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
  • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups

Definitions

• This invention relates to methods of treating fabrics and other substrates with exhaustible cationic silicone compounds which impart improved softness and antistatic properties to the treated fabric without yellowing.
• Fabrics have been treated for many years to improve their properties and acceptability to consumers. Improved softness, reduction in static, greater ease in ironing and prevention of yellowing are among the desired effects. Some treatments used to achieve these results, however are counter productive. For example, application of durable press resins to improve ease of ironing is known to give fabrics a harsher hand.
• conditioners have been well known to apply various types of textile conditioners to make textiles softer, and reduce static.
• conditioners used have been nonionic silicones, cationic emulsions of nonionic silicones and organic quaternary compounds.
• Nonionic silicones such as dimethyl silicone oil, silanol silicone fluids, silanic hydrogen fluids and an epoxy functional silicone available from Union Carbide Corporation under the tradename UCARSIL® T-29, have been used as textile softeners for a number of years. These materials, however, have no particular affinity for the textile substrate. Therefore, they are applied only by physical contact with the textile. These silicones are applied mostly by pad bath techniques because they are not exhaustible, i.e. because of their lack of affinity for the textile substrate they are not adsorbed from the pad bath solution onto the textile substrate.
• Exhaustible organic quaternary softeners are known such as methyl-1 (tallow amido ethyl) 2-(tallow) imidazolinium methyl sulfate, dimethyl alkyl(C12 - C16) benzyl ammonium chloride available from Sherex Chemical Co. Corp. under the tradenames Varisoft 475® and Variquat 50 MC®, respectively, and N-cetyl-­N-ethyl morpholinium ethosulfate available from Atlas Chemical Co. under the tradename Atlas G-263®, but they are deficient in their softening properties and tend to yellow the textile substrate, especially when white or pastel fabrics are used.
• quaternary ammonium functional silicones to treat fabrics is also known in the art.
• U.S. - A - 4,384,100, 4,511,727 and 4,615,706 concern quaternary ammonium functional silicone compounds prepared by reacting carboxylic acid functional quaternary ammonium compounds with carbinol functional silicon compounds. These materials are claimed to improve the antistatic properties of the fabric, however no mention is made of improved fabric softness or non-yellowing properties.
• U.S. - A - 4,390,713 and 4,394,517 disclose processes for preparing quaternary ammonium-functional silicon compounds by reacting carbinol functional quaternary ammonium compounds with carboxylic acid-functional silicon compounds and by reacting carboxylic acid functional quaternary ammonium compounds with amino functional silicon compounds, respectively.
• Both patents assert that the resultant cationic silicones are useful as antistatic finishes for textiles. No mention is made in either patent of softness, non-yellowing or exhaustability improvements.
• U.S. - A - 4,417,066 discloses a process for preparing organosiloxane polymers, which are useful as soil release agents, made by reacting a silanol terminated polydiorganosiloxane and a quaternary ammonium silane. No yellowing or exhaustability improvements were noted.
• U.S. - A - 4,448,810 discloses the use of a polydiorganosiloxane containing at least one quaternary ammonium salt substituent which is used as a soil release agent and to impart an antistatic finish.
• An additional siloxane is added to provide soft hand, lubricity or recovery from creasing. No mention is otherwise made of improved softness, yellowing properties or the ability to exhaust from solution.
• U.S. - A - 4,614,675 discloses a composition for treating a solid material to give it antimicrobial, hydrophilic and antistatic properties comprising a siloxane compound which has one or more alkoxy silylalkyl groups and one or more polyoxyalkylene groups and a silane having antimicrobial properties. No improvements in hand, yellowing properties or the ability to exhaust from solution is disclosed.
• U.S. - A - 4,585,563 discloses a detergent composition containing an organosiloxane that can have quaternary functionality, to improve softness.
• German Offenlegungsshrift DE 3542725 discloses a composition comprising an aqueous mixture of a cationic silicone oil, a cationic fatty acid condensate, and a cationic film former for treating laundry added to the final rinse to facilitate ironing.
• U.S. - A - 4,504,541 discloses the use of quaternary monomeric silicon structures as fabric antimicrobial treatments where the quaternary ammonium cation is at least partially sealed with an anionic surfactant. Improved susceptibility to discoloration is also disclosed, however no mention is made of fabric softening.
• U.S. - A - 4,767,547 discloses a rapidly biodegradable fabric softening composition which may contain a silicone component. Cationic silicones are preferred.
• GB - 1,549,180 discloses a fabric treatment composition containing a cationic compound, and an emulsion containing a cationic siloxane compound.
• GB - 2,201,696 and 2,201,433 disclose quaternary silicones for use in fabric conditioning compositions to provide improved wettability and softness. While the silicones broadly disclosed in these applications appear to include the silicones used in the present invention, the compounds specifically disclosed therein are shown to be no better than organic softeners in improving textile softness.
• cationic quaternary ammonium compounds with the structure used in the present invention were previously known and are described in U.S. - A - 3,389,160 where they were described as being useful as surfactants, surface tension depressants and corrosion inhibitors.
• Cationic silicone compounds of the same class as used in the present invention were also described as being useful hair conditioners in U.S. - A - 4,185,087.
• our invention comprises treating fabrics with a bath containing 0.05-5.0% by weight, based on the total fabric weight, of cationic silicone solids of the formula MD20 ⁇ 200D′3 ⁇ 60M together with O-2% by weight, based on the total bath weight, of an electrolyte such as NaCl, KCl, Na2SO4 or MgSO4. Ideally, 0.1 to 10 percent by weight, based on the weight of the fabric, of the cationic silicone is adsorbed by the textile.
• the cationic silicones may be applied to a solid substrate in an amount of 0.1-10% by weight of said substrate so that the cationic silicones can be imparted to textiles by placing the substrate with clothes or fabrics in a dryer.
• the fabric treatment composition may also include other fabric treatment agents known to those skilled in the art.
• Suitable cationic silicones according to the present invention may be either water soluble, water dispersible or water insoluble.
• Both x and y segments of the cationic silicone are repeated randomly throughout the molecule. It is preferred that x is more than 20, because when x is less than 20 the improvements in fabric hand of this invention are marginal. It is also preferred for practical reasons that x not exceed 200, because when x exceeds 200, the resultant cationic silicone is much more difficult to handle and emulsify. Y is preferably greater than three to ensure the compound has sufficient cationic character to achieve the exhaustability benefits of this invention.
• water soluble cationic silicones examples include MD90D′30M and MD165 D′50M.
• the water soluble cationic silicones have enhanced antistatic properties.
• the non-water soluble cationic silicones are preferable to the water soluble compounds because they provide even greater improvements in softness.
• a preferred water insoluble cationic silicone compound is MD165D′ 16.5 M. The most preferred is MD150D′10M.
• the cationic silicones of the present invention may be synthesized by methods known in the art, as disclosed, for example in U.S. - A - 3,389,160, whose disclosure is incorporated by reference herein.
• a 500 ml three-neck flask was equipped with a stirrer, addition funnel, dry ice/acetone condenser, thermocouple and electric heating mantle. A nitrogen blow-by was placed on the outlet from the dry ice/acetone condenser.
• a solution of trimethylamine in isopropanol was prepared by sparging the amine through the isopropanol.
• the resulting solution had an amine concentration of 0.0027 milliequivalents per gram.
• the contents were stirred and heated to 80°C; about 5 minutes after this temperature was reached all of the trimethylammonium chloride had gone into solution. After heating and stirring at 80°C for 4.5 hours the flask was cooled and sparged overnight with dry nitrogen.
• the quarternary ammonium pendant siloxane copolymer produced had the formula MD30D′10M A 61.66 g portion of the reaction product mixture and 20 g of propylene glycol were charged to a rotovap and stripped at 45°C at a nine speed for 1.5 hours to remove isopropanol and other low-boiling materials. In this example the ratio of free tertiary amine equivalent to tertiary amine acid salt equivalent is 0.001:1.
• MD ⁇ 40M, octamethylcyclotetrasiloxane and (CH3)3-Si-O-­Si-(CH3)3 were charged to a 3-neck flask equipped with a mechanical stirrer, condenser, and nitrogen purge. Concentrated sulfuric acid was added and stirred for 24 hours. NaHCO3 was added and neutralized for 2 hours. The product was then filtered.
• the resulting cationic silicone/isopropanol formulation contains a target of 69-71% of silicone solids.
• the cationic silicone has a targeted viscosity of 800-1,000 mm2/s and a pH of 5-7.
• the water soluble cationic silicones of the present invention may be directly incorporated into the medium used to treat the textiles, in an amount sufficient to deposit 0.1 to 10 percent by weight of the cationic silicone on the textile, based on the weight of the textile.
• emulsifiers may be used including, but not limited to alkanolamides, aklylaryl sulfonates, amine oxides, sulfonated and/or ethoxylated amines and amides, betaine derivatives, carboxylated alcohol ethoxylates, ethoxylated alcohols (primary or secondary) ethoxylated alkyl phenols, ethoxylated fatty acids, ethoxylated fatty esters and oils, fatty acid esters, glycerol and glycol esters, imidazolines and imidazoline derivatives, isethionates, olefin sulfonates, phosphate esters, and alkylaryl quaternary ethosulfates.
• the emulsifiers used may be nonionic or cationic.
• Preferred nonionic emulsifiers are TERGITOL® 15-S-15 and TERGITOL® 15-S-3 which are secondary alcohol ethoxylates available from Union Carbide, and Tween 80, polyoxyethylene sorbitan monooleate, available from ICI, Americas.
• Preferred cationic emulsifiers are Atlas G-263®, morpholinium ethosulfate, and Varisoft 475® (Sherex) which is methyl 1 -(tallow amido ethyl) 2-(tallow) imidazolinium-methyl sulfate.
• an emulsion for use in accordance with the present invention will contain 2 to 80 parts by weight of a cationic silicone formulation, said formulation containing 70 parts by weight silicone solids in an inert solvent such as isopropanol.
• suitable inert solvents include ethanol, methanol and butanol.
• the emulsion contains 5 to 40 weight parts by weight of the cationic silicone formulation, and most preferably 10 to 25 parts by weight of the cationic silicone formulation.
• the emulsion is made using an emulsifier in a quantity amounting to 5 to 40% by weight of the amount of cationic silicone formulation used.
• the emulsifier is used in an amount of 10-30% by weight, and most preferably about 15-25% by weight of the amount of cationic silicone formulation used.
• the balance of the composition is of course, water.
• a preferred emulsion made with non-ionic emulsifiers contains 14.3 parts of MD150D′10M formulation (70% active silicone in isopropanol and water), 1.8 parts TERGITOL 15-S-15®, 1.2 parts TERGITOL 15-S-3® and 82.7 parts water. All parts are by weight.
• the emulsion may contain other additives as desired, including antimicrobial agents, antifoam agents, as well as other silicones and organic softeners.
• a preferred cationic emulsion is made with 14.3 parts MD150D′10M (70% actives, balance isopropanol and water), 81.5 parts water and 4.2 parts Atlas G-263®. Again, all parts are by weight.
• one preferred emulsification method involves adding the emulsifiers to the cationic silicone followed by mixing at moderate speed for 10 minutes. 15 parts of the water is then charged to the mixture followed by another 10 minutes of mixing at moderate speed. Ten additional parts of H2O are added with another 10 minutes of mixing thereafter. The balance of the water is then added followed by additional mixing for 10 minutes. The speed of the mixer is reduced as the emulsification nears completion.
• the chosen emulsifier is solid at room temperature, it is recommended that it be heated to a fluid state prior to its addition to the cationic silicone component.
• the cationic silicones may be applied in accordance with the present invention to any suitable textile, including, but not limited to wool, cotton, rayon, hemp, natural silk, polypropylene, polyethylene, polyester, polyurethane, polyamide, cellulose acetate, polyacrylonitrile fibers, and mixtures of such fibers.
• the textile materials may consist of staple fibers or monofilaments.
• the fabrics may be knits, weaves, papers and other non-wovens, resin finished fabrics and their sewn products.
• the cationic silicones may be applied in the textile manufacturing process by any suitable method known in the art including but not limited to pad baths, spraying, foam finishing, minimum application, screen printing, sizing baths, etc.
• the preferred methods of application are by pad bath and exhaustion from solution processes.
• cationic silicone including, but not limited to optical brighteners, soil release agents, water repellents, durable press resins, other softeners, or even dyes.
• antimicrobial properties may be imparted by application of cationic quaternary compounds to various substrates.
• Application of the cationic silicones of the present invention can also impart antimicrobial activity to the textile substrate.
• cationic silicones compositions may be added to the wash or rinse cycles in the laundry. Or they may be absorbed onto a solid substrate and applied to clothes in the dryer. The cationic silicone could also be pre-blended with detergent and added to the washing machine.
• the presence of inorganic electrolyte can in some cases enhance the exhaustion of the cationic silicones.
• the fabrics to be treated are contacted with a composition containing about 0.05 - 2% of the cationic silicone component and about O-2% of an electroyte such as NaCl, KCl, Na2SO4 and MgSO4.
• an electroyte such as NaCl, KCl, Na2SO4 and MgSO4.
• About 0.1 to about 10% by weight of the cationic silicone, based on the weight of the textile, will be adsorbed by the textile.
• Example 1 The improved softening of the present invention is demonstrated in Example 1.
• a series of cationic silicone polymers were prepared and emulsified if necessary.
• Emulsions containing MD150D′10M and MD165D′ 16.5 M were prepared using 20 parts of a cationic silicone formulation which contained 50% actives in isopropanol, 1.2 parts TERGITOL 15-S-15®, 0.8 parts TERGITOL 15-S-3®, and 78 grams water.
• the MD90D′30M and MD165D′50M compounds are water soluble and were therefore added to the bath without emulsification.
• the emulsions were applied to 100% cotton and 65/35 polyester/cotton by pad bath with and without 15 parts Intex FC510®, dimethylol dihydroxy ethylene urea (DMDHEU), a durable press resin and Intex FC58® a catalyst which enables cross-­linking of the resin, such that 0.6% silicone solids were deposited on the fabric.
• the amount of silicone deposited on the fabric is determined by the analytical procedures described in G.W. Heylmun, et al., "Analysis of Methyl Fluorosilanes from Methypolysiloxanes by Gas Chromatography", J. of Gas Chrom. 1965, 266-268.
• An emulsion containing MD150D′10M was prepared using 20 parts of a cationic silicone formulation which contains 50% actives in isopropanol, 2 parts Varisoft 475® and 78 parts water.
• the emulsified MD150D′10M and an organic quaternary softener, Varisoft 475 which was simply dispersed in water, were separately applied to 65/35 polyester/cotton and 100% cotton fabrics with or without the durable press resin DMDHEU, then dry/cured for one and a half minutes at 171°C.
• the pad bath contained 15 parts of the durable press resin INTEX FC510® and 2.25 parts of INTEX Catalyst FC58.
• An emulsion containing ten percent actives of the cationic silicone MD150D′10M was prepared using two parts Varisoft 475 per 10 parts silicone actives and 78 parts H2O.
• the level of silicone deposited onto the fabric was measured by analyzing the treating solution by use of atomic absorption for silicon metal before and after the exhaustion process as well as by analyzing the level of silicone on the fabric before and after the exhaustion process.
• Example 3 As described in Example 3, a variety of fabrics were utilized to demonstrate the broad exhaustible utility of the cationic silicone, MD150D′10M in an emulsion made with Varisoft 475. In every case the softness properties of the treated fabric were markedly improved.
• An emulsion containing MD150D′10M was prepared using 20 parts of a cationic silicone formulation containing 50% actives in isopropanol, 2 parts Varisoft 475® and 78 parts water.
• the emulsified cationic silicone MD150D′10M and an organic quaternary VARISOFT 475® were pad bath applied to a variety of fabrics such that 0.6 wt% silicone or organic solids resulted on the fabric.
• the fabrics were dried for 1.5 minutes at 171°C and conditioned at 30% relative humidity for 3 days.
• Antistat testing according to the test methods AATCC-76-1982 (Electrical Resistivity of Fabric) and FTMS4046-101C (Electrostatic Properties of Materials) were carried out.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=23288343

Family Applications (1)

Country Status (4)

Cited By (10)

Citations (3)

Family Cites Families (1)

• 1990
  • 1990-03-28 CA CA 2013222 patent/CA2013222A1/en not_active Abandoned
  • 1990-03-28 EP EP19900105915 patent/EP0394689A3/de not_active Ceased
  • 1990-03-28 JP JP7713990A patent/JPH02277888A/ja active Pending
  • 1990-03-28 BR BR9001421A patent/BR9001421A/pt not_active Application Discontinuation

Patent Citations (3)

Also Published As

Similar Documents

Legal Events