WO2012085653A1

WO2012085653A1 - Waterproofing treatment

Info

Publication number: WO2012085653A1
Application number: PCT/IB2011/003147
Authority: WO
Inventors: Alessio BENELLI; Simona BENELLI
Original assignee: Individual
Current assignee: Individual
Priority date: 2010-12-23
Filing date: 2011-12-23
Publication date: 2012-06-28
Anticipated expiration: 2013-06-23
Also published as: IT1403226B1; ITFI20100246A1

Abstract

The present invention relates to a composition and its use for imparting water repellency to a substrate selected from fibers, textiles, leather, hides, fur, paper, paperboard and blends thereof; the processes for providing water repellence to these substrates; and the treated substrates.

Description

"REPELLING TREATMENT"

FIELD OF THE INVENTION

The present invention relates to a composition and its use for imparting repellent properties to a substrate selected from fibers, fabrics, leather, hides, fur, paper, paperboard and blends thereof; the process to provide repellent properties to these substrates; and the treated substrates.

BACKGROUND OF THE INVENTION

The treatment of various fabrics to impart water-oil repellency thereto has an important commercial role. The use of fluoropolymers compositions to impart water-oil repellency to fibers and fibrous materials such as fabrics, paper and leather, is known. Generally, ^«* . perfluorocarbons are combined with silicones to impart water-oil repellency properties. For example, US 3681266 describes the use of perfluoro derivates and silicones to import hydrophobic properties to textiles.

GB 2085491 describes a composition comprising a polyurethane foam and, optionally, a wax or a waxes mixture, metallic compounds, silicone compounds or fluorocarbons, which makes the treated substrate water resistant.

US 20020142162 describes a process to partially impregnate the hemp fibers and enhance their properties, by using a mixture of fluorinated monomers in organic solvents, or, alternatively, a mixture comprising paraffin, zirconium salts and acetic acid.

US 348691 1 describes a composition containing a C2-C4 perfluoro aliphatic compound, or a chromium co-ordination complex of perfluoro octanoic acid, a natural wax, Al or Zr salts in a liquid vehicle to impart repellency to fabrics, leather and paper. This composition provides water and oil repellency to the treated material only after heating the fabric to elevated temperatures for a commensurate time period.

WO 2009088564 describes a treatment of a nanofiber surface having specific weight and sizes to obtain water repellent fabrics, such treatment preferably comprising calendering. This treatment is carried out with DUPONT Zonyl® surfactants and resins, such as isocyanates, formaldehyde resins, paraffin mixtures and zirconium or aluminium salts, in ratio of 2:1 up to 4: 1, in water and/or other solvents, such as esters of acetic acid, chetones, diols and glycol ethers. The repellency methods sofar known require a heating treatment at temperatures higher than 110-130°C, with deleterious effects on wool and silk fibers. The treatment with fluorinated polymers may affect the fabric characteristics such as softness, colour,

Nowadays, environmental and safety concerns require the preferential use of aqueous compositions in place of organic solvents compositions.

An object of this invention is to provide a composition able to confer good water and oil repellent properties to the treated materials, as well as a simple, economic, eco-compatible, laundering resistant process, in order to impart repellency to the treated materials without altering their original characteristics.

SUMMARY OF THE INVENTION

We have now found a simple, economic, eco-compatible, laundering resistant process to provide repellency to the treated materials without altering their original characteristics.

The present invention relates to a process for imparting repellent properties to a substrate selected from fibers, fabrics, leather, hides, fur, paper, paperboard and blends thereof, comprising:

a. dipping the substrate with an acqueous dispersion of a repellent composition diluted until a concentration of 5-35%, comprising fluorinated monomers, fluorinated polymers with a C6-C21 fluoroalkyl or fluoroalkenyl chain, paraffins with a melting point comprised between 0 and 80°C and zirconil compounds;

b. drying the treated substrate to room temperature, sun drying or with a dryer;

c. optionally humidification and vaporization of the treated substrate;

d. optionally ironing.

In one embodiment this invention relates to a process for providing repellency to a yarn, comprising:

a. adding an aqueous dispersion of the repellent composition until a concentration of 5-35%, comprising fluorinated monomers, fluorinated polymers with a C6-C21 fluoroalkyl or fluoroalkenyl chain, paraffins with a melting point comprised between 0 and 80°C and zirconil compounds, diluted until a concentration of 20-25%, preferably 25-45%, more preferably 35%, during the finish;

b. yarn drying;

c. optionally ironing. In a further embodiment the present invention relates to a substrate treated with the above mentioned repellent composition.

In another embodiment this invention relates to a repellent composition in form of an aqueous dispersion diluted until a concentration of 5-35%, comprising fluorinated monomers, fluorinated polymers with a C6-C21 fluoroalkyl or fluoroalkenyl chain, paraffins with melting point comprised between 0 and 80°C and zirconil compounds.

In another embodiment this invention relates to the use of the above mentioned composition and processes for treating substrates selected from fibers, fabrics, leather, hides, fur, paper, paperboard and blends thereof.

Surprisingly, the repellent composition according to the present invention is able to confer water and oil repellency together with stains resistance to the treated substrate without using high temperatures. This allows the treated substrate to maintain its original properties such as, for example, mechanical properties, such as elasticity, flexibility, colour, stability to light, soft feeling, breathability. The repellent effect persists through repeated launderings and/or ^dry cleanings. Any kind of substrate may acquire repellent properties both when treating raw material or finished products.

The repellent composition according to this invention is used in the form of an aqueous dispersion, thus avoiding using chemical solvents, with consequent problems for disposal, environmental toxicity, particular precautions for the operators or equipments, specific machinery.

LIST OF DRAWINGS

The annexed drawings show schematically the preferred examples according to the invention in which:

- fig. 1 shows a process scheme according to the invention, applied to garments;

- fig. 2 shows a process scheme according to the invention, applied to wool fabrics, e.g. berets;

- fig. 3 shows a process scheme according to the invention, applied to fabrics, e.g. raw material cones for hats manufacturing;

- fig. 4 shows a process scheme according to the invention, applied to textile fibers or yarns; - fig. 5 shows the results of a water-repellency test on a fabric;

DETAILED DESCRIPTION OF THE INVENTION All terms as used herein in this application, unless otherwise stated, shall be understood in their ordinary meaning as known in the art. Other more specific definitions for certain terms as used in the present application are as set forth below and are intended to apply uniformly through-out the specification and claims unless an otherwise expressly set out definition provides a broader definition.

The term "substrate" refers both to raw material and finished products. The term "raw material" refers, but is not limited, to yarns, fabrics, leather, hides, fur, paper, paperboard, blends thereof and the like.

Any fibrous material, yarn, fabric known to the skilled in the art, may be used in the present invention, e.g., natural fibers, cellulose fibers, synthetic fibers, semi-synthetic fibers, micro- fibers and combinations thereof. Examples of fibers, yarns, fabrics include, but are not limited to, fine fabrics, resistant fabrics, cotton, wool, angora, cachemire, camel hair, mohair, alpaca, llama, vicuna, pashmina, silk, satin, linen, hemp, iuta, sisal, straw, acrylic, polyamide, nylon, aramid fiber, polyester, polypropylene, viscose, rayon, polyurethane, cellulose and the like. The term "finished products" refers, but is not limited to, inside and outside clothing, garments, such as, for example, hats, berets, woolen caps, gloves, socks, vests, shirts, t-shirts, polo shirts, suits, woolen cloths, pullover, skirts, trousers, pyjamas, underwear, undervests, lingerie, bathing costumes, tracksuit, jackets, overcoats, mantles, raincoats; technical and sportswear, for example wind jackets, ski, jogging, football, bike, and golf wear; rain wear, for example mantles; working wear, for example white coat, overalls, shoes, boots; accessories such as belts, bags, umbrellas; military equipment; camping equipment, for example, sleeping bags, backpacks, tents, awning, tarpaulins, boat-covers, gazebo, upholstery, carpets, suitcases, trunks, and the like.

The terms "hat", "hats" refer to "cones" and "bonnet": hat raw material, before ironing, shaping and finishing touches.

The term "repellent" refers to the ability to impart water and oil repellency and stain resistance. The water/oil repellency is the characteristic of a substrate to provide water and oil repellence, to be waterproof, to be resistant to water and oil penetration from outside to inside. The water repellency is evaluated according to the substrate resistance to superficial dipping, assessing the wetting index through the Spray Test method, according to UNI EN 24920 (corresponding to AATCC Test Method 22-1996 and AATCC Test method 22-2005) and assessing the resistance to water penetration (test under hydrostatic pressure) by measuring the hydrostatic pressure born by the tested sample according to UNI EN 2081 1 : 1993 (corresponding to UNI 4818 Part 32 - May 1992 and AATCC Test Method 127-2003).

The oil repellency is evaluated according to the resistance to hydrocarbons (Hydrocarbon Resistance Test) in accordance with 1 18-2002 AATCC Test Method (C16-C7 Hydrocarbons) (corresponding to UNI EN ISO 14419-2010).

The repellence to aqueous solutions has been evaluated through the Aqueous Liquid Repellency Test: Water/ Alcohol Solution Resistance Test according to AATCC Test Method 193-2005 Stain Repellency, described in the experimental part.

The term "breathability" relates to the ability of materials, such as fabrics, to transfer from inside to outside the greatest possible quantity of water vapor.

The assessment of the substrate water vapor transmission speed is carried out by measuring the tested sample mass by grams, before and after the test, according to UNI 4818-26:1992. The term "laundering" relates to domestic and/or industrial washing, hand or machine washing, or dry cleaning of the substrate to a temperature between 30°C and 90°C.

The term "dipping" relates to the substrate treatment by immersion in a solution, emulsion, aqueous dispersion containing the composition according to the invention.

The terms "fluoralkyl or fluoralkenil chain C6-C21" refer to alkyl or alkenyl chains, with one or more double bonds, linear, branched, cyclic or blends thereof, having at least an H atom substituted by an F atom, containing from 6 to 21 atoms of carbon, preferably, and from 6 to 14 carbon atoms (C6-C14). Examples include, but are not limited to, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorononane, perfluorodecane, perfluoroundecane, perfluorododecane, perfluorohexene, perfluoroheptene, perfluoroctene, perfluorononene, perfluorodecene, perfluoro n-octhylethylene, perfluorooctyl acrylate and the like.

The terms "fluorinated monomers", "fluorinated polymers" refer to monomers, omopolymers, copolymers, comprising for example, terpolymers, tetrapolymers and superior terms in which the most part of the present chemical bonds is of the C-F type and having a C6-C21 fluoralkyl or fluoralkenil chain, preferably C6-C14. It is evident that fluorinated monomers, fluorinated polymers may include non fluorinated parts.

The fluorinated monomers and fluorinated polymers according to the invention include perfluorinated monomers, perfluorinated polymers. Hydrogen, other halogens and other elements may be present in lower quantities. Fluorinated monomers and fluorinated polymers are well known to the skilled in the art, and include, but are not limited to, fluorinated compounds such as C6-C21 alcohols or acids which have reacted with appropriate chemical compounds to form esters, starches or polymers, vinyl polymers, such as acrylates, metacrylates and the like. Examples include, without limitation, perfluorohexane, perfiuoroheptane, perfluorooctane, perfluorononane, perfluorodecane, perfluoroundecane, perfluorododecane, perfluorohexene, perfluoroheptene, perfluoroctene, perfluorononene, perfluorodecene, perfluoro n-octhylene, perfluorooctyl acrylate, and the like.

Preferably, fluorinated monomers, fluorinated polymers are perfluorohexane, perfluorohexene, perfluoroctene, perfluorodecene, perfluoro n-octhylethylene, perfluoroocthyl acrylate.

They are commercially available, for example, under the trade name Draig 300^® (Bozzetto Group), REAPRET^® FCT (Bozzetto Group), QUECOPHOB PC 6 (Thor), Unidyne TG-5543 (Daikin) and are more characterized by their properties rather than by their chemical composition. The fluorinated monomers, fluorinated polymers according to this invention have a melting point comprised between 30 and 80°C, preferably 30-60°C, more preferably 40-50°C. They do not contain toxic compounds, such as nonylphenols (APEO), perfluorooctanoic acid (PFOA) and sulphonated perfluorooctane (PFOS).

Preferably, the fluorinated monomers and fluorinated polymers of the invention are dispersed in an aqueous solution (see in general Fluorine-Containing Polymers, Encyclopedia of Polymers Science & Technology, pp. 179-203, Interscience, 1967); preferably at dilutions of 5-35%, more preferably 20-30%, most preferably 30% by weight.

The fluorinated monomers, fluorinated polymers according to this invention provide to the aqueous solution in which they are dispersed a pH ranging between 1 and 6, preferably 2- r more preferably 2.5-4.5.

The term "paraffin" refers to any saturated hydrocarbon, comprising normal paraffins, branched paraffins, iso-paraffins, cyclic paraffins, micro-waxes and blends thereof. The paraffins according to the invention have a melting point comprised between 0 and 80°C, preferably 20-60°C, more preferably 50-60°C.

Any Zirconil derivate known to the skilled in the art, may be used according to the present invention. Zirconil derivates comprise, for example, zirconium oxide, zirconium hydroxide, zirconium sulfate, zirconium silicate; zirconium salts, for example, zirconium nitrate, zirconium disulfate, zirconium phosphate, zirconium salts with fatty acids containing 2-21 carbon atoms chains, for example zirconium stearate; zirconium halides, for example zirconium chloride, zirconium fluoride, zirconium tetrafluoride; zirconium esters, for example zirconium acetate, zirconium tetraacetate, zirconium proprionate, zirconium butylate, zirconium valerate, zirconium hexanate, zirconium heptanate, zirconium octoate, zirconium stearate; zirconium alkoxides, for example zirconium tetrapropoxide, zirconium tetrabutoxide; alkyl zirconates and polymeric zirconates with alkyl groups with 2-21 carbon atoms, and the like.

Zirconil derivates function is to fix paraffin. Any metal derivates known to the skilled in the art, which can fix paraffin, may be used according to the present invention.

Preferably paraffin and zirconil derivate/derivates are previously dispersed in an aqueous solution, properly diluted according to requirements, preferably at dilutions of 5-35%, more preferably 20-30%; most preferably 30% by weight.

The aqueous dispersion of paraffin and zirconil derivate/derivates has a pH comprised between 1 and 5, preferably 2-5, more preferably 2.5 - 4. The total concentration of metallic zirconium in this dispersion is comprised between 0.01 - 3%, preferably 0.1-1%, more preferably 0.15-0.18%. Such mixtures are commercially available, for example, under the trade name of Draig NSZ^®, Draig Z^® (Bozzetto Group), Contraqua PZ (Thor).

The term "fatty acids" refers to saturated or unsaturated monocarboxylic aliphatic acids, branched or linear, containing from 4 to 32 carbon atoms, preferably 4 - 22, more preferably 6-18 carbon atoms. Examples of fatty acids include, without limitation, saturated aliphatic monocarboxylic acids, for example butyric, valerenic, caproic, enantic, caprylic, pelargonic, caprynic, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, margaric, iso- heptadecanoic, stearic, iso-stearic, nonadecanoic, arachidic, behenic, tricosanoic, lignoceric, cerotic, montanic, melissic, laceroic, and the like; unsaturated, monounsaturated aliphatic monocarboxylic acids, for example myristoleic, undecylenic, palmitoleic, oleic, petroselenic, heptadecenoic, elaidic, vaccenic, gadoleic, cetoleic, erucic, nervonic, or polyunsaturated for example linoleic acid, linolenic, stearidonic, arachidonic, timnodonic, clupanodonic, cervonic and the like. Fatty acids may be optionally substituted.

Examples of substituted fatty acids include, without limitation, ricinoleic acid, hydroxystearic, mercaptoundecanoic, methyltetradecanoic, methylpentadecanoic, and the like. The term "about" encompasses the range of experimental error that may typically occurs in a measurement.

The composition according to this invention includes fluorinated monomers, fluorinated polymers having a C6-C21 fluoralkyl or fluoralkenyl chain, paraffins with a melting point comprised between 0 and 80°C and zirconil derivates. Other additives, such as for example, resins, colorants, perfumes, preservatives, germicides, ... may be added to such a composition. The composition according to this invention is used in the form of aqueous dispersion at a 5-35% concentration, mixing the fluorinated monomers, the fluorinated polymers optionally pre-dispersed in water and the paraffins and the zirconil derivate/derivates, optionally pre-dispersed in water. The composition according to this invention is properly diluted in water according to requirements and/or materials to be treated. If necessary, pH is adjusted to the desired values. Preferably the composition according to this invention is diluted in water so as to obtain a 10-15% concentration, preferably 13-14%. Such dispersion is stable, above all during the storing and working steps and has good fixing properties. It may be further diluted up to the desired level and may be applied to the substrate to be treated through any process known to the skilled in the art, for example, dipping, spraying , rolling and the like.

Preferably, the substrate to be treated is dipped in the composition according to this invention, up to complete and uniform absorption, for about 1-5 minutes. The removal of the excess dispersion is made through any process known to the skilled in the art, for example, by centrifugation. Preferably, the excess aqueous mixture is eliminated through a 4-5 minutes centrifugation. The recovered dispersion, may be completely re-used for further working cycles. The so treated substrate becomes repellent after complete drying at room temperature, or sun drying or with a domestic or industrial dryer. Temperatures ranging from 40 to 70°C are enough to provide repellency to the treated substrate.

Ironing is one of the preferred heating treatment processes, but it is not always required to obtain repellency.

In a further embodiment, the invention relates to a process for providing repellency to a substrate selected from fibers, fabrics, leather, hides, fur, paper, paperboard and mixtures thereof, comprising:

a. dipping the substrate with an aqueous dispersion of a repellent composition diluted until a concentration of 5-35% comprising fluorinated monomers, fluorinated polymers with a C6-C21 fluoralkyl or fluoralkenyl chain, paraffins with a melting point comprised between 0 and 80°C and zirconil derivates. Preferably, the repellent composition is diluted up to obtain a 10-15% concentration, more preferably 13-14%;

b. drying of the treated substrate at room temperature, sun drying or with a dryer;

c. optionally humidification and vaporization of the treated substrate;

d. optionally ironing.

According to the nature and characteristics of the substrate to be treated, the process for providing repellency may include further working steps. For example, in the case of hats, after the dipping process and after drying at room temperature for 12-24 hours according to the material, the hats are humidified through any method known to the skilled in the art, for example through spraying, then vaporized for about 5-10 minutes and finally, after arranging them on a shaping frame, they are ironed.

Ironing is made at different temperatures and times according to the substrate to be treated. For example, materials such as straw, paper, viscose, etc, are ironed at a temperature of 50°C for 2-5 minutes; materials such as angora, thermoplastic angora, woolen felt, lapin felt, etc. are ironed at a temperature of 80-100°C for about 2-5 minutes. The treated hats can then be well finished as desired.

Dipping with the composition according to this invention may be carried out in any of the substrate working steps. For example, the berets and the woolen caps are dipped in a steel tub, during the "fulling" where the fabric and the fibers are pressed with the addition of sulfuric acid. The berets and the woolen caps, properly arranged on an a shaping frame, are then dried preferably by ironing, at a temperature of about 40-45°C.

The process according to the present invention may be used at the beginning of a fabric production cycle. The process and the repellent composition according to the present invention may be used directly on the yarns by dipping them during "finish" step. No procedure and no production time typical of the spinning operations must be modified.

In particular, the fibers are directed to the beater which carries out dust and impurities removal. The yarns are opened, for example, with the aid of the opener. Substrate division is induced with the aid of machines and the process goes on with the dipping with t¼e composition according to the invention during the finish step. Preferably the composition according to the invention is diluted up to a concentration of 20-50%, preferably 25-45%, more preferably 35%. The fibers are then collected by means of a cutter and all of the yarn working steps, such as carding, ironing and the final spinning are carried out, thus obtaining the repellent yarn. Once the yarn has been produced, the start of the composition repelling process takes place during the finishing (in the case of fabrics) or during washing, drying and ironing (in the case of knitwear).

The process according to the invention provides repellent properties to a substrate in an uniform, homogeneous, extremely simple and quick way, under very mild conditions, without having to use high temperatures to dry the treated substrate. The use of mild temperatures required to start the repelling process of the composition according to the invention allows the maintenance of the original characteristics of the treated substrate as well as costs reduction. The fabrics susceptible to thermal treatments, such as silk, may undergo a repelling treatment with the composition of this invention.

The process according to this invention is carried out in an aqueous solution, with no use of solvents, toxic solvents, or envinronmentally dangerous solvents, which would always require waste disposal. The process of the present invention does not require any equipment, any specific machinery, any closed machinery. The used substances are not toxic, do not cause irritation and can easily be disposed of.

In a further embodiment, this invention relates to the substrates treated with the repellent composition according to this invention, such as fibers, fabrics, leather, hides, fur, paper, paperboard and blends thereof.

The process according to this invention allows to provide repellency to a substrate without altering its characteristics: colors do not change, remain light resistant, do not fade; white or light materials are prevented from being tinged yellow; soft feel, elasticity, flexibility, resistance, mechanical characteristics remain unchanged.

Fabrics and garments treated with the process according to this invention do not irritate skin. The repellent composition according to this invention coats homogeneously the treated substrate and may be applied, always with excellent repellency results, both to the raw material and the finished product.

The water repelling characteristic persists to repeated launderings and dry cleanings, even when a softener is used.

In case of a substrate washing, a natural drying or a simple ironing are sufficient to re-activate the repellent composition. The treatment of the materials of interest with the composition according to this invention persists to at least seven washings. Resistance to washings is an index of the stability on the treated substrate surface of the composition according to this invention.

The treated substrate presents excellent water and oil repellent characteristics, as it can be seen from the data shown in Tables 1, 3, 4-7 and is stains resistant (Tables 4-7). The treated substrate has a very good breathability (Table 2), allows evaporation of perspiration, which is an important characteristic for the sportswear and rainwear.

After several washings, the repellency of the material of interest, for example a fabric or a garment, may be immediately restored simply through washing and subsequent ironing. This advantage is very important in the case of garments, such as knitwear, t-shirts, shirts, trousers, which are frequently subjected to washings.

In another embodiment, the present invention relates to the use of the composition for treating substrates selected from fibers, fabrics, leather, hides, fur, paper, paperboard and blends thereof.

Although the present invention has been described in terms of its specific embodiments, some modifications and equivalents which will be evident to those skilled in the art are included within the scope of the present invention. Further on, the present invention will be illustrated by means of some examples, which are not construed to be viewed as limiting the scope of the invention itself.

Examples

The following abbreviations refer respectively to the definitions hereunder:

hr (hours); min. (minutes), RT (room temperature)

Example 1

Preparation of mixture C

A dispersion of fluorinated polymers (Draig 300^® cone, Bozzetto Group) in water and a mixture of paraffins and zirconil derivates ((Draig NSZ^®, Bozzetto Group) are blended in ratio 1 :1 at room temperature and diluted in water (fluorinated polymers mixture, paraffins and zirconil derivates 13.40% / water 86.60%). The resulting mixture may be stored.

Example 2

Material Treatment

The material to be treated is dipped in the mixture described in Example 1 until complete and uniform absorption (1-5 min.). The excess aqueous mixture is eliminated through centrifugation (about 5 min.). The treated material is then completely suA dried, or by domestic or industrial dryer. (40-70°C).

Example 3

Material treatment

The treated material according to Example 2, is ironed through domestic ironing.

Example 4

Hat treatment

The hat to be treated is dipped in the mixture of Example 1 until complete and uniform absorption (1-5 min.). The excess aqueous solution is eliminated through centrifugation (5 min.). The hat is dried completely at room temperature for 12-24 hours according to the material used. It is then humidified by spraying for the time required to get superficially wet. It is finally vaporized for 5-10 minutes. After vaporization it is arranged on a shaping frame and ironed. Then it is taken off the shaping frame and well finished as desired.

Example 5

Woolen Berets Treatment

The mixture of Example 1 is added during "fulling". The berets are soaked in a steel tub, where the fabric and the fibers are pressed with the addition of sulfuric acid. The mixture according to Example 1 is added and the berets are left soaking for about 30 min. at a temperature of about 40°C. The excess aqueous solution is eliminated through centrifugation (5 min.). The material, arranged on appropriate shaping frames, is dried by ironing at a temperature of about 40-45°C.

Example 6

Yarn Treatment "Carded wool spinning"

After opening the material bales, the fibers of a cachemire mix material are directed to the beater which carries out the dust and impurities removal operations. The fibers are opened by means of an opener. Material division is induced by means of machines. The fibers are treated with the mixture of example 1 during "finishing". The fibers are then collected by means of a cutter (possible second or third passing through the flock opening machine according to the product refinement and quality desired) carding, ironing and final spinning.

Resistance to superficial dipping: Spray Test

(UNI EN 24920: 1993 corresponding to AATCC Test Method 22-1996, Water Repellency; Spray Test and AATCC Test Method 22-2005, Water Repellency; Spray Test). Evaluation of resistance to superficial dipping of material has been carried out by measuring the wetting index according to UNI EN 24920 (Spray Test).

The grade of repellence to water is indicated according to UNI EN 24920: value ISO 1 (50) (min) - value ISO 5 (100) (max).

In particular:

value ISO 1 means "wetting of the whole exposed surface"

value ISO 2 means "wetting of half exposed surface"

value ISO 3 means "wetting limited to small separated areas of the exposed surface"

Value ISO 4 means "no wetting, but only small drops"

Value ISO 5 means "no wetting, no drops".

The indexes of ISO descriptive scale correspond to the values of AATCC scale, as follows:

ISO 1 = AATCC50

ISO 2 = AATCC70

ISO 3 = AATCC80

ISO 4 = AATCC90

ISO 5 = AATCC 100

Table 1

AATCC scale values;

VI: viscose; ^c WA: angora; ^d WO: wool; ^e PA: polyammidic; ^f Lapin Felt: Lapin fur Felt ISO 5 (100) values show a better resistance of the treated material to superficial wetting.

Determination of water vapor transmission speed

(UNI 4818-26: 1992)

The material water vapor transmission speed has been determined by measuring the tested sample mass by grams before and after the test, according to UNI 4818-26: 1992.

The water vapor transmission speed, expressed by grams per sq.mt. in 24 hours, results as follows:

1000 (mi - m₂)

wherein:

mj = tested sample mass expressed by grams before the test

m₂ =tested sample mass expressed by grams after the test

An arithmetical average of two determinations is calculated.

Table 2

arithmetical average of two tests

b VI: viscose; ^c WA: angora; ^d WO: wool; ^e PA: polyammidic; ^f Lapin Felt: Lapin fur Felt ISO 5 (100) values show a better resistance of the treated material to partial dipping.

Resistance to water penetration (test under hydrostatic pressure)

UNI EN 20811:1993

The evaluation of resistance to water penetration (test under hydrostatic pressure) has been carried out by measuring the hydrostatic pressure born by the tested sample, according to UNI EN 20811 :1993 (corresponding to UNI 4818 Part 32 -May 1992 and AATCC Test Method

127-2003).

Table 3

arythmetical average of two tests

b WO: wool; ⁰ Lapin Felt: Lapin Felt

Tests carried out in normal atmosphere, temperature = 20°C, relative humidity= 65%; water temperature: 21°C, water pressure increase: 10 mm/s; side of the tested fabric: from the right side to the other side.

Example 7

Water and oil repelling treatment of different fabrics

Water and oil repellent treatment used:

Composition 1 (A+B)

DRAIG 300/DRAIG NSZ/H20 have been mixed = 1/1/13 (weight ratio), corresponding to about 2% of A and B dry weight (total 4% dry weight).

Composition 2 (O+B

Quecophob PC6/DRAIG NSZ/H20 have been mixed = 1/1/13 (weight ratio), corresponding to about 2% of Q and B dry weight (total 4% dry weight).

Composition 3 (T+B

Teratex 2912/DRAIG NSZ/H₂0 have been mixed = 1/1/13 (weight ratio), corresponding to about 2% of T and B dry weight (total 4% dry weight).

Composition 4 (TG+B)

UNIDYNE TG5543/DRAIG NSZ/H₂0 have been mixed = 1/1/13 (weight ratio), corresponding to about 2% of TG and B dry weight (total 4% dry weight)

Impregnation method: dipping

Drying: at RT + 1 hour at 80°C

The following tests have been carried out on the material treated as above: • Oil Repellency: carried out according to Hydrocarbon Resistance Test, according to AATCC Test Method 118-2002 (C16-C7 hydrocarbons) (corresponding to UNI EN ISO 14419:2010)

• Aqueous Liquid Repellency: carried out according to the Water/Alcohol Solution Resistance Test, according to AATCC Test Method 193:2005.

• Stain Repellency: repellency to aqueous solutions has been evaluated through the Aqueous/Liquid Repellency Test: Water/ Alcohol Solution Resistance Test according to AATCC Test Method 193-2005 Stain Repellency: resistance to stains has been tested by applying to the different water repelling substrates three 0.05 ml drops of a mixture of Vaseline oil and normal-heptane at different concentrations, according to what is reported in Table 3A. The shape and the wetting properties of the deposited drops are observed for 180 seconds and the repellency grade is assigned with reference to the mixture with the best grade which does not wet the treated substrate, with reference to Figure 5.

Table 3: The test liquids scale for stain resistance, and the corresponding value from 0 to 7 for fabrics assessment

Water repellency - Spray Test: carried out according to AATCC Test Method 22-2005 (corresponding to UNI EN 24920:1993, AATCC Test Method 22-1996, Water Repellency: Spray). The Spray Test on a jeans fabric has been repeated after 3, 15 and 25 washing and drying cycles so as to assess the extent of the water repellency decrease. Hand washings with a conventional detergent and a softener have been made at a temperature of 30°C; subsequently the fabric was spin-dried at 1000 rpm for 5 minutes, and dried with an industrial dryer at a temperature of about 60-70°C for 5-7 minutes. The results are shown in table 4.1. • Resistance to water penetration (test under hydrostatic pressure) carried out according to UNI 4818 Part 32 - May 1992 (corresponding to UNI EN 20811 : 1993 and AATCC Test Method 127-2003).

In conformity with the results reported in Example 6, the water repellence grade is expressed according to UNI EN 24920: value ISO 1 (50) (min) - Value ISO 5 (100) (max).

The results are indicated in the following tables 4-7

Table 4

a arithmetical average of three tests

b AATCC scale values

Table 4.1

AATCC scale values Table 5

^♦Polyester Decathlon white sport sweater a arithmetical average of three tests b AATCC scale values

Table 6

* 70% Wool + 30 Nylon

a Arithmetical average of three tests b AATCC scale values Table 7

a Arithmetical average of three tests

b AATCC scale values In Fig. 1-4 are schematically reported the preferred processes for carrying out the invention, wherein:

Fig. 1 shows an fl garments dipping step, in a tub 2 containing the composition according to this invention.

At the end of the dipping step the garments are preferably treated in a spinning drier, 3 (f2 step) and then subjected to the β drying step, for example with a dryer 4, and/or sun drying, and/or ironing 5, so as to start the water repellent process of the treated garments.

Advantageously, it has been found that an increased repellent property of the garment is achieved when the drying step is carried out alone or in combination with ironing.

Fig. 2 shows the treatment of wool berets 1 , laid in a tub 2, to carry out the fl dipping step. Preferably, during the dipping step in tub 2, in addition to the composition of the invention, additives are used in order to achieve the beret felting 1 (fulling treatment).

At the end of the dipping and/or fulling steps, the beret 1 is preferably sent to a centrifuge'

(f2 step) and then sent to dry (f3 step) preferably through ironing processes 6 at a preferred temperature of about 40-45°C.

Fig. 3 shows the treatment of cones or bonnet 1 that is the material used for hats manufacturing 13. In the illustrated example, the fl dipping step includes the cones immersion 1 in a tub 2 containing the composition according to the invention.

Preferably, during the dipping step, following the immersion in tub 2, an f4 humidification step through sprinkling and an f5 step for the absorption of the composition may be foreseen, for example, for a 12-24 hours time period.

At the end of the absorption step, the cone 1 is subjected to the G drying phase, preferably through ironing processes 7, at a preferred temperature depending on the treated material. Fig. 4 shows the treatment of textile fibers, that is the material used for the production of yarns 1 1, fabrics and/or knitwear 12.

In the illustrated example, the dipping step fl is carried out during the fibers "finish" treatment, adding in tub 2 the composition of the invention and the other known additives required for the "finish" operations.

At the end of the dipping and "finish" steps, the fibers are treated by means of known equipments 9 to obtain yarns. 11

Preferably, the yarns 1 1 used for fabrics production are subjected to the f3 drying step during "finishing" so as to start the repelling process.

In a further embodiment the yarns are used for knitwear production 12 and the G drying step is carried out through garments 12 ironing.

Claims

A process for imparting repellent properties to a substrate selected from fibers, fabrics, leather, hides, fur, paper, paperboard and blends thereof, comprising:

a. dipping the substrate with an acqueous dispersion of a repellent composition diluted until a concentration of 5-35%, comprising fluorinated monomers, fluorinated polymers with a C6-C21 fluoroalkyl or fluoroalkenyl chain, paraffins with a melting point comprised between 0 and 80°C and zirconil compounds; b. drying the treated substrate to room temperature, sun drying or with a dryer;

c. optionally humidification and vaporization of the treated substrate;

d. optionally ironing.

The process according to claim 1, step b., wherein the drying is between 40-70 °C. The process for imparting water repelling properties to a substrate according to claims 1-2 comprising:

a. dipping the substrate with an aqueous dispersion of the repellent composition diluted until a concentration of 5-35% comprising fluorinated monomer^, fluorinated polymers with a C6-C21 fluoroalkyl or fluoroalkenyl chain, paraffins with a melting point comprised between 0 and 80 °C and zirconil compounds during fulling;

c. humidification and vaporization of the treated substrate;

d. ironing.

The process according to claim 3, wherein the substrate is selected from berets, wool caps.

A process for imparting repellency to a yarn, comprising:

a. adding an aqueous dispersion of the repellent composition diluted until a concentration of 5-35%, comprising fluorinated monomers, fluorinated polymers with a C6-C21 fluoroalkyl or fluoroalkenyl chain, paraffins with a melting point comprised between 0 and 80°C and zirconil compounds, diluted unitl a concentration of 20-50%, preferably 25-45%, more preferably 35%, during the finish;

b. yarn drying;

c. optionally ironing

6. The process according to claims 1-5 wherein:

a. the fluorinated monomers, fluorinated are perfluorohexane, perfluoroheptane, perfluooctane, perfluorononane, perfluorodecane, perfluoroundecane, perfluorododecane, perfluorohexene, perfluoroheptene, perfluoro n-octhylethylene, perfluorooctyl acrylate, perfluoroctene, perfluorononene, perfluorodeceue; preferably perfluorohexane, perfluorohexene, perfluoroctene, perfluorodecene, perfluoro n-octhylethylene, perfluorooctyl acrylate;

b. the fluorinated monomers, fluorinated polymers have a melting point comprised between 30 and 80 °C, preferably comprised between 30 and 60 °C, more preferably comprised between 40 and 50 °C;

c. the fluorinated monomers, fluorinated polymers are optionally dispersed in an aqueous solution with a diluition of 5-35%; preferably 20-30%; more preferably a dilution of 30% by weight;

d. the fluorinated monomers, fluorinated polymers give to the aqueous solution wherein they are dispersed a pH comprised between 1 and 6, preferably 2 - 5, more preferably 2.5 - 4.5;

e. paraffins with a melting point comprised between 20 - 60 °C, preferably between 50

- 60 ⁰ C;

f. paraffins and zirconil compounds are optionally dispersed in water in advance to dilutions of 5-35%; preferably 20-30%; more preferably 30% by weight and the pH of the aqueous dispersion is comprised between 1 and 5, preferably 2 - 5, more preferably 2.5 - 4; the total concentration of the metallic zirconium in this dispersion is between 0.1-3%, preferably 0.1-1%, more preferably 0.15-0.18%.

7. The process according to claims 1-4, wherein the aqueous solution of the repellent composition is diluted until a concentration of 10-15%, preferably 13-14.

8. A substrate treated with the repellent composition according to the previous claims.

9. Substrate according to claim 8 selected from fibers, fabrics, leathers, hides, fur, paper, paperboard and blends thereof.

10. A repellent composition in form of an aqueous dispersion diluted until a concentration of 5-35%, comprising fluorinated monomers, fluorinated polymers with a C6-C21 fluoroalkyl or fluoroalkenyl chain, paraffins with melting point comprised between 0 and 80°C and zirconil compounds.

11. The composition, according to claim 10, diluted until a concentration of 10-15%, preferably 13-14%.

12. The composition according to claim 10, wherein the fluorinated monomers, fluorinated polymers are perfluorohexane, perfluoroheptane, perfluooctane, perfluorononane, perfluorodecane, perfluoroundecane, perfluorododecane, perfluorohexene, perfluoroheptene, perfluoro n-octhylethylene, perfluorooctyl acrylate, perfluoroctene, perfluorononene, perfluorodecene; more preferably perfluorohexane, perfluorohexene, perfluoroctene, perfluorodecene, perfluoro n-octhylethylene, perfluorooctyl acrylate

13. The composition according to claim 10, wherein the fluorinated monomers, fluorinated polymers have a melting point comprised between 30 and 80 °C, preferably 30 - 60 °C, more preferably 40 - 50 ° C; and are optionally dispersed in advance in water at dilutions of 5-35%; preferably 20-30%»; more preferably 30% by weight and give to the aqueous solution wherein they are dispersed a pH comprised between 1 and 6, preferably 2-5, more preferably 2.5-4.5.

14. The composition according to claim 10, wherein:

a. paraffins have a melting point comprised between 20 - 60 °C, preferably 50-60°C; b. paraffins and zirconil compound/compounds are optionally dispersed in advance in water at dilutions of 5-35%; preferably 20-30%; more preferably at dilutions of 30%) by weight; the resulting aqueous solution has a pH comprised between 1 and 5, preferably 2 - 5, more preferably 2.5 - 4; the total concentration of metallic zirconium in the dispersion is comprised between 0.1-3%, preferably 0.1-1%), more preferably 0.15-0.18%.

15. Use of a composition according to claim 10 and of the processes according to claims 1- 7 for treating substrates selected from fibers, textiles, leather, hides, fur, paper, paperboard and blends thereof.