EP2150555A1 - Complexe de zinc, son procédé de préparation et procédé de traitement d'un tissu avec celui-ci - Google Patents

Complexe de zinc, son procédé de préparation et procédé de traitement d'un tissu avec celui-ci

Info

Publication number
EP2150555A1
EP2150555A1 EP08749775A EP08749775A EP2150555A1 EP 2150555 A1 EP2150555 A1 EP 2150555A1 EP 08749775 A EP08749775 A EP 08749775A EP 08749775 A EP08749775 A EP 08749775A EP 2150555 A1 EP2150555 A1 EP 2150555A1
Authority
EP
European Patent Office
Prior art keywords
complex
fabric
zinc
acid
solution
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Withdrawn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
EP08749775A
Other languages
German (de)
English (en)
Inventor
Nitesh Omprakash Bhalla
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 EP2150555A1 publication Critical patent/EP2150555A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention relates to a method of fabric treatment, particularly to a method of increasing the stain repellence by increasing hydrophobicity of fabrics using complexes of Zinc.
  • Fabric or textile fibres easily stain upon contact with aqueous stains. These stains include inks, dyes, tea, coffee and other beverages. Repellence refers to the ability of a textile to repel aqueous or oil based liquids.
  • a material which has good repellence will not readily absorb liquids, but instead liquids will tend to "roll-up" or be repelled from the surface of such a textile.
  • Achieving relatively high degree of repellence is generally desirable. This is especially the case for stains caused by products containing persistent dyestuffs or pigments for instance present in coffee, tea, wine, fruit juices, and inks.
  • One approach is to coat or impregnate the fabrics such that subsequent removal of stains during washing becomes relatively easy. Thus hydrophobically treated fabrics are able to repel stains.
  • Zinc-amine complexes have also been reported in the art.
  • GB 1198060 (British Petroleum) describes complexes of Zinc having the following structure : (RCOO) ZnO (R1NH2) n wherein R represents an alkyl, cycloalkyl, aryl, aralkyl or alkaryl group, having not more than 24 carbon atoms, Rl represents an alkyl group having from 1 to 30 carbon atoms, and which can be saturated or unsaturated, branched or straight-chain, and n is an integer from 1 to 8.
  • the zinc atoms in the complex are arranged tetrahedrally around a central oxygen atom.
  • Hydrophobic polymers particularly fluorocarbons and silicones have been reported to render fabric surface stain repellent .
  • the present inventors have found a new class of compounds of Zinc that surprisingly give superior benefits when used in fabric treatment. It has been observed by the present inventors that these compounds impart high degree of hydrophobicity to surfaces, particularly fabrics.
  • the complex has the following structure:
  • the present invention relates to a process for preparing a complex comprising the step of:
  • the present invention relates to a method for treating fabric comprising the steps of:
  • the method includes an additional step of contacting the fabric with a solution of a fatty acid.
  • the present invention relates to use of a complex according to the invention for treatment of fabrics.
  • the invention will now be explained in detail.
  • the present invention relates to a complex of Zinc having the empirical formula Zn x (AA) y (BB) z , where;
  • AA represents neutral or deprotonated mono-, di- or tri- alkanolamines
  • x, y and z are integers that satisfy the bivalency of zinc.
  • the alkanolamine is selected from methanolamine, monoethanolamine, diethanolamine or triethanolamine, more preferably it is triethanolamine .
  • a particularly preferred complex has the following structure :
  • any known method of separating the complex from the liquor may be employed, although it is preferred that the solvent is evaporated to get the complex.
  • the liquor along with the complex, dissolved therein may be cooled to about 0°C to get the complex, and the solvent may be decanted off.
  • Zinc acetate is the most preferred salt.
  • Preferred solvents are alcoholic solvents selected from Methanol, Ethanol or Isopropanol, Ethanol being the most preferred solvent for low toxicity as compared to Methanol, low viscosity as compared to Isopropanol and relatively low boiling point.
  • the molar ratio of Zinc salt to alkanolamine is from 3:1 to 1:3, more preferably from 2:1 to 1:2 and most preferably 1:1.
  • the present invention also provides a method for treating fabric comprising the steps:
  • the pH is between 6 and 8.
  • Preferred concentration of the alcoholic solution is from 0.05% to 2.0%, and more preferably between 0.1% and 0.5%, the % being by weight.
  • the fabric after contacting with the alcoholic solution, is removed from the solution and thereafter contacted with an aqueous medium.
  • the alcohol from the alcoholic solution may be removed and thereafter the fabric may be contacted with the aqueous solution.
  • the aqueous solution may be water or an aqueous solution containing detergents or electrolytes.
  • the order of contact can be reversed, i.e. the fabric can be first contacted with an aqueous medium e.g. detergent solution, followed by contacting with an alcoholic solution of the complex according to the invention. Drying is preferably by air drying, although forced air drying and drying by blowing hot air is also possible.
  • the treated fabric may be ironed, which helps in fixing the particles, which are believed to be formed due to the hydrolysis of the complex.
  • the process includes an additional step of contacting the fabric with a solution of a fatty acid, selected from Cio to Cis straight or branched chain carboxylic acids.
  • a fatty acid selected from Cio to Cis straight or branched chain carboxylic acids.
  • Preferred fatty acids are Laurie acid and Stearic acid.
  • the solution of fatty acid is prepared in a non-aqueous solvent selected from primary alcohols, alkanes or ketones, preferably primary alcohols, more preferably Ethanol. It is preferred that the concentration of this solution is between 0.25% wt and 2 %wt, more preferably between 0.5 %wt and 1.0 %wt .
  • the increased hydrophobicity of fabric treated in accordance of the invention may be attributed to the deposition of particles, which generally are in size range of 100-1000 nm and more particularly between 200 nm and 500 nm.
  • the particles could be a dough-nut shaped or a dimpled hemispherical shaped.
  • Any suitable fabric may be chosen for the invention, but is preferred that it is cotton, polycotton, polyester, silk, wool or other synthetics used for applications like making garments, shoes, upholstery, curtains, carpets and paintings .
  • the hydrophobicity is measured by contact angle measurement of water droplet in air. It is preferably in the range of 90° to 140°. On treatment with a fatty acid a contact angle of water droplet in air in the range of 145° to 170° could be achieved. Increased contact angles imply higher hydrophobicity which can be equated to repellence of aqueous stains .
  • the contact angle is the angle at which a liquid/vapor (or two immiscible liquids) interface meets the solid surface.
  • the contact angle is specific for any given system and is determined by the interactions across the three interfaces. Most often the concept is illustrated with a small liquid droplet resting on a flat horizontal solid surface. The shape of the droplet is determined by Young-Laplace equation.
  • One of the ways to measure contact angle is using a contact angle goniometer on a sessile drop of the liquid. This method is used to estimate wetting properties of a localized region on a solid surface. Angle between the baseline of the drop and the tangent at the drop boundary is the contact angle as shown in figure-1.
  • 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-1A in the form of a white powder.
  • the spectrum shows a broad band around 3500 cm “1 corresponding to the hydroxyl groups (OH) , a peak at 1580 cm “ 1 , that corresponds to the carbonyl moeity of the acetate group.
  • the spectrum has been included as figure-2.
  • the spectrum was recorded on a Perkin Elmer model by dissolving the sample in deuterated Methanol.
  • the spectrum shows 4 peaks, represented by figure-3 (excluding solvent peak) .
  • the transparent sol obtained in example-1 was taken in glass vial and the solvent was allowed to evaporate for about 30 days. The individual crystals were then collected and observed under optical microscope. A suitable single crystal of size 0.40 mm x 0.15 mm x 0.10 mm was chosen for the structure elucidation. Diffraction data were collected using Enraf-Nonius CAD-4 (MACH-3) single crystal X-ray diffractometer at ambient temperature, and the structure was solved and refined by full-matrix least-square technique using SHELX-97 and SHELXTL program packages [G. M. Sheldrick, SHELX-97, Program for crystal structure solution and refinement, University of Gottingen, Gottingen, Germany, 1997]. The solved structure is given as figure-5.
  • Crystal structure confirmed the molecule to be a tetranuclear zinc complex having centrosymmetric structure with two different zinc environments, one tetracoordinated and the other, pentacoordinated.
  • Two of the OH groups of the triethanolamine moiety are deprotonated (02, 03 and their symmetry equivalents in the figure) and act as bridging groups between two zinc atoms.
  • the third OH (Ol and its symmetry equivalent) remains protonated (not shown in the figure for clarity) , and coordinated to only one Zinc .
  • Zinc propionate (0.1 M) and monoethanolamine (0.05 M) was added to isopropanol in a round bottom flask and refluxed for 30 min. Solvent was slowly removed from the system in a rotavapor, leaving behind a gummy mass. The mass was then dissolved in methanol, to get a methanolic solution of Compound-ID .
  • the swatch was then dipped in distilled water, soaked for 15 minutes, removed from it and was allowed to dry in open sun. Thereafter, the swatches were ironed.
  • a 10cm x 10cm strip of the treated fabric was cut and pasted on a smooth glass slide by applying adhesive to the corners of the fabric.
  • the slide was then placed on the platform of a goniometer fitted with a camera.
  • a drop of water was placed on the fabric by using a syringe and photographed.
  • the contact angle of the drop of water in air on the fabric surface was determined. In this case, the contact angle of water on the untreated and treated fabric swatch was 0° and 145° respectively.
  • the swatches were dried and ironed.
  • the swatches were first soaked in a solution of compound-lA for 30 minutes, followed by soaking in 3% detergent solution. The swatches were then rinsed twice with deionised water and thereafter dried and ironed.
  • the contact angles of water droplets on fabrics treated by these, as determined by the technique mentioned in Example 5 are summarised in table -1 below.
  • Samples 1-5 were cotton swatches while samples 6-9 were polycotton swatches.
  • illustrated compound-lA provides superior water repellence benefits as demonstrated by the contact angles. It will also be appreciated that there is flexibility in the sequence of treatment as the treatment with compound-lA can be done prior to or after the step of rinsing, without any major difference in the contact angle.
  • a polycotton (67% polyester: 33% cotton) fabric swatch was treated by the process as mentioned in Example 5. It showed a contact angle of water in air of 142°.
  • the treated fabric was soaked in a 0.5% ethanolic solution of stearic acid for 30 min, taken out, washed 3 times with water and dried in air. After this treatment, the contact angle of water in air for the fabric went up to 165°, which can be equated to uniform hydrophobic surface.
  • S. epidermidis or Corynebacterium sp was cultured on Tryptone Soy Broth for 24 hrs at 37°C in presence of the control or treated cotton swatches. This was centrifuged and the pellet was suspended in Phosphate Buffered Saline (PBS) containing 0.1% Tributyrin for S. epidermidis and in Phosphate Buffered Saline (PBS) containing 0.1% Tributyrin for S. epidermidis and in
  • the illustrated examples provide for a complex that can be used to impart superior hydrophobicity to fabrics and a method for increasing the hydrophobicity of fabrics, thereby the stain repellence.

Landscapes

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

Abstract

La présente invention porte sur un complexe de zinc, sur un procédé de fabrication du complexe de zinc et sur un procédé de traitement de tissu, en particulier sur un procédé d'augmentation de la résistance aux taches en augmentant le caractère hydrophobe des tissus avec des complexes de zinc.
EP08749775A 2007-06-04 2008-04-28 Complexe de zinc, son procédé de préparation et procédé de traitement d'un tissu avec celui-ci Withdrawn EP2150555A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN1047MU2007 2007-06-04
PCT/EP2008/055143 WO2008148610A1 (fr) 2007-06-04 2008-04-28 Complexe de zinc, son procédé de préparation et procédé de traitement d'un tissu avec celui-ci

Publications (1)

Publication Number Publication Date
EP2150555A1 true EP2150555A1 (fr) 2010-02-10

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP08749775A Withdrawn EP2150555A1 (fr) 2007-06-04 2008-04-28 Complexe de zinc, son procédé de préparation et procédé de traitement d'un tissu avec celui-ci

Country Status (4)

Country Link
EP (1) EP2150555A1 (fr)
CN (1) CN101687888B (fr)
BR (1) BRPI0810352A2 (fr)
WO (1) WO2008148610A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102858941A (zh) 2010-04-30 2013-01-02 荷兰联合利华有限公司 防污组合物
DE102010043896A1 (de) 2010-11-15 2012-05-16 Henkel Ag & Co. Kgaa Verwendung von in situ hergestellter Zinkseife
WO2020030414A1 (fr) 2018-08-09 2020-02-13 Unilever N.V. Composition antitranspirante
BR112022009183A2 (pt) * 2019-11-20 2022-07-26 Unilever Ip Holdings B V Composição antiperspirante e método para reduzir a transpiração

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE572385A (fr) * 1958-01-20
US3480653A (en) * 1966-07-05 1969-11-25 Stauffer Chemical Co Metal organic compounds containing metal - o - n linkage
GB1198060A (en) * 1966-11-10 1970-07-08 British Petroleum Co Zinc Complexes
US4172841A (en) * 1978-08-17 1979-10-30 The United States Of America As Represented By The Secretary Of Agriculture Antibacterial textile finishes utilizing zinc acetate and hydrogen peroxide
US4199322A (en) * 1978-08-17 1980-04-22 The United States Of America As Represented By The Secretary Of Agriculture Antibacterial textile finishes utilizing zinc acetate and hydrogen peroxide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008148610A1 *

Also Published As

Publication number Publication date
CN101687888B (zh) 2012-11-14
WO2008148610A1 (fr) 2008-12-11
CN101687888A (zh) 2010-03-31
BRPI0810352A2 (pt) 2014-10-21

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