DE1052943B - Process for the production of protective colloid-free concentrated, aqueous emulsions of silicone - Google Patents
Process for the production of protective colloid-free concentrated, aqueous emulsions of siliconeInfo
- Publication number
- DE1052943B DE1052943B DEC9001A DEC0009001A DE1052943B DE 1052943 B DE1052943 B DE 1052943B DE C9001 A DEC9001 A DE C9001A DE C0009001 A DEC0009001 A DE C0009001A DE 1052943 B DE1052943 B DE 1052943B
- Authority
- DE
- Germany
- Prior art keywords
- silicone
- production
- aqueous emulsions
- protective colloid
- silicones
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001296 polysiloxane Polymers 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 6
- 239000000839 emulsion Substances 0.000 title description 16
- 238000004519 manufacturing process Methods 0.000 title description 5
- 230000001681 protective effect Effects 0.000 title description 4
- 239000001993 wax Substances 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 5
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 4
- 150000003754 zirconium Chemical class 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000001632 sodium acetate Substances 0.000 description 5
- 235000017281 sodium acetate Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- -1 B. Stearic acid Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ILXDAXZQNSOSAE-UHFFFAOYSA-N [AlH3].[Cl] Chemical compound [AlH3].[Cl] ILXDAXZQNSOSAE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
Description
Verfahren zur Herstellung schutzkolloidfreier konzentrierter, wässeriger Emulsionen von Silikonen Während die Herstellung konzentrierter, wässeriger Emulsionen wasserunlöslicher Stoffe, wie Paraffin, Wachs, Fette usw., bei dem heutigen- Stande der Technik keine besonderen Schwier,igkeiten bereitet, lassen sich die unter dem Sammelbegriff »Silikone« bekannten Verbindungen nur schwierig in wässerige Emulsionen iiberführen. Nur verhältulismäß ig wenige Emulgatoren sind überhaupt geeignet, jedoch haben auch diese Emulsionen, den Nachteil einer mangelhaften Beständigkeit. Process for the production of protective colloid-free concentrated, aqueous Emulsions of silicone During the production of concentrated, aqueous emulsions water-insoluble substances, such as paraffin, wax, fats, etc., in the current state the technology does not cause any particular difficulties, the under the Collective term »silicones«, compounds known only with difficulty in aqueous emulsions transfer. Only relatively few emulsifiers are suitable at all, however these emulsions also have the disadvantage of inadequate stability.
Diese Erscheinung tritt besonders auf, wenn die Emulsionen Aluminium- oder Zirkon.salze enthalten, wie es für die Behandlung von porösen Werkstoffen, besonders Textilmaterialien, erwünscht ist. In solchen Fällen werden die Silikone, welche meist in organischen Lösungsmitteln gelöst sind, mit dem Emulgator versetzt und in die für die technische Anwendung erforderliche Wassermenge eingerührt. This phenomenon occurs particularly when the emulsions aluminum or zirconium salts, such as those used for the treatment of porous materials, especially textile materials, is desirable. In such cases the silicones, which are mostly dissolved in organic solvents, mixed with the emulsifier and stirred into the amount of water required for the technical application.
Gegebenenfalls kann der Emulgator auch in dem Wasser gelöst und dann das Silikon einemulgiert werden. Hierauf fügt man das in einer kleinen Wassermenge gelöste Aluminium- oder Zfrkonsalz zu Diese verdünnten Emulsionen sind jedoch selbst bei Herstellung mittels maschineller Emulgi,ersrorrichtungen, wie z. B. einem Turbomischer, nur sehr wenig beständig und ergeben schon nach kurzem Stehen Abscheidungen. Ihre industrielle Verwertbarkeit, insbesondere zum wasserabweisenden Imprägnieren von Textilie oder anderen Faserstoffen, ist daher eine begrenzte.Optionally, the emulsifier can also be dissolved in the water and then the silicone can be emulsified. Then add that in a small amount of water However, these diluted emulsions are themselves in the case of production by means of machine emulsions, ersrorrichtungen, such as. B. a turbo mixer, only very poorly stable and give deposits after standing for a short time. Her industrial usability, especially for water-repellent impregnation of Textile or other fibrous material is therefore a limited one.
Es wurde nun schon überraschenderweise festgestellt, daß man konzentrierte, wässerige Emulsionen von Silikonen, welche sehr beständig sind, sich leicht mit Wasser verdümeen lassen und auch in diesem Zustand eine hohe Beständigkeit besitzen, ohne Mitverwendung von Schutzkolloiden, wie Leim. u. dgl., herstellen kann, wenn man die Silikone unter Zusatz von etwa 10 b,is 20 °/o ihres Gewichtes an höheren Fett-, tEl- oder Wachs säuren in geschmolzenem Zustand mit konzentrierten wässerigen Lösungen basischer Salze des Aluminiums und/oder Zirkons in bekannten Vorrichtungen innig vermischt. DieSilikone können teilweise durch Paraffin u. dgl. ersetzt werden. It has now been found, surprisingly, that one concentrated, Aqueous emulsions of silicone, which are very resistant, can easily be mixed with Let the water evaporate and have a high resistance even in this state, without the use of protective colloids such as glue. and the like. Can produce if the silicones with the addition of about 10 b, is 20 per cent of their weight higher Fatty, tElic or waxy acids in the molten state with concentrated aqueous ones Solutions of basic salts of aluminum and / or zirconium in known devices intimately mixed. The silicones can be partially replaced with paraffin and the like.
Bei Verwendung basischer Zirlçonsalze fügt man vorzugsweise der wässerigen Lösung von Zirkonoxychlorid, dem gebräuchlichen Zitrkonsalz, kristallisiertes Natriumlazetat in einer Menge zu, die der Chloridmenge äquivalent ist. Solche basische Zirkonsalz.-lösungen sind zur Emulgierung von Silikonen, denen etwa 10% einer höheren Fettsäure, z. B. Stearinsäure, zugegeben wurde, besonders geeignet. If basic zirlconium salts are used, the aqueous ones are preferably added Solution of zirconium oxychloride, the common citrus salt, crystallized sodium acetate in an amount equivalent to the amount of chloride. Such basic zirconium salt solutions are used to emulsify silicones containing about 10% of a higher fatty acid, e.g. B. Stearic acid, added, is particularly suitable.
Es ist zwar schon bekannt, Paraffinkohllenwasserstoffe, Wachse u. dgl. mit basischen Salzen des Aluminiums oder Zirkons unter Zusatz von kleinen Mengen Fettsäuren in beständige wässerige Emulsionen überzuführen (s. deutsche Patentschrift 749 740). Da sich aber die Silikone, abgesehen von ihrer konstitutionellen Verschiedenheit, gerade bei der Überführung in wässerige EmuLsionen vötiliig anders verhalten als Wachse, Paraffin usw., war nicht vorauszusehen, daß sich das für diese Stoffe bekannte Verfahren auf Silikone mit Erfolg übertragen lassen wird. Silikone sind grundsätzlich schwerer zu emulgieren als Paraffine, Wachse usw. Während sich diese ferner in ihrer Emulgierfähigkeit gegenüber den verschiedenen Emulgatoren gleich oder ähnlich verhalten, trifft diles für die Silikone nicht zu. It is already known to use paraffin hydrocarbons, waxes and the like. Like. With basic salts of aluminum or zirconium with the addition of small amounts Converting fatty acids into stable aqueous emulsions (see German patent specification 749 740). But since the silicones, apart from their constitutional difference, behave completely differently than when transferring them to aqueous emulsions Waxes, paraffin, etc., could not have been foreseen that they would be known for these substances The process can be successfully transferred to silicones. Silicones are fundamental harder to emulsify than paraffins, waxes, etc. While these are further in their Emulsifying ability behave the same or similar to the various emulsifiers, does not apply to diles for the silicones.
Der Vorschlag, Salze mehrwertiger Metalle z. B. des Aluminiums als Härtungsmittel für Silikone anzuwenden, ist bekannt. Die dazu benötigten Mengen sind sehr gering und würden zu einer Emulsionsbildung gemäß vorliegender Erfindung nicht ausreichen. Im übrigen wurden die Metall salze bisher zu vorhandenen S il.ilkonemu,Ls-ionen zugesetzt. The proposal to use salts of polyvalent metals e.g. B. of aluminum as It is known to use hardeners for silicones. The quantities required for this are very low and would emulsify in accordance with the present invention not suffice. Apart from that, the metal salts have hitherto been the existing Siilkonemu, Ls-ions added.
Die erfindungsgemäß hergestellten Emulsionen sind besonders zum wasserabweisenden Imprägnieren von Textilien aller Art geeignet. The emulsions produced according to the invention are particularly water-repellent Suitable for impregnating all kinds of textiles.
Beispiel Zu einer 70° C warmen Lösung von 80 g Zirkonoxychlorid und 9 g Harnstoff in 250 g Wasser gibt man 20 g Natriumbicarbonat. Unter ständigem Rühren wird in dünnem Strahl eine Mischung von 200!g Dimethylsiloxan mit einer Viskosität von 500 cit, 20 g Ölsäure und 80 g Testbenzin zugegeben. Nach Einrühren von 35 g Natriumazetat und 30 g Essigsäure, 60%ig, in 350 ccm Wasser wird das ganze homogenisiert. Die entstandene Emulsion läßt sich leicht mit Wasser zu feinteiligen, beständigen Emulsionen verdünnen. Example To a 70 ° C solution of 80 g of zirconium oxychloride and 9 g of urea in 250 g of water are added to 20 g of sodium bicarbonate. With constant stirring a mixture of 200 g of dimethylsiloxane with a viscosity is applied in a thin stream of 500 cit, 20 g of oleic acid and 80 g of white spirit were added. After stirring in 35 g Sodium acetate and 30 g of acetic acid, 60%, in 350 ccm of water are homogenized. The resulting emulsion can easily be finely divided with water and made stable Dilute emulsions.
Der Harnstoff dient als Abpufferungsmittel für die aus dem Zirkonoxychlorid stammende Salzsäure und kann auch durch Natriumazetat ersetzt werden. In diesem Falle verwendet man 40.g Natriumazetat an Stelle des Natriumbicarbonats und fügt der am SchluB eingerührten Essigsäurelösung nur 5 g Natriumazetat zu. The urea serves as a buffering agent for the zirconium oxychloride derived from hydrochloric acid and can also be replaced by sodium acetate. In this Trap is used 40.g of sodium acetate in place of the sodium bicarbonate and adds add only 5 g of sodium acetate to the acetic acid solution stirred in at the end.
An Stelle der Ölsäure können auch 30 g eines Wachses mit der Säurezahl 135 verwendet werden. Instead of oleic acid, 30 g of a wax with the acid number can also be used 135 can be used.
Eine gleichartige Emulsion läßt sich auch mit basischen Aluminiumsalzlösungen herstellen, wenn an Stelle der abgepufferten basischen Zirkonsalziösung z. B. 500 g einer hochbasischen Aluminiumchlorfdr lösung (etwa 20e/o Aluminiumoxyd und etwa 7 0/o Chlor) verwendet werden. A similar emulsion can also be made with basic aluminum salt solutions produce if, instead of the buffered basic zirconium salt solution z. B. 500 g of a highly basic aluminum chlorine solution (about 20e / o aluminum oxide and about 7 0 / o chlorine) can be used.
PATENTANSPR8CHE 1. Verfahren zur Herstellung schutzkolloid: freier, konzentriefter, wässeriger Emulsionen von Silikonen, die mit Wasser verdünnbar sind und zum wasserabweisenden Imprägnieren von Textilien dienen, dadurch gekennzeichnet, daß man diese in verflüssigtem Zustande mit etwa 10 bis 20/o ihres Gewichtes an höheren Fettsäuren vermischt und mit konzentrierten wässerigen Lösungen von basischen Salzen des Aluminiums und/ oder Zirkons in geeigneten Vorrichtungen emulgiert. PATENT CLAIM 1. Process for the production of protective colloid: free, concentrated, aqueous emulsions of silicone that can be diluted with water and serve for the water-repellent impregnation of textiles, characterized in that that they are in a liquefied state with about 10 to 20 / o of their weight higher fatty acids mixed with concentrated aqueous solutions of basic Salts of aluminum and / or zirconium emulsified in suitable devices.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC9001A DE1052943B (en) | 1954-03-09 | 1954-03-09 | Process for the production of protective colloid-free concentrated, aqueous emulsions of silicone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC9001A DE1052943B (en) | 1954-03-09 | 1954-03-09 | Process for the production of protective colloid-free concentrated, aqueous emulsions of silicone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1052943B true DE1052943B (en) | 1959-03-19 |
Family
ID=7014440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC9001A Pending DE1052943B (en) | 1954-03-09 | 1954-03-09 | Process for the production of protective colloid-free concentrated, aqueous emulsions of silicone |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1052943B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1186025B (en) * | 1959-05-16 | 1965-01-28 | Rotta Chem Fab Theodor | Process for the waterproofing of textiles with aqueous stable emulsifier and protective colloid-free silicone emulsions |
| DE1207332B (en) * | 1958-06-28 | 1965-12-23 | Pfersee Chem Fab | Storable, water-dilutable textile impregnation agent in gel form based on organopolysiloxanes |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1645692A (en) * | 1927-10-18 | of portland | ||
| FR967442A (en) * | 1948-06-08 | 1950-11-03 | Union Chimique Belge Sa | Process for the preparation of compounds containing silicic esters or their polymers |
| GB695514A (en) * | 1950-09-29 | 1953-08-12 | Dow Corning Ltd | Improvements in or relating to polishing compositions |
-
1954
- 1954-03-09 DE DEC9001A patent/DE1052943B/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1645692A (en) * | 1927-10-18 | of portland | ||
| FR967442A (en) * | 1948-06-08 | 1950-11-03 | Union Chimique Belge Sa | Process for the preparation of compounds containing silicic esters or their polymers |
| GB695514A (en) * | 1950-09-29 | 1953-08-12 | Dow Corning Ltd | Improvements in or relating to polishing compositions |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1207332B (en) * | 1958-06-28 | 1965-12-23 | Pfersee Chem Fab | Storable, water-dilutable textile impregnation agent in gel form based on organopolysiloxanes |
| DE1186025B (en) * | 1959-05-16 | 1965-01-28 | Rotta Chem Fab Theodor | Process for the waterproofing of textiles with aqueous stable emulsifier and protective colloid-free silicone emulsions |
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