EP2563895A1 - A stain repellence composition - Google Patents

A stain repellence composition

Info

Publication number
EP2563895A1
EP2563895A1 EP11711938.8A EP11711938A EP2563895A1 EP 2563895 A1 EP2563895 A1 EP 2563895A1 EP 11711938 A EP11711938 A EP 11711938A EP 2563895 A1 EP2563895 A1 EP 2563895A1
Authority
EP
European Patent Office
Prior art keywords
composition
substrate
stain repellence
repellence
stain
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.)
Withdrawn
Application number
EP11711938.8A
Other languages
German (de)
French (fr)
Inventor
Somnath Das
Kingshuk Dutta
Amitava Pramanik
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP2563895A1 publication Critical patent/EP2563895A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/06—Inorganic compounds
    • C11D9/08—Water-soluble compounds
    • C11D9/10—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/30—Organic compounds, e.g. vitamins containing nitrogen
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/17—Halides of elements of Groups 3 or 13 of the Periodic Table
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/20—Halides of elements of Groups 4 or 14 of the Periodic Table, e.g. zirconyl chloride
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/24—Halides of elements of Groups 6 or 16 of the Periodic Table, e.g. chromyl chloride
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/28—Halides of elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/59—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
    • D06M11/62—Complexes of metal oxides or complexes of metal salts with ammonia or with organic amines
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
    • D06M11/65—Salts of oxyacids of nitrogen
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/01—Stain or soil resistance

Definitions

  • the present invention relates to a stain repellence composition for treating a substrate. More particularly the present invention relates to a composition for hydrophilic stain repellence and process for making a substrate repellent to hydrophilic stains.
  • next time cleaning benefit any treatment of a substrate prior to the deposition of dirt that enables easier cleaning upon the subsequent cleaning.
  • compositions for the treatment of hard and soft surfaces e.g. kitchen tops, tiles, carpets, upholstery, windows, including car windscreens, etc
  • fabrics need to be cleaned from time to time depending on the perception of the cleanliness of the consumers.
  • washing a fabric causes fabric damage. The more often a garment is washed, the more is the damage to the fabric. The damage of the fabric leads to the weariness and which subsequently leads to the older appearance of the fabric.
  • WO 91/04305 discloses an aqueous water repellent composition
  • an aqueous water repellent composition comprising the reaction product of one or more of a carboxylic acid or anhydride containing from 3 to 22 carbon atoms and a polyfunctional aromatic or aliphatic amine or substituted amine containing from 2 to 25 carbon atoms and a water soluble metal complex crosslinking agent containing one or more metals selected from Groups la, lla, Ilia, IVa and the first and second rows of transition metals from the Periodic Table of Elements.
  • the composition may contain wax and is dispersed in water to form a water repellent system.
  • GB 849275 discloses an anti-fungal composition for treating fabrics comprises an aqueous solution containing a thermosetting aminoplastic resin and a water-soluble complex of 8-hydroxyquinoline with copper and chromium.
  • GB 1257107 discloses compositions for rendering a fabric water repellent by means of the application of metal soaps.
  • WO 2008/148610 discloses a zinc complex for water repellence, however, the present inventors have found that this composition is difficult to formulate in the form of an easy to use direct application product.
  • WO 2010/057743 discloses compositions comprising Zinc, and amino compound and soap.
  • a composition which will make a substrate e.g. fabrics and/or surfaces
  • a substrate e.g. fabrics and/or surfaces
  • repellent soils and stains which are hydrophilic in nature, remains to be desired.
  • a complex of zinc and triethanolamine in the presence of soap and a salt of a trivalent metal ion and/or tetravalent metal ion in an alcohol based medium is suitable for use as a direct application hydrophilic stain repellence composition on the substrate and can make the substrate hydrophobic.
  • the invention provides a liquid direct application composition for treating a substrate comprising 0.25-5% by weight of a stain repellence composition comprising 25-50% by weight of the stain repellence composition of a soap; 10-30% by weight of the stain repellence composition of a complex of zinc and triethanolamine (TEA); 30- 65% by weight of the stain repellence composition of a salt of a trivalent metal ion and/or tetravalent metal ion a solvent comprising a lower alcohol and water in a ratio of between 99:1 and 85:15.
  • a stain repellence composition comprising 25-50% by weight of the stain repellence composition of a soap; 10-30% by weight of the stain repellence composition of a complex of zinc and triethanolamine (TEA); 30- 65% by weight of the stain repellence composition of a salt of a trivalent metal ion and/or tetravalent metal ion a solvent comprising a lower alcohol and water in a ratio of between 99
  • the invention provides a process for making a substrate hydrophilic stain repellence comprising the steps of applying the composition according to any one of the preceding claims onto a substrate; and drying the substrate.
  • the invention provides the use of a composition according to any one of claims 1 to 4 to make a fabric hydrophobic.
  • the invention provides a trigger spray dispenser comprising the composition according to any one of claims 1 -4.
  • hydrophilic stain repellence in the present invention is meant that, the composition according to the invention will make a substrate hydrophobic. Due to the enhanced hydrophobicity of the substrate, it will not attract any hydrophilic material therefore becomes repellent to hydrophilic stains.
  • a liquid direct application composition for treating a substrate which comprises a stain repellence composition and a solvent comprising a lower alcohol and water.
  • the stain repellence composition comprises a soap, a complex of zinc and triethanolamine (TEA) and a salt of a trivalent metal ion and/or tetravalent metal ion.
  • TAA zinc and triethanolamine
  • the soap according to the invention is present in a concentration of between 25 and 50% of the stain repellence composition, preferably at least 30%, more preferably at least 35%, but preferably less than 45% by weight of the stain repellence composition.
  • the soap is a preferably selected from C 8 -C 2 o soap, preferably Ci 2 -Ci 6 soap, more preferably C12-C14 soap.
  • the cation is selected from alkali metals. Alkaline earth metals are generally not preferred.
  • Non-limiting examples of water-soluble soaps that can be used according to the present invention include sodium or potassium laurate, sodium or potassium caprylate, and sodium/potassium myristate and mixtures thereof.
  • saturated soap is meant in the context of the present invention that the iodine value of the soap, which is commonly known and used in the art to indicate the degree of unsaturation, is preferably less than 20, more preferably less than 10, and most preferably less than 5. Saturated soap having no carbon-carbon double bond or triple bond is particularly preferred.
  • the complex of zinc and triethanolamine is present in a concentration of 10-30% by weight of the stain repellence composition.
  • the complex is preferably present in a concentration of at least 15%, but preferably not more than 25% by weight of the stain repellence composition.
  • a formula of the structure is found below.
  • carboxylate groups are represented by the formula,
  • the trivalent cation is preferably selected from cations of aluminium, titanium (III), chromium or iron (III) or mixtures thereof. These trivalent ions are preferably added to the composition in the form of their salts. If the trivalent metal ion is aluminium the counter ion is preferably selected from chloride, nitrate, sulphate, acetate or formate or mixtures thereof, more preferably chloride, nitrate, sulphate, and mixtures thereof. The most preferable trivalent salts are selected from aluminium chloride, titanium (III) chloride, ferric chloride, chromium chloride, aluminium nitrate, chromium nitrate, ferric nitrate. The tetravalent metal ion is preferably selected from titanium (IV). The preferred salt of the tetravalent metal ion is selected from titanium (IV) chloride.
  • the salt of a trivalent metal ion and/or tetravalent metal ion is present in a concentration of 30-65% by weight of the stain repellence composition.
  • the stain repellence composition preferably comprises at least 35%, but preferably not more than 60%, more preferably not more than 55%, still more preferably not more than 50%, or even not more than 45% by weight of the stain repellence composition.
  • the liquid direct application composition further comprises a solvent.
  • the solvent comprises a lower alcohol and water.
  • the lower alcohol is an alcohol comprising from 1 to 4 carbon atoms, more preferably selected from methanol, ethanol, propanol, preferably 2-propanol.
  • lower alcohols typically contain low amounts of water, typically 1 -5%. A low amount of additional water may optionally be added.
  • the ratio between the lower alcohol and water is typically between 99:1 and 85:15, more preferably the ratio is between 98:2 and 90:10, or even between 97:3 and 95:5.
  • the liquid direct application composition preferably comprises between 1 and 5% of the stain repellence composition in the solvent, more preferably at least 2% by weight, but the composition more preferably comprises less than 4%by weight of the stain repellence composition in the solvent.
  • the liquid direct application compositions may be packaged in a trigger spray dispense, a roll-on dispenser or any other kind of direct application dispenser. A trigger spray dispenser is the most preferred.
  • the substrate may be any substrate and includes hard and soft surfaces (e.g. fabrics, carpets, upholstery, metal surfaces, kitchen tops, tiles, windows, including car windscreens, etc).
  • hard and soft surfaces e.g. fabrics, carpets, upholstery, metal surfaces, kitchen tops, tiles, windows, including car windscreens, etc.
  • the invention provides a process for making a substrate hydrophilic stain repellent comprising the steps of: (a) applying the direct application composition according to the invention onto a substrate, and (b) drying and optionally ironing the substrate.
  • the direct application step is to ensure that the surface of the substrate is substantially coated by the composition of the invention. It will be appreciated that any other means apart from spraying, that give rise to the coating of a substrate.
  • the drying step is carried out at an ambient temperature, i.e. 20-25°C, but, it also can be carried out at an elevated temperature.
  • Example 1 Making a Zn-triethanolamine complex
  • Zn acetate dihydrate (Merck) and TEA (Merck) were ground together at a molar ratio of 2:1 for 30 minutes using a mortar and pestle.
  • the solid mass obtained after the mixing was washed with ethanol (99%) twice, purified and the residue was dried at 60 C for 4 hours.
  • the material was characterized by FT-IR and Powder X-Ray diffraction.
  • the complex as isolated has a molecular formula Zn 4 (OAc-t) 2 (OAc-b)2(TEAH)2 where t means terminal and b means bridging ligand respectively.
  • Example 2 Making a Zn-TEA complex
  • Triethanolmine AR (ex. SD Fine Chem) was dissolved in 100ml absolute alcohol. This solution was added dropwise to the round bottom flask containing alcoholic solution of Zinc acetate with constant stirring. A transparent sol was obtained. The alcohol was then evaporated to get the Compound-1 A in the form of a white powder.
  • the material was characterized as having the molecular formula Zn 4 (OAc-t) 2 (OAc-b) 2 (TEAH) 2 .
  • compositions 1 to 4, 22 and 23 contain all 3 required ingredients; in compositions 5 to 20 at least one of the required ingredients is not present and in composition 21 none are present. In compositions 1 -
  • the treatment composition was dissolved in ethanol (99.9%) and in compositions 22 and 23, the composition was dissolved in water.
  • the table shows the relative concentration of the 3 ingredients by weight of the total amount of ingredients of the stain repellence composition, and the concentration of the total stain repellence composition in the solvent.
  • compositions 1 -21 are clear solutions, compositions 22 and 23 are turbid.
  • Desized cotton fabric swatches (of 100 cm 2 ex, Bombay Dyeing) are treated by adding 3 mL of any of the above mentioned compositions by a pipette. The swatches were then dried in air. The fabric was ironed at a temperature of 105 °C. Water repellency was checked by the so called Drop test method.
  • This test determines a treated fabric's resistance to wetting by aqueous liquids. Drops of water-alcohol mixtures of varying surface tensions are placed on the fabric, and the extent of surface wetting is determined visually. This test provides a rough index of aqueous stain resistance; the higher the solution number up to which the fabric does not wick, the more water repellent the fabric is..
  • the test solutions used for the experiment are as follows:
  • the fabric swatches were treated as follows. The test fabric was placed face up on a glass microscopic slide. Beginning with Test Liquid No. 0, 10 ⁇ _ droplet of the solution was placed on the test fabric. The drop was observed for 10 seconds from an approximate 45° angle. If the droplet did not wet the fabrics then the next mixture solution was added in the same manner. The fabric's water repellency rating was the highest numbered liquid for which at the droplet did not wet or wick into the fabric. The results are given in the table below Drop test result score
  • Example 4 treatment of a hard surface
  • composition 2 0.5 mL was added to a glass slide and a stainless steel plate, left for drying and wiped off with a tissue paper till completely dry.
  • the contact angle (degree) was measured by putting a 10 microlitre of water droplet on the treated and the untreated surfaces.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Detergent Compositions (AREA)
  • Paints Or Removers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to a stain repellence composition for treating a substrate. More particularly the present invention relates to a composition for hydrophilic stain repellence and process for making a substrate repellent to hydrophilic stains. It is an object of the present invention to provide a composition that renders a substrate hydrophobic; and thereby make a substrate repellent to hydrophilic stains. It has now been found that, a complex of zinc and triethanolamine in the presence of soap and a salt of a trivalent metal ion and/or tetravalent metal ion in an alcohol based medium is suitable for use as a direct application hydrophilic stain repellence composition on the substrate and can make the substrate hydrophobic.

Description

A STAIN REPELLENCE COMPOSITION
Field of the Invention
The present invention relates to a stain repellence composition for treating a substrate. More particularly the present invention relates to a composition for hydrophilic stain repellence and process for making a substrate repellent to hydrophilic stains.
Background and Prior Art
Present days consumers are not only looking for fabric washing composition to remove the dirt. But, they are also looking for fabric treatment composition before-wash or after-wash to keep the fabric better and long-lasting. Different types of fabric care/treatment compositions are known in the art. Fabric care compositions serve a variety of purposes. The use of a fabric care composition is one of the ways to deliver and deposit different types of benefit agents onto the fabrics.
Fabric cleaning or care compositions that provide a so called next time cleaning benefit, are highly appreciated by present day consumers. By next time cleaning benefit is meant any treatment of a substrate prior to the deposition of dirt that enables easier cleaning upon the subsequent cleaning.
Similarly there is a need for compositions for the treatment of hard and soft surfaces (e.g. kitchen tops, tiles, carpets, upholstery, windows, including car windscreens, etc) that render the surfaces hydrophobic and/or repellent to aqueous stains. Fabrics need to be cleaned from time to time depending on the perception of the cleanliness of the consumers. However, washing a fabric causes fabric damage. The more often a garment is washed, the more is the damage to the fabric. The damage of the fabric leads to the weariness and which subsequently leads to the older appearance of the fabric.
One of the ways of keeping fabrics clean is not to expose it to the environment which will eventually make the fabric dirty. Less dirty the fabric is the frequency of washing will also be less. Due to reduced frequency of fabric washing the weariness will also be less and the fabrics will become long lasting. Coating compositions using different fabric compatible polymers to reduce the dirt on the fabric have been disclosed in the art.
WO 91/04305 discloses an aqueous water repellent composition comprising the reaction product of one or more of a carboxylic acid or anhydride containing from 3 to 22 carbon atoms and a polyfunctional aromatic or aliphatic amine or substituted amine containing from 2 to 25 carbon atoms and a water soluble metal complex crosslinking agent containing one or more metals selected from Groups la, lla, Ilia, IVa and the first and second rows of transition metals from the Periodic Table of Elements. The composition may contain wax and is dispersed in water to form a water repellent system.
GB 849275 discloses an anti-fungal composition for treating fabrics comprises an aqueous solution containing a thermosetting aminoplastic resin and a water-soluble complex of 8-hydroxyquinoline with copper and chromium.
GB 1257107 discloses compositions for rendering a fabric water repellent by means of the application of metal soaps. WO 2008/148610 (co-pending) discloses a zinc complex for water repellence, however, the present inventors have found that this composition is difficult to formulate in the form of an easy to use direct application product.
WO 2010/057743 (co-pending) discloses compositions comprising Zinc, and amino compound and soap.
A composition which will make a substrate (e.g. fabrics and/or surfaces) hydrophobic and therefore repellent soils and stains, which are hydrophilic in nature, remains to be desired.
In view of the foregoing, it is an object of the present invention to provide a composition that renders a substrate hydrophobic; and thereby make a substrate repellent to hydrophilic stains. It is another object of the invention to provide substrates that are resistant to getting soiled or stained by hydrophilic stains.
It is yet another object of the invention to provide a direct application composition for treating substrates.
Surprisingly it has now been found that, a complex of zinc and triethanolamine in the presence of soap and a salt of a trivalent metal ion and/or tetravalent metal ion in an alcohol based medium is suitable for use as a direct application hydrophilic stain repellence composition on the substrate and can make the substrate hydrophobic.
Summary of the invention
Accordingly the invention provides a liquid direct application composition for treating a substrate comprising 0.25-5% by weight of a stain repellence composition comprising 25-50% by weight of the stain repellence composition of a soap; 10-30% by weight of the stain repellence composition of a complex of zinc and triethanolamine (TEA); 30- 65% by weight of the stain repellence composition of a salt of a trivalent metal ion and/or tetravalent metal ion a solvent comprising a lower alcohol and water in a ratio of between 99:1 and 85:15.
In another aspect the invention provides a process for making a substrate hydrophilic stain repellence comprising the steps of applying the composition according to any one of the preceding claims onto a substrate; and drying the substrate. In yet another aspect the invention provides the use of a composition according to any one of claims 1 to 4 to make a fabric hydrophobic.
In still another aspect the invention provides a trigger spray dispenser comprising the composition according to any one of claims 1 -4.
By the term hydrophilic stain repellence in the present invention is meant that, the composition according to the invention will make a substrate hydrophobic. Due to the enhanced hydrophobicity of the substrate, it will not attract any hydrophilic material therefore becomes repellent to hydrophilic stains. These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description. For the avoidance of doubt, any feature of one aspect of the present invention may be utilised in any other aspect of the invention. The word "comprising" is intended to mean "including" but not necessarily "consisting of" or "composed of." In other words, the listed steps or options need not be exhaustive. It is noted that the examples given in the description below are intended to clarify the invention and are not intended to limit the invention to those examples per se. Similarly, all percentages are weight/weight percentages unless otherwise indicated. Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word "about". Numerical ranges expressed in the format "from x to y" are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format "from x to y", it is understood that all ranges combining the different endpoints are also contemplated.
Detailed description of the invention
According to the present invention a liquid direct application composition for treating a substrate is provided, which comprises a stain repellence composition and a solvent comprising a lower alcohol and water.
Stain repellence composition.
The stain repellence composition comprises a soap, a complex of zinc and triethanolamine (TEA) and a salt of a trivalent metal ion and/or tetravalent metal ion.
Soap
The soap according to the invention is present in a concentration of between 25 and 50% of the stain repellence composition, preferably at least 30%, more preferably at least 35%, but preferably less than 45% by weight of the stain repellence composition.
The soap is a preferably selected from C8-C2o soap, preferably Ci2-Ci6 soap, more preferably C12-C14 soap. The cation is selected from alkali metals. Alkaline earth metals are generally not preferred. Non-limiting examples of water-soluble soaps that can be used according to the present invention include sodium or potassium laurate, sodium or potassium caprylate, and sodium/potassium myristate and mixtures thereof.
By saturated soap is meant in the context of the present invention that the iodine value of the soap, which is commonly known and used in the art to indicate the degree of unsaturation, is preferably less than 20, more preferably less than 10, and most preferably less than 5. Saturated soap having no carbon-carbon double bond or triple bond is particularly preferred.
Complex of zinc and triethanolamine
The complex of zinc and triethanolamine is present in a concentration of 10-30% by weight of the stain repellence composition. The complex is preferably present in a concentration of at least 15%, but preferably not more than 25% by weight of the stain repellence composition.
The present invention relates to a complex of Zinc having the empirical formula Znx(TEA)y(BB)z, where; "TEA" is triethanolamine, also known as TEAH3, wherein the TEA may be present in the complex in a deprotonated state, such as TEAH; "BB" represents carboxylate groups of the formula H(CH2)PC02", where p = 1 -5, which are bonded to Zinc either by terminal or bridged oxygen atoms; and, x, y and z are integers that satisfy the bivalency of zinc, wherein x is preferably at least 2. A formula of the structure is found below.
In a preferred form, the carboxylate groups are represented by the formula,
H(CH2)pC02 ", where p = 1 -5. This includes Acetic acid, Propionic acid, Butyric acid, Valeric acid and Caproic acid. It is preferred that the acid is Acetic acid. Salt of a trivalent metal ion and/or tetravalent metal ion
The trivalent cation is preferably selected from cations of aluminium, titanium (III), chromium or iron (III) or mixtures thereof. These trivalent ions are preferably added to the composition in the form of their salts. If the trivalent metal ion is aluminium the counter ion is preferably selected from chloride, nitrate, sulphate, acetate or formate or mixtures thereof, more preferably chloride, nitrate, sulphate, and mixtures thereof. The most preferable trivalent salts are selected from aluminium chloride, titanium (III) chloride, ferric chloride, chromium chloride, aluminium nitrate, chromium nitrate, ferric nitrate. The tetravalent metal ion is preferably selected from titanium (IV). The preferred salt of the tetravalent metal ion is selected from titanium (IV) chloride.
The salt of a trivalent metal ion and/or tetravalent metal ion is present in a concentration of 30-65% by weight of the stain repellence composition. The stain repellence composition preferably comprises at least 35%, but preferably not more than 60%, more preferably not more than 55%, still more preferably not more than 50%, or even not more than 45% by weight of the stain repellence composition.
Solvent
The liquid direct application composition further comprises a solvent. The solvent comprises a lower alcohol and water.
The lower alcohol is an alcohol comprising from 1 to 4 carbon atoms, more preferably selected from methanol, ethanol, propanol, preferably 2-propanol.
These lower alcohols typically contain low amounts of water, typically 1 -5%. A low amount of additional water may optionally be added. The ratio between the lower alcohol and water is typically between 99:1 and 85:15, more preferably the ratio is between 98:2 and 90:10, or even between 97:3 and 95:5.
Liquid direct application composition
The liquid direct application composition preferably comprises between 1 and 5% of the stain repellence composition in the solvent, more preferably at least 2% by weight, but the composition more preferably comprises less than 4%by weight of the stain repellence composition in the solvent. The liquid direct application compositions may be packaged in a trigger spray dispense, a roll-on dispenser or any other kind of direct application dispenser. A trigger spray dispenser is the most preferred.
Treating a substrate
The substrate may be any substrate and includes hard and soft surfaces (e.g. fabrics, carpets, upholstery, metal surfaces, kitchen tops, tiles, windows, including car windscreens, etc).
In one embodiment the invention provides a process for making a substrate hydrophilic stain repellent comprising the steps of: (a) applying the direct application composition according to the invention onto a substrate, and (b) drying and optionally ironing the substrate. The direct application step is to ensure that the surface of the substrate is substantially coated by the composition of the invention. It will be appreciated that any other means apart from spraying, that give rise to the coating of a substrate.
According to one of the preferred aspect of the present invention the drying step is carried out at an ambient temperature, i.e. 20-25°C, but, it also can be carried out at an elevated temperature. Now the invention will be demonstrated by way of non-limiting examples. Examples
The examples are for illustration only and do not limit the scope of the invention in any manner. Example 1 : Making a Zn-triethanolamine complex
Zn acetate dihydrate (Merck) and TEA (Merck) were ground together at a molar ratio of 2:1 for 30 minutes using a mortar and pestle. The solid mass obtained after the mixing was washed with ethanol (99%) twice, purified and the residue was dried at 60 C for 4 hours. The material was characterized by FT-IR and Powder X-Ray diffraction. The complex as isolated has a molecular formula Zn4(OAc-t)2(OAc-b)2(TEAH)2 where t means terminal and b means bridging ligand respectively.
Example 2: Making a Zn-TEA complex
1 1 g (0.05M) Zinc acetate 2H20 AR (Ex Merck) was taken in a round bottom flask and 500 ml Ethanol (HPLC grade absolute alcohol) was added to it. The alcohol was evaporated on rotary evaporator till about 250 ml alcohol was evaporated. The flask was then cooled in ice bath to 0°C.
In a 250ml beaker, 7.45g Triethanolmine AR (ex. SD Fine Chem) was dissolved in 100ml absolute alcohol. This solution was added dropwise to the round bottom flask containing alcoholic solution of Zinc acetate with constant stirring. A transparent sol was obtained. The alcohol was then evaporated to get the Compound-1 A in the form of a white powder. The material was characterized as having the molecular formula Zn4(OAc-t)2(OAc-b)2(TEAH)2.
Example 3: Water repellence tests
Twenty compositions (see table below) were prepared, with at least one of the ingredients for the stain repellence composition. Compositions 1 to 4, 22 and 23 contain all 3 required ingredients; in compositions 5 to 20 at least one of the required ingredients is not present and in composition 21 none are present. In compositions 1 -
21 , the treatment composition was dissolved in ethanol (99.9%) and in compositions 22 and 23, the composition was dissolved in water. The table shows the relative concentration of the 3 ingredients by weight of the total amount of ingredients of the stain repellence composition, and the concentration of the total stain repellence composition in the solvent.
Compositions 1 -21 are clear solutions, compositions 22 and 23 are turbid.
Desized cotton fabric swatches (of 100 cm2 ex, Bombay Dyeing) are treated by adding 3 mL of any of the above mentioned compositions by a pipette. The swatches were then dried in air. The fabric was ironed at a temperature of 105 °C. Water repellency was checked by the so called Drop test method.
Drop test method
This test determines a treated fabric's resistance to wetting by aqueous liquids. Drops of water-alcohol mixtures of varying surface tensions are placed on the fabric, and the extent of surface wetting is determined visually. This test provides a rough index of aqueous stain resistance; the higher the solution number up to which the fabric does not wick, the more water repellent the fabric is.. The test solutions used for the experiment are as follows:
The fabric swatches were treated as follows. The test fabric was placed face up on a glass microscopic slide. Beginning with Test Liquid No. 0, 10 μΙ_ droplet of the solution was placed on the test fabric. The drop was observed for 10 seconds from an approximate 45° angle. If the droplet did not wet the fabrics then the next mixture solution was added in the same manner. The fabric's water repellency rating was the highest numbered liquid for which at the droplet did not wet or wick into the fabric. The results are given in the table below Drop test result score
1 2
2 4
3 4
4 2
5 0
6 0
7 0
8 0
9 0
10 0
1 1 0
12 0
13 0
14 0
15 0
16 0
17 0
18 0
19 0
20 0
21 0
22 0
23 0
The above results show that only when all 3 ingredients (Zn-TEA, Soap and a tri- or tetra-valent metal) are present in the composition, the required effect is obtained. Example 4: treatment of a hard surface
0.5 mL of composition 2 (see above) was added to a glass slide and a stainless steel plate, left for drying and wiped off with a tissue paper till completely dry.
The contact angle (degree) was measured by putting a 10 microlitre of water droplet on the treated and the untreated surfaces. untreated Treated
Glass slide 16 80
Stainless steel 42 75
The higher the contact angle the higher the water repellence.

Claims

Claims
1 A liquid direct application composition for treating a substrate comprising:
a 0.25-5% by weight of a stain repellence composition comprising:
i 25-50% by weight of the stain repellence composition of a soap ii 10-30% by weight of the stain repellence composition of a complex of zinc and triethanolamine (TEA) having the formula Znx(TEA)y(BB)z, wherein "BB" represents carboxylate groups of the formula H(CH2)pCC>2", where p = 1 -5 and, x, y and z are integers that satisfy the bivalency of zinc. iii 30-65% by weight of the stain repellence composition of a salt of a trivalent metal ion and/or tetravalent metal ion
b a solvent comprising a lower alcohol and water in a ratio of between 99:1 and 85:15; the lower alcohol comprising from 1 to 4 carbon atoms.
2 A composition according to claim 1 , where in the soap is selected from water soluble soaps having C8-C2o carbon atoms.
3 A composition according to anyone of claims 1 or 2, wherein the aluminium salt is selected from AI(N03)3, AICI3 and AI2(S04)3 and mixtures thereof.
4 A composition according to anyone of claims 1 to 3, wherein the solvent is a mixture of water and a lower alcohol selected from methanol, ethanol or propanol, where in the ratio of alcohohwater is between 99:1 and 70:30.
5 A process for making a substrate hydrophilic stain repellence comprising the steps of: a Applying the composition according to any one of the preceding claims onto a substrate; and
b Drying and optionally ironing the substrate.
6 The use of a composition according to any one of claims 1 to 4 to make a fabric hydrophobic.
7 A trigger spray dispenser comprising the composition according to any one of claims 1 - 4.
EP11711938.8A 2010-04-30 2011-04-05 A stain repellence composition Withdrawn EP2563895A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IN1373MU2010 2010-04-30
EP10168997 2010-07-09
PCT/EP2011/055262 WO2011134756A1 (en) 2010-04-30 2011-04-05 A stain repellence composition

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EP2809757B1 (en) 2012-01-31 2016-04-27 Unilever N.V. A composition and method for treating substrates

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GB849275A (en) 1955-11-25 1960-09-21 Cfmc New water-soluble complexes of 8-hydroxy-quinoline and a process for their preparation
GB1257107A (en) 1969-05-07 1971-12-15
GB8921041D0 (en) 1989-09-16 1989-11-01 Rtz Chemicals Ltd Water-borne water repellents and their use
CN101687888B (en) 2007-06-04 2012-11-14 荷兰联合利华有限公司 A zinc complex, process for preparing thereof and a method for treating fabric therewith
WO2010057743A2 (en) 2008-11-20 2010-05-27 Unilever Nv Method of treating a fabric

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