EP2990527A1 - Procédé de préparation de textiles en coton ayant des propriétés de résistance au lavage et autonettoyantes - Google Patents

Procédé de préparation de textiles en coton ayant des propriétés de résistance au lavage et autonettoyantes Download PDF

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Publication number
EP2990527A1
EP2990527A1 EP15468007.8A EP15468007A EP2990527A1 EP 2990527 A1 EP2990527 A1 EP 2990527A1 EP 15468007 A EP15468007 A EP 15468007A EP 2990527 A1 EP2990527 A1 EP 2990527A1
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EP
European Patent Office
Prior art keywords
particles
siloxane particles
cotton
process according
textile
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EP15468007.8A
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German (de)
English (en)
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EP2990527B1 (fr
Inventor
Milena Zorko
Barbara Simoncic
Jelena Vasiljevic
Brigita Tomsic
Ivan Jerman
Miran Gabrscek
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Univerza v Ljubljani
Kemijski Institut
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Univerza V Ljubljani Naravoslovnotehnoloska Fakulteta Oddelek Za Tekstilstvo
Kemijski Institut
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    • 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
    • D06M11/77—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 silicon or compounds thereof
    • D06M11/79—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 silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • 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
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • 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
    • 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
    • D06M2200/05—Lotus effect
    • 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
    • D06M2200/11—Oleophobic properties
    • 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
    • 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
    • D06M2400/00—Specific information on the treatment or the process itself not provided in D06M23/00-D06M23/18
    • D06M2400/01—Creating covalent bondings between the treating agent and the fibre
    • 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
    • D06M2400/00—Specific information on the treatment or the process itself not provided in D06M23/00-D06M23/18
    • D06M2400/02—Treating compositions in the form of solgel or aerogel

Definitions

  • the invention relates to a process for the preparation of self-cleaning wash-resistant and air-permeable superhydrophobic and oleophobic cotton textiles,
  • the coating is applied in-situ to the surface of the cotton textile. This resulted in water sliding angles smaller than 10 degrees even after ten washings.
  • Cotton fibres are natural cellulosic fibres that are widely used as a raw material for the manufacturing of various textile products. Their attractiveness is directly related to the chemical structure and morphological characteristics of the cellulosic fibres. These fibres are pleasant to the touch and exhibit a hydrophilic character to ensure product comfort, respiratory activity, and aesthetic appearance, The fibres are biodegradable, which, in terms of ecology and sustainable development, is their major advantage over synthetic fibres.
  • Cotton fibres have been gaining attention as components in the production of specialized high-tech textiles; this is due to their advantages and successfully outcompeting ecologically less acceptable synthetic fibres.
  • Such high-tech materials include bio-mimetic self-cleaning textiles, which must ensure simultaneous wetting resistances for a variety of polar and non-polar liquids, in addition to air and water vapour permeabilities. These requirements can only be achieved by careful chemical modifications of the cellulosic fibre surface.
  • textiles that are easy on the skin and, at the same time, offer the user welfare and protection against the environment arc very common in everyday life.
  • Such fabrics are on the one hand suitable for sports and leisure (e.g., obstacle courses, mountaineering, cross-country running, downhill skiing, motocrossing, mountain biking) and, on the other hand, serve as protective technical textiles.
  • Technical textiles are used by professionals who frequently encounter water and soilage (e.g., butchers, plumbers, hairdressers, bricklayers, fine mechanics or firefighters). All of the mentioned users are also likely to be physically active, which results in sweating and may also stain the textiles. In such cases, it is recommended that the textile allows for the passage of body sweat, so that end users are not completely drenched with sweat for long periods.
  • Superhydrophobicity and oleophobicity are basic properties of a solid surface that are dependent on the chemical composition and the surface roughness of a substrate. Chemical composition determines surface free energy and, consequently, surface wettability. Micro-and nanostructured surfaces can further influence wettability, if the roughness is inappropriate.
  • EP 2,589,578 A1 patent application shows that a reduction in surface wettability can be achieved by the derivatives of catechols.
  • the fluorinated catechol derivatives have been known to form vesicles (70 nm) or capsules with a hollow core 200 to 1000 nm in size, which increase microstructure. This combination of features enables the preparation of surfaces, such as carbon nanotubes, iron oxide nanoparticles and mesoporous silica, with water-repellent properties.
  • U.S. Patent 7,732,497 B2 discloses the use of pre-prepared surface-treated particles for the preparation of a liquid repellent layer. A minimum of two particle sizes are used, and at least one particle surface is further functionalized by alkyl chains.
  • US 7,985,475 B2 patent describes the preparation of superhydrophobic coatings by placing well-defined silicon nano-fibres on a surface coated with exogenous hydrophobic or amphiphilic materials.
  • fluorinated molecules are also used to achieve hydrophobic properties.
  • U.S. Patent 8,541,056 B2 discloses the preparation of water-repellent textiles by mechanical abrasion.
  • the previously abraded substrates are coated with colloidal dispersions of various metal oxides (commercial products) and cross-linked using isocyanate compounds, which usually form at the end of polyurethane bonds.
  • the preparation of water-repellent textiles is also possible by integrating fumed SiO 2 particles with the fibres through the use of binders without formaldehyde, as indicated in US patent application 20110287245 .
  • Alkali metal salts of phosphorous are used as a catalyst for polymerization, which allows the matrix and the cellulose fibres to bond together.
  • a method for preparing water-repellent coatings also includes the use of SiO 2 particles prepared from dimethyldichlorosilanes and coated with polycarboxylic acids.
  • US patent application 20110250422A1 discloses the use of a porous matrix built from fluorosilanes for the preparation of hydro- and oleophobic coatings.
  • the main significance of the coating given the pore size and the distribution of pores by volume, is its suitable surface roughness in combination with a low surface free energy that are provided by the building blocks of the porous structures.
  • the coatings can also be used to reduce adhesion, which provides the surfaces with a self-cleaning effect.
  • Colloid Interface Sci., 392 (2013) 194-200 report on the use of a single-stage emulsion to prepare monodisperse polysiloxane spherical particles surface-functionalized with a variety of organic groups.
  • the authors analyse the influence of the organic groups on the properties of the coatings, e.g., thermal stability, The purpose of generating particles on the surface of cotton was to imitate the surface structure of a lotus leaf.
  • the present invention relates to a process that enables the preparation of wash-resistant, air-permeable superhydrophobic, oleophobic, and self-cleaning coatings from a variety of organic-modified silanes.
  • in - situ monodisperse particles of SiO 2 are formed with the use of silanes.
  • the formed particles are chemically bonded to the surface of cotton textiles, which acquire a low surface energy.
  • An appropriate surface roughness, resulting from the chemical bonding between the SiO 2 spherical particles and the cotton fibre surface, is maintained on the cotton even after four washing cycles according to ISO 105-C06: 1994 (E), which is equivalent to twenty washings in a household washing machine.
  • the SiO 2 -cotton chemical links are further consolidated by the porous structure of hardened perfluoro-modified silanes.
  • the process enables the preparation of finishes for cotton-based textiles and products that require durable superhydrophobic and oleophobic properties in combination with a highly breathable textile, which provides air and water vapour (perspiration) permeation.
  • the preparation of wash-resistant textiles is conducted using a wet process without compounds that release toxic formaldehyde.
  • the process allows the chemical bonding of spherical SiO 2 particles to the cotton fibre surface, providing an appropriate surface roughness to the fabrics and is responsible for the following characteristics:
  • the described wash-resistant properties can be achieved only with the use of the proposed process.
  • siloxane particles which are spherical SiO 2 particles.
  • the spherical SiO 2 particles grow in - situ over the cotton fibre surface and form a network, thus, enabling the formation of chemical bonds between amorphous SiO 2 particles and the cotton fibre surface.
  • These chemical bonds further consolidate in the third step and form a network with a water- and oil-repellent layer derived from a water-based precursor.
  • wash-resistant, respiratory active textiles with superhydrophobic, highly oleophobic and self-cleaning properties.
  • These textiles have a passive antibacterial protection and can be used for clothing, as in the above-described case.
  • Superhydrophobic and oleophobic properties are derived from the roughness of a suitable double nano- and microstructured textile surface. Double roughness is achieved by applying pre-manufactured spherical SiO 2 particles to the surface of the textile, in the first step, and is supplemented by the in-situ formation of spherical SiO 2 particles on the surface of the textile, in the second step.
  • the pre-manufactured spherical SiO 2 particles are responsible for the increase in the surface roughness, whereas the application of in-situ SiO 2 particles in the second step is unavoidable because of the lack of a chemical connection between the spherical SiO 2 particles and the cotton fibre surface.
  • Non-bonded spherical SiO 2 particles are removed from the surface of the textile with the first washing. This disadvantage, which is inherent to the classical single step process, is eliminated by a second step.
  • This step consists of covering and soaking the entire surface, i.e., the spherical SiO 2 particles and the fibres, with a solution of tetraethoxysilane (TEOS), base, water and alcohol, during which the in - situ formation of spherical SiO 2 particles with a size between 50 and 200 nm occurs.
  • TEOS tetraethoxysilane
  • the formation of a thin porous coating allows the chemical bonding of spherical SiO 2 particles, deposited in the first step, to the surface of cotton.
  • the spherical SiO 2 particles from the first step are used directly from the solution in which they have been prepared to avoid the problem of particle agglomeration, which is probable when dried particles are re-dispersed.
  • Water- and alcohol-based dispersions in the proposed invention are characterized by a high content of cross-linked polysilsesquioxanes. Nanometre-sized siloxane spheres are responsible for the formation of
  • a process for the preparation of the wash-resistant, vapour permeable, self-cleaning, and highly hydrophobic and oleophobic cotton textiles involves the following steps:
  • the aqueous/alcoholic dispersions of SiO 2 particles include pre-prepared monodisperse spherical SiO 2 particles. It is desirable that at least 95% of the particles in the dispersion are the same size.
  • the siloxane particle and SiO 2 particle size is 200 - 1000 nm.
  • the weight ratio of alcohol:TEOS:NH 3 :water is 46:2:1:5. Preparation of the particles is not the subject of the patent.
  • the dispersion of SiO 2 particles is 10% by weight and is used in the first step of the process for the cotton modification, i.e., for the application of the first coating on the cotton fibre surface.
  • the ratio of the weight of the aqueous alcoholic dispersion of SiO 2 particles and the weight of the textiles should be 1:15.
  • a padder is used to squeeze the excess dispersion from the textiles while passing the textile sample between two rollers at a pressure of 0.4 bar; the fabric is then air dried at room temperature for 10 min.
  • the advantage of the first layer is that the deposited SiO 2 particles are well separated from each other, which enables a high surface roughness of the textile.
  • SiO 2 particles are preferably prepared from tetraethoxysilane, so their surface is full of free-OH bonds, which will enable chemical linking between the SiO 2 particles and the cotton fibres of the textile in the next stage.
  • the in - situ growth of particles by a sol-gel method allows greater coating density after a suitable thermal treatment.
  • the cotton fibre surface, modified by spherical SiO 2 particles is coated by a second layer of siloxane particles.
  • the weight ratio of alcohol:TEOS:NH 3 :water is in this case 30:5:2:5. This coating enables the chemical bonding of SiO 2 particles, which were deposited on the cotton fibre surface in the first step.
  • the reactivity of the substrate which consists of cellulosic OH groups and surface OH groups on the spherical SiO 2 particles from the first layer, facilitates the connection to particles from the second step of the process.
  • the colloidal dispersion at the concentration described for the in - situ process generates uniform spherical SiO 2 particles that are sized 50 - 200 nm.
  • the in - situ deposited SiO 2 spherical particles give the cotton fibre surface a double roughness, or a bi-hierarchical roughness, and at the same time secures the SiO 2 particles deposited in the first step.
  • the weight ratio between the pre-manufactured siloxane particles used in the first step and the in - situ siloxane particles prepared in the second step is between 1:2 and 1:3.
  • the biomimetic surface of the textile which has already hardened, is coated again with a thin layer of hydrophobic and oleophohic silanes, preferably from hydrolysed fluorosilane (FAS), bis [(ureapropyl) triethoxysilane] bis(propyl)-terminiran-polydimethylsiloxane (PDMSU) or a mixture of FAS and PDMSU.
  • FOS hydrolysed fluorosilane
  • PDMSU bis [(ureapropyl) triethoxysilane] bis(propyl)-terminiran-polydimethylsiloxane
  • a 10% aqueous/alcohol solution of silane is used for the coating.
  • the thickness of such a thin layer may not exceed 150 mn. Hardening of the surface is possible due to the covalent bonding between the free-OH groups present on the surface of the porous coating applied in the second step and the OH groups of the hydrolysed silane. Thermal curing of the coating results in an increased density and stability, as well as an increased washing fastness.
  • Hydrophobic and oleophobic silanes which are used for the hardening of the rough surfaces, are selected from the groups of perfluoroalkyl-trialkoxysilanes, perfluoroalkyl-alkyldialkoxysilanes, perfluoroalkyl-dialkylalkoxysilanes, perfluoroalkyl-trihalosilanes, perfluoroalkyl-alkyldihalosilanes, perfluoroalkyl-dialkylhalosilanes and (trialkoxysilyl)alkyl terminated polydimethylsiloxane.
  • the formation of individual layers with a specific particle size depends on the properties of the applied colloidal dispersions but is preferably within the conditions set out below.
  • Various alcohols such as methanol, ethanol, isopropanol, and butanol, should be used in the preparation of colloidal dispersions. These solvents affect the growth and size of the particles.
  • additional organic-modified silanes may also be used for the preparation of SiO 2 particles in the first and second steps, such as methyltriethoxysilane, vinyltriethoxysilane, and aminopropyltriethoxysilane.
  • Monodisperse SiO 2 particles provide a uniform roughness over the entire surface of the textile. Application can be performed by the exhaustion method, dipping, or sputter deposition.
  • Cotton fibres already possess their own roughness ( Figure 1 ), but because of their chemical composition (cellulose), they are extremely hydrophilic.
  • the surface roughness is improved by the proposed process, as shown in Figure 2 .
  • High washing fastness is provided by the in-situ growth of particles in the second layer and by further consolidation of the fluorosilane coating.
  • the final coating maintains its properties after the first washing cycle, according to the standard ISO 105-C06: 1994 (E), and is equivalent to five washings in a household washing machine ( Figure 3 ). It is slightly changed after four washing cycles ( Figures 4 to 6 ).
  • the modified textile displays high hydrophobic and oleophobic properties after twenty washings with static contact angles for n-hexadecane higher than 130°.
  • the results that indicate the preservation of the superhydrophobicity and oleophobicity are disclosed in Figures 7 and 8 .
  • the extremely low sliding angles for the modified textile ( Figure 9 ) allow rolling of the droplets and the simultaneous removal of dirt from the surface, demonstrating the self-cleaning properties.
  • reaction conditions for the preparation of SiO 2 particles from tetraethoxysilane (TEOS 98%, Aldrich) in alcohol are as follows:
  • a bottle 250 mL was filled with 130 g of ethanol and 8 g of TEOS. The solution was well mixed and allowed to stand for an additional 10 min at room temperature (RT).
  • a mixture of ammonia (4 g (25%)) and water (20 g) was added to the prepared solution of EtOH and TEOS. The solution was re-mixed and left for 3 h at RT. The prepared solution was used for finishing the cotton fabric. After soaking the textile in the above described reaction mixture, the fabric was squeezed with an 85% spin effect and air dried.
  • the application of a 10% FAS solution was followed by the impregnating procedure with full soaking, squeezing with an 85% spin effect, drying at 100 °C and curing at 150 °C for 5 min.
  • the as-prepared cotton fabrics were added, in the next step, to the mixture of 2-propanol (100 g) and TEOS (20 g), mixed well, and left for 10 min at 50°C, Then, a solution of ammonia (4 g) in water (20 g) was added to the TEOS solution, which was re-mixed again and left for 1 h at 50 °C.
  • the immersed cotton textile was taken out from the reaction mixture, rinsed with water three times and dried at room temperature. This was followed by applying a 10% FAS solution, performing the impregnating procedure with full soaking, squeezing with an 85% spin effect, drying at 100 °C and curing at 150 °C for 5 min.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP15468007.8A 2014-08-18 2015-08-11 Procédé de préparation de textiles en coton ayant des propriétés de résistance au lavage et autonettoyantes Active EP2990527B1 (fr)

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SI201400289A SI24784A (sl) 2014-08-18 2014-08-18 Postopek za pripravo samočistilnih pralno obstojnih bombažnih tekstilij

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Cited By (9)

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CN110172835A (zh) * 2018-09-13 2019-08-27 纳智源科技（唐山）有限责任公司 防水透气面料及其制备方法
EP3543398A1 (fr) * 2018-03-22 2019-09-25 Palo Alto Research Center Incorporated Prétraitement textile pour impression numérique
CN111172761A (zh) * 2020-02-20 2020-05-19 旷达纤维科技有限公司 一种耐洗超疏水涤纶面料的制备方法
CN111501357A (zh) * 2020-05-13 2020-08-07 兰州交通大学 一种织物超疏水表面的制备方法
CN112376281A (zh) * 2020-11-05 2021-02-19 台州市路桥区静荷纺织有限公司 一种防污抗油纺织面料及其制备方法
CN112813683A (zh) * 2021-02-05 2021-05-18 武汉理工大学 一种超双疏织物及其制备方法
CN114657789A (zh) * 2022-04-26 2022-06-24 暨南大学 一种有机硅超疏水涂料及基于其的超疏水涂层与应用
CN115369651A (zh) * 2021-05-20 2022-11-22 盐城工学院 表面多孔的强粘附性改性纤维及其制备方法与应用
US11708494B2 (en) 2020-02-14 2023-07-25 Icp Construction, Inc. Oleophobic and hydrophobic composition

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WO2016197146A1 (fr) 2015-06-05 2016-12-08 Cornell University Compositions cellulosiques modifiées ayant une hydrophobicité accrue et procédés pour leur production

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