Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
  • C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
  • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
  • C08J3/095—Oxygen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
  • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2383/04—Polysiloxanes
  • C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2483/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/52—Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/54—Aqueous solutions or dispersions
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

• the present invention relates to method of making aminosiloxane polymer nanoemulsions and nanoemulsion preparable by said method.
• Fluoropolymers such as those used in Scotchguard® from 3M, have become well established as soil-repellant molecules.
• fluoropolymers are not preferred due to environmental, health and safety concerns, such as the potential and possibility of persistent bioaccumulation and toxicity.
• Amino-modified silicone microemulsions that contain an amino- modified silicone and a high concentration of both ethylene glycol monoalkyl ether and nonionic surfactant, e.g.,
• polyoxyalkylene branched decyl ether are known and generally described as transparent in appearance and having a small particle diameter. However, these compositions have the
• the overall stability of the emulsion and finished product can be greatly enhanced.
• repellency benefit can be maximized, whilst minimizing the potential for negative results often seen with silicone- containing compositions, such as staining or spotting of fabrics, laundry machine residues, and product discoloration.
• the present invention provides a method of making a
• nanoemulsion comprising the steps of:
• aminosiloxane polymer to obtain an aminosiloxane
• the present invention attempts to solve one more of the needs by providing, in one aspect of the invention, a method of making an aminosilicone nanoemulsion which can be incorporated into a surface treatment composition.
• substantially free from means that the indicated material is at the very minimum not deliberately added to the composition to form part of it, or, preferably, is not present at
• compositions whereby the indicated material is present only as an impurity in one of the other materials deliberately
• substantially free from surfactant means that the emulsion comprises at most 1 percent by weight of surfactant, more preferably at most 0.1 percent by weight of surfactant .
• nanoemulsion refers to
• thermodynamically stable oil in water emulsions that have extremely small droplet sizes (below 750 nm, or typically below 250 nm) . These materials have special properties, including optical translucency, very large dispersed phase surface-to- volume ratios and long term kinetic stability. Due to
• microemulsions which belong to another class of stable (thermodynamically) and optically clear
• Microemulsions are spontaneously formed by "solubilizing" oil molecules with a mixture of surfactants, co- surfactants and co-solvents.
• surfactants co- surfactants and co-solvents.
• concentration in a microemulsion is typically several times higher than that in a nanoemulsion and significantly exceeds the concentration of the dispersed phase (generally, oil) .
• nanoemulsions in accordance with the present invention are formed by judiciously selecting solvent systems that provide adequate dissolution of the siloxanes and also exhibit some level of miscibility with water, thus a stable aqueous emulsion can be achieved without the use of surfactants.
• aminosiloxane polymer microemulsions and methods for preparing aminosiloxane polymer microemulsions employ high levels of solvent and nonionic surfactant (e.g., 12% ethylene glycol monohexyl ether per 100% of aminosiloxane polymer and 40% polyoxyalkylene branched decyl ether per 100% of
• aminosiloxane polymer nanoemulsions disclosed herein provide highly efficient deposition on a target surface. Benefits derived from this deposition may generally apply in the area of repellency of water and/or water-based compositions and/or oil and/or oil-based compositions, such as water-based stains and oily soils. Without being bound by theory, it is believed that the aminosiloxane polymer nanoemulsions disclosed herein comprise self-assembled, spherical, positively charged
• aminosiloxane polymer nano-particles which contain reduced levels of solvent and surfactant.
• These self-assembled, spherical, positively charged nano-particles exhibit efficient deposition and controlled spreading, that is believed to form a structured film on a surface that provides the repellency benefit as determined by the below specified time to wick method .
• the average particle sizes of the disclosed nanoemulsions range from 20 nm to 750 nm, or 20 nm to 500 nm, or 50 nm to 350 nm, or 80nm to 200 nm, or 90nm to 150 nm (as measured by
• the disclosed nanoemulsions are generally transparent or slightly milky in appearance .
• the aminosiloxane polymer nanoemulsion of the present invention comprises a silicone resin.
• An example of a silicone resin is a mixture of
• each of the one or more silicone resins of the polyorganosiloxane-silicone resin mixture contains at least about 80 mol% of units selected from the group consisting of units of the general formulas 3, 4, 5, 6 :
• R is selected from H, -OR 10 , or -OH residues or monovalent hydrocarbon residues with 1 to 40 carbon atoms, optionally substituted with halogens, where at least 20 mol% of the units are selected from the group consisting of units of the general formulas 5 and 6, and a maximum of 10 wt% of the R residues are -OR 10 and -OH residues.
• the silicone resins may preferably be MQ silicon resins (MQ) comprising at least 80 mol% of units, preferably at least 95 mol% and particularly at least 97 mol% of units of the general formulae 3 and 6.
• MQ MQ silicon resins
• the average ratio of units of the general formulae 3 to 6 is preferably at least 0.25, particularly at least 0.5, preferably at most 4, and more preferably at most 1.5.
• the silicon resins may also preferably be DT silicone resins (DT) comprising at least 80 mol% of units, preferably at least 95 mol% and particularly at least 97 mol% of units of the general formulae 4 and 5.
• DT silicone resins comprising at least 80 mol% of units, preferably at least 95 mol% and particularly at least 97 mol% of units of the general formulae 4 and 5.
• the average ratio of units of the general formulae 4 to 5 is preferably at least 0.01,
• Preferred halogen substituents of the hydrocarbon residues R are fluorine and chlorine.
• Preferred monovalent hydrocarbyl radicals Rare methyl, ethyl, phenyl.
• Preferred monovalent hydrocarbyl radicals R 10 are methyl, ethyl, propyl and butyl.
• Suitable aminosiloxane polymers are represented by of one or more liquid aminoalkyl-containing polyorganosiloxanes (P) comprising at least 80 mol% of units selected from units of the general formulae 7, 8, 9 and 10
• R 1 represents monovalent hydrocarbyl radicals having 1-40
• R 5 represents divalent hydrocarbyl radicals having 1-40 carbon atoms .
• y has an integer value from 1 to 6 , and 15 067055
• R 3 represents hydrocarbyl radicals having 1-40 carbon atoms and optionally substituted with halogens
• polyorganosiloxanes (P) comprise at least 95 mol%, more preferably at least 98 mol% and particularly at least 99.5 mol% of units selected from units of the general formulae 7, 8, 9 and 10.
• the polyorganosiloxanes (P) are obtainable via known chemical processes such as, for example, hydrolysis or equilibration.
• Suitable alkyl groups include methyl, ethyl, propyl, butyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, phenyl, and dodecyl groups, as well as acetate groups of each.
• the aminosiloxane polymer nanoemulsions further comprise carnauba wax, paraffin wax, polyethylene wax, or a mixture thereof.
• the nanoemulsions may comprise up to about 5% by weight of the nanoemulsion or from 0.05% to 2.5% by weight of the nanoemulsion of such further substances .
• treatment compositions include, but are not limited to, laundry spray treatment products, laundry pre-treatment products, fabric enhancer products, hard surface treatment compositions (hard surfaces include exterior surfaces, such as vinyl siding, windows, and decks) , carpet treatment
• the treatment composition may be provided in combination with a nonwoven substrate, as a treatment
• surfaces it is meant any surface. These surfaces may include porous or non-porous, absorptive or non-absorptive substrates. Surfaces may include, but are not limited to, celluloses, paper, natural and/or synthetic textiles fibers and fabrics, imitation leather and leather. Selected aspects of the present invention are applied to natural and/or synthetic textile fibers and fabrics.
• 12 t- shirts are added to the drum of a standard washing machine, set on Heavy Duty wash cycle, water level equal to 17 gallons (Super load size) , warm water, selected with single rinse option. Water is regulated to standardize the wash temperature to 90° F, Rinse to 60° F, and water hardness to 6 grain per gallon.
• Detergent is added to the wash water, such as Tide liquid Detergent (50. Og dose), Clean Breeze scent. With the fabrics in the washer, the rinse water is allowed to fill the tub. Prior to agitation, the fabric treatment composition of the present invention (40 grams) is equally dispersed and added to the rinse water, followed by completion of the rinse cycle.
• the garments are then placed in a standard dryer, such as a Kenmore standard 80 series, cotton cycle (high heat) , for 30 minutes or until dry.
• a standard dryer such as a Kenmore standard 80 series, cotton cycle (high heat)
• the fabrics are then removed from the dryer and placed in a cool, well ventilated room with controlled humidity set at 50 % RH, and temperature regulated to 70° F, for a period of 24-48 hours.
• the section of the fabric that will be measured for Time to Wick is subjected to UV light, such as standard overhead lab lighting, for 24-48 hours prior to measurement.
• Treated test fabric is compared for Time to Wick value versus an untreated control fabric that has been prepared in a similar manner as the test fabric without the addition of the fabric treatment composition.
• the Time to Wick value is measured as follows: On a flat, level hard surface (e.g. benchtop) a fresh square of a paper towel at least 10 cm x 10cm in size, is placed inside the prepared t- shirt so that 1 layer of fabric is being measured. A 300 ⁇ _, drop of DI water is then dispensed onto the fabric surface from a calibrated pipette. The process of absorption of the liquid drop is visually monitored and recorded counting the time elapsed in seconds. Eight drops are administered per t- shirt, with each drop placed at a different location separate from all adj acent drops .
• the time at drop absorption is defined as being the earliest time point at which no portion of the drop is observed remaining above the surface of the fabric. If the drop remains after 10 minutes, observation is discontinued. Such drops are recorded as having a time differential of 600 seconds.
• the Time to Wick value for a given liquid on fabric is the average of the time differentials recorded for 8 drops of that liquid. In order to determine the effect of a treatment, comparisons are made between the average Time to Wick value obtained from the treated fabric, versus the average obtained from its untreated control fabric using the same liquid, where longer times indicate greater repellency.
• silicone emulsions are diluted at a concentration of 1:500 and 1:1000 and finish products are measured as neat and diluted to a concentration of 1:10 in DI water. • Before diluting the sample, gently invert it several times to mix it well.
• the particle size measurements are made via Malvern Zetasizer Nano Series ZS, with model #ZEN3600 with the fixed parameter settings for both Silicone emulsion and finish product:
• Samples of the liquid composition to be tested are prepared for microscopic analysis in order to observe nanopartxcles that may be suspended in the composition.
• Sample preparation involves pipetting approximately 5 ⁇ of the liquid composition onto a holey carbon grid (such as Lacey Formvar Carbon on 300 mesh copper grid, P/N 01883-F, available from Ted Pella Inc.,
• a holey carbon grid such as Lacey Formvar Carbon on 300 mesh copper grid, P/N 01883-F, available from Ted Pella Inc.
• the excess liquid is blotted away from the edge of the grid with a filter paper (such as Whatman brand #4, 70 mm diameter, manufactured by GE Healthcare / General Electric Company, Fairfield, Connecticut, U.S.A., or similar) .
• the grid-mounted sample is plunged rapidly into liquid ethane using a freezing apparatus capable of producing a flash- frozen vitreous thin film of sample lacking crystalline ice (such as a Controlled Environment Vitrification System (CEVS device) , or similar apparatus) .
• a freezing apparatus capable of producing a flash- frozen vitreous thin film of sample lacking crystalline ice
• CEVS device Controlled Environment Vitrification System
• Liquid ethane may be prepared by filling an insulated container with liquid nitrogen and placing a second smaller vessel into the liquid nitrogen. Gaseous ethane blown through a syringe needle into the second vessel will condense into liquid ethane. Tweezers pre-cooled in liquid nitrogen are used to rapidly handle the frozen grids while taking great care to T/EP2015/067055
• the grid-mounted samples After being flash frozen the grid-mounted samples are stored under liquid nitrogen until being loaded into the cryo-TEM via a cryo transfer holder (such as Gatan model 626 Cryo-Holder available from Gatan Inc., Warrendale, Pennsylvania, U.S.A., attached to a TEM instrument such as the model Tecnai G 2 20 available from FEI Company, Hillsboro, Oregon, U.S.A., or similar).
• the cryo- TEM is equipped with a camera such as the Gatan Model 994 UltraScan 1000XP (available from Gatan Inc., Warrendale,
• the grid-mounted frozen samples are imaged in the cryo-TEM using low beam dosages (such as 200 KV in Low Dose Mode) in order to minimize sample damage.
• Suitable magnifications are selected in order to observe the size of nanoparticles which may be present. This may include
• magnifications in the range of 5,000x - 25,000x are measured in the range of 5,000x - 25,000x.
• the sample is kept as cold as possible, typically at or near the temperature of liquid nitrogen (approximately minus 175 °C) .
• Images of the samples are carefully examined to detect the presence of artefacts.
• a grid-mounted sample is discarded if any crystalline ice.
• Images are inspected for beam damage artefacts and are rejected if damage is observed.
• representative images are captured of approximately 40 fields of view which are representative of the sample. These images are used to determine the range of nanoparticle typical diameters, and to determine the presence or absence of nanoparticle aggregates. In each image, the diameters are measured from nanoparticles which are typical of that image.
• the range of typical diameter values reported for the composition is the range of the diameters measured across all images captured from that composition. In each image, the spacing between nanoparticles is observed.
• a nanoparticle aggregate is defined as a cluster which contains at least 10 nanoparticles clumped together, rather than being individually dispersed. Nanopartxcle aggregates are reported as present if at least one nanopartxcle aggregate is observed in at least one image captured from that composition.
• the amine oil U has a viscosity about 1000 mm 2 /s at 25°C
• the amine oil W has a viscosity about 1000 mm 2 /s at 25 °C
• Tripropyleneglycol n-butyl ether Available from Dow Chemical, Midland MI
• Isopropyl Myristate Available from Evonik Corporation, Hopewell, VA.
• Silicone MQ Resin Wacker MQ 803TF, available from Wacker Chemie, AG; Burghausen, Germany
• Butyl Carbitol available from Dow Chemical, Midland MI Surfactant: TAE-80, Tallow Alkyl ethoxylate, available from Akzo-Nobel
• Glacial Acetic Acid 97%, available from Sigma-Aldrich, St. Louis, MO
• Deposition Aid Polymer Terpolymer of acrylamide, acrylic acid and methacrylamidopropyl trimethylammonium chloride; Available from Nalco Chemicals, Naperville, IL Preservative: Proxel GXL, available from Lonza Group, Basel, Switzerland
• Dye Liquitint Blue AH; available from Milliken, Spartanburg, SC Data :

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• Dispersion Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Processes Of Treating Macromolecular Substances (AREA)

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• 2014
  • 2014-07-28 EP EP14178766.3A patent/EP2980126A1/en not_active Ceased
• 2015
  • 2015-07-24 US US15/500,282 patent/US10329387B2/en not_active Expired - Fee Related
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  • 2015-07-24 EP EP15752937.1A patent/EP3174920A1/en not_active Withdrawn
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