binder as one or several successive layers, such that the composition of the present invention is formed directly on the substrate.
[0052] Such post-layers from at least one hydrophobizing and / or hydrophilizing agent can generally be applied to any of the above-described coating formulations, i.e. they can also be additionally applied to the coating with a mixture of hedge-shaped particles, at least one hydrophobicizing agent. and / or hydrophilising and binder mixtures as well as pre-treated mixtures of particles having been pre-treated with at least one hydrophobising agent and / or at least one hydrophilizing agent or mixtures thereof, and binders to which, optionally, further additions can be made at least one hydrophobizing agent and / or at least one hydrophilizing agent which may be the same or different from the one used for pre-treatment or after-treatment.
[0053] It may also be convenient to apply post-layers from other ingredients and additives to the coatings described above, preferably materials selected from the group consisting of resins, silicones and tetrafluoro compounds.
[0054] Coating of the coating as well as follow-up layers can be carried out by conventional techniques well known in the art and suitable for suitable substrates, e.g. by spraying, dip coating, roller or brush application, wherein the post-treatment layer is conveniently applied in the form of a suitable solution or dispersion at least one hydrophobizing agent and / or at least one hydrophilizing agent or other component or additive when the coating is already dry.
[0055] Coatings as well as successive layers with the same or different compositions and components can be applied once or several times.
[0056] The substrate may be substantially any substrate, e.g. a substrate selected from the group consisting of paper, board, wallpaper, wood, wood composites, such as particle board, plastics, foil, concrete, coated or uncoated renders, plaster, metals, ceramics, stone, brick, glass, etc.
[0057] The coated substrate is conveniently dried, at room temperature or at an elevated temperature, depending on the solvent that is optionally used. [0058] By suitable selection of hydrophobizing agents, hydrophilizers or mixtures thereof, the substrates can be super-hydrophobic to provide the lotus surface effect of the substrate or the super hydrophilicity to provide super-wettability and hydrophobicity / hydrophilicity can be adjusted as required by the appropriate mixture.
[0059] Accordingly, mixtures of pre-hydrophobized and pre-hydrophilized hollow-shaped particles can be advantageously used, e.g. individual hydrophobic centers connected to hydrophobic domains are first formed in a hydrophilic environment. When the amount of hydrophobized particles exceeds the percolation threshold, the system may exhibit lotus-like downward rolldown while still maintaining hydrophilic centers that collect water by adsorption and allow droplets to grow to a given size at which gravity exceeds adhesion forces.
[0060] By suitable selection and mixture of hydrophobizing agents and hydrophilizing agents, contact angles can be obtained that are close to 0 ° to 160 °. For example, contact angles of from 2 ° to 145 °, preferably from 7 ° to 140 °, more preferably from 29 ° to 133 °, especially from 34 ° to 127 °, in particular from 44 ° to 110 °, even more preferably from 48 ° ° to 100 °, most preferably from 58 ° to 86 °.
[0061] Accordingly, the use of the composition described above for the regulation of wettability of the substrate is a further aspect of the present invention, as is the use of the composition of the invention in the coating formulation.
[0062] Therefore, the coatings may be customized as different properties regarding wetting, dehumidifying, coalescence of drops and other fluid interactions are useful in many applications, such as protective coatings for packaging materials ( paper, boards, plastics, foils), for wallpaper, wood, wood composites, such as chipboard, plastic, foil, concrete, coated or uncoated renders, plaster, metals, ceramics, stone, bricks, glass, etc.
[0063] Accordingly, the material comprising the above-described composition is the final aspect of the invention, e.g. a material that is selected from the group consisting of paper, plate, wallpaper, wood, wood composites, such as particle board, plastics, foil, concrete, coated or uncoated plaster, plaster, metals, ceramics, stone, brick, glass, etc. [0064] The following figures, examples and tests will illustrate the present invention, but without intending to limit the invention in any way.
Description of the figures:
[0065]
Figures 1a and 1b show SEM images of Hedge shaped PCC particles for use in the invention.
Figures 2a and 2b show SEM images of Hedge shaped PCC particles for use in the invention.
Figures 3a and 3b show SEM images of Hedge shaped PCC particles for use in the invention.
Figure 4 shows the contact angles of substrates coated with different samples of pre-hydrophobised and / or pre-hydrophilized hedge-shaped particles according to the invention.
Figure 5 shows a photograph of a droplet on a substrate coated with a coating preparation according to the invention with a high contact angle.
Figure 6 shows the contact angles coated with different samples of highly coated, pre-hydrophobised and / or pre-hydrophilized hedge-shaped particles according to the invention, as well as additional hydrophilizing agents.
Figure 7 shows the contact angles coated with different samples of slightly coated, pre-hydrophobised and / or pre-hydrophilized hedge-shaped particles according to the invention, as well as additional hydrophilizing agents.
Figure 8 shows the contact angles of substrates coated with different samples of pre-hydrophilized hedge-shaped particles and various binders.
Figure 9 shows a photo of a droplet on a substrate coated with a coating formulation according to the invention with a small contact angle.
Figure 10 shows the contact angles coated with different samples of pre-hydrophobized and pre-hydrophilized hedge shaped particles according to the invention, as well as additional hydrophilizing agents and binders. Figure 11 shows the contact angles of substrates coated with different samples of pre-hydrophobized hedge shaped particles in association with silicone follow-on layers.
Figure 12 is a photograph illustrating the behavior associated with wetting substrates coated with pre-hydrophilized, hedge shaped particles.
Figure 13 is a photograph illustrating the behavior associated with wetting substrates coated with pre-hydrophobized, hedge-shaped particles.
Figure 14 is a photograph illustrating the behavior associated with wetting substrates coated with pre-hydrophobized hedge shaped particles and with two silicone successive layers.
Figure 15 is a photograph illustrating the behavior associated with wetting substrates coated with pre-hydrophobized hedge shaped particles and with three silicone successive layers.
Figure 16 shows the contact angles coated with different samples of pre-hydrophobized hedge shaped particles using different hydrophobicizing agents and post-layers of hydrophobizing agents.
Figure 17 shows the contact angles of the substrates coated with the various coating formulations and subsequent layers of the invention.
EXAMPLES [0066] The following experiments were performed to determine the properties of the compositions of the invention with respect to wetting substrates. This is achieved by preparing coating formulations, applying them to the substrates, wetting the surface of the substrate, and then measuring the contact angles of the water droplets present on the surface of the substrate, the contact angle being indicative of the hydrophobicity / hydrophilicity of the surface.
[0067] For this purpose, coating formulations of pre-hydrophobic pre-hydrophilized and untreated PCC-shaped hedgehogs, as well as their mixtures, optionally containing further components, have been prepared.
[0068] Such coating formulations were applied to Synteape film<sup>®</sup> and raw paper and, after drying and, in some cases, applying the post-layers from the hydrophobizing agent and other agents, the contact angle and / or the wetting behavior were determined.
Example 1: Hedge-shaped particles pretreated
1. Material
1.1. Laboratory equipment and measurement methods
For coating substrates:
[0069] - Erichsen K-Control-Coater K202 bar coater, Model 624 / serial number 570974 / rod wrapped with wire No. 1 // belt dryer 7.0 mmin<sup>-1</sup>/ 150 ° C
Viscosity measurement [0070] All Brookfield viscosities were measured with a Brookfield DV-II Viscometer viscometer equipped with a LV-3 spindle, at 100 rpm at room temperature (20 ± 3 ° C).
Solids content in an aqueous suspension [0071] In all mineral formulations the solids content (also referred to as "dry mass") was measured using a Mettler Toledo HB 43 -S Moisture instrument
Analyzer.
SEM images:
RDS-ARM-MIC Lims: 220017 [0072] Scanning electron micrographs (SEM) were performed to bring the solids content to a concentration of 20% by weight. in water using ultraturax (rotor-stator mixer). A few drops (about 100 mg) were diluted in 250 ml of distilled water and filtered through a 0.2 gm membrane filter. The preparations obtained in this way on a membrane filter were sprayed with gold and evaluated in SEM at various magnifications.
[0073] With respect to the SEM images of the coatings a sample of the coated substrate was gold-sprayed and evaluated in SEM at various magnifications.
Measurements of the contact angle:
[0074] For measuring the contact angle 4, drops of water, each with a volume of 5 g, were applied on 4 Synteape films<sup>®</sup> and the photo was taken 120 seconds after application. Determination of the contact angle was made with the help of the Image Access database module version 8, based on droplets taken and the mean value calculated.
Camera: Canon EOS 5D Mark II
Lens: Canon EF 100 mm f / 2 8L Macro IS USMDDDD
Setting the difference: 0.3 m
Distance rings - Kenko 12 + 24 + 36 mm spacer rings:
Tripod and lighting
Trigger:
Kaiser three-legged microstatics with drive + 2x Repro RB5055 HF illuminator
Canon with remote control / Time controller TC-80N3
Registration data:
Balance of brightness: Aperture:
Lighting time:
Trigger delay:
Drop size:
automatically
Adjustment of the aperture 32
Automatically
120 s after applying a drop μl
1.2. Raw material [0075]
- PCC 1: precipitated calcium carbonate; solids content 18% by weight; BET specific surface area: 2 m<sup>2</sup>/ g, d50: 8 μm; calcite content> 99%, crystals having a cluster scalenohedral morphology (see Figures 1a and b)
- PCC 2: precipitated calcium carbonate; solids content 14% by weight; BET specific surface area: 11.7 m<sup>2</sup>/ g (see Figures 2a and 2b) [0076] PCC 2 was prepared as follows:
a) Step 1: Preparation of seed material [0077] 160 kg of quicklime, CaO (e.g. quick lime supplied by Mississippi
Lime Co., Ste. Genevieve, Mo) was quenched by adding compound to 1300 liters of tap water at 50 ° C in a stirred reactor. The quicklime was quenched for minutes under continuous stirring and the resulting suspension of calcium hydroxide ("milk of lime") was adjusted to a solids content of 13% by dilution with water at 60 ° C and then sieved through a 100 μm sieve. Prior to carbonation, 5.0% by weight Sr (OI l) 2'8 l of I2O (calculated on the dry weight of calcium hydroxide) was added to milk of lime.
[0078] The precipitation of the PCC seeding material was conducted in a 1000L cylindrical stainless steel reactor with baffles, equipped with gassing stirrer, stainless steel tube for carbonation, gas flow carbon dioxide / air to the rotor, and pI monitoring probe and suspension conductance . 800 liters of the calcium hydroxide slurry obtained in the above quenching step brought to 60 ° C was added to the carbonation reactor. The gas in the form of 6% by volume CO2 in the air in the form of bubbles was then passed up through the suspension at a flow rate of 100 m<sup>3</sup>/ h for 15 minutes (counted to start introducing CO2 gas) while stirring the suspension at 1480 rpm. Subsequently, the volume fraction of CO2 in the gas was increased to 24% and the gas flow rate increased to 200 m<sup>3</sup>/ H. The values for the volume fraction of CO2 and the gas flow rate were maintained at these levels until the end of the reaction. During carbonation, the temperature of the reaction mixture was not controlled and allowed to grow under the influence of heat generated in the exothermic precipitation reaction. After reaching the minimum conductivity value corresponding to the complete conversion of Ca (OI) 2 in PCC, gasification was continued for another 8 minutes before the gas introduction was interrupted. The carbonation time, counted from the start of gas injection to the minimum conductivity, was 84 minutes. The slurry of PCC seeding material was then sieved through a 45 μm sieve and the filtered product was recovered as an aqueous slurry of PCC seeding aragonite. As a result of carbonation of the aragonitic seeding material with the addition of 5.0 wt.%. Sr (OIl) 2'8l I2O yielded an aragonite PCC seed material containing 96.1% aragonite.
[0079] The slurry of PCC seeding aragonite material was post-treated by dewatering and milling to give SSA particles 20.6 m<sup>2</sup>/ g and a weighted median diameter of 0.22 μm.
b) Step 2: Preparation of final aragonite PCC2 [0080] The quenching and carbonation was carried out in the same manner as described above in Step 1, except that no S ^ OffL0.5 O and 2.5 wt% (counted as dry calcium carbonate based on the dry weight of calcium hydroxide) ground aragonite PCC seeding material prepared in Step 1 was added to the milk of lime prior to impregnation with carbon dioxide. The test of the final product in the form of aragonite PCC showed that 77.6 wt. the product had an aragonite crystalline form. In addition, a post-treatment was carried out, as described above in Step 1, yielding particles with an SSA of 11.7 m<sup>2</sup>/ g and median diameter 0.41 gm. Then, an aqueous suspension was prepared having a solids content of 14% by weight. The shape of the hedge shaped PCC2 particles can be seen in detail in Figures 2a and 2b.
Hydrophobizing agents:
[0081] - Mixture of palmitic acid and stearic acid (weight ratio: 1: 1) (30% by weight in 95% ethanol): 0.4 g / 100 g (0.4 pph, parts per 100 parts) (slight coating) ) and 1.9 g / 100 g (1.9 pph) (strong coating) based on PCC mass
Hydrophilizing agents:
[0082]
- Polymer solution, 0.33 wt% partially soluble polyacrylic acid with a molecular weight of 12,000 g / mol and polydispersity D (Mw / Mn) around 3, in which approximately
50 mole% carboxyl groups are neutralized with Na ions<sup>+</sup>; and 0.17 wt%.
NaI2PO4; 0.5 g / 100 g (0.5 pph) based on the PCC mass
- K4-HEDP (potassium salt of hydroxyethane-1,1-diphosphonic acid); solids content 55% by weight; prepared under stirring conditions by adding potassium hydroxide to HEDP until pH 12 is reached:
- Potassium hydroxide (SIGMA-Aldrich Art. No .: 60370)
- HEDP (hydroxyethane-1,1-diphosphonic acid, solids content 60% by weight, CF Budenheim, trade name Budex 5120)
- Al (OH) 3-HEDP (aluminum hydroxide chelate / hydroxyethane-1,1-diphosphonic acid, weight ratio 1: 5); solids content 53% by weight; prepared under stirring conditions by adding aluminum hydroxide to HEDP in a weight ratio of 1: 5 at room temperature until a homogeneous mixture is obtained; then heating to 90 ° C for 1 h until obtaining a chelate solution)
- Al (OH) 3, Martinswerk (ALBEMARLE company), MARTIFIN OL-107
- HEDP (hydroxyethane-1,1-diphosphonic acid, solids content 60% by weight, CF Budenheim, trade name Budex 5120)
Binders [0083]
- Acronal<sup>®</sup> S360D (styrene-acrylic latex); solids content 50% by weight, BASF Art .: 50005 562
- Hycar 1562X117 Emulsion (polar latex with an average acrylonitrile content); solids content 41.4% by weight, Emerald Performance Materials
- PVA BF 05 (polyvinyl alcohol) Chang Chun Petrochemicals Taiwan, diluted with boiling water and cooled, solids content 18% by weight
- Linseed oil, Aldrich Art. No. 430021-250 ML
Agents for forming a post-treatment layer [0084]
- GE Bayer Release Agent M: (silicone agent)
- Stearic acid solution (saturated in 95% ethanol at room temperature (20 ± 3 ° C).
Subsoil:
[0085]
- YUPO (Synteape<sup>®</sup>) / Art .: 675227, white semi-matt PP 18x26 (468 cm<sup>2</sup>); 62 g / m<sup>2</sup>
- Raw paper: Sappi Magno matt classic 18x26 (468 cm<sup>2</sup>) 82 g / m<sup>2</sup>
2. Methods
2.1. Preparation of samples
2.1.1 Pre-treated hydrophobized particles [0086] 4000 g of the respective PCC suspensions were heated to 80 ° C and a blend of palmitic acid and stearic acid (weight ratio: 1: 1) diluted in warm 95% ethanol (about 50 ° C) was added at within 10 minutes. The mixture was stirred for 1 h at 80 ° C in a 5 liter dual walled steel tank equipped with viscosity stirrer and thermostat for temperature control. After cooling the slurry was dried in an oven for 15 h at 120 ° C.
2.1.2. Pre-treated hydrophilized particles [0087] Up to 8000 g of corresponding PCC suspensions of 0.5 pph of the aforementioned polymer solution in the form of a partially-solubilized polyacrylic acid were added within 10 minutes. The mixture was stirred for 1 h at room temperature in a 10-liter plastic pail. The suspensions were dried in an oven for 15 h at 120 ° C.
2.1.3. Coating Formulations [0088] Coating formulations were prepared by adding portions of pre-hydrophobized and / or pre-hydrophilized PCC particles, and optionally further components, such as further hydrophilizing agents (as indicated below) to the mixture (ideally to the solution) of the appropriate binder. in tap water while mixing in the VMA Dispermat<sup>®</sup> (VMA-Getzmann GmbH, Reichshof, Germany) with a dispersing disc with a diameter of 70 mm, followed by mixing the mixture for 1 hour. The coating formulations were filtered through a small tea strainer having a mesh size of 500 μm and the viscosity and solids content were determined (see Tables 1 to 5). [0089] All coating formulations exhibited thixotropic properties and settled.
All coating formulations containing hydrophobic particles exhibited anti-wettability. [0090] The coating formulations were applied as a coating on an impermeable plastic substrate (Synteape®) (two papers per color) and on raw paper for samples 20 (crude) and 21 (crude). For Synteape foils<sup>®</sup> preparations were applied, dried 3 times in
150 ° C under a heater on the conveyor belt and dry for 24 hours at room temperature. The thickness of the obtained films was from 0.1 to 0.3 mg / cm<sup>2</sup>.
2.1.4. Follow-up layer [0091] To confirm the effect of applying the post-treatment layer, the sample 1 was post-treated by applying a silicone aftercoat layer to the top of the coating
PCC after drying. This was done by means of an industrial spray, applying sprayed fog for 3 seconds to the surface coated with the composition. Thus, 1 (sample 22S1), 2 (sample 22S2) and 3 (sample 22S3), silicone follow-up layers were formed on top of the PCC coating.
Table 1: Mixtures of pre-hydrophobized and pre-hydrophilized PCC 1
<td></td><td>Sample 1</td><td>Sample 2</td><td>Sample 3</td><td>Sample 4</td>
<td>Hydrophobized PCC 1 (dry) (0.4 pph)</td><td>190.5 g</td><td>133.3 g</td><td>57.1 g</td><td>-</td>
<td>Hydrophilized PCC 1 (dry)</td><td>-</td><td>57.1 g</td><td>133.2 g</td><td>190.5 g</td>
<td>Acronal S 360 D</td><td>19.0 g</td><td>19.0 g</td><td>19.0 g</td><td>19.0 g</td>
<td>Tap water</td><td>290.5 g</td><td>290.5 g</td><td>290.5 g</td><td>290.5 g</td>
<td>Together</td><td>500.0 g</td><td>500.0 g</td><td>500.0 g</td><td>500.0 g</td>
<td>Viscosity, mPa ^ s / 100 rpm</td><td>130</td><td>102</td><td>160</td><td>152</td>
<td>Final solid content,% by weight</td><td>38.9</td><td>37.9</td><td>39.6</td><td>39.8</td>
Table 2: Mixtures of highly coated, pre-hydrophobized and pre-hydrophilized PCC 2 and additional hydrophilicizing agents
<td></td><td>Sample 5</td><td>Sample 6</td><td>Sample 7</td><td>Sample 8</td>
<td>Hydrophobized PCC 2 (dry) (1.9 pph)</td><td>94.1 g</td><td>85.8 g</td><td>36.8 g</td><td>-</td>
<td>Hydrophilized PCC 2 (dry)</td><td>-</td><td>36.8 g</td><td>85.8 g</td><td>122.5 g</td>
<td>Acronal S 360 D</td><td>9.4 g</td><td>12.3 g</td><td>12.3 g</td><td>12.3 g</td>
<td>Tap water</td><td>294.3 g</td><td>362.8 g</td><td>362.7 g</td><td>362.8 g</td>
<td>K4-HEDP, 55%</td><td>2.0 g</td><td>2.2 g</td><td>2.2 g</td><td>2.2 g</td>
<td>Al (OH) 3-HEDP, 53%</td><td>0.2 g</td><td>0.2 g</td><td>0.2 g</td><td>0.2 g</td>
<td>Together</td><td>400.0 g</td><td>500.0 g</td><td>500.0 g</td><td>500.0 g</td>
<td></td><td>Sample 5</td><td>Sample 6</td><td>Sample 7</td><td>Sample 8</td>
<td>Viscosity mPa ^ s / 100 rpm</td><td>340</td><td>170</td><td>130</td><td>121</td>
<td>Final solid content,% by weight</td><td>24.9</td><td>24.9</td><td>24.8</td><td>25.3</td>
Table 3: Mixtures of slightly coated, pre-hydrophobized and pre-hydrophilized PCC 2 and additional hydrophilizing agents
<td></td><td>Sample 9</td><td>Sample 10</td><td>Sample 11</td><td>Sample 12</td>
<td>Hydrophobized PCC 2 (dry) (0.4 PP<sup>h)</sup></td><td>151.9 g</td><td>86.0 g</td><td>36.9 g</td><td>---</td>
<td>Hydrophilized PCC 2 (dry)</td><td>-</td><td>36.9 g</td><td>86.0 g</td><td>122.9 g</td>
<td>Acronal S 360 D</td><td>15.2 g</td><td>12.3 g</td><td>12.3 g</td><td>12.3 g</td>
<td>Tap water</td><td>561.1 g</td><td>363.0 g</td><td>363.0 g</td><td>363.0 g</td>
<td>K4-HEDP, 55%</td><td>1.6 g</td><td>1.6 g</td><td>1.6 g</td><td>1.6 g</td>
<td>Al (OH) 3-HEDP, 53%</td><td>0.2 g</td><td>0.2 g</td><td>0.2 g</td><td>0.2 g</td>
<td>Together</td><td>730.0 g</td><td>500.0 g</td><td>500.0 g</td><td>500.0 g</td>
<td>Viscosity mPa ^ s / 100 rpm</td><td>110</td><td>130</td><td>130</td><td>127</td>
<td>Final solid content,% by weight</td><td>21.9</td><td>26.0</td><td>26.0</td><td>26.0</td>
Table 4: Various binders used with pre-hydrophilized PCC1
<td></td><td>Sample 13</td><td>Sample 14</td><td>Sample 15</td><td>Sample 16</td>
<td>Hydrophilized PCC 1 (dry)</td><td>152.0 g</td><td>145.5 g</td><td>142.9 g</td><td>136.5 g</td>
<td>Hycar, 41.4 wt%</td><td>18.4 g</td><td>35.1 g</td><td>-</td><td>-</td>
<td>PVA, 15 wt.%</td><td>-</td><td>-</td><td>49.3 g</td><td>94.1 g</td>
<td>Tap water</td><td>249.6 g</td><td>319.4 g</td><td>182.9 g</td><td>164.4 g</td>
<td>Together</td><td>420.0 g</td><td>500.0 g</td><td>275.0 g</td><td>395.0 g</td>
<td>Viscosity mPa ^ s / 100 rpm</td><td>177</td><td>177</td><td>719</td><td>388</td>
<td>Final solid content,% by weight</td><td>37.4</td><td>31.4</td><td>39.5</td><td>38.1</td>
Table 5: Various PCC in the presence of further hydrophilizing agents
<td></td><td>A sample 17</td><td>A sample 18</td><td>A sample 19</td><td>A sample 20</td><td>A sample 21</td>
<td>Hydrophilized PCC 1 (dry)</td><td>73.5 g</td><td>-</td><td>-</td><td>-</td><td>-</td>
<td>Hydrophobized PCC 1 (su<sup>ch</sup>y)</td><td>---</td><td>---</td><td>---</td><td>---</td><td>10.0 g</td>
<td>Hydrophobized PCC 2 (dry) (1.9 pph)</td><td>---</td><td>10.4 g</td><td>10.4 g</td><td>10.0 g</td><td>---</td>
<td>Acronal S 360 D</td><td>-</td><td>-</td><td>-</td><td>-</td><td>-</td>
<td>Linseed oil</td><td>-</td><td>-</td><td>-</td><td>20.0 g</td><td>20.0 g</td>
<td>K4-HEDP</td><td>1.3 g</td><td>-</td><td>-</td><td>-</td><td>-</td>
<td>Al (OH) 3-HEDP</td><td>0.1 g</td><td>-</td><td>-</td><td>-</td><td>-</td>
<td>PVA, 18 wt%</td><td>20.1 g</td><td>69.6 g</td><td>69.6 g</td><td>-</td><td>-</td>
<td>Tap water</td><td>205.0 g</td><td>-</td><td>120.0 g</td><td>-</td><td>-</td>
<td>Together</td><td>300.0 g</td><td>80.0 g</td><td>200.0 g</td><td>30.0 g</td><td>30.0 g</td>
<td>Viscosity mPa ^ s / 100 rpm</td><td>102</td><td></td><td></td><td></td><td></td>
<td>Final solid content,% by weight</td><td>25.2</td><td>24.1</td><td>10.6</td><td></td><td></td>
2.2. Determination of the contact angle [0092] To determine the contact angle of a water droplet, each 5g is applied to a coated Synteape film<sup>®</sup>. The drops obtained in this way were photographed and the contact angle was determined using the Image Access database measurement module, Image Access Version 8. The below-set contact angles are means of several measurements of the same set.
Table 6: Coated sheets and contact angles
<td>A sample</td><td>Shell/ sheet (sheet 1) [mg]</td><td>Coating / sheet (sheet 1) [Mg / cm<sup>2</sup>]</td><td>Shell/ sheet (sheet 2) [mg]</td><td>Coating / sheet (sheet 2) [Mg / cm<sup>2</sup>]</td><td>Ratio weight Hydrofob./ Hydrophil. PCC</td><td>Average contact angle [°]</td><td>Std. standard [°]</td>
<td>1</td><td>148.8</td><td>0.3</td><td>115.6</td><td>0.3</td><td>100: 0</td><td>139</td><td>9</td>
<td>2</td><td>129.8</td><td>0.3</td><td>110.7</td><td>0.3</td><td>70:30</td><td>112</td><td>4</td>
<td>3</td><td>133.4</td><td>0.3</td><td>163.2</td><td>0.3</td><td>30:70</td><td>107</td><td>10</td>
<td>4</td><td>140.2</td><td>0.3</td><td>86.8</td><td>0.2</td><td>0: 100</td><td>102</td><td>2</td>
<td>A sample</td><td>Shell/ sheet (sheet 1) [mg]</td><td>Coating / sheet (sheet 1) [mg / cm<sup>2</sup>]</td><td>Shell/ sheet (sheet 2) [mg]</td><td>Coating / sheet (sheet 2) [mg / cm<sup>2</sup>]</td><td>The Hydrophob / Hydrophil weight ratio. PCC</td><td>Average contact angle [°]</td><td>Std. standard [°]</td>
<td>5</td><td>59.8</td><td>0.2</td><td>49.2</td><td>0.2</td><td>100: 0</td><td>100</td><td>4</td>
<td>6</td><td>45.9</td><td>0.2</td><td>37.5</td><td>0.2</td><td>70:30</td><td>67</td><td>3</td>
<td>7</td><td>50.3</td><td>0.2</td><td>51.3</td><td>0.2</td><td>30:70</td><td>61</td><td>9</td>
<td>8</td><td>56.8</td><td>0.2</td><td>51.4</td><td>0.2</td><td>0: 100</td><td>44</td><td>8</td>
<td>9</td><td>38.6</td><td>0.1</td><td>42.7</td><td>0.2</td><td>100: 0</td><td>102</td><td>2</td>
<td>10</td><td>50.7</td><td>0.1</td><td>55.7</td><td>0.2</td><td>70:30</td><td>58</td><td>9</td>
<td>11</td><td>62.5</td><td>0.2</td><td>60.0</td><td>0.2</td><td>30:70</td><td>44</td><td>9</td>
<td>12</td><td>66.0</td><td>0.2</td><td>54.3</td><td>0.2</td><td>0: 100</td><td>29</td><td>7</td>
<td>13</td><td>70.5</td><td>0.3</td><td>84.6</td><td>0.3</td><td>0: 100</td><td>86</td><td>2</td>
<td>14</td><td>85.5</td><td>0.3</td><td>72.8</td><td>0.3</td><td>0: 100</td><td>81</td><td>4</td>
<td>15</td><td>115.8</td><td>0.3</td><td>105.1</td><td>0.3</td><td>0: 100</td><td>48</td><td>11</td>
<td>16</td><td>134.2</td><td>0.3</td><td>113.4</td><td>0.3</td><td>0: 100</td><td>thirty</td><td>8</td>
<td>17</td><td>205.3</td><td>0.7</td><td>197.0</td><td>0.7</td><td>0: 100</td><td>7</td><td>1</td>
<td>18</td><td>300.5</td><td>0.8</td><td>332.5</td><td>0.8</td><td>100: 0</td><td>46</td><td>3</td>
<td>19</td><td>158.2</td><td>0.5</td><td>157.6</td><td>0.5</td><td>100: 0</td><td>34</td><td>3</td>
<td>20</td><td>472.5</td><td>1.5</td><td>405.5</td><td>1.3</td><td>100: 0</td><td>88</td><td>2</td>
<td>20 raw</td><td>---</td><td>---</td><td>---</td><td>---</td><td>100: 0</td><td>110</td><td>3</td>
<td>21</td><td>-</td><td>-</td><td>-</td><td>-</td><td>100: 0</td><td>85</td><td>2</td>
<td>21 raw</td><td>---</td><td>---</td><td>---</td><td>---</td><td>100: 0</td><td>103</td><td>3</td>
<td>22S1</td><td>-</td><td>-</td><td>-</td><td>-</td><td>100: 0</td><td>132</td><td>2</td>
<td>22S2</td><td>-</td><td>-</td><td>-</td><td>-</td><td>100: 0</td><td>133</td><td>5</td>
<td>22S3</td><td>-</td><td>-</td><td>-</td><td>-</td><td>100: 0</td><td>130</td><td>4</td>
[0093] As can be inferred from the above contact angles, the hydrophobicity / hydrophilicity of the substrate surface can be precisely controlled by a tailor-made PCC according to the invention using a hedge shaped PCC.
[0094] As can be seen from samples 1 to 4, the contact angle and therefore the hydrophobicity of the substrate surface can be accurately adjusted by mixing hydrophobized and hydrophilized PCC-shaped hedgehog (see Fig. 4).
[0095] The large contact angle of sample 1 is illustrated in figure 5.
[0096] The same applies to samples 5 to 8 using a slightly different particle form. Also in these tests the contact angle and therefore the hydrophobicity of the substrate surface can be accurately adjusted by mixing hydrophobized and hydrophilized PCC in the shape of a hedgehog. In addition, as can be deduced from these samples, by mixing in further hydrophilizing agents, the hydrophobicity can be reduced if necessary, which is reflected by the smaller contact angles (see Fig. 6).
[0097] As can be seen from the results for samples 9 to 12, which are substantially identical to samples 5 to 8, with the exception that the hydrophobized PCC contains less hydrophobizing agent, the effects can already be observed with a relatively smaller amount of hydrophobizing agent (see Figs. 7).
[0098] In samples 13 to 16, the effect of various binders was evaluated and it was found that even using different binders, hydrophilic properties could be additionally adjusted. Thus, for the same type of hydrophilized PCC, the hydrophilicity can be increased using Hycar instead of Acronal, and can even be further increased using PVA (see Fig. 8).
[0099] As can be deduced from the results for sample 17, this effect can be further increased by the addition of further hydrophilizing agents, which results in almost complete wettability of the substrate surface. The small wetting angle of the sample 17 is shown in Figure 9.
[0100] The effect of different binders on the hydrophobized PCC can be determined from the results for samples 18 to 21. Thus, PVA reduces hydrophobicity compared to Acronal, wherein the effect is dependent on the amount of water in the coating formulation. In this aspect, it has also been shown that hydrophobicity regulation is possible not only for aqueous formulations, but also for oil-based formulations, such as that based on linseed oil (see samples 20 and 21), with similar effects (see Fig. 10).
[0101] Furthermore, by analyzing contact angles for samples 20 and 21 on a Synteape film<sup>®</sup> and raw paper, it can be concluded that a larger contact angle, i.e. increased hydrophobicity, can be obtained on raw paper.
[0102] In the samples 22S1, 22S2, 22S3 the effect of the silicone aftercoating layer was verified. For this purpose, the coating of sample 1 was coated once to three times with silicone successive layers. The results show that the high degree of hydrophobization of the sample 1 is essentially the same as for the siliconized samples (see Fig. 11).
2.3. Wetting [0103] For testing the wetting behavior, in particular the wetting behavior of finely divided droplets of water simulating fog or dew, sheets coated with samples 1, 12, 22S2 and 22S3 were mounted on a metal panel. Deionized water was applied using a microdiffuffer. After each stroke a photo of the sheet was taken and the weight of the deionized water applied was measured. From Table 7, the amounts of deionized water applied can be obtained.
Table 7
<td>Suw no</td><td>Sample 1 [g]</td><td>Sample 12 [g]</td><td>Sample 22S2 [g]</td><td>Sample 22S3 [g]</td>
<td>0</td><td>0,000</td><td>0,000</td><td>0,000</td><td>0,000</td>
<td>1</td><td>0.327</td><td>0.375</td><td>0.256</td><td>0.483</td>
<td>Suw no</td><td>Sample 1 [g]</td><td>Sample 12 [g]</td><td>Sample 22S2 [g]</td><td>Sample 22S3 [g]</td>
<td>2</td><td>0.756</td><td>0.807</td><td>0.668</td><td>0.889</td>
<td>3</td><td>1,253</td><td>1,143</td><td>1,185</td><td>1,240</td>
<td>4</td><td>1,783</td><td>1,467</td><td>1,643</td><td>1,759</td>
<td>5</td><td>2,277</td><td>1,758</td><td>2,022</td><td>2,152</td>
<td>6</td><td>2,753</td><td>2,110</td><td>2,520</td><td>2,623</td>
<td>7</td><td>3.546</td><td>2,480</td><td>3,064</td><td>3,090</td>
<td>8</td><td>3,528</td><td>2,796</td><td>3,599</td><td>3,555</td>
<td>9</td><td>3,970</td><td>3,120</td><td>4,359</td><td>4.005</td>
<td>10</td><td>4,411</td><td>3,421</td><td>4.941</td><td>4,516</td>
<td>11</td><td>4,797</td><td>3,685</td><td>5.491</td><td>4,956</td>
<td>12</td><td>5.271</td><td>3,950</td><td>6,022</td><td>5.468</td>
<td>13</td><td>5.767</td><td>4.209</td><td>6,556</td><td>5,983</td>
<td>14</td><td>6.178</td><td>4,607</td><td>7.044</td><td>6,492</td>
<td>15</td><td>6.677</td><td>5.039</td><td>7.577</td><td>6.959</td>
<td>16</td><td>7.129</td><td>5,461</td><td>8,006</td><td>7.393</td>
<td>17</td><td>7.639</td><td>5.944</td><td>8.422</td><td>7,920</td>
<td>18</td><td>7,992</td><td>6.355</td><td>8.859</td><td>8.363</td>
<td>19</td><td>8.366</td><td>6.799</td><td>9.325</td><td>8.879</td>
<td>20</td><td>8,740</td><td>7,200</td><td>9.828</td><td>9.323</td>
<td>21</td><td>9.129</td><td>7,701</td><td>10.253</td><td>9.874</td>
<td>22</td><td>9.466</td><td>8.149</td><td>10.731</td><td>10.366</td>
<td>23</td><td>9,870</td><td>8.636</td><td>11,185</td><td>10.970</td>
<td>24</td><td>10.143</td><td>9.275</td><td>11.609</td><td>11.529</td>
<td>25</td><td>10.542</td><td>9.776</td><td>12.090</td><td>11.987</td>
[0104] From the images shown in Figures 12 to 15, the wetting behavior (super-wetting) of the hydrophilized PCC 12 sample supporting film wetting can be clearly observed, and droplet formation prevention can be observed compared to samples 1, 22S2 and 22S3 showing non-wettable / super-hydrophobic droplet assisting and rolling of drops, wherein any of these samples were sprayed with the same amount of water of about 5 g, as can be inferred from Table 7 (the bold amounts refer to the samples illustrated in figures 12 to 15) .
Example 2: untreated hedge-shaped particles [0105] In Example 2, instead of pre-hydrophobic / pre-hydrolyzing hedge-shaped particles, untreated particles were combined with suitable hydrophilizing and / or hydrophobizing agents as a result of only preparing the formulation. coating and / or with one or more follow-up layers.
1. Material
1.1. Laboratory instruments and measurement methods
For coating substrates:
[0106] - Erichsen coater K-Control-Coater K202, Model 624 / serial number 570974 / coating rods 1 - 5 (liquid flow regulation) // Belt dryer 7.0 mmin<sup>-1</sup> / 150 ° C
spraying
Eco Spray microburifier, Labo Chimie
Solids content in an aqueous suspension [0107] In all mineral preparations, the solids content (also referred to as "dry weight") was measured with a Mettler Toledo HB 43 -S Moisture Analyzer.
SEM images:
RDS-ARM-MIC Lims: 220017 [0108] Scanning electron micrographs (SEM) were carried out by adjusting the solids content to a concentration of 20% by weight. in water using ultraturax (rotor-stator mixer). A few drops (about 100 mg) were diluted in 250 mL of distilled water and filtered through a 0.2 μm membrane filter. The obtained preparations on the membrane filter were sprayed with gold and evaluated in SEM at various magnifications.
Measurements of the contact angle:
The camera:
Lens:
Adjusting the difference: Spacer rings
Tripod and lighting
Trigger:
Canon EOS 5D Mark II
Canon EF 100 mm f / 2 8L Macro IS USMDDDD
0.3 m
Kenko 12 + 24 + 36 mm spacer rings
Kaiser three-legged microstatics with drive + 2x Repro RB5055 HF illuminator
Canon with remote control / Time controller TC-80N3
Registration data:
Balance of brightness: Aperture:
Lighting time:
Trigger delay:
automatically
Adjustment of the aperture 32
Automatically
120 s after applying a drop
Drop size: 5 μl
1.2. Raw material [0109]
- PCC 2: precipitated calcium carbonate; solids content 14% by weight; BET specific surface area: 11.7 m<sup>2</sup>/ G; refined as described above (see Figures 2a and 2b)
- PCC 3: precipitated calcium carbonate Omya Syncarb<sup>®</sup> (available from Omya AG, Switzerland); solid content: 14% by weight; BET specific surface area: 3.5 - 6.5 m<sup>2</sup>/ g (see Figures 3a and 3b)
Hydrophobizing agents:
[0110]
- ASA Nalsize 7541 (alkylsuccinic anhydride); a solid content of 22.29% by weight, Ondeo Nalco Co.
AKD DR28XL (alkyl ketene dimer); solids content 23.9% by weight, Eka Chemicals
- Stearic acid, Sigma S4751-100G
- Wϋkoseal® 805; solids content of 40% by weight; Sϋddeutsche Emulsions-Chemie GmbH (SEC), Mannheim-Neckarau, Germany
- Silres BS 1306 (functional silicone modified polysiloxane), solids content 55% by weight; Wacker Chemie AG
Binders [0111] - Acronal<sup>®</sup> S360D (styrene-acrylic latex) solids content 50% by weight,
BASF Art .: 50005 562
Subsoil:
[0112] - YUPO (Synteape®) / Art .: 675227, white semi-matt PP 18x26 (468 cm)<sup>2</sup>); 62 g / m<sup>2</sup>
2. Methods
2.1. Sample preparation [0113] By using the following samples in Tables 8 and 9, several embodiments of the invention were verified:
a) Samples 23 to 26 (PCC2) and 28 to 29 (PCC3): Combining hedge-shaped particles with a binder and a hydrophobizing agent to obtain a suitable coating formulation
b) Samples 26 SA1 (PCC2), 26 SA2 (PCC2), 28 SA (PCC3) and 29 SA (PCC3): Combining a sample 26 comprising hedge-shaped particles, a binder and a hydrophobizing agent with an additional hydrophobizing agent in the form of one or two successive layers of stearic acid after application as a coating on the substrate.
c) Samples 27 SA (PCC3): The combination of hedge-shaped particles and binders, while the hydrophobizing agent is combined with this mixture as a follow-up layer of stearic acid after application as a coating to the substrate.
Table 8:
<td></td><td>Sample 23</td><td>Sample 24</td><td>Sample 25</td><td>Sample 26</td>
<td>PCC 2 (dry)</td><td>238.5 g</td><td>242.1 g</td><td>249.6 g</td><td>236.0 g</td>
<td>Acronal S360D</td><td>6.9 g</td><td>7.0 g</td><td>7.0 g</td><td>6.8 g</td>
<td>AKD Eka DR 28 XL</td><td>5.8 g</td><td>-</td><td>-</td><td>5.7 g</td>
<td>Wϋkoseal 805</td><td>-</td><td>0.9 g</td><td>-</td><td>0.9 g</td>
<td>Silres BS 1306</td><td>-</td><td>-</td><td>0.6 g</td><td>0.6 g</td>
<td></td><td>Sample 23</td><td>Sample 24</td><td>Sample 25</td><td>Sample 26</td>
<td>Tap water</td><td>148.8 g</td><td>150.0 g</td><td>211.8 g</td><td>150.0 g</td>
<td>Total weight</td><td>400.0 g</td><td>300.0 g</td><td>460.0 g</td><td>400.0 g</td>
<td>Final solid content,% by weight</td><td>18.5</td><td>18.0</td><td>15.7</td><td>18.8</td>
Table 9:
<td>stuff</td><td>Sample 27</td><td>Sample 28</td><td>Sample 29</td>
<td>PCC 3 (dry)</td><td>82.8 g</td><td>82.2 g</td><td>44.3 g</td>
<td>Acronal S360D</td><td>3.1 g</td><td>3.1 g</td><td>1.7 g</td>
<td>AKD Eka DR 28 XL</td><td>-</td><td>2.6 g</td><td>-</td>
<td>ASA Nalsize</td><td>-</td><td>-</td><td>1.5 g</td>
<td>Tap water</td><td>14.1 g</td><td>12.1 g</td><td>2.5 g</td>
<td>Total weight</td><td>100.0 g</td><td>100.0 g</td><td>100.0 g</td>
<td>Final solid content,% by weight</td><td>33.2 wt.%</td><td>33.6 wt%</td><td>36.2 wt%</td>
[0114] Coating formulations were prepared by adding PCC2 or PCC3, respectively, as well as hydrophobizing agents (if present) to the mixture (ideally to the solution) of the appropriate binder in tap water with mixing in a VMA Dispermat apparatus, respectively.<sup>®</sup> (VMA-Getzmann GmbH, Reichshof, Germany) with a dispersing disc with a diameter of 70 mm, after which the mixture was stirred for 1 hour. The coating formulations were filtered through a small tea strainer with a mesh size of 500 μm and the solid content determined (see Tables 8 and 9). The solids content was then adjusted by adding more water.
[0115] The resulting coating formulations were applied as a coating on an impermeable plastic substrate (Synteape<sup>®</sup>) using coating rods 1-3. Two papers were coated for each color and coating rod.
[0116] Drying cycles were carried out in a belt dryer at 150 ° C at belt speed
6-7 until a dry colored coating is obtained.
[0117] Addition to Synteape papers<sup>®</sup> coated with samples 26, 27, 28 and 29, a 2.8 g stearic acid solution was sprayed in 46.0 g ethanol (6 wt% solution) under a small extract. The solution was prepared by heating ethanol to 50 ° C in a water bath. Once the solvent reached this temperature, stearic acid was added manually, mixed by rotation in a round bottom flask, and the solution was sprayed directly onto the surface of the coated papers.
[0118] For samples 26SA1 and 26 SA2, one or two spraying cycles were respectively performed to obtain a good coating layer (see table 11). For samples 27 to 29, the coated sheets were sprayed until the layer weight given in table 12 was obtained.
2.2. Determination of the contact angle [0119] To determine the contact angle, the coated sheets were wetted by spotting 5 μΐ of deionized water over 120 s onto the surface of the sheet. A picture of the drop thus formed and the contact angle were determined using the Image Access image access module, version 8.
Table 11: Coating weight
<td>Attempt</td><td>Medium shell / sheet [mg]</td><td>Medium coating / sheet [mg / cm<sup>2</sup>]</td><td>Medium angle wetting [°]</td><td>Std. standard [°]</td>
<td>Sample 23</td><td>265.0</td><td>0.1</td><td>128</td><td>5</td>
<td>Sample 24</td><td>321.0</td><td>0.1</td><td>132</td><td>2</td>
<td>Sample 25</td><td>200.5</td><td>0.1</td><td>124</td><td>3</td>
<td>Sample 26</td><td>313.5</td><td>0.1</td><td>144</td><td>5</td>
<td>A sample 26SA2</td><td>313.5</td><td>0.1</td><td>140</td><td>3</td>
<td>A sample 26SA2</td><td>313.5</td><td>0.1</td><td>131</td><td>6</td>
Table 12: Weight of coatings and follow-up layers
<td>Attempt</td><td>Average shell/ sheet [Mg]</td><td>Medium coating / sheet [Mg / cm<sup>2</sup>]</td><td>Average layer follow-up / sheet [Mg]</td><td>The average follow-up layer / sheet [Mg / cm<sup>2</sup>]</td><td>Average contact angle [°]</td><td>Std. standard [°]</td>
<td>A sample 27SA</td><td>34.7</td><td>0.1</td><td>149.7</td><td>0.3</td><td>139.8</td><td>9.5</td>
<td>A sample 28</td><td>140.3</td><td>0.3</td><td>---</td><td>---</td><td>130.9</td><td>3.0</td>
<td>A sample 28SA</td><td>140.3</td><td>0.3</td><td>149.2</td><td>0.3</td><td>144.9</td><td>8.1</td>
<td>A sample 29</td><td>105.6</td><td>0.2</td><td>---</td><td>---</td><td>103.2</td><td>12.1</td>
<td>A sample 29SA</td><td>105.6</td><td>0.2</td><td>148.8</td><td>0.3</td><td>122.7</td><td>12.5</td>
[0120] In Figure 16, the effect of unprocessed PCC 2 combined with various hydrophobicizing agents and the binder after the formation of the coating formulation is illustrated by the contact angles for samples 23 to 26, the desired of which does not provide good hydrophobicity, which is reflected by contact angles around 124 to 132 °.
[0121] The hydrophobization can even be increased by combining the hydrophobizing agents, which reflects the sample 26 with a contact angle of 144 °.
[0122] In addition, a number of studies have been carried out with reference to the further hydrophobization of the sample 26 by applying a post-treatment layer of stearic acid. As can be seen in Figure 16, such a treatment reduces the hydrophobization.
[0123] The contact angle of the sample 27 being an example of hydrophobization only by applying a post-treatment layer, illustrates that a high degree of hydrophobization can also be achieved by applying a post-treatment layer.
[0124] Finally, the contact angles of samples 28 and 29 exhibit the effect of different hydrophobizing agents connected to untreated PCC and the binder in the production of the coating formulation, where hydrophobization in both cases can be increased by applying a post-treatment layer as exemplified by 28SA samples and 29SA (see Fig. 17).
34 members in 20 offices
Priority claims3
| Document | Office | Kind | Date |
|---|---|---|---|
| 12154687 | European Patent Office (EPO) | A | |
| 121546873 | – | – | – |
| EP20120154687 | – | – | – |
Members34
| Document | Office | Kind | |
|---|---|---|---|
| EP2626388A1 | European Patent Office (EPO) | A1 | |
| CA2863150A1 | Canada | A1 | |
| WO2013117511A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU2013218156A1 | Australia | A1 | |
| CO7020934A2 | Colombia | A2 | |
| MX2014008987A | Mexico | A | |
| CN104105763A | China | A | |
| KR20140130162A | Republic of Korea | A | |
| CL2014002006A1 | Chile | A1 | |
| EP2812401A1 | European Patent Office (EPO) | A1 | |
| US2014373757A1 | United States of America | A1 | |
| AU2013218156B2 | Australia | B2 | |
| IN1779MUN2014A | India | A | |
| RU2014136461A | Russian Federation | A | |
| EP2626388B1 | European Patent Office (EPO) | B1 | |
| DK2626388T3 | Denmark | T3 | |
| CN104105763B | China | B | |
| PT2626388T | Portugal | T | |
| SI2626388T1 | Slovenia | T1 | |
| HRP20160906T1 | Croatia | T1 | |
| ES2585833T3 | Spain | T3 | |
| RU2599668C2 | Russian Federation | C2 | |
| HUE029313T2 | Hungary | T2 | |
| BR112014019011A2 | Brazil | A2 | |
| BR112014019011A8 | Brazil | A8 | |
| PL2626388T3This record | Poland | T3 | |
| KR101776373B1 | Republic of Korea | B1 | |
| US2018016466A1 | United States of America | A1 | |
| CA2863150C | Canada | C | |
| US10047247B2 | United States of America | B2 | |
| US10377920B2 | United States of America | B2 | |
| US2019309189A1 | United States of America | A1 | |
| BR112014019011B1 | Brazil | B1 | |
| US11162001B2 | United States of America | B2 |
Numbers
- Publication
- 2626388
- Publication, DOCDB
- 2626388
- Publication, EPODOC
- PL2626388T
- Application
- 12154687
- Application, DOCDB
- 12154687
- Application, EPODOC
- PL12154687T
Titles2
- English
- A COMPOSITION AND METHOD FOR CONTROLLING THE WETTABILITY OF SURFACES
- Polish
- KOMPOZYCJA I SPOSÓB REGULACJI ZWILŻALNOŚCI POWIERZCHNI
Classification
- CPC, 23
- C09C1/021
- C09D191/00
- C01P2004/03
- C01P2004/61
- C01P2004/62
- C01P2006/12
- C01P2006/22
- D21H17/17
- D21H19/385
- D21H21/16
- D21H17/00
- B05D5/00
- C08K3/26
- C09C3/006
- C08K2003/265
- C09D5/1681
- B05D7/06
- B05D7/14
- B05D7/548
- C08K9/04
- C09D125/14
- C09D129/04
- C09D133/08
- IPC, 14
- D21H17 17
- B05D5 00
- B05D7 00
- B05D7 06
- B05D7 14
- C08K9 04
- C09C1 02
- C09D125 14
- C09D129 04
- C09D133 08
- C09D191 00
- D21H17 00
- D21H19 38
- D21H21 16