Patent application title: Silicate Shell Microcapsules For Treating Textiles
Thomas Bekemeier (Midland, MI, US)
Lorry Deklippel (Piaton, BE)
Tatiana Dimitrova (Braine L'Alleud, BE)
Russel Elms (Midland, MI, US)
Fabrizio Galeone (Buvrinnes, BE)
Bertrand Lenoble (Silly, BE)
Leon Marteaux (Bxl (auderghem), BE)
Josef Roidl (Saulheim, DE)
Martin Severance (Midland, MI, US)
Stephane Ugazio (Soignies, BE)
Brett Zimmerman (Midland, MI, US)
IPC8 Class: AB05D500FI
Class name: Coating processes application to opposite sides of sheet, web, or strip (excluding processes where all coating is by immersion)
Publication date: 2011-12-22
Patent application number: 20110311723
Compositions containing suspended silicate shell microcapsules of a
silicone textile treatment are disclosed. These compositions are
particularly useful as textile treatments to impart hydrophobicity,
softness, and flame retardant properties.
1. A composition comprising suspended silicate shell microcapsules of a
silicone textile treatment composition wherein the silicate shell
microcapsules are obtained by; I) mixing an oil phase containing the
silicone textile treatment composition and II) an aqueous solution of a
cationic surfactant to form an oil in water emulsion, and III) adding a
water reactive silicon compound to the oil in water emulsion so that the
water reactive silicon compound polymerises at the oil/water interface of
the oil in water emulsion to form the microcapsules having a core
containing the silicone textile treatment composition and a silicate
2. The composition of claim 1 wherein the silicone treatment composition comprises a silanol terminated polydialkylsiloxane fluid.
3. The composition of claim 1 wherein the silicone treatment composition comprises; a) a siloxane resin and b) a polydialkylsiloxane fluid.
4. The composition of claim 3 wherein the weight ratio of the polydialkylsiloxane fluid to the siloxane resin is from 0.5/1 to 4/1.
5. The composition of claim 3 wherein the siloxane resin is a DT resin.
6. The composition of claim 3 wherein the siloxane resin is a MQ resin.
7. The composition of claim 1 wherein the water reactive silicon compound comprises tetraethoxysilane.
8. The composition according to claim 1 further comprising a fluorocarbon.
9. A method of treating textiles comprising applying to the textile the composition according to claim 1.
10. The method of claim 9 further comprising applying to the textile an auxiliary agent selected from a organopolysiloxane condensation catalyst or a coupling agent.
11. The method of claim 9 further comprising applying to the textile an auxiliary agent selected from a fluorocarbon.
13. A method of making silicate shell microcapsules, the method comprising mixing an oil phase containing a silicone textile treatment composition and an aqueous solution of a cationic surfactant to form an oil in water emulsion, and adding a water reactive silicon compound to the oil in water emulsion so that the water reactive silicon compound polymerises at the oil/water interface of the oil in water emulsion to form the microcapsules having a core containing the silicone textile treatment composition and a silicate shell.
14. The composition according to claim 3 further comprising a fluorocarbon.
15. The composition of claim 3 wherein; the weight ratio of the polydialkylsiloxane fluid to the siloxane resin is from 0.5/1 to 4/1, the water reactive silicon compound comprises tetraethoxysilane, and the siloxane resin is selected from a DT resin or a MQ resin.
16. The composition according to claim 15 further comprising a fluorocarbon.
 This disclosure relates to silicate shell microcapsules containing a silicone textile treatment composition and their use for treating textiles.
 Textiles intended for uses as mattress coverage, curtains, protective clothing, tenting etc. are frequently referred to as "industrial textiles". Contrary to the fashion textiles (the ones indented for clothing, for example) the industrial ones have to meet severe requirements with regard to their safety and durability. First, they must be flame retardant, a property which is generally achieved via a surface treatment, and standardized in norms as for example DIN 4102-B2. Second, these textiles have to be hydrophobic, i.e. not to allow the water to pass-through. Moreover, hydrophobicity must be retained after numerous cycles of washing, which on itself is not evident. Thirdly, an additional criterion, namely softness is required for the textiles which are used for protective clothing. Furthermore, the fabrication of industrial textiles should respect ecological standards, as for example OEKO TEX STANDARD 100. The latter bans the use of a vast number of chemicals, considered dangerous for environment and human health, during the fabrication and conditioning of the textiles in general.
 Therefore, there is a need to develop compositions and methods for the treatment of industrial textiles which impart hydrophobicity, softness and flame retardant properties while using chemicals which do not have adverse effect on environment and/or or human health.
 EP-A-941761 describes a process for preparing microcapsules with an organopolysiloxane shell and a core material, in which the shell is formed in situ by hydrolysis and polycondensation of an organosilane and/or a condensation product thereof having at most 4 silicon atoms. WO-A-03/066209 describes a lipophilic cosmetic, chemical, biological or pharmaceutical active material composition such as a sunscreen encapsulated within a shell of the emulsion polymerisation product of a tetraalkoxysilane. WO-A-2008/002637 discloses a process for preparing microcapsules by mixing an oil phase and an aqueous solution of a cationic surfactant to form an oil in water emulsion, and adding a water reactive silicon compound comprising tetraalkoxysilane to the emulsion so that the tetraalkoxysilane condenses and polymerises at the oil/water interface. The amount of cationic surfactant is 0.1% to 0.3% by weight based on the oil phase and the shell thickness of the microcapsules is at least 18 nm.
 The present inventors have discovered silicone containing microcapsules, which when applied to industrial textiles, impart benefits such as softness and hydrophobicity while maintaining flame retardant properties. These benefits persist after washing of the textile. Furthermore, the softening and hydrophobicity benefits of the present compositions are compatible with the flame retardant properties of the textiles.
 This disclosure relates to compositions comprising suspended silicate shell microcapsules of a silicone textile treatment composition wherein the silicate shell microcapsules are obtained by;  I) mixing an oil phase containing a silicone textile treatment composition and an aqueous solution of a cationic surfactant to form an oil in water emulsion, and  II) adding a water reactive silicon compound to the oil in water emulsion so that the water reactive silicon compound polymerises at the oil/water interface of the emulsion to form microcapsules having a core containing the silicone treatment composition and a silicate shell.
 This disclosure further provides a method for treating textiles by applying to textiles the composition comprising suspended silicate shell microcapsules of a silicone textile treatment composition.
 The present disclosure provides compositions and methods for treating textiles. The compositions are aqueous suspensions of silicate shell microcapsules containing a silicone textile treatment composition core. The compositions containing suspended silicate shell microcapsules of a silicone textile treatment composition may be obtained by;  I) mixing an oil phase containing a silicone textile treatment composition and an aqueous solution of a cationic surfactant to form an oil in water emulsion, and  II) adding a water reactive silicon compound to the oil in water emulsion, so that the water reactive silicon compound polymerises at the oil/water interface of the emulsion to form a microcapsule having a core containing the silicone treatment composition and a silicate shell.
 Step I involves mixing an oil phase containing a silicone textile treatment composition and an aqueous solution of a cationic surfactant to form an oil in water emulsion.
 The silicone textile treatment composition may contain any silicone or organopolysiloxane known in the art for treating textiles. As used herein, treatment includes conditioning, hydrophobing, softening, or modification in any way the "feel" or physical surface properties of a textile.
 Typically, the silicone textile treatment composition is a hydrophobic liquid, so as to enable the formation of an oil in water emulsion, as per step I of the process to prepare the microcapsules.
 The silicone textile treatment composition may contain a single organopolysiloxane or a mixture of various organopolysiloxanes. Organopolysiloxanes are polymers containing siloxane units independently selected from (R3SiO0.5), (R2SiO), (RSiO1.5), or (SiO2) siloxy units, where R may be any monovalent organic group. When R is a methyl group in the (R3SiO0.5), (R2SiO), (RSiO1.5), or (SiO2) siloxy units of an organopolysiloxane, the siloxy units are commonly referred to as M, D, T, and Q units respectively. The organopolysiloxane useful in the silicone treatment compositions of the present invention may have any combination of (R3SiO0.5), (R2SiO), (RSiO1.5), or (SiO2) siloxy units. The organopolysilxoxanes may have cyclic, linear, or branched structures. The organopolysiloxanes may be volatile, have varying viscosities ranging from low viscosity fluids to high viscosity fluids/gums, be elastomeric, or resinous. If a solid or high viscosity organopolysiloxane is to be included in the silicone treatment composition, such organopolysiloxane may be dispersed or solubilized in a lower viscosity fluid so as to provide a hydrophobic liquid (i.e. an oil phase) for preparation of the oil in water emulsion of step I.
 The silicone treatment composition may contain a siloxane resin. As used herein, "siloxane resin" refers to any organopolysiloxane containing at least one T or
 Q units, as defined above. Typically, the siloxane resin contains at least 10 T or Q siloxy units. Thus, the siloxane resins useful in this invention could be any organopolysiloxane (or a mixture of organopolysiloxanes) of the formula MxDyT.sub.zQw, where x,y,z,w represent the mole % of the corresponding units, with the proviso that x+y+z+w=100% and that the z+w>10, alternatively z+w>30, or alternatively greater than 50. The siloxane resin may contain OH groups or groups hydrolysable to OH groups (as alkoxy for example) bounded to the Si atoms. Typically, 0.5 to 20% (mole) of the Si atoms should bear OH or hydrolysable groups.
 The siloxane resin may be selected from those known in the art as silsesquioxane, DT, or MQ resins.
 In one embodiment, the siloxane resin is an MQ siloxane resin. MQ siloxane resins are known as those resins containing M and Q siloxy units. They have been described in a number of publications and are commercially available. Typical MQ resins useful in the present compositions are those consisting essentially of (CH3)3SiO1/2 units and SiO4/2 units wherein the ratio of (CH3)3SiO1/2 units to SiO4/2 units is from 0.4:1 to 1.2:1 or a condensate of said MQ resin with other organosilicon compounds. Alternatively, the MQ resin is a siloxane resin copolymer consisting essentially of (CH3)3SiO1/2 units and SiO2 units in a molar ratio of approximately 0.75:1. A non-limiting example of such material is DC 5-7104 from Dow Corning Corp. (Midland, Mich.).
 In another embodiment the siloxane resin is a DT resin, Typical DT resins useful in the present compositions are those consisting essentially of (CH3)2SiO2/2 units and (CH3) SiO3/2 units wherein the ratio of (CH3)2SiO2/2 units to (CH3) SiO3/2 units is from 0.5:2 to 2:0.5. We have found that better durability results are obtained when 1 to 20% of the CH3 groups are substituted with alkoxy radicals having one or two carbon atoms. Non-limiting examples of useful DT resins include DC 3037 and DC 3074 (Dow Corning Corp. Midland, Mich.).
 The silicone treatment composition may contain a polydialkylsiloxane fluid. The polydialkylsiloxane fluid may be any organopolysiloxane having primarily D siloxy units of the formula [R'2SiO] where R' represents an alkyl group having 1 to 30 carbon atoms. The number of repeating D siloxy units is considered as the degree of polymerization, and may vary. However, the degree of polymerization is such that the polydialkylsiloxane is a fluid at 25° C.
 In a further embodiment, the polydialkylsiloxane fluid is selected from a trimethylsiloxy terminated polydimethylsiloxane fluid having a viscosity varying from 10 to 100,000 mm2/s at 25° C., alternatively from 60 to 60,000 mm2/s at 25° C., alternatively from 100 to 50,000 mm2/s at 25° C. Representative commercially available polydimethylsiloxane fluids include Dow Corning® 200 fluids (Dow Corning Corporation, Midland Mich.).
 In another embodiment, the polydialkylsiloxane fluid is selected from a silanol terminated polydimethylsiloxane fluid having a viscosity varying from 10 to 100,000 mm2/s at 25° C., alternatively from 60 to 60,000 mm2/s at 25° C., alternatively from 100 to 50,000 mm2/s at 25° C.
 In another embodiment, the silicone treatment composition contains a mixture of the siloxane resin and the polydialkylsiloxane fluid. The siloxane resin and polydialkylsiloxane fluid are the same as described above. The weight ratio of the polydialkylsiloxane fluid to the siloxane resin may vary, but typically is from 0.5/1 to 4/1, alternatively, from 1/1 to 3/1.
 The silicone treatment composition is mixed with an aqueous solution of a cationic surfactant to form an oil in water emulsion.
 Cationic surfactants may be quaternary ammonium hydroxides such as octyl trimethyl ammonium hydroxide, dodecyl trimethyl ammonium hydroxide, hexadecyl trimethyl ammonium hydroxide, octyl dimethyl benzyl ammonium hydroxide, decyl dimethyl benzyl ammonium hydroxide, didodecyl dimethyl ammonium hydroxide, dioctadecyl dimethyl ammonium hydroxide, cetyl trimethyl ammonium chloride, tallow trimethyl ammonium hydroxide and coco trimethyl ammonium hydroxide as well as corresponding salts of these materials, fatty amines and fatty acid amides and their derivatives, basic pyridinium compounds, quaternary ammonium bases of benzimidazolines and polypropanolpolyethanol amines but is not limited to this list of cationic surfactants. A preferred cationic surfactant is cetyl trimethyl ammonium chloride.
 The cationic surfactant may be selected from an amphoteric surfactant such as cocamidopropyl betaine, cocamidopropyl hydroxysulfate, cocobetaine, sodium cocoamidoacetate, cocodimethyl betaine, N-coco-3-aminobutyric acid and imidazolinium carboxyl compounds but is not limited to this list of amphoteric surfactants.
 The cationic surfactants described above may be used individually or in combination. The cationic or amphoteric surfactant is dissolved in water and the resulting aqueous solution used as a component in aqueous or continuous phase of the oil in water emulsion of step I).
 The concentration of the cationic surfactant during the formation of the oil in water emulsion should be between 0.1% and 0.3% by weight of the oil phase concentration used.
 Auxiliary surfactants, and in particular nonionic surfactants, may be added during the formation of the oil in water emulsion. Suitable non-ionic surfactants are; polyoxyalkylene alkyl ethers such as polyethylene glycol long chain (12-14C) alkyl ether, polyoxyalkylene sorbitan ethers, polyoxyalkylene alkoxylate esters, polyoxyalkylene alkylphenol ethers, ethylene glycol propylene glycol copolymers, polyvinyl alcohol and alkylpolysaccharides, for example materials of the structure R1--O--(R2O)m-(G)n wherein R1 represents a linear or branched alkyl group, a linear or branched alkenyl group or an alkylphenyl group, R2 represent an alkylene group, G represents a reduced sugar, m denotes 0 or a positive integer and n represent a positive integer as described in U.S. Pat. No. 5,035,832 but is not limited to this list of non-ionic surfactants.
 The oil phase containing the silicone textile treatment composition and the aqueous solution of the cationic or amphoteric surfactant are mixed together to form an oil in water emulsion. Mixing and emulsion formation may occur using any known techniques in the emulsion art. Typically, the oil phase and aqueous solution of the cationic or amphoteric surfactant are combined using simple stirring techniques to form an emulsion. Particle size of the oil in water emulsion may then be reduced before addition of the tetraalkoxysilane by any of the known in the art emulsification device. Useful emulsification devices in this invention can be homogenizer, sonolator, rotor-stator turbines, colloid mill, microfluidizer, blades, helix and combination thereof but is not limited to this list of emulsification devices. This further processing step reduces the particle size of the starting cationic oil in water emulsion to values ranging from 0.2 to 500 micrometers, with typical particle sizes ranging between 0.5 micrometers and 100 micrometers.
 The weight ratio of oil phase to aqueous phase in the emulsion can generally be between 40:1 and 1:50, although the higher proportions of aqueous phase are economically disadvantageous particularly when forming a suspension of microcapsules. Usually the weight ratio of oil phase to aqueous phase is between 2:1 and 1:3. If the oil phase composition is highly viscous, a phase inversion process can be used in which the oil phase is mixed with surfactant and a small amount of water, for example 2.5 to 10% by weight based on the oil phase, forming a water-in-oil emulsion which inverts to an oil-in-water emulsion as it is sheared. Further water can then be added to dilute the emulsion to the required concentration.
 Step II) involves adding a water reactive silicon compound to the oil in water emulsion.
 The water reactive silicon compound which is added to the emulsion of conditioning agent to form the microcapsules can be any silicon compound capable of polymerizing to form a silicon-containing network polymer. Such a silicon compound generally has an average of more than 2 silicon-bonded hydrolysable groups per molecule. The hydrolysable groups are preferably alkoxy groups bonded to silicon, although alternative hydroxyl groups such as acetoxy can be used. Preferred alkoxy groups are those having 1 to 4 carbon atoms, particularly ethoxy and methoxy groups.
 The water reactive silicon compound can for example comprise a tetraalkoxysilane or a mixture of a tetraalkoxysilane and an alkoxysilane having an amino- or quaternary ammonium-substituted alkyl group. The tetraalkoxysilane can for example be tetraethoxysilane (TEOS), which can be used in monomeric form or as a liquid partial condensate.
 The tetraalkoxysilane may be used in conjunction with one or more other water-reactive silicon compound having at least one, typically containing at least two, alternatively three, Si--OH groups or hydrolysable groups bonded to silicon, for example an alkyltrialkoxysilane such as methyltrimethoxysilane or a liquid condensate of an alkyltrialkoxysilane, or a (substituted alkyl)trialkoxysilane.
 The water reactive silicon compound may also comprise an alkoxysilane having an amino- or quaternary ammonium-substituted alkyl group. These include trialkoxysilanes containing substituted alkyl groups, aminoalkyltrialkoxysilanes and quaternised aminoalkyltrialkoxysilanes. One preferred type of quaternised aminosilane has the formula R'3--Si-A-N+R''3, wherein each group R' is an alkoxy group having one or two carbon atoms, each group R'' is an alkyl group having 1 to 18 carbon atoms, and A is a divalent organic radical of the formula CnH2n where n is an integer from 1 to 18.
 Representative non-limiting examples of aminoalkyltrialkoxysilanes and quaternised aminoalkyltrialkoxysilanes useful as alkoxysiloxanes in the present disclosure include those having the formula;
(CH3O)3SiCH2CH2CH2N+(CH3)2(CH.su- b.2)17CH3 Cl.sup.
 The water reactive silicon compound can for example comprise 10-100% by weight tetraalkoxysilane and 0-90% trialkoxysilane, for example 10-95% tetraalkoxysilane and 5-90% trialkoxysilane, particularly a trialkoxysilane having an amino or quaternary ammonium substituted alkyl group. We have found mixtures of quaternised aminoalkyltrialkoxysilanes with tetraalkoxysilane to be particularly effective in encapsulating the silicone textile treatment composition as described above.
 The tetraalkoxysilane and the trialkoxysilane, for example trialkoxysilane having an amino or quaternary ammonium substituted alkyl group, are usually mixed before contacting the oil in water emulsion, so that a mixture of the tetraalkoxysilane and the trialkoxysilane is added to the emulsion. Alternatively the tetraalkoxysilane and the trialkoxysilane can be added separately but simultaneously to the oil in water emulsion, or can be added sequentially to the oil in water emulsion. If they are added sequentially, the tetraalkoxysilane is preferably added before the trialkoxysilane having an amino or quaternary ammonium substituted alkyl group.
 The water reactive silicon compound polymerises at the oil/water interface of the emulsion to form a microcapsule having a core containing the silicone treatment composition and a silicate shell.
 The polymerization of the tetraalkoxysilane at the oil/water interface typically is a condensation reaction which may be conducted at acidic, neutral or basic pH. When the water reactive compound is a mixture of a tetraalkoxysilane and a trialkoxysilane, for example an alkoxysilane having an amino- or quaternary ammonium-substituted alkyl group, both silanes copolymerize together.
 The condensation reaction is generally carried out at ambient temperature and pressure, but can be carried out at increased temperature, for example up to 95° C., and increased or decreased pressure, for example under vacuum to strip the volatile alcohol produced during the condensation reaction.
 Encapsulation of the oil phase can be achieved without any catalyst for the condensation reaction. However use of a catalyst may be preferred. Any catalyst known to promote the polymerization of the tetraalkoxysilane may be added to step III to form the shell of the microcapsule. The catalyst can be an oil soluble organic metal compound, for example an organic tin compound, particularly an organotin compound such as a diorganotin diester, for example dimethyl tin di(neodecanoate), dibutyl tin dilaurate or dibutyl tin diacetate, or alternatively a tin carboxylate such as stannous octoate, or an organic titanium compound such as tetrabutyl titanate. An organotin catalyst can for example be used at 0.05 to 2% by weight based on the water reactive silicon compound. An organotin catalyst has the advantage of effective catalysis at neutral pH. The catalyst can be mixed with the oil phase components before it is emulsified, since this promotes condensation of the water reactive silicon compound at the surface of the emulsified oil phase droplets. A catalyst can alternatively be added to the emulsion before the addition of the water-reactive silicon compound, or simultaneously with the tetraalkoxysilane, or after the addition of the tetraalkoxysilane to harden and make more impervious the shell of silicon-based polymer which has been formed. The catalyst, when used, can be added undiluted, or as a solution in an organic solvent such as a hydrocarbon, alcohol or ketone, or as a mutiphasic system such as an emulsion or suspension.
 The method of the present invention comprises applying to textiles the composition comprising suspended silicate shell microcapsules of a silicone textile treatment composition, as described above. The amount applied is a "hand improving" effective amount of the treatment composition and is applied to the fiber and/or textile by any convenient method. Hand for purposes of the invention means the softness and smoothness of the fabric. For example, the treatment composition can be applied by padding, dipping, spraying or exhausting. After the treatment composition is applied to the fiber and/or fabric, it can be dried by heat.
 The textile treatment composition can be applied to the fiber and/or textile during making the fibers or textiles, or later by padding, which is the preferred method of this invention. The preferred concentration of the silicone treatment composition in the padding bath is in the range of 5 to 200 g/L, more preferably between 20 and 150 g/L and even more preferable between 40 and 120 g/L. After application, carriers (if any) can be removed from the treatment composition for example by drying the composition at ambient or elevated temperature.
 Auxiliary agents may be added along with the present treatment compositions to enhance deposition and/or adhesion of the treatment compositions to the textile surface. These auxiliary agents may be selected from any catalysts known to effect condensation reactions of organopolysiloxanes, such as for example an acid or base. In this regard, amine compounds may be added as a catalyst.
 The auxiliary agent may be selected from those considered as "coupling agents", and in particular organosilane coupling agents. These may be organofunctional alkoxysiloxanes. Representative organofunctional alkoxysilanes useful as an auxiliary agent in the present disclosure include; DC Z6020, Z6030, Z6040, 9-6346 (Dow Corning Corporation, Midland Mich.).
 Additional auxiliary agents may be added along with the present treatment compositions to provide further enhancements to the treated textiles or fabrics. These additional auxiliary agents may be any compositions known in the art for providing water or oil repellency to textiles. Exemplary treatments include fluorocarbon based compounds such as various fluorocarbon oils, or fluorocarbon based polymers.
 Fibers and textiles that can be treated with the presently disclosed compositions include natural fibers such as cotton, silk, linen, and wool; regenerated fibers such as rayon and acetate; synthetic fibers such as polyesters, polyamides, polyacrylonitriles, polyethylenes, and polypropylenes; combinations, and blends thereof. The form of the fibers can include threads, filaments, tows, yarns, woven fabrics, knitted materials, non-woven materials, paper, carpet, and leather.
 The compositions and methods as disclosed are particularly useful to treat industrial flame retardant textiles. Representative, non-limiting examples of such flame retardants include Piruvatex® or Trevira® CS. The latter is a intrinsically flame retardant polyester. The flame retardant properties may be evaluated according to industry standardized norms such as DIN 4102-B2.
 These examples are intended to illustrate the invention to one of ordinary skill in the art and should not be interpreted as limiting the scope of the invention set forth in the claims. All measurements and experiments were conducted at 23° C., unless indicated otherwise.
 31 g of DC593 fluid (a blend of polydimethylsiloxane fluid (PDMS) having a viscosity of 100 mm2/s at 25° C. and MQ resin at weight ratio of 67/33) were emulsified in 59 g water containing 0.4 g solution of cetriammonium chloride at 29% 0.2 g of lauryl alcohol ethoxylate (3 EO units) and 0.2 g 2.5M HCl. The resulting emulsion was characterized as having median particle size D(v,0.5) in the range of 0.4 to 10 microns, depending on the level of the shear applied. Then 9.2 g of a mixture of TEOS was added with moderate agitation and allowed to polymerize for 18 hours. Capsules containing a core of resin--PDMS blend and a shell being composed of polymerized Si-network were obtained. Particle size measurements were made by laser diffraction technique using a "Mastersizer 2000" from Malvern Instruments Ltd., UK. (Further information on the particle size determination can be found in "Basic Principles of Particle Size Analytics", Dr. Alan Rawle, Malvern Instruments Limited, WR14 1XZ, UK and the "Manual of Malvern Particle Size Analyser". Particular reference is made to the user manual number MNA 0096, Issue 1.0, November 1994. All particle sizes indicated in the present application are mean average particle size according to D(v, 0.5) and are measured with a Malvern Mastersizer.
 The composition from Example 1 was applied to different textiles (cotton treated with Piruvatex® or Trevira® CS): The textile was treated using a standard padding machine. The formulation from example 1 was diluted in water at 50 g/L and placed in the padding equipment. After the padding, the fabric was dried for 5 minutes at 120° C. and left at room temperature and controlled humidity for 24 hours before testing. The flame retardant properties has been tested according the DIN 4102-B2, Table 1 below shows the results for cotton fabric:
TABLE-US-00001 TABLE 1 Direction 1 Direction 2 REFERENCE COTTON SURFACE ignition After flame time [s] 0 0 0 Max damaged length [mm] 120 90 70 Melting debris [YES/NO] N N N Flaming debris [YES/NO] N N N Mark line reached N N N [min 20 s] RESULT PASS PASS PASS COTTON EDGE ignition After flame time [s] 0 0 0 Max damaged length [mm] 85 80 40 Melting debris [YES/NO] N N N Flaming debris [YES/NO] N N N Mark line reached N N N [min 20 s] RESULT PASS PASS PASS
 Samples 1 to 17 were applied to cotton and polyester fabrics as described in example 2. Samples 1-3 are control experiments shown for reference. Samples 4 to 16 are representative silicone materials that were used for comparison. They are outside the scope of this invention. Sample 17 is the material described in Example 1.
 The treated textiles were assessed after drying for:  1. softness--evaluation of the feel of the textile surface  2. flame retardancy following DIN 4102-B2  3. ecological friendliness of the material i.e. solvent free and/or easy handling.
 The results are summarized in Table 2.
TABLE-US-00002 TABLE 2 Solventless Delivery Composition of PASS and easy Overall # Composition (carrier) padding bath Flame test Soft handling rating 1 REFERENCE -- NA YES NO YES -- 2 water WATER WATER YES NO YES -- 3 Iso-propyl alcohol (IPA) IPA IPA YES NO NO -- 4 Amino-silicone Emulsion WATER 12.47 g/100 g water NO YES YES NO 5 Si resin emulsion WATER 4.49 g/100 g water YES NO YES NO 6 Silane dispersion WATER 2.24 g/100 g water YES NO YES NO 7 DOW CORNING ® MH 1107 FLUID IPA 1.58 g/50 g ipa YES YES NO NO 8 Mix of SiH + SiVinyl polymers WATER 5.6 g/100 g water NO YES NO NO 9 DOW CORNING ® 593 FLUID IPA 1.58 g/50 g ipa YES YES NO NO 10 DOW CORNING ® 670 FLUID IPA 3.16 g/50 g ipa NO YES NO NO 11 DOW CORNING ® 1-2577 COATING IPA 2.21 g/50 g ipa YES YES NO NO 12 DOW CORNING ® FA 4001 SILICONE IPA 5.27 g/50 g ipa YES NO NO NO ACRYLATE 13 Amino-modified silicone gum-in-water WATER 3.2 g/100 g water NO YES YES NO emulsion 14 Silicone gum-in-water emulsion WATER 2.8 g/100 g water YES NO YES NO 15 High MW Silicone polyether WATER 4.49 g/100 g water NO NO YES NO 16 DOW CORNING ® Q1-6083 WATER 5.61 g/100 g water YES NO NO NO 17 EXAMPLE 1 WATER 5 g/100 g water YES YES YES YES
 Several compositions, described herein as M1 to M19 were prepared following the process described in Example 1. In all compositions, either DC 593 fluid or a blend of a silicone resin and poly-siloxane or a polysiloxane fluid was used. The compositions are listed in Table 3. A mixture of TEOS and 3-(trimethoxysilyl)-propyl-N,N-dimethyl-octadecylammonium chloride, (72 wt % in methanol, abbreviated N1) (different weight ratios) was used to prepare the silicate shell microcapsules. The silanes were added with moderate agitation and allowed to polymerize for 18 h.
 Material M5 and M19 are non encapsulated emulsions (i.e neither TEOS, nor N1 is added). M5 and M19 are therefore out of the scope of this invention.
 The compositions were applied to Polyester-Cotton and Tervira (polyester) flame retardant fabrics following the procedures described in example 2. The fabrics have been then tested for hydrophobicity, following a standard spray test described by the American Association of textile chemist and colorists (AATCC 22). The flame retardant properties were evaluated as described in example 2. Following notation has been used to describe the softness:  "∘"=some  "+"+some, but acceptable  "++"=good  "+++"=very good The results are summarised in Table 3.
TABLE-US-00003  TABLE 3 Ratio Hydro- Hydro- Ratio Resin/ phobicity Softness phobicity Softness TEOS: Flame Resin/fluid 200 fl PE/COT PE/COT COTTON COTTON D(v, 0.5) NI test M1 DC 593 (replica of EXAMPLE 1) NA 50 o 80 o 4.86 um 100:0 PASS M2 DC 593 NA 90 + 90 + 4.86 um 1:1 PASS M4 DC 593 NA 70 ++ 70 ++ 4.86 um 1:3 Not tested M5 DC 3037/DC 200 fluid 100 cSt 50/50 70 + 0 + 3 um NA PASS M6 DC 3037/DC 200 fluid 100 cSt 50/50 50 + 70 + 3 um 3:2 PASS M7 DC 3037/DC 200 fluid 100 cSt 50/50 70 + 70 + 0.44 u 3:2 PASS M8 DC 3074/DC 200 fluid 100 cSt 65/35 90 o 80 o 6.3 um 3:2 PASS M9 DC 3074/DC 200 fluid 100 cSt 35/65 80 o 80 o 7.1 um 3:2 PASS M10 DC 3037/ NA 70 ++ 50 + 2/10 3:2 PASS M11 DC 200 fluid 100 cSt NA 80 + 0 + 4.3 um 3:2 PASS M12 Methoxy resin/DC 200 fluid 100 35/65 70 + 0 + 4.3 um 3:2 PASS cSt M13 DC 3074/DC 200 fluid 100 cSt 65/35 80+ 2.7 um 3:2 PASS M14 PDMS Silanol terminated, 100 NA 80 ++ 70 ++ 4.0 um 3:2 PASS cSt M15 DC 3074/Silanol 14000 cSt 65/35 80 +++ 70+ +++ 5.3 um 3:2 PASS M16 DC 3074/Silanol 50000 cSt 65/35 80 +++ 70+ +++ 5.6 um 3:2 PASS M17 PDMS Silanol terminated, 50000 NA 90 +++ 90 +++ 3.0 um 3:2 PASS cSt M18 PDMS Silanol terminated, 50000 NA 90 ++ 90 ++ 10.0 um 3:2 PASS cSt M19 PDMS Silanol terminated, 50000 NA 0 + 0 ++ 3.6 um NA Not tested cST
 Different textiles were treated with M16 and M17 from example 3, employing the method described in example 2. In some cases, an anchorage enhancer has been added to the padding bath. The durability of the treatment was evaluated via the retention of the hydrophobicity after a multitude of washings. The latter were performed in a front loading European style washer, using a commercial detergent and a standard washing program for the particular type of textile. The results are summarized in Table 4.
TABLE-US-00004 TABLE 4 HYDROPHOBICITY Composition of After One Three Textile type the padding bath preparation wash washes POLYESTER M17 at 100 g/l 100 70 70 POLYESTER M16 at 100 g/l 80 70 70 POLYESTER M17 at 100 g/L + 80 80 70 monoamino trialkoxysilane POLYESTER M16 at 100 g/L + 80 70 70 monoamino trialkoxy silane POLYESTER M17 at 100 g/L + 80 70 70 diamino trialkoxy silane POLYESTER M16 at 100 g/L + 80 80 80 diamino trialkoxy silane POLYESTER M17 at 100 g/L + vinyl 80 70 70 triacetoxysilane POLYESTER REFERENCE - untreated 0 0 0 COTTON M17 at 100 g/L 90 80 70 COTTON M16 at 100 g/L 90 80 70 COTTON M17 at 100 g/L + 80 50 50 momoamino trialkoxy silane COTTON M16 + monoamino 70 0 0 trialkoxy silane COTTON M17 at 100 g/L + 80 50 50 diamino trialkoxy silane COTTON M16 at 100 g/L + 70 0 0 diamino trialkoxy silane COTTON M17 at 100 g/L + vinyl 90 50 50 triacetoxysilane COTTON M17 at 100 g/L + 100 80 70 melamine COTTON REFERENCE - untreated 0 0 0
Compatibility with Other Textile Treatment Compositions
 Material M17, alone and in combination with a commercially available fluorocarbon PYMAGARD USD (PYMAG, S.A. Barcelona--Spain) was applied to cotton and polyester-cotton fabrics using a padding equipment. The M17 and fluorocarbon were mixed at a weight ratio of 1:2. Very good compatibility of M17 and fluorocarbon was observed. The dried fabrics were tested for hydrophobicity and softness in the manner as described above. The oil repellency was measured according to AATCC Test Method 118-2002. This method consists of placing drops of standard test liquids (a selected series of hydrocarbons) with varying surface tensions on the fabric surface, followed by an observation of the wetting, wicking, and contact angle. The textile was then ranked from 1 to 6, with a higher number indicating that the fabric has greater oil repellency. The results are provided in Table 5. Material FC is the fluorocarbon alone, which did not confer any softness to the fabrics.
TABLE-US-00005 TABLE 5 Polyester/cotton Cotton Products (conc. Spray Oil Spray Oil In padding bath) test Softness repellency test Softness repellency M17 (100 g/L) 70+ good 1 100 good 1 FC (100 g/L) 100 NONE 6 100 NONE 6 M17 and FC 100 good 6 100 good 6 (total 100 g/L)
Patent applications by Bertrand Lenoble, Silly BE
Patent applications by Fabrizio Galeone, Buvrinnes BE
Patent applications by Josef Roidl, Saulheim DE
Patent applications by Leon Marteaux, Bxl (auderghem) BE
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Patent applications in class APPLICATION TO OPPOSITE SIDES OF SHEET, WEB, OR STRIP (EXCLUDING PROCESSES WHERE ALL COATING IS BY IMMERSION)
Patent applications in all subclasses APPLICATION TO OPPOSITE SIDES OF SHEET, WEB, OR STRIP (EXCLUDING PROCESSES WHERE ALL COATING IS BY IMMERSION)