WO2015187093A1

WO2015187093A1 - Water repelling article

Info

Publication number: WO2015187093A1
Application number: PCT/SG2015/050122
Authority: WO
Inventors: Kankani Gamage Gayan YAPA; Lasantha Srimal KOLAMUNNA; Dilhan SAMARAGUNARATHNA
Original assignee: Linea Aqua (Private) Limited; MATTEUCCI, Gianfranco
Priority date: 2014-06-05
Filing date: 2015-05-25
Publication date: 2015-12-10
Also published as: US20170081800A1

Abstract

Disclosed herein is a water repelling article for use in clothing comprising, at least one inner material and at least one outer material that substantially covers the inner material, wherein the article further comprises at least one water repelling agent uniformly distributed throughout the article and the article has a resiliently deformable non-flat three dimensional shape. In addition, a process for forming a water repelling article for use in clothing is disclosed.

Description

WATER REPELLING ARTICLE

TECHNICAL FIELD The present invention relates to a water repelling article and a process for forming the same.

BACKGROUND The listing or discussion of an apparently prior-published document in this specification should not necessarily be taken as an acknowledgement that the document is part of the state of the art or is common general knowledge.

The field of highly functionalised textiles is a growing market for many garment related industries. One of the most important properties for textiles, and one that demands a high value, is the ability to repel water. This ability to repel water is generally achieved by subjecting a textile to chemical treatment before further processing steps such as colouring, cutting, shaping, forming and sewing etc. The conventional methods used to perform this chemical treatment normally include a step of wetting the textile with a water repelling chemical before performing drying and curing steps.

The water repelling chemicals used to treat textiles to provide water repelling properties work by chemically modifying the surface of the textiles, such that water is at least partially repelled by the chemically modified textile.

While standard techniques used to provide textiles and articles of clothing with water repellent properties are able to provide a reasonable level of water repellence, there are still major problems associated such standard techniques, especially when treating non-flat articles. These problems include an uneven distribution of chemical across the textiles/articles and the deformation of non-flat articles. This can lead to an inconsistent water repelling performance from the final products.

Accordingly, there remains a need for improved articles (and therefore processes) with improved water repellence properties. SUMMARY OF INVENTION

In a first aspect of the invention, there is provided a water repelling article for use in clothing comprising at least one inner material and at least one outer material that substantially covers the inner material, wherein the article further comprises at least one water repelling agent uniformly distributed throughout the article and the article has a resiliently deformable non-flat three dimensional shape. In embodiments of the invention, the at least one outer material may completely cover the inner material.

In further embodiments of the invention, the article: (a) may have a curvilinear topography. For example, the article may be shaped like a cup; and/or

(b) may form part of a shoe, medical equipment (e.g. a casting liner inner), or, more particularly, a bra, a brassiere, swimwear, sportswear or casual wear; and/or

(c) may be one where at least part of the article has a fixed three-dimensional shape that is complementary in shape to one of the group consisting of hands, arms, and, more particularly, the head, shoulders, buttocks, breasts, knees, elbows and feet. In further embodiments of the invention, the article may have an improved texture in a blind test compared to a water repelling article prepared in a process comprising the step of immersing said article into a water-repellant precursor solution.

In yet further embodiments of the invention, the at least one water repelling agent may have been impregnated within the article following plasma activation of said article to provide an improved feel and appearance. For example, the at least one water repelling agent may comprise paraffin waxes, silicones, silanes, fluorinated polymers, non- fluorinated water repelling polymers or a combination thereof, or the water repelling agent comprises fluorine and carbon atoms. A particular example of the water repelling agent comprises fluoroacrylate polymer.

In still further embodiments of the invention, the at least one inner material may be an open or closed-cell foam.

In embodiments of the invention, the at least one outer material may be a fabric. For example the fabric is laminated.

In a second aspect of the invention, there is disclosed a process comprising the steps of:

(a) providing a starting article comprising at least one inner material and at least one outer material that substantially covers the inner material;

(b) treating a starting article with at least one water repelling agent precursor to form a treated article; and

(c) curing the treated article to generate the water repelling agent and form the water repelling article, wherein

the starting article has a resiliently deformable, non-flat three-dimensional shape.

In an embodiment of the invention, treating the starting article may comprise immersing the starting article in the at least one water repelling agent precursor. For example, the at least one water repelling agent precursor comprises paraffin waxes, silicones, silanes, fluorinated polymers, non-fluorinated water repelling polymers or a combination thereof, or the water repelling agent comprises fluorine and carbon atoms. A particular example of the water repelling agent precursor is at least one fluoroacrylate polymer.

In further embodiments of the invention, a step of removing excess water repelling agent precursor is performed before curing the treated article. For example, the step of removing excess water repelling agent comprises feeding the treated article through a roller and/or subjecting the treated article to centrifugation to provide an extracted article. Optionally, the extracted article may be sprayed with the at least one water repelling agent precursor.

In certain embodiments of the invention, the treatment step comprises an activating step, where the starting article is treated with an activating plasma to generate an activated article and a coating step, where the activated article is treated with an inert plasma and the at least one water repelling agent precursor (e.g. a water repelling agent precursor disclosed hereinbefore) to generate the treated article.

In embodiments of the invention, the activating plasma is generated:

(a) from argon or, more particularly, nitrogen or oxygen gas; and/or

(b) under a reduced pressure (e.g. from 0.1 to 0.5 mbar, such as from 0.12 to 0.45 mbar, or, more particularly, from 0.2 to 0.5 mbar) and using a power of from 200W to 300W (e.g. 250W) or under a reduced pressure (e.g. from 0.2 to 0.5 mbar and using a power of from 50W to 200W (e.g. 70W).

In certain embodiments of the invention, the flow rate of the gas is from 10 to 80 seem (e.g. 60 seem). In still further embodiments of the invention, a drying step is performed before curing the treated article.

In certain embodiments of the invention, the at least one water repelling agent precursor in step (b) further comprises at least one wetting agent.

In further embodiments of the invention, the curing in step (c) comprises infrared curing and/or microwave curing.

In yet further embodiments of the invention, the article is as described in the first aspect of the invention.

Further Aspects and embodiments of the invention are provided in the following numbered clauses. 1 . A water repelling article for use in clothing comprising:

at least one inner material; and

at least one outer material that substantially covers the inner material,

wherein the article: further comprises at least one water repelling agent uniformly distributed throughout the article; and

the article has a resiliently deformable non-flat three dimensional shape. 2. The article according to Clause 1 , wherein the at least one outer material completely covers the inner material.

3. The article according to Clause 1 or Clause 2, wherein the article has a curvilinear topography.

4. The article according to Clauses 1 to 3, wherein the article has a cup shape.

5. The article of any one of Clauses 1 to 4, wherein the article forms part of a shoe, medical equipment (e.g. a casting liner inner), or, more particularly, a bra, a brassiere, swimwear, sportswear or casual wear.

6. The article of any one of the preceding clauses, wherein at least part of the article has a fixed three-dimensional shape that is complementary in shape to one of the group consisting of hands, arms, and, more particularly, the head, shoulders, buttocks, breasts, knees, elbows and feet.

7. The article of any one of the preceding clauses, wherein the article has an improved texture in a blind test compared to a water repelling article prepared in a process comprising the step of immersing said article into a water-repellant precursor solution.

8. The article of any one of the preceding clauses, wherein the at least one water repelling agent has been impregnated within the article following plasma activation of said article to provide an improved feel and appearance. 9. The article according to any one of the preceding clauses, wherein the at least one inner material is an open or closed-cell foam.

10. The article according to any one of the preceding clauses, wherein the at least one outer material is a fabric. 11. The article according to Clause 10, wherein the fabric is a laminated fabric.

12. The article according to any one of the preceding clauses, wherein the at least one water repelling agent comprises paraffin waxes, silicones, silanes, fluorinated polymers, non-fluorinated water repelling polymers or a combination thereof, or the water repelling agent comprises fluorine and carbon atoms.

13. The article according to Clause 2, wherein the water repelling agent is at least one fluoroacrylate polymer.

14. A process for forming a water repelling article for use in clothing, the process comprising the steps of:

a) providing a starting article comprising at least one inner material and at least one outer material that substantially covers the inner material;

b) treating a starting article with at least one water repelling agent precursor to form a treated article; and

c) curing the treated article to generate the water repelling agent and form the water repelling article, wherein

15. The process according to Clause 14, wherein treating the starting article comprises immersing the starting article in the at least one water repelling agent precursor.

16. The process according to Clause 15, wherein a step of removing excess water repelling agent precursor is performed before curing the treated article.

17. The process according to Clause 16, wherein removing excess water repelling agent precursor comprises feeding the treated article through a roller and/or subjecting the treated article to centrifugation to provide an extracted article.

18. The process according to Clause 7, wherein the extracted article is sprayed with the at least one water repelling agent precursor. 19. The process according to Clause 14, wherein the treatment step comprises an activating step, where the starting article is treated with an activating plasma to generate an activated article and a coating step, where the activated article is treated with an inert plasma and the at least one water repelling agent precursor to generate the treated article.

20. The process according to Clause 19, wherein the activating plasma is generated from nitrogen or oxygen gas, optionally wherein the flow rate of the gas is from 10 to 80 seem (e.g. 60 seem). 21. The process according to Clause 19 or Clause 20, wherein the activating plasma is generated under a reduced pressure and using a power of from 200W to 300W.

22. The process according to Clause 21 , wherein the reduced pressure is from 0.1 to 0.5 mbar (e.g. such as from 0.12 to 0.45 mbar or, more particularly, from 0.2 to 0.5 mbar).

23. The process according to Clause 21 or Clause 22, wherein the power is 250W.

24. The process according to any one of Clauses 19 to 23, wherein the inert plasma is generated from argon gas, optionally wherein the flow rate of the gas is from 10 to 80 seem (e.g. 60 seem).

25. The process according to one of Clauses 19 to 24, wherein the inert plasma is generated under a reduced pressure and using a power of from 150W to 200W. 26. The process according to Clause 25, wherein the reduced pressure is from 0.2 to 0.5 mbar (e.g. such as from 0.12 to 0.45 mbar or, more particularly, from 0.2 to 0.5 mbar).

27. The process according to Clause 25 or Clause 26, wherein the power is 170W. 28. The process according to any one of Clauses 14 to 27, wherein a drying step is performed before curing the treated article.

29. The process according to any one of clauses 14 to 28, wherein the at least one water repelling agent precursor comprises paraffin waxes, silicones, silanes, f!uorinated polymers, non-fluorinated water repelling polymers or a combination thereof, or the water repelling agent comprises fluorine and carbon atoms.

30. The process according to Clause 29, wherein the at least one water repelling agent precursor is at least one fluoroacrylate polymer

31. The process according to any one of Clauses 14 to 30, wherein the at least one water repelling agent precursor in step (b) further comprises at least one wetting agent. 32. The process according to any one of Clauses 14 to 31 , wherein the article has a curvilinear topography.

33. The process according to any one of Clauses 14 to 32, wherein the article has a cup shape.

34. The process according to any one of Clauses 14 to 33, wherein the process further comprises the step of forming a garment that comprises said article.

35. The process according to Clause 34, wherein the garment is a shoe, medical equipment (e.g. a casting liner inner), or, more particularly, a bra, a brassiere, swimwear, sportswear or casual wear.

36. The process according to any one of Clauses 14 to 35, wherein the curing in step c) comprises infrared curing and/or microwave curing.

37. The process according to any one of Clauses 14 to 36, wherein the at least one outer material completely covers the inner material.

38. The process according to any one of Clauses 14 to 37, wherein at least part of the starting article has a fixed three-dimensional shape that is complementary in shape to one of the group consisting of hands, arms, or, more particularly, the head, shoulders, buttocks, breasts, knees, elbows and feet.

BRIEF DESCRIPTION OF FIGURES Aspects and embodiments will be described with reference to the following figures, wherein: Figure 1 illustrates a padding roller for extracting water repellent agent precursor from a treated article.

Figure 2A illustrates a front view, side view and cross-sectional view of a bra cup. Figure 2B illustrates a cross-sectional view of the bra cup before and after treatment.

Figure 3 illustrates the water repelling performance of an untreated specimen, a plasma treated specimen and a chemical treated specimen. Figure 4 shows an article made according to the current invention and illustrates sections used to test the water repellence of the article.

Figure 5 depicts the contact angle of the inner and outer layers of the article depicted in Figure 4.

DETAILED DESCRIPTION

Surprisingly, it has been found that an article with improved water repellence can be produced by a modified process wherein a non-flat, multi-layered article is subjected to a water repellent treatment.

Thus, there is provided a water repelling article for use in clothing that comprises at least one inner material and at least one outer material that substantially covers the inner material, wherein the article further comprises at least one water repelling agent uniformly distributed throughout the article and the article has a good recovery at a low force range, is resiliently deformable and has a non-flat three dimensional shape.

The articles described above may be provided by a process comprising the steps of: a) providing a starting article comprising at least one inner material and at least one outer material that substantially covers the inner material;

b) treating the starting article with at least one water repelling agent precursor to form a treated article; and

the starting article has a resiliently deformable, non-flat three dimensional shape.

As used herein, the term, "resiliently deformable non-flat three dimensional shape" refers to an object that has a defined three-dimensional shape that can be deformed by the application of pressure and/or force onto said object, but which will return to the defined shape once said pressure and/or force is removed from the object. When the pressure and/or force applied onto said object is less than or equal to 570 newton (N) the object may return to its defined shape once the pressure or force is removed. Where the pressure and/or force applied onto said object exceeds 570 N, the object may not return to its defined shape once the pressure or force is removed, that is, the object will remain permanently deformed. Any suitable non-flat three dimensional shape that is suitable for use in clothing may be used. For example, the shape may have a curvilinear topography 130, as illustrated by the bra cup 100 in Figure 2A. Alternatively or additionally, the defined shape may be a shape that is complimentary to the contours of part of a body (such as one of the group consisting of hands, arms, or more particularly, the head, shoulders, buttocks, breasts, knees, elbows and feet). Thus, the defined three-dimensional shape may be a cup (e.g. complementary in shape to breasts). As shown in Figure 2A, the bra cup 100, includes an inner material 110 (e.g. foam) and an outer material 120 as a liner. Possible inner and outer materials that may be used for one or more applications are set out hereinbelow. Figure 2B depicts the inner material 110 and outer material before treatment 200 and after treatment 300. As depicted in Figure 2B, it is believed that the current process and articles contain a uniform penetration of chemicals between the layers, which provides the unexpectedly good properties of the garments discussed herein. The water repelling article of the present invention may be used for clothing. More specifically, the article may form part of a shoe, medical equipment, or, more particularly, a bra, a brassiere, swimwear, sportswear or casual wear. As an example of medical equipment, the article may be formed into a pre-formed casting inner liner. In this example, the inner liner has a three-dimensional shape and is shaped to conform to the surface of the fractured area (and surrounding area covered by the cast), such as a long-armed tube for a fracture of the forearm. The pre-formed liner enables perspiration to be channelled away from the skin/cast and helps to minimise the inconvenience of the subject due to an accumulation of sweat in the cast.

In certain embodiments of the invention, the shoe may not require the presence of the inner material. In other embodiments, the shoe requires the presence of the inner material. Alternatively, the article may be used for upholstery. In particular, the article may form part of a textile covering for any one of the group consisting of chairs, beds and tables (e.g. a massage table where the water repelling article forms part of the upholstery of said table). Given the above, the starting article must also be suitable for use in clothing. When used herein, the term "water repelling article" may be used to describe the water repellent article comprising at least one inner layer and at least one outer layer. When used herein, it will be understood that an "item of clothing" or an "item of upholstery" relates to an item that comprises the non-fiat three dimensional article mentioned herein as a component part. Such items may comprise other components that may also be water repellent. For example, items of clothing may be selected from the group consisting of a shoe, medical equipment (e.g. a casting liner inner), or, more particularly, a bra, a brassiere, swimwear, sportswear or casual wear, while an item of upholstery may be selected from the group consisting of a covering for a chair, a bed and a table. It will be understood that a "starting article" refers to an object that may be used to make the "article" described above and references to "treated article" and "extracted article" should be construed accordingly. Collectively, the terms, "water repelling article", "starting article", "treated article" and "extracted article" may be referred to herein as an "article". The article requires there to be an inner material. This inner material is responsible for the resiliently deformable, non-flat three dimensional shape of the article. As such any material that can provide a resiliently deformable, non-flat three dimensional shape may be used as the inner material. For example, the inner material may comprise a foam. When the inner material comprises a foam, the foam may be selected from one or more of the group consisting of a closed cell foam, an open cell foam, a reticulated foam and a multilayered foam or combinations thereof (e.g. the foam may be a foam that has 95% closed cells and 5% open cells, such as a foam with 85% or less closed cells and 15% or more open cells). Such foams may be made from, but are not limited to, polyurethane, polyvinyl chloride, polystyrene, natural rubber or synthetic rubber.

As discussed herein, the inner material is responsible for the resiliently deformable, non-flat three dimensional shape of the article. Thus, in a precursor step to the process disclosed above, there is a step of providing a starting article with the desired non-flat three dimensional shape. This shape may be obtained by any suitable means of shaping the resiliently deformable material. For example, the shaping may be accomplished by moulding, pressing, cutting, sanding, sculpting, etching or any suitable combination thereof. The outer material may be attached to the inner material prior to, or after to, the inner material has been shaped into the desired non-flat three dimensional shape.

When used herein, the term "substantially covers" may refer to the situation where the majority of the inner material is covered by the outer material or to a situation where the inner material is entirely covered by the inner material (i.e. the inner material has no external facing surfaces). The outer material may be a single piece material or it may be two or more pieces (e.g., two to ten, four to six or five pieces) joined together to cover the inner material. When the outer material is in two or more pieces, the two or more pieces may be joined together by any means of fastening, for example by stitching, stapling, a fabric hoop and loop fastener, or by the use of an adhesive. The outer material may be, but is not limited to, a group comprising (or consisting of) leather, suede leather, composites made using man-made or natural materials and, more particularly, a fabric material. When the outer material is a fabric material, each piece of fabric material may be selected from one or more of the group consisting of canvas, and, more particularly, laminated fabrics, microfiber polyester fabrics, nylon fabrics, spandex fabrics and knitted fabrics. For example, the outer material may be a polyester fabric. It will be appreciated that when the material used is a fabric, it may be woven, non-woven or knitted. The outer material covers the inner material in such a way that the inner material is held within said outer material. This may be by the conformation of the outer material, such that the inner material cannot be released from the outer material without substantial mechanical effort (e.g. where the outer material comprises a first piece and a second piece, where the first piece is applied to a first face of the inner material and the second piece is applied to the other face of the inner material, where the first piece and second piece of material overlap sufficiently that they can be fastened together using stitches and entirely envelop the inner material).

Alternatively or additionally, the outer material may also be bound to the inner material by any suitable means of fastening, for example by stitching, stapling, a fabric hoop and loop fastener, or by the use of an adhesive. In certain embodiments the outer material is bound to the inner material using adhesives.

In order to obtain the desired water repelling properties, a water repelling agent is uniformly distributed throughout the article. When used herein "uniformly distributed" means that the water repelling agent is evenly distributed across the at least one inner material and the at least one outer material. Any suitable water repelling agent may be used. Such water repelling agents include paraffin waxes, silicones, silanes, fluorinated polymers, non- fluorinated water repelling polymers or any combination thereof that may be cured or uncured. In particular, the water repelling agent may comprise a fluoroacrylate that has optionally been subjected to curing.

It will be appreciated that curing of the water repelling agents will cause a number of chemical changes in said agents. These changes will depend on the agent itself.

The uniform distribution of the water repelling agent throughout the article may help to provide the article with an improved and longer lasting water repelling effect. Without wishing to be bound by theory, it is also speculated that the uniform distribution of the water repelling agent throughout the inner and outer layers of the article is responsible for the particularly good effects demonstrated by the article of the current invention, as described in the Examples Section below.

An article may have an improved texture in a blind test compared to a similar water repelling article that has been prepared in a process comprising the step of immersing said article into a water repelling agent precursor solution.

As described herein, "water repelling agent precursor" is a mixture comprising a water repelling agent component. The water repelling agent precursor is used to treat a starting article, thus impregnating the water repelling agent precursor into the starting article, in a uniform distribution. Following curing of the treated or extracted article comprising the water repelling agent precursor, there is formed an article with a uniform distribution of water repelling agent throughout the outer and inner materials of said article. The water repelling agent precursor may include any suitable water repelling agent component including paraffin waxes, silicones, silanes, fluorinated polymers or any combination thereof. For example, the water repelling agent precursor may be a mixture of the water repelling agent component and any suitable solvent. Typical solvents used may include water and/or acetic acid.

In addition, the water repelling agent precursor may further comprise a wetting agent, cross-linking agent, fillers additive, dyeing auxiliary, sizing residue, softening agent, other surface-active compounds or a combination thereof. In the current process, treating a starting article with a water repelling agent precursor may include any suitable method that results in the uniform distribution of the water repelling agent precursor throughout the outer and inner layers of the starting article to form a treated article. For example, such methods may include the application of said water repelling agent precursor by immersion treatment or by the application of an inert plasma of the water repelling agent to a plasma-activated starting article or combinations thereof.

Treating the starting article with the plasma treatment method disclosed herein improves the feel and appearance of the resulting water repelling article compared to a starting article treated using an immersion treatment method. Without wishing to be bound by theory, the improved feel and appearance of the resulting water repelling article may be attributed to the low temperature conditions that can be used in the subsequent curing step of the plasma-treated article. When a starting article is subjected to an immersion treatment, it may be necessary to subject the starting article to a preparation step that removes surface impurities. Any suitable method to remove said surface impurities may be used, for example, scouring the starting article or performing a detergent wash. Without wishing to be bound by theory, removing surface impurities from the starting article may enable efficient penetration of the water repelling agent precursor throughout the starting article during treatment.

The starting article may be immersed in the water repelling agent precursor agent solution for a period of from 10 seconds to 20 minutes, such as 1 minute to 5 minutes. In general, the temperature of the water repelling agent precursor solution will be between 10° and 50°C, such as from 15° to 30°C, e.g. 20°C. The pH of said solution may be from 5.0 to 7.0 and the water repelling agent precursor may be present in the water repelling precursor agent solution in a concentration of from 30-50 g/L, optionally, a wetting agent may also be present in the solution at a concentration of from 1 to 10 mL/L, such as 5 mL/L. When a starting article undergoes immersion treatment with a water repelling agent precursor to form a treated article, an excess of the water repelling agent precursor may be present when the article is removed from the immersion (e.g. the excess may be within the outer material, inner material and/or on the surface of the treated article). This excess water repelling agent precursor may be extracted using any suitable method to form an extracted article. The extracted article may be formed, for example, by feeding the treated article through a padding roller and/or subjecting the treated article to centrifugation.

In particular, a suitable method of removing excess water repelling agent precursor to form a treated article may include feeding the treated article between at least one padding roller to extract excess water repelling agent precursor out from the treated article. The padding roller 10 may be a soft rubber padding roller, having a soft rubber pad 20 (see Figure 1 ). More in particular, the padding roller may have an International Rubber Hardness Degree (IRHD) of 45-55. A series of padding rollers may be used to optimise the amount of excess water repelling agent precursor removed. Alternatively, the treated article may be fed through the padding roller multiple times to remove excess water repelling agent precursor.

Suitable rollers for use in the processes described herein are capable of applying a pressure range from 0.75 to 1.25 bar (0.075 to 0.125 MPa).

The extracted article may have a wet pick-up percentage (%) of 40-90%. in particular the wet pick-up percentage may be 40-65%, 55-70%, 65-90%, 50-90%, 80-90%, 40-50%. The wet pick-up percentage of an extracted article can be determined using the following equation:

Wet pick-up percentage (%) = ((weight of extracted article - weight of starting article) / weight of stating article) x 100

In certain cases, the extracted article following the removal of the excess water repelling agent precursor by the means discussed above may result in an uneven amount of said agent on the surface of the extracted article. In such cases, spray coating of the extracted article with the water repelling agent precursor may be used to rectify this unevenness.

When plasma treatment is used, the starting article is subjected to a low pressure and temperature plasma treatment, followed by the application of an atomised version of the water repelling agent precursor in a low temperature and low pressure plasma environment.

The plasma treatment first requires that the starting article is placed into a low pressure environment (e.g. from 0.10 to 0.5 mbar, such as from 0.12 to 0.45 mbar, or more particularly, from 0.2 to 0.5 mbar, such as 0.33 mbar at low temperature (e.g. < 100°C) in a reaction chamber. Subsequently, the starting article is activated by the admission of the process gas (e.g. nitrogen or oxygen) into the low-pressure reaction chamber and said gas is subsequently ignited to form a plasma (e.g. by the application of electrical power of from 180 W to 300 W, such as 200 W to 260 W, such as 250 W). The flow rate of the gas may be from 10-80 seem (e.g. from 30 to 70 seem, such as 60 seem), for example when measured at 0.3 mbar and 70°C. It will be appreciated by the skilled person that any suitable flow rate may be used, provided that it enables the coating of the article as described herein. As such, it will be appreciated that simple adjustments to the flow rate may be made when operating at a different temperature and pressure to ensure that this is accomplished. The starting article may be treated for at least 5 minutes, for example from 7 minutes to 20 minutes, such as 10 minutes) in the plasma. It will be recognised that the plasma formed under such conditions has a low temperature (e.g. < 100°C). Following the activation treatment, the plasma gas is evacuated and is replaced by an inert gas (e.g. argon) in the low-pressure reaction chamber, along with an aerosolised form of the water repelling agent precursor (e.g. introduced by the use of an atomiser into said reaction chamber). The inert gas is ignited to form a plasma (e.g. by the application of electrical power of from 100 W to 200 W, such as 125 W to 175 W, such as 170 W) and the plasma and water repelling agent precursor are allowed to interact with the starting article for at least 10 minutes (e.g. from 10 minutes to 1 hour, such as 15 minutes to 30 minutes, e.g. 20 minutes). The weight ratio of the water repelling agent to the inert gas may be 4:1 to 1 :2, such as 2:1 to 1 :1 , such as 1.5:1 or 1.46:1.

Where a starting article undergoes plasma treatment, with a water repelling agent precursor to form a treated article, removing excess water repelling agent precursor is generally not necessary.

Following the treatment of the article by immersion and/or plasma treatment, the article will undergo a drying step. In the case of an article that has been subjected to immersion, the drying step will follow the extraction step (e.g. where the water repelling agent precursor remains evenly distributed following extraction) or the spraying step (e.g. when the water repelling agent is unevenly distributed following extraction). While any temperature under the curing temperature of the water repelling precursor may be used, it is preferred that the temperature used to dry the treated/extracted article is under 100°C. For example, the treated or extracted article may undergo drying at a temperature of 80-100°C for 20-30 minutes.

While any oven may be used, it is preferred to use a convection-type curing oven with closed heat elements. This type of heating element may help to prevent yellowing of articles dried therein. The treated or extracted article must undergo a suitable method of curing to provide the water repelling article. Suitable methods of curing include heat curing, ultraviolet radiation curing, chemical curing, electron beam curing or any combination thereof. Further, examples of heat curing include infrared curing, microwave curing, hot air impingement or any combination thereof.

Heat curing may be performed under any suitable conditions, for example, at a temperature of 110-150°C. In particular, the heat curing may be performed at a temperature of 110- 125°C, 130-145°C, 125-135°C, 115-150°C, 110-145°C, 40-145°C, 40-150°C. Even more in particular, the heat curing may be carried out at a temperature of 110-145°C. In addition, suitable conditions may include heat curing at a temperature as defined above for 2-5 minutes. In order for curing to occur, the temperature must be at least 110°C and/or the time greater than or equal to 2 minutes, otherwise the material will not have good wash durability. If the curing temperature is more than 150°C (e.g. more than 145°C) and/or the time is greater than 5 minutes, then the article may have a harsh hand-feel and may suffer from yellowing, neither of which are desirable for aesthetic reasons.

Upon curing of the treated or extracted article, the impregnated water repelling agent precursor undergoes a chemical transformation to provide the water repellent article impregnated with a water repelling agent. Without being bound by theory, this chemical transformation may include cross-linking of the water repelling agent's precursor component polymer chains.

Experimental Section

Example 1 - Immersion Preparation of Water Repellent Articles Example 1a - Immersion Preparation of 2D Fabric, Foam Sheet or 3D Foam Cup Water Repellent Articles

A chemical solution containing OLEOPHOBOL™ CP-C fabric protector (a dispersion of fluoroacrylate polymers) at a concentration of 40 g/L, PHOBOL™ XAN at a concentration of 5 g/L and INVADI E™ at a concentration of 5 mL/L was prepared. The chemical solution was maintained at a pH 7 (±0.7) by adding acid before being used in a chemical bath. A suitable article, in this case a bikini bra cup, was immersed into the chemical bath for approximately 5 minutes with manual agitation. During this immersion step 7%, 1% and 1% of the original amounts of OLEOPHOBOL™ PHOBOL™ XAN and INVADINE™ were consumed.

Subsequently, the article was removed from the chemical bath and the excess chemical solution was removed by extraction. Extraction was performed using a padded roller (for example a pad roller hydro-extractor), having an International Rubber Hardness Degree 50 and at a pressure of 0.1 MPa to provide an extracted article with a wet pick-up percentage of approximately 80%. The extracted article was then subjected to drying at 100°C for 25 minutes in a convection oven with covered heat elements. After cooling, the dried article was then heat-cured for 5 minutes at 145"C to provide a water repellent article. The resulting water repellent article was then subjected to the water repelling performance tests as described below.

Example 1b - Immersion Preparation of Complex 3D Textile Water Repellent Articles (e.g. High Depth Foam Cup or Finished Garments) A chemical solution containing OLEOPHOBOL™ CP-C fabric protector (a dispersion of fluoroacrylate polymers) at a concentration of 40 g/L, PHOBOL™ XAN at a concentration of 5 g/L and INVADINE™ at a concentration of 5 mL/L was prepared. The chemical solution was maintained at a pH 7 (±0.7) by adding acid before being used in a chemical bath. A suitable article, in this case a bikini bra cup, was immersed into the chemical bath for approximately 5 minutes with manual agitation. During this immersion step 7%, 1 % and 1 % of the original amounts of OLEOPHOBOL™ PHOBOL™ XAN and INVADINE™ were consumed.

Subsequently, the article was removed from the chemical bath and the excess chemical solution was removed by extraction. Extraction was performed using a centrifuge hydro- extractor (centrifuge diameter ~ 800 mm) at ~ 900 revolutions per minutes (RPM), to provide an extracted article with a wet pick-up percentage of approximately 80%. Optionally, additional chemical solution may be applied to selected areas of the extracted article, via chemical spraying, to ensure the even distribution of the chemical solution across the entire article.

The extracted article was then subjected to drying at 100°C for 25 minutes in a convection oven with covered heat elements. After cooling, the dried article was then heat-cured for 5 minutes at 145°C to provide a water repellent article. The resulting water repellent article was then subjected to water repelling performance tests as described below.

Example 2 - Plasma Preparation of Article

A bikini cup was prepared with a pre-formed foam inner material having 85% closed cells and 15% open cells and a fabric covering. Said cup was subjected to the following treatment steps.

Stage Duration Conditions

Pressure 0.33 mbar /

Vacuuming 5 Min Plasma generator Power

Ow / No gas

Pressure 0.33 mbar /

Activation 10 Min Plasma generator Power

250W / gas used N₂

Pressure 0.33 mbar /

Coating 20 Min Plasma generator Power

170W / gas used Argon In the coating step, the amount of gas used was 3.57 g, while the water repelling agent precursor was present in an amount of 5.36 g in the reaction chamber.

Alternatively, the bikini cup was subjected to the following treatment steps.

The alternative method provided a bikini cup having substantially identical properties.

The flow rate of the gas in the activation and coating steps for the plasma treatments described above was 60 seem. WATER REPELLING PERFORMANCE TEST

A water repelling performance test was performed to assess the water repelling performance of an untreated specimen (i.e. a bikini foam cup covered in fabric that has not been subjected to any treatment), a water repelling specimen produced via plasma treatment (i.e. Example 2; plasma specimen) and a water repelling specimen produced via immersion treatment (i.e. Example 1 ; immersion specimen). The tests were carried out under the same conditions (i.e. humidity and temperature) and the specimens were conditioned prior to testing as set out below. The test was carried out according to following step:

1. The untreated specimen, and a specimen made according to each of Example 1 and Example 2 were dried in an air conditioned room for 1 day at a temperature of

24^°C and relative humidity of 65-67. 2. The dry specimens were then weighed.

3. The specimens were then dipped into a 15cm deep water tank (containing purified water) for 15 minutes. A metal paper weight was used to ensure that the specimens were fully immersed in the water. 4. Once taken out of the tank the specimens were allowed to drip for 5 minutes.

5. Specimens were then weighed again.

6. The specimens were then hung in an air conditioned room at 24^°C.

7. The weight of the specimens were then measured at 15 minute intervals.

As illustrated by Figure 3, the plasma specimen demonstrates a superior water repelling performance compared to the immersion specimen (ART as referred to in Figure 3), which in turn is superior to an untreated specimen.

CONTACT ANGLE TEST A cup (outer and inner layer) made using the immersion method (e.g. as described in Example 1 b) was provided. The cup was divided into six notional sections, as illustrated by Figure 4. A water droplet of 1/20^th of a mL was deposited onto each section and the contact angle was measured. The outer layer was then stripped off the cup and the contact angle was measured as described before for water droplets in direct contact with the inner material. The results are summarised in Table 1 and Figure 5.

As shown in the Table and Figure 5, the contact angles for the inner and outer layers are greater than 100 and less than 120 degrees. A contact angle of greater than 100 degrees is indicative of good water repeilency. Therefore, this test demonstrates that the water repelling agent is evenly distributed throughout the inner and outer layers of the cup.

BLIND TESTS This test was carried out with the purpose of assessing the change in the hand feel of a garment after application of a water repellent finish, either in chemical form or plasma form. One product (a bikini bra) was left untreated, while one product was treated with plasma and another with wet chemicals. Two sets of samples were prepared in this manner. Each set including a Regular Garment (untreated), a Plasma treated Garment and a Chemical treated garment.

The samples were provided to a set of 10 people who were able to provide an expert opinion on the hand feel of the garments. This group of people consisted of experts from quality, product development and the laboratory. The assessors were not informed of the condition of the products and were asked to compare the hand feel of treated and untreated samples blindly in the two sets of samples.

For each product, the hand feel was assessed and rated. They assessors were asked to rate the hand feel on a scale of 1 -5, where 1 is the harshest feel, while 5 is the softest. Table 2 illustrates the results obtained from the experts for each product and the summarized hand feel observation for the two treatment options.

Assessor Sample Set Regular Plasma Wet

1 (Prod Dev) 1 3 5 1

2 3 5 1

2 (Quality) 1 5 3 1

2 5 3 1

3 (Quality) 1 1 5 3 Assessor Sample Set Regular Plasma Wet

4 (Quality) 1 1 5 3

2 5 3 1

5 (Quality) 1 5 1 3

2 3 1 5

6 (Quality) 1 3 5 1

2 3 5 1

7 (Lab) 1 5 3 1

2 5 1 3

8 (Lab) 1 5 1 3

2 5 1 3

9 (Lab) 1 1 5 3

2 3 5 1

10 (Lab) 1 3 5 1

2 5 3 1

Average 3.7 3.4 1 .9

Standard Deviation of Sample 1.5 1.7 1.2

Table 2

The hand-feel of the plasma treated sample is similar to the hand-feel obtained for an untreated sample, while the hand feel for the chemically immersed product is considerably worse than the untreated and plasma treated samples.

Claims

1. A process for forming a water repelling article for use in clothing, the process comprising the steps of:

2. The process according to Claim 1 , wherein the treatment step comprises an activating step, where the starting article is treated with an activating plasma to generate an activated article and a coating step, where the activated article is treated with an inert plasma and the at least one water repelling agent precursor to generate the treated article.

3. The process according to Claim 2, wherein the activating plasma is generated from nitrogen or oxygen gas, optionally wherein the flow rate of the gas is from 10 to 80 seem (e.g. 60 seem).

4. The process according to Claim 2 or Claim 3, wherein the activating plasma is generated under a reduced pressure and using a power of from 200W to 300W (e.g. the power is 250W), optionally wherein the reduced pressure is from 0.1 to 0.5 mbar (e.g. such as from 0.2 to 0.5 mbar or from 0.12 to 0.45 mbar).

5. The process according to any one of Claims 2 to 5, wherein:

(a) the inert plasma is generated from argon gas; and/or

(b) the inert plasma is generated under a reduced pressure and using a power of from 150W to 200W (e.g. the power is 70W), optionally the reduced pressure is from 0.1 to 0.5 mbar (e.g. such as from 0.2 to 0.5 mbar or from 0.12 to 0.45 mbar); and/or

(c) the flow rate of the gas is from 10 to 80 seem (e.g. 60 seem).

6. The process according to Claim 1 , wherein treating the starting article comprises immersing the starting article in the at least one water repelling agent precursor.

7. The process according to Claim 6, wherein a step of removing excess water repelling agent precursor is performed before curing the treated article.

8. The process according to Claim 7, wherein removing excess water repelling agent precursor comprises feeding the treated article through a roller and/or subjecting the treated article to centrifugation to provide an extracted article, optionally, wherein the extracted article is sprayed with the at least one water repelling agent precursor.

9. The process according to any one of the preceding claims, wherein a drying step is performed before curing the treated article.

10. The process according to any one of the preceding claims, wherein the at least one water repelling agent precursor comprises paraffin waxes, silicones, silanes, fluorinated polymers, non-fluorinated water repelling polymers or a combination thereof, or the water repelling agent comprises fluorine and carbon atoms, optionally wherein the at least one water repelling agent precursor is at least one fluoroacrylate polymer

11. The process according to any one of the preceding claims, wherein the at least one water repelling agent precursor in step (b) further comprises at least one wetting agent.

12. The process according to any one of the preceding claims, wherein the article has a curvilinear topography, optionally wherein the article has a cup shape.

13. The process according to any one of the preceding claims, wherein the process further comprises the step of forming a garment that comprises said article, optionally wherein the garment is a shoe, medical equipment (e.g. a casting liner inner), a bra, a brassiere, swimwear, sportswear or casual wear.

14. The process according to any one of the preceding claims, wherein the curing in step (c) comprises infrared curing and/or microwave curing.

15. The process according to any one of the preceding claims, wherein the at least one outer material completely covers the inner material.

16. The process according to any one of the preceding claims, wherein at least part of the starting article has a fixed three-dimensional shape that is complementary in shape to one of the group consisting of hands, arms, the head, shoulders, buttocks, breasts, knees, elbows and feet.

17. A water repelling article for use in clothing comprising:

at least one inner material; and

at least one outer material that substantially covers the inner material,

wherein the article:

further comprises at least one water repelling agent uniformly distributed throughout the article; and

the article has a resiliency deformable non-flat three dimensional shape.

18. The article according to Claim 1 , wherein the at least one outer material completely covers the inner material.

19. The article according to Claim 17 or Claim 18, wherein the article has a curvilinear topography, optionally wherein the article has a cup shape.

20. The article of any one of Claims 17 to 19, wherein:

(a) the article forms part of a shoe, medical equipment (e.g. a casting liner inner), a bra, a brassiere, swimwear, sportswear or casual wear; and/or

(b) at least part of the article has a fixed three-dimensional shape that is complementary in shape to one of the group consisting of hands, arms, the head, shoulders, buttocks, breasts, knees, elbows and feet.

21. The article of any one of Claims 17 to 20, wherein the article has an improved texture in a blind test compared to a water repelling article prepared in a process comprising the step of immersing said article into a water-repellant precursor solution.

22. The article of any one of Claims 17 to 21 , wherein the at least one water repelling agent has been impregnated within the article following plasma activation of said article to provide an improved feel and appearance.

23. The article according to any one of Claims 17 to 22, wherein:

(a) the at least one inner material is an open or closed-cell foam; and/or

(b) the at least one outer material is a fabric, optionally wherein the fabric is a laminated fabric.

24. The article according to any one of Claims 17 to 23, wherein the at least one water repelling agent comprises paraffin waxes, silicones, silanes, fluorinated polymers, non- fluorinated water repelling polymers or a combination thereof, or the water repelling agent comprises fluorine and carbon atoms, optionally wherein the water repelling agent is at least one fluoroacrylate polymer.