• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention includes a method of providing the outer, inner and inner surfaces of a footwear with a water and / or oil repellent coating by means of a low pressure plasma polymerization deposition process, by gassing the footwear beforehand. this deposition process.
    公开号:BE1022765B1
    申请号:E2015/5032
    申请日:2015-01-21
    公开日:2016-08-30
    发明作者:Eva Rogge；Filip Legein
    申请人:Europlasma Nv；
    IPC主号:
    专利说明:

    Method to make a footwear with improved wearing comfort, and footwear made according to this method
    Technical domain
    The present invention relates to footwear with improved comfort for the wearer or user, such as a decrease in the absorption of fluid in the textile material from which the footwear is made, which leads to a decrease in weight gain during use and a quick-drying effect, and further as dryness keep the wearer's feet. A quick drying effect has clear advantages for running and water sports. When the footwear is used in colder or wet environments, such as trekking, skiing, mountain climbing and the like, a dry textile material will also prevent the feet from cooling, and become cold and damp. The present invention is also related to innovative ways of producing such footwear.
    BACKGROUND OF THE INVENTION
    The footwear industry is a large industry. Footwear for a variety of uses is produced and sold around the world. The design and structure of the footwear can be different for each application. The materials used to produce the footwear can also differ.
    Sport shoes must, for example. are light and breathable and have quick-drying properties for optimum sweat and moisture regulation, and are often made of synthetic materials and porous structures. During the use of sports footwear, weight gain due to water absorption is not desirable at all. The footwear must also be breathable to prevent damp and damp feet, since this causes friction of the skin with the sock and the shoe, leading to pain and blisters at the points of friction of the foot.
    Sports shoes for water sports should have a quick drying effect after use, and a reduced weight gain during use for optimum wearing comfort as this way the feet stay dry and the footwear does not get heavier due to water saturation.
    Reduced weight gain in terms of reduced water uptake, and a quick drying effect are particularly suitable for marine water sports, since the salty water tends to leave marks on the footwear during drying. If little or no water is absorbed, no drying spots will occur.
    Personal protective equipment footwear must be fluid repellent and resistant to penetration of harmful liquids, and often have reinforcements to protect the foot from injury.
    Trekking, skiing and mountaineering footwear must be as watertight as possible to reduce water ingress into the textile material from which the footwear is made, since wet footwear can lead to wet or damp feet, and therefore cold feet in cold environments.
    Fashion and fashion footwear is all about design and wearing comfort. This type of footwear can be made from a wide range of materials. Wearing comfort is assessed by the end users in function of the support during wearing, breathability, and dry and warm but not damp or wet feet, low weight, and protection against stains on the footwear. For example, water absorbed while walking in the snow, rain or on the beach can leave stains after drying.
    Several documents describe a way to keep the feet dry from moisture, rain and wetness in the atmosphere. Other documents describe ways to reduce weight gain during use, such as walking, pulling and the like. EP0263665 discloses a watertight, water vapor permeable fabric structure wherein a porous PTFE membrane, which is watertight and water vapor permeable, is laminated to a non-watertight fabric construction made of polyester (PES), polyamide (PA, nylon), and the like. The structure can be used for hats and footwear. When used in footwear, the non-waterproof fabric structure is the structure on the outside and the membrane on the inside and is invisible to the end user. Footwear made with this structure keeps the feet dry. However, the outer material is not waterproof and can therefore absorb liquids, water, rain and the like, and increase in weight. Furthermore, this outer material can cool the feet when it gets wet, especially in colder conditions. JPH0670804 (A) describes the use of a watertight, water vapor permeable bag-shaped or stocking-like structure that is placed in the footwear to protect the foot from getting wet. The bag-shaped structure is a laminate of a polyurethane film or membrane and a protective textile structure. The bag-shaped structure has a fixed position inside the footwear. JPH0759604 (A) describes a similar structure that can be removed from the footwear for washing, drying, etc. The outer fabric can be non-watertight and can absorb liquids and moisture and thus increase in weight. In addition, liquids penetrated into the outer structure can accumulate in the space between the bag-shaped structure and the outer textile, which may allow the feet to cool down while wearing the footwear, particularly in colder environments. The breathability of such membranes is limited in order to guarantee sufficient watertightness. However, a limited breathability will limit the discharge of heat and moisture coming from the feet to the outside. US6065227 describes a footwear that consists of a watertight membrane lining on the inside of an upper part of a footwear. The bottom piece, top piece and the liner are joined together by seams which pierce the waterproof liner. The seams are sealed with a waterproof ribbon. Footwear according to US6065227 will keep the feet dry. However, the outer material can absorb liquids, water, etc., and can increase in weight. Further, when this outer fabric is moist, it can cause cooling of the feet, particularly in colder environments and especially when the outer material is leather, since wet leather has a cold feel. The combination of membrane lining and seams limits the breathability of the footwear, which can limit the removal of heat and moisture coming from the feet to the outside. WO2007 / 007369 describes footwear that consists of a watertight membrane liner placed on the inside of the footwear and glued to the outer material of the footwear. The production process is quite complex, and a water-resistant adhesive is required. Footwear containing this structure will keep the feet dry. However, the outer material is non-water-tight, and can therefore absorb liquids, water, etc., and can increase in weight. Further, when this outer fabric is moist, it can cause cooling of the feet, particularly in colder environments and especially when the outer material is leather, since wet leather has a cold feel. The combination of membrane lining and seams limits the breathability of the footwear, which can limit the removal of heat and moisture coming from the feet to the outside. WO2007083124 describes a method of depositing a coating on a surface of a garment, accessory (e.g., a shoe), and the like, via low pressure plasma polymerization. The technical problem that is solved here is the protection against contamination of liquids, and resistance to the appearance of odors, and color fastness. The coating is deposited on the surface of the material to reduce the penetration of liquids in the most normal conditions. The document does not provide information about keeping the feet dry and preventing the feet from cooling down. WO2009056809 describes a method to reduce the penetration of water over time. A protective coating is deposited on the surface of the footwear or on the top produced by means of low pressure plasma polymerization. The cover layer would be durable and watertight to reduce the ingress of water over time during use, while maintaining the breathability of the footwear. Although the penetration of water is reduced, the document provides no information about keeping the feet dry and preventing the feet from cooling down. WO2009010741 describes a method for providing a footwear with a liquid-repellent coating via low-pressure plasma polymerization. The coating is deposited on the entire footwear, including closures, laces, zippers, etc., in order to reduce the absorption of liquid during use, thereby reducing the weight gain of the footwear during use. The document provides no information about the breathability of the treated footwear, and about keeping the feet dry and preventing the feet from cooling down. WO2009010738 describes a method of producing a footwear with a liquid-repellent covering layer and a liquid-absorbing foot bed that supports the foot. A liquid-repellent coating is deposited on at least a portion of the surface of the footwear via low-pressure plasma polymerization. A liquid-absorbing footbed or insole (insole) is placed in the footwear after the covering layer has been deposited, to absorb the sweat which is subsequently removed via the outer material of the footwear. The document suggests that a hydrophilic interior and a hydrophobic exterior are recommended for optimum wearing comfort. The technical problem that is solved here is how the feet can be kept dry from the inside. However, the document provides no information about a decrease in weight gain, about keeping the feet dry from outside fluids, and about preventing the feet from cooling due to a damp outer material. In particular, the method described in this document does not protect the textile material of the footwear against the absorption of sweat from the user's foot, ie sweat from the foot can be absorbed from the inside by the textile material of the upper part of the footwear since the method of WO2009010738 does not guarantee that there is an essentially water-and / or oil-repellent coating on the inside of the footwear all the way into the tip. Ulcer is also absorbed by the fluid-absorbing footbed or insole. The method of WO2009010738 does not lead to the coating of the internal surfaces.
    This sweat absorption has a number of disadvantages, such as: - The foot may come into contact with the wet textile material and with the wet insole during use. Since the wetness is absorbed through the textile material, it is in the vicinity of the outer surface and can cool rapidly, leading to a wet and cold feel for the wearer, a feel that may be present for a long time due to the high thermal capacity from sweat. Furthermore, an excess of sweat cannot be evaporated, but it cools and remains as a cold layer on the wearer's foot. - The sweat vapor that penetrates through the textile from the inside to the outside can condense and become absorbed by the interior surfaces of the textile. Since a cover layer is deposited on the outside of the textile, this cover layer will prevent the condensed sweat vapor from leaving the footwear. Consequently, the textile material can cool quickly, which will lead to wet and cold-feeling feet. - Unwanted odors remain longer in the footwear, since the sweat inside the textile material and in particular in the insole is not easily evaporated. - The increase in weight due to moisture is only slowed down, but continues: regardless of whether the footwear gains weight by absorbing water from the outside or from the inside, the upper textile on the internal surfaces will eventually become saturated with liquid, that can only evaporate very slowly.
    Furthermore, a coating applied to an outer surface of a footwear is more susceptible to wear.
    Although the above documents, available in the professional knowledge, offer a solution to a single problem - namely keeping feet of liquid, water and humidity in the atmosphere, or reducing the weight gain of the shoe from the outside - all these succeed documents not in it to solve multiple technical problems with a single solution. However, the customer is looking for footwear that does not increase in weight when used, that can keep the feet dry and that has an outer textile that stays dry so that the feet do not cool.
    The current application improves prior art documents by providing a method that, surprisingly, solves all these technical problems at once with a single method. This makes no sense in the light of the prior art, since the prior art solutions to keep the feet dry greatly limit the breathability of the footwear, and the prior art solutions to reduce weight gain do not offer a solution to dry the feet. since only the outside of the textile material of the upper part of the footwear is covered.
    Combination of these two prior art solutions would result in footwear with limited breathability, which does not provide a solution for sweat produced on the inside. Moreover, water penetration would not be maximally reduced since only the outside of the upper part of the footwear would be provided with a coating and the inside of the upper part would therefore not be protected against liquids.
    The technical problems solved with the method of the present invention are: Keeping the feet of other liquids, such as rain and snow and the like, dry. - Maintaining the breathability of the footwear, and keeping the feet of sweat produced during use dry. - Reduction of the weight increase of the upper material as a result of the absorption of fluid through the thickness of the upper material of the footwear during use, which reduces in a quick-drying effect. - Prevent the feet from cooling. - Ensure that evaporated sweat does not condense on the internal surfaces of the footwear, e.g. the internal surfaces of a fabric, mesh or foam of the footwear, thereby preventing liquid sweat from being absorbed by the footwear, thereby reducing the weight gain.
    Summary of the invention
    The current application solves the technical problems mentioned above by providing a method that can selectively coat the footwear from the outside to the inside, whereby the coating is not only deposited on the surface of the outer material - textile, mesh, foam with open structure, but also velor, leather and the like - but where the cover layer also fully penetrates the structure of the outer material so that the cover layer is deposited on the inner surfaces of the material - e.g. the textile material that is under decorations and reinforcing plastic structures - and also on the inside of the footwear. Consequently, the coating deposited according to methods of the present invention remains present longer than coatings deposited via techniques already described.
    Brief description of the figures
    Figure 1 shows the front view of an example of a low pressure plasma machine according to the present invention. This low pressure plasma system has a volume of 1836 liters and is designed to handle up to 40 - 60 pairs of footwear in a single process run.
    Figure 2 illustrates the water contact angle as a function of the number of abrasion cycles.
    Figure 3 illustrates a weight comparison after an immersion test.
    Figure 4 illustrates the drying time of a foam structure after immersion.
    Figure 5 illustrates the drying time of faux fur (A4 format)
    Figure 6 shows the water vapor permeability results. Figure 7 shows the air permeability results
    Figure 8 shows, from left to right: untreated, plasma treated and conventionally treated.
    Detailed description of the invention
    As used herein, the following terms have the following opinions: "A", "de" and "it" as used herein refer to both singular and plural unless the context clearly dictates otherwise. For example, "a compartment" refers to one or more compartments. "Approximately" as used herein refers to a measurable value such as a parameter, an amount, a duration, and so on, and is used to include variations of +/- 20%, more preferably +/- 10% or less, even more preferably +/- 5% or less, more preferably +/- 1% or less, and even more preferably +/- 0.1% or less relative to the specified value, to the extent such variations are applicable to be performed in the present invention. However, it is to be understood that the value to which "approximately" refers is specifically mentioned. "Include", "comprising" and "includes" as used herein are synonyms for "containing", "containing", "contains", and "consist of", "consisting of", "consists of" and are inclusive terms which specify the presence of what follows, e.g. a component, and do not exclude the presence of additional, non-listed components, aspects, elements, members, parts or steps, known in the professional knowledge or stated herein.
    The numerical intervals listed by end values contain all values and fractions within that range, as well as the stated end values.
    The term "weight percent", throughout and throughout the specification, except otherwise defined, refers to the relative weight of the respective component based on the overall weight of the formulation. "Footwear" such as a "shoe" as described herein describes a product worn on the feet. Footwear can consist of parts that are easy to identify, such as a sole, an outer sole, an insole, an upper, a fastener such as a loop and hook type fastener such as Velcro® or a lace, decorations, stitching, reinforcements, etc. The parts are assembled into a footwear in various ways, including ways for permanent and semi-permanent assemblies, such as "pouring over", gluing and stitching, or methods for releasing a whole, such as laces. In the context of the present invention, a footwear may refer to a complete footwear - including closures, laces, outsole, insole, decorations, stitching, reinforcements, and the like - or, if one or more zones are shielded from the cover, may refer to parts or a semi-finished product of the entire item, where this is clearly stated. In preferred embodiments of the present invention, the footwear includes a component that is at least partially breathable, that is, at least water vapor permeable or permeable to evaporated sweat and preferably also permeable to air, such as a textile, mesh, and / or foam, and / or the footwear comprises a component that is capable of absorbing a liquid, in particular water or sweat, and / or which is permeable to a liquid, in particular water or sweat. Non-limiting examples of such footwear are: sports shoes, sports shoes for water sports such as wet-suit footwear or wet-suits containing shoes, personal protection footwear (PPE), trekking footwear, skiing and mountain climbing, designer footwear, shoes, boots, sandals, closed shoes, open shoes, etc.
    The term "inner surface" as used herein refers to the inner surface of the footwear that may be, or is intended to be, in contact with a wearer's foot. The term "outer surface" as used herein refers to the outer surface of the footwear that is in direct contact with the atmosphere. The term "inner surface" as used herein refers to surfaces that are not directly exposed to the base of the wearer and not directly exposed to the atmosphere. Examples of internal surfaces are surfaces between the textile material of the upper part of the footwear and decorations or reinforcements attached to the inner surface or outer surface of the upper part, surfaces present inside the textile material such as side surfaces of pores of the textile material, or surfaces defined by open cells inside the upper part of the sole, e.g. open cells of foam material incorporated in the construction of the footwear, for example as used for the tongue of the footwear.
    The terms "fumigation" and "fumigation" as used herein are used interchangeably and refer to a process to remove gases and liquids, more particularly within the context of this document, to remove fouling, gases and liquids from footwear or parts of footwear, so that a good adhesion between the cover layer and at least a part and preferably the entire internal surface of the footwear.
    The present invention solves the technical problems described above by providing a method that selectively provides the footwear with a water and / or oil-repellent covering layer from the outside to the inside, the covering layer not only covering the surface of the outer material is deposited - textile structure, mesh, open foam, but also velor, leather and the like - but also the structure of the outer material penetrates so that the cover layer is also deposited on the inner surfaces of the material and on the inner surface of the material. The water and / or oil-repellent coating is deposited by means of low pressure plasma polymerization.
    In contrast to the state of the art that appears to indicate a hydrophilic inner surface of the footwear for moisture regulation, e.g. by using a hydrophilic, liquid-absorbing insole, the present invention ensures sufficient breathability of the treated material of the footwear to eliminate the need for a hydrophilic inner surface.
    The advantage of selectively providing the cover on certain zones is that this allows optimum protection for the footwear. The applicant surprisingly discovered that in some cases it is not necessary, and sometimes even disadvantageous, to coat certain areas or components of the footwear.
    Applicants have discovered that with a method according to the present invention it is possible to deposit a water and / or oil-repellent covering layer through the entire upper material of the footwear, from the outside to the internal surfaces. The applicants have surprisingly discovered that this makes it possible to deposit a coating on the upper material covered with decorative and / or functional plastic strips and pieces, for example as reinforcement for the ankles and the heel of the wearer, or for the logo or the brand name of the footwear seller. This is an unexpected result of the present invention and method, since the decorative and / or functional plastic pieces cover part of the outer surface of the upper material from which the footwear is made, so that these covered surfaces / zones are not directly exposed to the plasma .
    Consequently, the advantage of the method according to the present invention is that a coating is not only deposited on the surface of the upper material directly exposed to the plasma, but also that a coating will be deposited on the upper material that is protected from direct exposure to the plasma. This is a clear improvement over the prior art, and contributes greatly to a decrease in water penetration and thus to a decrease in weight gain over time during use, and to a quick drying effect, since that when the coating is on the outer surface would be damaged, the inner and inner surfaces are still coated and prevent the absorption of liquids through capillary effects. Moreover, the coated inner and inner surfaces make the use of liquid-repellent membranes as described in the prior art superfluous, so that with the method of the present invention the breathability of the footwear is retained.
    It is a first aspect of the present invention to provide a method to obtain a water and / or oil repellent coating on footwear to keep the feet dry while at the same time reducing the weight gain of the material from which the footwear is made, and also the drying time is reduced (so-called quick-drying effect), and wherein the breathability of the material is retained, the cover layer being selectively deposited by means of low-pressure plasma polymerization.
    It is a second aspect of the present invention to provide a method to obtain a water and / or oil repellent coating on footwear to keep the feet dry while at the same time reducing the weight gain of the material from which the footwear is made, and also the drying time is reduced (so-called quick-drying effect), and wherein the breathability of the material is retained, the cover layer being deposited through the material from the outer surface of the material to the inner surfaces of the material via low-pressure plasma polymerization such that the upper material of the footwear that is covered with decorative and / or functional plastic pieces is also provided with a low-pressure plasma coating for improved protection against the ingress of liquids.
    It is a third aspect of the present invention to provide a footwear with a water and / or oil-repellent coating that keeps the feet dry and at the same time reduces the weight gain of the material from which the footwear is made, and also reduces the drying time (so-called quick-drying effect), and wherein the breathability of the material is retained, the cover layer being selectively deposited through the material from the outer surface to the inner surfaces of the material by means of low pressure plasma polymerization so that also the upper material of the footwear covered with decorative and / or functional plastic pieces is provided with a low-pressure plasma coating for improved protection against the ingress of liquids.
    It is a fourth aspect of the present invention to provide a water and / or oil repellent coating that is selectively deposited through the material from the outer surface to the inner surfaces of the material by means of low pressure plasma polymerization so that also the upper material of the footwear covered with decorative and / or functional plastic pieces is provided with a low-pressure plasma coating for improved protection against the ingress of liquids, whereby the coating reduces the weight increase of the material from which the footwear is made, and also the reduces drying time (so-called quick-drying effect), while maintaining the breathability of the material and keeping the feet dry.
    Applicants have found that in order to achieve optimum protection in terms of keeping feet dry, reducing water absorption of the material from which the footwear is made for reduced weight gain, reduced drying time and non-cooling of the feet due to damp material, it is advantageous to selectively deposit the coating. The selective treatment can be done by preventing the coating from being deposited on one or more zones or components, or by removing one or more components from the footwear before depositing the coating. The removed components can be coated in a separate process for optimum results, or can remain untreated when there is no benefit or even a negative impact on performance when these components are coated.
    Applicants have further developed a method in which the cover layer is deposited through the material from which the footwear is made, from the outside to the inside, instead of merely covering the outside - as is typically done in the documents that state the position describe the technology. The applicants have surprisingly discovered that by depositing a coating on both the outer surface and the inner surface, the breathability of the material is not affected, while at the same time the increase in weight during use and the drying time after use are reduced (so-called quick-drying effect), and that the material of the footwear is protected against getting wet, so that the feet stay dry and water - a wet or damp footwear can lead to cold feet. Furthermore, the coating deposition method of the present invention also allows a low pressure plasma coating to be deposited on the upper material of the footwear covered by covering elements, such as decorative and / or functional plastic strips, stitching, printing, printing of brand name, in order to obtain improved protection against the penetration of liquids.
    In a first embodiment of the present invention, selective treatment is done by depositing a coating on the footwear without laces or other closures such that no coating is deposited on the entire footwear in the same process step. In production this can be done by performing the deposition step on a semi-finished product of the footwear, without closures or laces, after which the closures and laces in the footwear are placed in the production line. Alternatively, this can be achieved by removing the closures or laces from the footwear before performing the low pressure plasma polymerization process.
    When laces are used, they are preferably provided with a coating in a separate process, e.g. in another process chamber designed to handle a large amount of laces for a large flow. The applicants have surprisingly discovered that the optimum process for coating the laces and the optimum process for coating the footwear (without laces) may differ, since the materials of which both are made have a different structure. Laces are usually strong and round in diameter. Furthermore, the applicants have surprisingly discovered that when the laces are treated separately, the openings in the shoe where the laces are placed, and the surrounding material, such as the tongue, are more easily reached by the plasma and thus treated in a better, more uniform manner to become.
    Whether or not fasteners other than laces are treated in a separate process depends on the type of fasteners.
    The applicants have surprisingly discovered that for loop and hook type closures there is no advantage in depositing a coating thereon. When such closures are exposed to the plasma and provided with a liquid-repellent coating, the adhesive effect of the closures is reduced, resulting in footwear that is more difficult to close and therefore less comfortable to wear.
    Preferably, a selective deposition method according to the present invention will prevent a water and / or oil-repellent covering layer from being deposited on loop-and-hook type closures by depositing the covering layer on the semi-finished product of the footwear, before the loop -and-hook closures are stitched on the upper material of the footwear.
    An alternative way is to perform the selective deposition method according to the present invention where the hatch and hook closures are shielded from the plasma so that no water and / or oil repellent nano coating is deposited on these closures.
    The screening is preferably done with a non-textile material that allows a perfect screening of exposure to the plasma. Preferably, a flexible plastic adhesive tape or other type of adhesive tape, or paper is used to prevent a water and / or oil-repellent nano-coating from being deposited on the closures.
    In a second embodiment according to the present invention, the selective treatment is done by coating the footwear with the outer sole of the footwear being shielded from the deposition of a coating.
    This is preferably done in the production process by depositing a cover layer on the upper textile material before the outer sole is attached or over-molded around the upper textile material in a subsequent step.
    An alternative way is to shield and cover the outsole before polymer coating is carried out, for example by placing the shoe in a specially designed drawer after which the drawer is placed in the plasma chamber, and where the drawer is designed to expose exposure to avoid the outsole on the plasma. This can be done in yet another way by a shielding material, e.g. to place an adhesive tape or plastic structure on the outsole to avoid exposure to the plasma.
    The applicants have surprisingly discovered that it is more advantageous not to deposit a coating on the outer sole of the footwear, since the coatings of the present invention tend to lower the frictional resistance. In that case, if the outsole were to be treated, the low-friction coating could lead to slippery shoes, which in some cases could be dangerous, e.g. on slippery floors.
    In a third embodiment of the present invention, the cover layer is deposited through the material of which the upper part of the footwear is made, from the outside to the inside, so that the cover layer is deposited not only on the outside surface of the material, but also on the interior surfaces and the inner surface of the footwear.
    The applicants have surprisingly discovered that in this way a nano-coating is also deposited on the upper material of the footwear covered by the decorative and / or functional plastic tape, e.g. in areas where reinforcement is needed for improved comfort, such as the ankles.
    The upper material or upper textile of which the footwear is made preferably has not only a nano coating on the outer surface of the textile or material, but also throughout the entire upper material.
    This therefore greatly contributes to a reduction in the penetration of water, and thus to a reduction in the weight gain during use and the drying time of the footwear after use (fast-drying effect), since if the cover layer were damaged on the outer surface, the coating is still present on the inner surfaces and the inner surface, so that the absorption of liquids by capillary effects is prevented. Furthermore, treated inner surfaces and inner surfaces make the use of liquid-repellent membranes described in the art superfluous, so that the breathability of the footwear is preserved by the method of the present invention. This therefore keeps the feet dry, and since the material of the footwear will not get damp or wet, this will not lead to cold feet, resulting in an increased wearing comfort.
    Furthermore, the applicants have surprisingly discovered that the cover layer deposited through the material of which the footwear is made so that a cover layer is deposited in the core, on the internal surfaces, has no negative impact on the breathability of the footwear, as opposed to membranes which keep the feet dry but have a limited breathability.
    The thickness of the nano coating is of the order of nanometers, typically from 10 to 1000 nm, which is less than the average dimensions of the openings in a fabric, knitted fabric or even non-woven fabric, mesh or 3D foam structure used to fit the footwear. to make. The deposited coating covers the individual fibers and yarns without blocking the openings in the textile, mesh or foam.
    The water- and / or oil-repellent protective nano-coating is selectively deposited and down to the core of the material from which the footwear is made, by means of a low-pressure plasma polymerization process.
    The present invention relates to a low-pressure plasma polymerization apparatus for depositing coatings on footwear with high loading capacity. Such a low pressure plasma polymerization device comprises a vacuum chamber in which the plasma polymerization process can take place.
    More specifically, the present invention is about a low pressure plasma polymerization apparatus with a high loading capacity to deposit a coating on footwear, the apparatus comprising at least two pairs of electrodes, each pair of electrodes comprising a grounded electrode and a radio frequency (RF) electrode , to ignite a plasma and to deposit a plasma polymerized coating on footwear that can be placed between the grounded electrode and the RF electrode of each pair, the distance between the grounded electrode of the first pair and the RF electrode of the second pair is larger than 1 mm and smaller than 50 mm. The distance between the two electrodes of the same pair is preferably greater than 5 mm, more preferably greater than 100 mm, and preferably less than 500 mm, even more preferably less than 250 mm.
    The present invention relates to a low pressure plasma polymerization apparatus for depositing coatings on footwear with high loading capacity, the apparatus being configured to perform a method as described in this document, preferably an apparatus with at least two pairs of electrodes as above or further described in this document.
    Figure 1 shows an embodiment of a low pressure plasma device according to the present invention, wherein a method according to the present invention can be performed. The plasma chamber has a volume of 1836 liters, and has radio frequency electrodes 10 and grounded electrodes 11, which are positioned in a vertical manner that creates an advantageous plasma in the wider zones 12 between the electrodes, so-called slots.
    Preferably, at least one radiofrequency electrode 10 and a grounded electrode 11 of an adjacent pair of electrodes are positioned close to each other, at a distance of 1 mm to 50 mm, such as from 2 mm to 40 mm, such as from 5 mm to 30 mm, for example 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6 or 5 mm.
    Preferably, the distance between the grounded electrode and the radio frequency RF electrode of a pair of electrodes marks a wider zone, or a so-called "slot", and the distance is from 50 mm to 500 mm, such as from 100 mm to 450 mm, such as 120 mm to 400 mm, for example 400, 390, 380, 375, 370, 360, 350, 340, 330, 325, 320, 310, 300, 290, 280, 275, 270, 260, 250, 240, 230, 225, 220, 210, 200, 190, 180, 175, 170, 160, 150, 140, 130, 125 or 120 mm.
    Applicants have discovered that by using electrode pairs in the plasma chamber, each pair consisting of a radio frequency electrode 10 and a grounded electrode 11, an advantageous, stable and uniform plasma is generated in the slots.
    By using the electrode configuration of the present invention, the applicants have discovered that the coating deposited on the footwear is preferably removed with the laces and covered with the outsole so as not to deposit a coating there - for the above mentioned advantages - is more uniform than when a single-electrode arrangement is used on both sides of a lock as described in the prior art.
    Preferably, the device comprises slots between the electrodes of each pair, the slots preferably comprising means for placing one or more product holders at variable or different positions, e.g. at variable or different heights. In this way the device can be configured to handle a wide variety of types of footwear, such as high boots or low sandals. In particular, the device comprises one or more product holders which are placed in the slots, the footwear or the components of the footwear being placed on these product holders.
    In the slots 12, it is possible to place the product holders 13 horizontally, such as perforated drawers or containers, which contain the footwear to be treated, preferably with the laces removed and covered with the outsole so as not to deposit a coating there - because of the advantages mentioned above. Perforated drawers are preferably used.
    The plasma chamber of Figure 1 has 4 slots 12, and each slot can contain up to 8 drawers 13, and up to 4 pieces of footwear (2 pairs) can be placed on each drawer, preferably with the laces removed and covered with the outsole so as not to coating because of the advantages mentioned above - which gives a total capacity of 64 pairs of footwear.
    Preferably, a frame or other structure is used in the plasma chamber to hold the trays 13 in place and to ensure smooth loading and unloading of the plasma chamber before and after each process run.
    The number of drawers 13 in each slot 12 is preferably varied as a function of the type of footwear to be treated. Summer shoes are generally limited in height, and up to 8 drawers can be used per slot. When the height of the footwear, preferably with the laces removed and covered with the outsole so as not to deposit a coating there - for the above-mentioned advantages - exceeds the distance between two drawers 13, the plasma chamber according to the present invention allows that one or more drawers per slot are removed from the room. Consequently, the number of footwear items that can be treated in a single batch will decrease. For example, if 6 instead of 8 drawers are used per slot, the capacity will still be 48 pairs of footwear (2 pairs of footwear per drawer). In most production environments, this is still sufficient to implement the plasma chamber in the production line.
    Since footwear contains substantial amounts of textiles, plastics and / or other adhesives such as glue, footwear can contain significant amounts of moisture and wetness when placed in the plasma chamber. This can have a negative impact on the performance of the coating after depositing it, but can also have a negative impact on the time of a cycle. Therefore, applicants have discovered that a fumigation can be advantageous, particularly in the case where large numbers of footwear, preferably with the laces removed and covered with the outsole, in order not to deposit a coating there - for the above mentioned advantages - are treated should be, e.g. in mass production.
    Furthermore, the applicants have surprisingly discovered that a fumigation allows for a better penetration of the plasma polymerization coating into the core of the material from which the footwear is made. This is because the fumigation not only removes dirt and moisture from the external surface, but also from the internal surfaces, which is not the case without fumigation. When the moisture has been thoroughly removed from the internal surfaces, these internal surfaces can be achieved during the deposition process of the present invention. The performance of the coatings, in terms of water / or oil repellency, dry feet, reduced weight gain during use, quick drying effect and breathability, will therefore be improved when a fumigation is used before depositing a coating.
    Therefore, the present invention is related to a method of depositing a coating on the outer surface, the inner surface and the inner surfaces of the footwear through a low pressure plasma polymerization process by pre-gassing the footwear, the footwear having an upper with covering elements mounted on an outer surface of the upper part.
    In one embodiment, the footwear is degassed to a fumigation level of at most 50 mTorr, more preferably at most 20 mTorr, even more preferably at most 10 mTorr. Additionally or in parallel, the footwear is gassed in a vacuum chamber until the vacuum chamber has a gassing level of max. 100 mTorr, more preferably max. 50 mTorr, such as 40 mTorr or less. The level of flushing out of the room may depend on the load, e.g. of the number of pieces of footwear and the nature of the footwear brought into the room.
    To determine the level of fumigation of a piece of footwear, the pressure rise in a vacuum chamber due to gases exempted from the footwear must be determined. For this purpose, the footwear is placed in a vacuum chamber, e.g. a plasma chamber evacuated to an outgassing pressure Pdegassing, which is lower than 500 mTorr, preferably lower than 250 mTorr, such as less than 100 mTorr, after which the inlets and outlets of the vacuum chamber are closed. After a predetermined time of 60 seconds, the pressure rise in the chamber, ΔP, is measured. The level of outgassing of an item is then given by the pressure rise, ΔP, minus the leakage pressure of the vacuum chamber at the outgassing pressure Pdegassing. When more than one piece of footwear is placed in the chamber, the outgassing level of one piece of footwear is given by the pressure increase ΔP minus the leakage pressure of the vacuum chamber at the outgassing pressure Pdegassing, divided by the number of pieces of footwear in the vacuum chamber. Hereby the leakage pressure of the vacuum chamber at the outgassing pressure Pdegassing is determined by repeating the same procedure for an empty chamber with all the footwear removed from the vacuum chamber - pumping out to the same outgassing pressure Pdegassing, closing all inlets and outlets of the vacuum chamber, and measuring the pressure rise after the same predetermined time as for the loaded room, e.g. 60 seconds.
    In a preferred embodiment, the low pressure plasma polymerization is preceded by a low pressure plasma pre-treatment step, wherein preferably the pre-treatment and the gasification are combined in a single process step.
    In one embodiment, said method involves shielding parts of the footwear from said deposition process, by removing parts of the item before performing said deposition process, and / or by separately treating components with said deposition process before assembling it in the final product.
    In one embodiment, the low pressure plasma polymerization uses a monomer of the following formula
    CuF2u + 1CwX2wCR13Y-OCO-C (R14) = CH2, where u is 2 to 6, w is 0 to 9, X and Y are H, F, Cl, Br or I, R13 is H or alkyl or a substituted alkyl, e.g. an at least partially halo-substituted alkyl, and R 14 is H or alkyl or a substituted alkyl, e.g. an at least partially halo-substituted alkyl.
    In another embodiment, the low pressure plasma polymerization uses an organosilane monomer, the organosilane being the following formula: - Y1-X-Y2 where X, O or NH, Y1 is -Si (Y3) (Y4) Y5 and Y2 Si is (Y3 ') (Y4') Y5 'wherein Y3, Y4, Y5, Y3', Y4 ', and Y5' are independently H or an alkyl group of up to 10 carbon atoms in length; wherein at most one of Y3, Y4 and Y5 is H, and at most one of Y3 ', Y4' and Y5 'is H; and the total number of carbon atoms is no more than 20; - cyclically according to - [Si (CH 3) q (H) 2-q-X-] n - wherein n is 2 to 10, wherein q is 0 to 2 and wherein the total number of carbon atoms is no more than 20; - CH 2 = C (R 1) -Si (R 2) (R 3) -R 4 wherein R 1 is H or an alkyl group, e.g. -CH 3, and wherein R 1, R 2 and R 3 are independently H, or an alkyl group of up to 10 carbon atoms or an alkoxy group -O-Z, wherein Z is preferably -CtH 2 t + 1, where t is 1 to 10; - R 5 -Si (R 6) (R 7) -R 8 wherein R 5 is H or an alkyl group, e.g. -CH 3, and wherein R 6, R 7 and R 8 are each independently H or an alkyl group of up to 10 carbon atoms or an alkoxy group -O-Z, wherein Z is preferably -CtH 2 t + 1, where t is 1 to 10; or - CH 2 = C (R 9) C (O) -O- (CH 2) p -Si (R 10) (R 11) -R 12 wherein R 9 is H or an alkyl group, e.g. -CH3, where p is from 0 to 10, and wherein R10, R11 and R12 are each independently H or an alkyl group of up to 10 carbon atoms or an alkoxy group-OZ where Z is preferably -CtH2t + 1, where t is 1 to 10 is.
    In a further aspect the present invention comprises the use of a method for depositing a covering layer, preferably selective deposition, on a footwear as defined herein, in order to ensure the safety and / or comfort of the wearer of the footwear obtained according to the current invention.
    In a further aspect, the present invention includes the use of a method as described in this document to reduce the weight gain of a footwear during use, to prevent the footwear from absorbing fluid so that the user's feet remain warm and dry, and to reduce the drying time of the footwear. Preferably, the drying time is reduced to an absolute minimum, the drying time being defined as the time required to achieve a weight gain of up to 5% relative to the initial weight of the footwear for wearing.
    In yet a further aspect, the present invention comprises a gassed footwear. In one embodiment the footwear comprises an upper part with covering elements which are arranged on the outer surface of the upper part.
    The fumigated footwear preferably has a fumigation level of less than 50 mTorr, more preferably less than 20 mTorr, even more preferably less than 10 mTorr, and / or this footwear is placed in a vacuum chamber loaded with a number of pieces of footwear, the vacuum chamber having a fumigation level has a maximum of 100 mTorr, preferably a maximum of 50 mTorr, even more preferably a maximum of 40 mTorr. For a fully loaded room, e.g. loaded with 50 pairs of footwear, the chamber with full load is preferably gasified to a gasification level of less than 100 mTorr, more preferably less than 50 mTorr, such as less than 40 mTorr.
    In one embodiment, this outgassing is performed in an outgassing device or outgassing chamber, which is different from the plasma chamber in which the low pressure plasma polymerization process is performed. Such a fumigation apparatus or fumigation chamber can contain a heating element and can be an oven.
    The present invention also includes a footwear with a water and oil repellent coating on the outer surface of an upper of the footwear, but also on the inner surfaces and the inner surface of the footwear, the coating being most preferably deposited by a method according to the present invention.
    To determine whether a water and / or oil repellent coating has been deposited on the internal surfaces of the treated footwear, the footwear can be cut open so that the internal surfaces along the cut can be reached and tested for their water and / or oil-repellent character. In preferred embodiments, the coating on the internal surfaces has an oil repellency that is at least level 1 according to the oil repellency test according to ISO 14419, and which is preferably at most 1 level lower than the water and / or oil repellent level of the coating on the inner and / or outer surfaces, e.g. when the inner and outer surface has an oil or water repellency level of 5, the coating on the inner surfaces preferably has an oil or water repellency level of at least 4, such as 4, 5, 6, etc.
    The present invention also includes a footwear with a water and / or oil repellent coating coated with a low pressure plasma polymerization process, wherein the footwear has a Drying time that is up to 50%, more preferably up to 40%, even more preferably up to 30%, preferably a maximum of 20%, and most preferably a maximum of 10%, such as 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1% and most preferably 0% of the drying time of a footwear without a covering layer, wherein the covering layer is preferably deposited by a method according to the present invention. The Drying time is defined as the time required for the weight of a used / tested footwear to fall to 5% weight gain, the weight gain being the weight gain of a footwear relative to the same dry footwear, i.e. for use / testing.
    The present invention also includes a footwear with a water and / or oil-repellent coating applied with a low pressure plasma polymerization process according to the present invention, wherein the footwear has a Direct Weight Gain of up to 50%, more preferably up to 40% more preferably up to 30%, even more preferably up to 20%, and most preferably up to 10%, such as 9%, 8%, 7%, 6%, 5%, 4% or less of the Direct Weight Gain of the same footwear without covering. The Direct Weight Gain is the weight gain of a footwear immediately after use / testing, compared to the same footwear in dry condition, i.e. before use / testing.
    The Direct Weight Gain and Drying Time are determined after a test that simulates the daily use of the footwear. This test is performed as follows: - Weigh the footwear before submersion (dry weight); - Put the footwear on the foot to simulate the actual use; - Immerse the foot with the footwear in a horizontal manner for 60 seconds in a container filled with water at room temperature (23 ± 2 ° C), and this to a depth where the edge of the water is equal to the height of the footwear where the foot and leg come from the footwear; - Take the foot with the footwear out of the water and remove the footwear from the foot; - Shake the footwear 20 times by hand (up and down movement); - Re-weigh the footwear (weight of the tested footwear).
    The difference in weight between the tested footwear and the dry footwear (weight for the test that simulates use) is the Direct Weight Gain, expressed in grams. The Direct Weight Gain expressed in% is the Direct Weight Gain in grams divided by the dry weight of the footwear, multiplied by 100.
    The footwear is then hung semi-horizontally with the foot opening facing downwards, to allow the footwear to dry. The footwear is weighed again every 5 minutes, until the weight increase (actual weight minus the dry weight for submerging) is 5% or less of the dry weight of the footwear. The time required for this is called the drying time.
    The amount of fumigation in a plasma chamber can depend on the number of pieces of footwear in the plasma chamber, but also on the design of the footwear and the materials from which this footwear is made.
    A fumigation is preferably carried out before starting the first process step.
    Optionally, but preferably, a low pressure plasma pre-treatment is performed before the coating deposition step, and after the outgassing step when it is performed. Pre-treatment in the form of an activation and / or cleaning and / or etching can be an advantage to improve the adhesion and cross-linking of the polymeric coating and to achieve better penetration into the materials of the footwear so as not only to have the outer surfaces but also to coat the internal surfaces.
    The applicants have furthermore surprisingly discovered that pre-treatment allows for a better penetration of the plasma polymerization coating into the materials of which the footwear is made, so that also the material of the upper part of the footwear covered by decorative and / or functional plastics and tapes are coated. This is because pre-treatment not only removes contamination from the surface, but also from the internal surfaces, which is not the case without pre-treatment. The resulting low-pressure plasma cover is more uniform, and thanks to a selective deposition process and a cover to the inside of the footwear materials, optimum performance is achieved in terms of a dry outer textile, reduced weight gain and drying time (so-called "quick-drying effect"), and dry feet. This is not possible without the fumigation and / or the plasma pre-treatment of the present invention.
    The outgassing for the first process step - the deposition step or a pre-treatment step - is preferably performed by evacuating the plasma chamber to a fixed low pressure that is equal to or higher than the fixed basic pressure for the first process step. After this, the pumping is continued for a predetermined time, after which the evacuation is stopped and all chamber inlets and chamber outlets are closed for a predetermined outgassing time, the pressure rise during this outgassing time being measured. When the pressure rise is below a certain value - a maximum pressure rise - the outgassing is considered sufficiently low to continue the process. However, if the pressure rise is higher than that determined value, there is still outgassing, and the same outgassing sequence is repeated until the pressure rise is below the maximum pressure rise.
    The parameters of the fumigation, such as the recorded low pressure, the pump-out time, the fumigation time and the maximum pressure increase, depend on the plasma device, the volume of the plasma chamber, the type of pump, the number of pieces of footwear, preferably with the laces removed and covered with the outsole so as not to deposit a coating there - for the sake of the advantages mentioned above - and on the design and material of the footwear.
    The recorded low pressure is preferably from 5 m Torr to 200 m Torr, more preferably from 10 m Torr to 150 m Torr, such as 15 m Torr to 125 m Torr, e.g. 125, 120, 110, 100, 90, 80, 75, 70, 60, 50, 40, 30, 25, 20, or 15 mTorr.
    The fixed pumping time is preferably from 10 s to 900 s, more preferably from 30 s to 840 s, more preferably from 45 s to 780 s, such as 60 s to 720 s, e.g. 720, 690, 660, 630, 600, 570, 540, 510, 480, 450, 420, 390, 360, 330, 300, 270, 240, 210, 180, 150, 120, 90, or 60s.
    The outgassing time is preferably 1 s to 120 s, more preferably 5 s to 90 s, such as 90, 80, 75, 70, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 s.
    The maximum pressure rise is preferably 10 mTorr to 500 mTorr, more preferably 15 mTorr to 250 mTorr, such as 20 mTorr to 100 mTorr, e.g. 100, 90, 80, 75, 70, 60, 50, 40, 30, 25 or 20 mTorr.
    When a pretreatment is carried out, it is preferably carried out with an inert gas such as Ar, N2 or He, additionally or alternatively combined with reactive gases such as H2 or O2, or with etching gases such as CF4. Mixtures of previous gases can also be used.
    The pre-treatment is preferably performed with Ar or He.
    The pre-treatment preferably lasts 30 seconds to 30 minutes, for example 45 seconds to 15 minutes, more preferably 1 minute to 10 minutes, e.g. 9, 8, 7, 6, 5, 4, 3, 2, or 1 minutes. The duration of the pre-treatment depends on the precursor monomer used and on the design and materials of which the footwear, preferably with the laces removed and covered with the outsole, in order not to deposit a coating there - because of the advantages mentioned above made.
    The capacity of the pre-treatment can be applied continuously or in a pulsed manner.
    Preferably, when applied in a continuous manner in an 1836 liter plasma chamber, the pre-treatment takes place at a power of 5 to 5000 W, more preferably 25 to 4000 W, even more preferably 50 to 3000 W, such as 75 to 2500 W, such as 100 to 2000 W, e.g. 2000, 1900, 1800, 1750, 1700, 1600, 1500, 1400, 1300, 1250, 1200, 1100, 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 175, 150, 125, or 100 W.
    Preferably, when applied in a pulsed manner in an 1836 liter plasma chamber, the pre-treatment takes place at a power of 5 to 5000 W, more preferably 25 to 4000 W, even more preferably 50 to 3000 W, such as 75 to 2500 W, such as 100 to 2000 W, e.g. 2000, 1900, 1800, 1750, 1700, 1600, 1500, 1400, 1300, 1250, 1200, 1100, 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 175, 150, 125, or 100 W.
    When applied in pulsed power, the pulsation frequency can be selected between 100 Hz and 10 kHz, with a switching duration of about 0.05 to 50%, the optimum parameters depending on the gas or gas mixture being used.
    The operating pressure for the pretreatment in an 1836 liter plasma chamber is preferably 10 to 500 mTorr, more preferably 15 to 250 mTorr, more preferably 20 to 200 mTorr, such as 25 to 175 mTorr, such as 30 to 150 mTorr, e.g. 150, 140, 130, 125, 120, 110, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, or 30 mTorr.
    For systems with different dimensions, with a different volume and / or a different electrode arrangement, the power, the operating pressure and the pretreatment time are varied in such a way that the best process parameters are used for the pretreatment.
    When the footwear, preferably with the laces removed and covered with the outsole, in order not to deposit a coating there - for the above-mentioned advantages - which contains a certain amount of moisture and wetness, is placed in the plasma chamber, the fumigation and pre-treatment combined in a single process step, where the fumigation takes place during the pre-treatment. This can for example. be done when the footwear is dried before being placed in the plasma chamber.
    After the outgassing and / or the pretreatment step, a plasma polymerization step is carried out, during which the nano-coating is selectively deposited on the footwear, and furthermore also within the material from which the footwear is made.
    In an embodiment of the present invention, the low pressure plasma polymerization as mentioned above - selectively and within the core of the material from which the footwear is made - is a low pressure plasma polymerization of an acrylate or a methacrylate precursor molecule, wherein the (meth ) acrylate of formula (I) is:
    wherein u is 2 to 6, w is 0 to 9, X and Y are H, F, Cl, Br or I, R 13 is H or alkyl or a substituted alkyl, e.g. an at least partially halo-substituted alkyl, and R 14 is H or alkyl or a substituted alkyl, e.g. an at least partially halo-substituted alkyl.
    The acrylate or methacrylate is preferably introduced into the plasma chamber without the use of a carrier gas, and the acrylate or methacrylate is capable of igniting the plasma.
    In another embodiment of the present invention, the low pressure plasma polymerization as described above - selectively and within the material from which the footwear is made - is a low pressure plasma polymerization of an organosilane precursor monomer, the organosilane of formula (II) , (III), (IV), (V) or (VI).
    - wherein for Formula (II) X is O, O or NH, Y 1 is -Si (Y 3) (Y 4) Y 5 and Y 2 is Si (Y 3 ') (Y 4') Y 5 'wherein Y 3, Y 4, Y 5, Y 3', Y 4 ', and Y 5' are independently H or an alkyl group of up to 10 carbon atoms in length; wherein at most one of Y3, Y4 and Y5 is H, and at most one of Y3 ', Y4' and Y5 'is H; and the total number of carbon atoms is no more than 20; - Formula (III) is cyclic wherein n is 2 to 10, wherein q is 0 to 2 and wherein the total number of carbon atoms is no more than 20; - wherein for Formula (IV), R 1 is H or an alkyl group, e.g. -CH 3, and wherein R 1, R 2 and R 3 are independently H, or an alkyl group of up to 10 carbon atoms or an alkoxy group -O-Z, wherein Z is preferably -CtH 2 t + 1, where t is 1 to 10; - wherein for Formula (V) R 5 is H or an alkyl group, e.g. -CH 3, and wherein R 6, R 7 and R 8 are each independently H or an alkyl group of up to 10 carbon atoms or an alkoxy group -O-Z, wherein Z is preferably -CtH 2 t + 1, where t is 1 to 10; or - wherein for Formula (VI), R 9 is H or an alkyl group, e.g. -CH 3, wherein p is from 0 to 10, and wherein R 10, R 11 and R 12 are each independently H or an alkyl group of up to 10 carbon atoms or an alkoxy group -O 2 where Z is preferably -CtH 2 t + 1, where t is 1 to 10 is.
    The alkyl groups can be linear or branched, but linear groups are preferred. Such alkyl groups are preferably methyl or ethyl groups of which methyl is preferred. Preferably, Y3, Y4, Y5, Y3 ', Y4' or Y5 are all alkyl groups.
    The alkoxy groups can be linear, branched or cyclic, but linear groups are preferred. Such alkoxy groups are preferably methoxy or ethoxy groups.
    The monomer of Formula II can contain six methyl groups. The monomer according to is preferably hexamethyldisiloxane. Preferably, the monomer according to Formula II is hexamethyldisilazane.
    The monomer of Formula III can be one wherein n is 3, or 4 or 5 or 6. Preferably, the monomer of Formula III is oxtamethylcyclotetrasiloxane. Preferably, the monomer according to Formula III is hexamethylcyclotrisilazane.
    The preferred monomer used in this invention is hexamethyldisiloxane or hexamethyldisilazane.
    The organosilane precursor monomer can be introduced into the plasma chamber with a carrier gas. Preferably, the carrier gas is H 2, N 2, O 2, N 2 O, CH 4, He, Ar, and / or a mixture of these gases. In a preferred process, a single gas is used, which is preferably O 2 or Ar.
    The amount of carrier gas used with the organosilane is preferably from about 1% to about 50% carrier gas (s) based on the monomer flow. Preferably, about 5% to about 30% carrier gas is used, e.g. about 10% carrier gas.
    The present invention also includes in a certain aspect a method of coating a footwear through low pressure plasma polymerization wherein the low pressure plasma polymerization uses a monomer as described above, in particular according to formulas (I) to (VI) , and as further described in this document.
    The plasma chamber preferably comprises one or more electrode layers, which can be radio frequency electrode layers or grounded electrode layers, in order to be able to generate an electromagnetic field.
    Preferably, the or each radiofrequency electrode generates a high frequency field at frequencies from 20 kHz to 2.45 GHz, more preferably at frequencies from 40 kHz to 13.56 MHz, with 13.56 MHz being preferred.
    To perform the low pressure plasma polymerization step, the plasma chamber is evacuated to a fixed low base pressure. Afterwards, one or more monomer inlets are opened to have a constant flow of monomer entering the chamber, optionally in combination with a carrier gas.
    Preferably, a fumigation step and / or pre-treatment is performed before the low pressure plasma polymerization process is performed.
    When the monomer is an acrylate or a methacrylate according to formula (I), the monomer is capable of igniting the plasma. Consequently, a carrier gas is not necessary to ignite the plasma.
    When the monomer is an organosilane monomer according to any of formulas (II) to (VI), a carrier gas can be used to ignite the plasma. Whether or not a carrier gas is used depends on the monomer used.
    After stabilizing the monomer, optionally combined with a carrier gas, to a predetermined operating pressure, a power is applied to the radiofrequency electrode or electrodes to create an electromagnetic field. A plasma is ignited and the monomer molecules are activated. The substrates or products in the plasma chamber act as a promoter or starting point of the initiation of the polymerization reaction, and will continue as long as activated monomer molecules are present in the plasma chamber. During the plasma polymerization process there is a constant flow of new monomer into the plasma chamber, optionally combined with a carrier gas, to keep the polymerization going.
    Once a fixed plasma polymerization time is reached, the power applied to the radiofrequency electrode or electrodes is turned off, and the chamber is brought back to atmosphere drum to allow the treated products to be taken out of the chamber.
    The plasma polymerization time is determined in function of the design and the materials from which the footwear is made, in order not only to have polymerization on the outer surface of the footwear, but also to the inside of the core such as the material of the upper part covered by decorative and / or functional plastic tape or printing, in order to obtain substantially better protection against water penetration and penetration, which leads to drier feet, feet that do not cool down, and reduced weight gain and drying time, and no wet outdoor fabric.
    Preferably, the plasma polymerization time, expressed as the time a power is applied to the electrodes, is about 30 seconds to about 45 minutes, more preferably from about 45 seconds to about 30 minutes, such as from 1 minute to 25 minutes, such as 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 minute.
    The plasma polymerization can be a continuous plasma polymerization. The plasma polymerization can also be a pulsed plasma polymerization. Whether a continuous or pulsed plasma is used for the polymerization depends on the chemistry used and on the volume and design of the plasma chamber.
    Preferably, the applied power in a plasma chamber of 1836 liters, with continuous wave plasma, is about 5 to 5000 W, more preferably about 10 to 2500 W, even more preferably about 15 to 2000 W, e.g. 20 to 1500 W, say 25 to 1000 W, such as 30 to 750 W, such as 35 to 500 W, e.g. 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 190, 180, 175, 170, 160, 150, 140, 130, 125, 120, 110, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, or 35 W.
    Preferably, the applied power in a plasma chamber of 1836 liters, with a pulsed plasma, is about 5 to 5000 W, more preferably about 10 to 2500 W, even more preferably about 20 to 1500 W, e.g. 30 to 1000 W, such as 50 to 900 W, such as 75 to 800 W, such as 100 to 750 W, e.g. 750, 725, 700, 675, 650, 625, 600, 575, 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 190, 180, 175, 170, 160, 150, 140, 130, 125, 120, 110, or 100 W.
    When applied in pulsed power, the pulsation frequency can be selected between 100 Hz and 10 kHz, with a switching duration of about 0.05 to 50%, the optimum parameters depending on the monomer being used.
    In an 1836 liter plasma chamber used to deposit a coating on 48 pairs of footwear in a single process run, the working pressure for the deposition step is about 10 to 500 mTorr, more preferably about 15 to 200 mTorr, even more preferably about 20 to 150 mTorr, take 30 to 100 mTorr, such as less than 100, 90, 80, 70, 60, 50, 40 or 30 mTorr.
    The method preferably comprises the step of depositing a polymeric coating with a thickness of 10 to 1000 nm on the outer surface as well as on the inner surfaces, more preferably from 20 to 750 nm, even more preferably from 50 to 500 nm, e.g. 500, 450, 400, 350, 300, 250, 200, 150, 100, 75 or 50 nm.
    In the present invention, super-hydrophobic surfaces can be created when using acrylate or methacrylate monomers of formula (II), wherein the super-hydrophobic surfaces have a water contact angle of more than 100 °, take 101, 102, 103, 104, 105 , 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119 or 120 ° according to ASTM D5946-04.
    The same coatings deposited via methacrylate or acrylate monomers of formula (I) are super oleophobic with oil repellency levels above or equal to and above 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5 or 8 e.g. to 6 following ISO 14419, take up to or including 4, 4.5, 5, 5.5, 6, 6.5, 7 7.5, or 8.
    In the present invention, hydrophobic surfaces can be obtained when organosilane monomers according to formulas (II) to. (VI) where the hydrophobic surfaces have a water contact angle of more than 90 °, take 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109 or 110 ° according to ASTM D5946-04.
    The water contact angle and / or the oil level achieved depends on the monomer used, on the optionally used carrier gases, on the process conditions used, but also on the substrate on which the nano-coating is deposited, e.g. of the polymer used, the weight and thickness of the material, the openness of the material, the material construction (fabric, non-fabric, mesh, foam), etc.
    Preferably because the method of depositing a polymeric coating with a variation in water contact angle of less than 10 ° according to ASTM D5946-04 and, for nano coatings coated with a methacrylate or acrylate monomer according to formula (I), a variation in the oil level of less then 0.5 according to ISO 14419.
    By using a method as described above, a low pressure plasma coating is deposited on the outer surface and the inner surfaces of a footwear by selectively depositing the coating into the material from which the footwear is made.
    The applicants have surprisingly discovered that with a method according to the present invention a water and / or oil-repellent nano-coating is deposited not only on the outer surface of the upper material of the footwear, but also on the internal surfaces and even the surfaces that are shielded from direct exposure to the plasma as a result of decorative and / or functional plastic tape or printing.
    By using this inventive process according to the invention, not a single technical problem is solved, but a combination of problems. Prior art documents fail to solve all these technical problems through a single method or solution.
    The present invention improves these prior art documents by providing a method that, surprisingly, solves all these technical problems in a single method. This is not logical according to the state of the art, since on the one hand the solutions described therein to keep the feet dry impose great limitations on the breathability of the footwear, and on the other hand the solutions described therein to reduce the weight gain do not offer a solution to the keep feet dry since only the outer surface of the upper material of the footwear is covered. A combination of these two solutions according to the prior art would lead to footwear with a limited breathability, which would not provide a solution for sweat generated on the inside. Furthermore, since only the outer surface of the footwear would have a covering layer, the ingression of water would not be maximally reduced, since the interior of the upper material is not protected against liquids.
    The technical problems solved with the invention as described above are, but are not limited to: - Keeping the feet of other liquids, such as rain, snow and the like; - Keeping the feet dry from sweat generated inside during use; - Reducing the weight gain of the footwear during use, resulting in a reduced drying time (so-called "quick-drying effect"); - Preventing cooling of the feet.
    The following non-limiting examples clarify these properties and demonstrate the advantage of using this method and nanodevices according to the present invention on footwear in general.
    EXAMPLES
    In order for the invention to be more easily understood, it will now be described with reference to a few examples which do not impose any limitation in terms of protection.
    Example 1: Advantage of outgassing before the deposition step
    A 680 liter chamber, designed to hold up to 40 pairs of footwear, was evacuated in its empty state to a predetermined fumigation pressure of 20 mTorr, after which all inlets and outlets were closed. The pressure rise over 60 seconds was measured and was 10 mTorr.
    After returning to atmospheric pressure, the same chamber was loaded with sneakers that had their laces removed. In a first process, the outgassing level of the footwear was determined by evacuating the chamber to the same predetermined outgassing pressure of 20 mTorr. The inlets and outlets were closed and the pressure rise over 60 seconds was measured. The total pressure increase was 100 - 120 mTorr, which is at least 10 times higher than for an empty room. Afterwards, a deposition process according to Table 1 was performed, including a pre-treatment. The oil level of the treated shoes was measured afterwards according to ISO 14419 and was level 1.
    The same experiment was repeated, after pumping to the pre-determined 20 mTorr gas pressure, the chamber was further evacuated for 10 minutes. Afterwards, all inlets and outlets were closed, and the pressure rise over 60 seconds was measured and was 35-40 mTorr. Afterwards, a deposition process according to Table 1 was performed, including a pre-treatment. The oil level of the treated shoes was measured afterwards according to ISO 14419 and was level 4.
    In both experiments the laces were treated separately with a method according to Table 2. After treatment of laces and shoes, the laces were placed back in the shoes.
    An untreated shoe of the same type, e.g. a left-hand shoe of a pair, including untreated laces, was tested to determine the Direct Geiwcht increase and the Drying time. Also, one piece of footwear, treated according to the process without adequate fumigation, including laces, was tested and one piece of footwear, treated according to the process with sufficient fumigation, including laces, was tested and the Direct Weight Gain and Drying Time was determined for both.
    The Direct Weight Gain and Drying Time are determined according to a test that simulates the daily use of the footwear. This test is performed as follows: - Weighing the footwear before submersion (dry weight); - Footwear is placed on the foot to simulate actual use; - The foot with the footwear is placed horizontally for 60 seconds in a container filled with water at room temperature (23 ± 2 ° C) up to the height where the foot and leg come out of the footwear; - Foot with footwear are removed from the water bowl and the footwear is taken off; - The footwear is shaken out 20 times manually (up-and-down movement); - The footwear is weighed again (tested footwear).
    The difference in weight between the tested footwear and the dry footwear (weight for the simulation test) is the Direct Weight Gain in grams. The Direct Weight Gain in% is the Direct Weight Gain in grams divided by the dry weight of the footwear, multiplied by 100.
    The footwear is now hung semi-horizontally with the foot opening facing down to dry. The footwear is weighed again every 5 minutes, until the increase in weight (actual weight minus the dry weight for immersion) is 5% or less of the dry weight of the footwear. The time required to achieve this is the drying time.
    For example, for a dry weight of 100 grams, the item is considered dry when the weight gain is 5 grams or less (footwear has a current weight of 105 grams or less).
    Parameter Value
    Pre-treatment
    Gas Argon
    Flow rate 500 - 1500 sccm
    Treatment time 1 - 10 min
    Power 100 - 1000 W
    Frequency 13.56 MHz
    Frequency mode Cw
    Plasma Zone
    Treatment time 10 - 20 min
    Temperature walls 40 - 50 ° C
    Monomer 1 H, 1 H, 2 H, 2 H-Perfluorooctyl acrylate
    Flow rate 30 - 100 sccm
    Electrodes & Generator
    Power during cover layer 50 - 500 W deposition
    Frequency 13.56 MHz
    Frequency mode cw
    Temperature RF electrode 30 - 50 ° C Pressure
    Basic pressure 10 - 50 mTorr
    Work pressure 20 - 150 mTorr
    Oil level 5 (ISO 14419-2010)
    Table 1: Process parameters for depositing a coating on footwear in a 680 liter room
    Parameter Value
    Pre-treatment
    Gas Argon
    Flow rate 100 - 1000 sccm
    Treatment time 1-10 min
    Power 100 - 1000 W
    Frequency 13.56 MHz
    Frequency mode Cw
    Plasma Zone
    Treatment time 10 - 20 min
    Temperature walls 40 - 50 ° C
    Monomer 1 H, 1 H, 2 H, 2 H-Perfluorooctyl acrylate
    Flow rate 20 - 50 sccm
    Electrodes & Generator
    Power during cover layer 50 - 500 W deposition
    Frequency 13.56 MHz
    Frequency mode cw
    Temperature RF electrode 30 - 50 ° C Pressure
    Basic pressure 10 - 50 mTorr
    Work pressure 20 - 150 mTorr
    Oil level 5 (ISO 14419-2010)
    Table 2: Process parameters for laces in a 490 liter room
    Table 3 summarizes the test results in terms of oil repellency, Direct Weight Gain and Drying Time. It is clear that a major and significant improvement is noted when the footwear is coated, and that the results are further improved by a thorough outgassing of the footwear.
    The thoroughly gassed footwear has a Direct Weight Gain of just 3.4%, which is less than 5% so that the Drying Time is equal to 0 minutes. For untreated footwear, the Direct Weight Gain, 18.6%, is clearly more than 5%. For coated footwear with insufficient outgassing, the Direct Weight Gain is 12.7%, which is less than the Direct Weight Gain of the untreated footwear, but is clearly more than 5%.
    The Drying time for thoroughly fumigated footwear (sports shoe in this example) is reduced by 100% compared to untreated footwear and even compared to treated footwear without thorough fumigation. The Drying time for thoroughly gassed footwear is therefore 0% (ZERO) of the Drying time of untreated footwear and 0% of the Drying time of treated but badly gassed footwear.
    The Direct Weight Gain for thoroughly fumigated footwear (sports shoe in this example) is reduced by 81.6% compared to untreated footwear and by 72.9% compared to treated but poorly fumigated footwear. The Direct Weight Gain for thoroughly gassed footwear is therefore only 18.4% of the Direct Weight Gain of untreated footwear and only 27.1% of the Direct Weight Gain of treated but badly gassed footwear.
    Table 3: Test results in function of level of fumigation
    Example 2: Penetration into the material 2.1 Penetration into the material
    A footwear for walking activities was treated according to the parameters in Table 4. The closures - laces - were removed from the footwear before being treated and were treated separately according to Table 2 in a 490 liter chamber, which can hold up to 250 or more laces.
    Before placing the footwear in the plasma chamber, the entire inside, including the tongue and the insole, was covered with several layers of paper tape (painter's adhesive tape) to shield the inside of the footwear from direct exposure to the plasma. Even the opening for the foot was closed with different layers of tape.
    After treatment, the tape was removed, and the treated footwear was compared to the same footwear but then untreated. The upper textile material of the running shoe is a porous mesh that has a highly hydrophilic character for an untreated shoe. The upper textile material for the treated shoe was super hydrophobic after the deposition process with water contact angles of 110 ° and more. Also the inside of the footwear, which was covered with the tape during the process, and which was hydrophilic before the deposition process, was surprisingly super-hydrophobic after the process.
    This clearly shows that, according to the method of the present invention, a coating is deposited not only on the outer surface of the material of the footwear, but also on the inner surfaces and the inner surfaces.
    Parameter Value
    Outgassing
    Draining time 10 min
    Waiting time 30 - 120 sec
    Maximum allowable 5 - 50 mTorr pressure rise in chamber Pre-treatment Gas Argon
    Flow rate 500 - 1500 sccm
    Treatment time 1 - 10 min
    Power 100 - 1000 W
    Frequency 13.56 MHz
    Frequency mode Cw
    Plasma Zone
    Treatment time 10 - 20 min
    Temperature walls 40 - 50 ° C
    Monomer 1 H, 1 H, 2 H, 2 H-Perfluorooctyl acrylate
    Flow rate 30 - 100 sccm
    Electrodes & Generator
    Power during 50 - 500 W coating deposition
    Frequency 13.56 MHz
    Frequency mode cw
    Temperature RF electrode 30 - 50 ° C Pressure
    Basic pressure 10 - 50 mTorr
    Work pressure 20 - 150 mTorr
    Oil level 5 (ISO 14419-2010)
    Table 4: Process parameters for selectively depositing a coating through the structure of the footwear in an 1836 liter room 2.2 Resistance to abrasion - simulation of use
    In order to gain insight into the daily use of the footwear, and in particular the abrasive (friction) during use, a cloth was rubbed manually according to a reciprocating movement on a treated footwear for sports applications. The footwear was treated according to the process parameters in Table 4, with the laces removed for the process, and the outsole was masked with a masking tape to prevent a coating from being deposited on the outsole.
    This test examines how good the adhesion of the cover layer to the material of the footwear is, and also how solid the deposition of the cover layer was inside the material, since any damage to the cover layer on the surface would lead to a drop in the water contact angle .
    The water contact angle or the tested mesh surface is measured as a function of the number of abrasion cycles. It is clear from Figure 2 that even after 1000 abrasion cycles the water contact angle of the treated mesh textile is still in the interval of the treated footwear before the start of the abrasion test simulation.
    Example 3: Reduced weight gain and improved drying time 2.1 Reduced weight gain during use
    A sneaker was treated in a batch process in a machine with a chamber volume of 1836 liters, according to the process parameters of Table 4. This plasma chamber can contain up to 40 - 60 pairs of footwear. For this deposition process, the closures were removed from the footwear, and these were treated in a separate process according to the parameters of Table 2 (selective treatment of footwear). The device used to handle the closures was a 490-liter chamber in which 150 to 250 closures (laces) can be treated in a single process run.
    The footwear deposition process includes a fumigation, pre-treatment and a plasma polymerization step. The outgassing is carried out to remove moisture, air and other gases from the room and from the footwear before starting the pre-treatment. The pretreatment removes contamination and contamination on the material in order to have a better deposition of the cover layer through the structure of the material. Applicants have discovered that this selective deposition through the material of the footwear leads to an improved performance of the treated footwear.
    Afterwards the laces were placed back in the sports shoe. The sports shoe was immersed for 1 minute in a 10-liter bucket of water, after which the shoe was shaken 20 times manually and then weighed. The same test was done for an untreated shoe of the same type.
    Figure 3 shows the test results. It is clear that after just 1 minute of immersion, the untreated shoe absorbs 40 grams of water, while the plasma treated shoe records only 9 grams of weight gain, which means a weight reduction of 31 grams, or 9% of the dry weight of the sports shoe. 2.2 Fast drying effect 2.2.1 Foam structure
    An open cell structure used as foam or mesh in footwear was treated with two different plasma processes, P1 and P2, according to Table 4. The only difference between P1 and P2 was the deposition time (P2 greater than P1).
    These structures were subsequently submerged for 5 minutes in a 5 kg container on top to force water penetration (worst case scenario). They were then removed from the container and dried in the air. The drying time was measured and is defined as the time required to reach a weight that is no more than 5% higher than the dry weight of the structure. The same test was performed on an untreated piece of foam.
    It is clear from Figure 4 that the drying time is greatly reduced by deposition of a plasma coating according to the present invention. 2.2.2 Fake fur
    Fake fur, in the form of a pile fabric, used to decorate footwear for leisure, and to insulate the inside of footwear for winter and cold environments, is treated on a roll according to a process of Table 5. Two processes P1 and P2 where the deposition rate of P2 is higher than that of P1 (shorter residence time in the plasma zone).
    Pieces of untreated and treated fake fur, the size of an A4, were tested with an immersion test. They were placed in a basket 10 cm under water at room temperature, with a weight of 2 kg on top of the basket to prevent the samples from starting to float.
    Afterwards, the samples were removed from the basket and allowed to drip and dry in a vertical position. The weight increase relative to the dry weight was calculated after drying for 1, 2, 3, 4 and 5 minutes.
    Parameter Value
    Pre-treatment
    Gas Argon
    Flow rate 500 - 1500 sccm
    Speed 6 m / min
    Power 1000 - 5000 W
    Frequency 13.56 MHz
    Frequency mode cw
    Plasma Zone
    Length of the plasma zone 6 m Deposition speed 2 m / min
    Voltage 1.5 kg (15 N)
    Temperature walls 40 - 50 ° C
    Electrodes & Generator
    Electrode configuration M / RF / M / RF / RF / M / RF / M
    Plasma type Primary
    Power 100 - 500 W
    Frequency 13.56 MHz
    Frequency mode cw
    Temperature RF electrode 30 - 35 ° C
    Monomer 1 H, 1 H, 2 H, 2 H-Perfluorooctyl acrylate
    Flow rate 50 - 150 sccm
    Busy
    Basic pressure 10 - 50 mTorr
    Work pressure 20 - 80 mTorr
    Residence time in plasma zone 3 minutes during deposition Oil level 5 (ISO 14419-2010)
    Table 5
    It is clear from Figure 5 that untreated faux fur absorbs an enormous amount of water, and in particular the bottom layer of the pile fabric. Once treated, the weight gain decreases enormously and the drying time is much shorter. When the drying time is defined as the time needed to have a weight gain of up to 5%, P2 has a drying time of just 4 minutes, while the untreated material still has a weight gain of 207% after drying for 5 minutes.
    Example 4: Breathable character
    A polyester (PES) fabric was coated on a 1.6m wide roll with a method according to the present invention, including a pre-treatment and a plasma polymerization deposition, with the process parameters of Table 5. The same textile was treated with a traditional dip dry-cross-linked process.
    The breathability was tested on all materials and evaluated in terms of water vapor permeability and air permeability. 4.1 Water vapor permeability
    Water vapor permeability is a measure for the transport of moisture inside the footwear coming from the feet. When used, the temperature of the feet will rise and sweat will be produced. Exemption from water vapor and therefore from evaporated sweat, and from the heat, are essential for good wearing comfort for the end user.
    Water vapor permeability is tested according to ASTM E96 (1995), and measures the weight gain in g / m2 day of silica beads. The increase in weight comes from the absorption of water vapor that has passed through the textile material, while the textile is placed in a closed environment at 20 ° C and 65% relative humidity.
    Each textile material has a water vapor permeability specific to the material, since the structure of the textile, the weave pattern, the openness, the polymer type, etc. all affect the inherent water vapor permeability.
    Figure 6 shows the results of the water vapor permeability of the materials (untreated, treated in a conventional manner and treated with plasma).
    It is clear that the water vapor permeability of the plasma treated textile is higher than for the textile treated in a conventional manner. Furthermore, the plasma coating impels the water vapor permeability of the material itself, because the water vapor is not absorbed by the textile fibers, where this is the case for the untreated material and the fibers tend to absorb moisture to a certain level. It is also clear from Figure 6 that a conventional covering layer reduces the water vapor permeability of the tested textile, since this covering layer tends to block the openings of the textile material, or at least to reduce its dimensions. 4.2 Air permeability
    The air permeability is a measure for the release of heat and for the openness of the textile material. It is measured via ISO 9237 (1995), which measures the amount of air that passes through a textile material (in l / (s.m2)) when a constant pressure difference of 100 - 200 Pa is applied on both sides of the textile.
    Figure 7 shows the results of the air permeability of the textile materials (untreated, treated in a conventional manner and treated with plasma). The plasma treated samples have been obtained with a process according to Table 5. It is clear that the air permeability of the plasma treated textile material is higher than that of the same material, treated in a conventional manner via a dip-dry-cross-linked process, and in the same range lies as the air permeability of the untreated material. SEM analysis (Figure 8) of the PES textile, untreated, treated in a conventional manner and treated with plasma according to Table 5 clearly shows that the plasma coating covers the individual yarns, while the conventional coating covers multiple yarns and thus adheres them to each other thereby the breathability is negatively affected.
    权利要求:
    Claims (15)
    [1]
    CONCLUSIONS
    A method of depositing a coating on the outer surfaces, inner surfaces and inner surfaces of a footwear, wherein the coating is water and / or oil repellent, by means of a low pressure plasma polymerization deposition process, by gasifying the footwear for this deposition process.
    [2]
    A method according to claim 1, wherein the footwear comprises an upper material that has covering elements attached to the outer surface of the upper material.
    [3]
    Method according to any of the preceding claims, wherein the footwear is gassed to a fumigation level of a maximum of 20 mTorr and / or wherein the footwear is fumigated in a vacuum chamber until this vacuum chamber has a fumigation level of a maximum of 50 mTorr.
    [4]
    The method according to any of the preceding claims, wherein the low pressure plasma polymerization is preceded by a low pressure plasma pre-treatment, wherein preferably the outgassing and the pre-treatment are combined in a single process step.
    [5]
    Method according to any of the preceding claims, wherein parts of the footwear are shielded before the deposition process, wherein parts of the footwear are removed from the footwear before the deposition process, and / or wherein parts of the footwear are treated separately via the deposition process before the parts are assembled into the footwear.
    [6]
    A method according to any of the preceding claims, wherein the low pressure plasma polymerization uses a monomer according to CuF2u + iCw X2wCR13Y-OCO-C (R14) = CH2 where u is 2 to 6, w is 0 to 9, X and Y are H , F, Cl, Br or I, R 13 is H or alkyl or a substituted alkyl, e.g. an at least partially halo-substituted alkyl, and R 14 is H or alkyl or a substituted alkyl, e.g. an at least partially halo-substituted alkyl.
    [7]
    The method according to any of the preceding claims, wherein the low pressure plasma polymerization uses an organosilane monomer according to - Y1-X-Y2 wherein X is O or NH, Y1 is -Si (Y3) (Y4) Y5 and Y2 is Si (Y3) ') (Y4') is Y5 'wherein Y3, Y4, Y5, Y3', Y4 ', and Y5' are independently H or an alkyl group of up to 10 carbon atoms in length; wherein at most one of Y3, Y4 and Y5 is H, and at most one of Y3 ', Y4' and Y5 'is H; and the total number of carbon atoms is no more than 20; - cyclically according to - [Si (CH 3) q (H) 2-q-X-] n - wherein n is 2 to 10, wherein q is 0 to 2 and wherein the total number of carbon atoms is no more than 20; - CH 2 = C (R 1) -Si (R 2) (R 3) -R 4 wherein R 1 is H or an alkyl group, e.g. -CH 3, and wherein R 1, R 2 and R 3 are independently H, or an alkyl group of up to 10 carbon atoms or an alkoxy group -O-Z, wherein Z is preferably -CtH 2 t + 1, where t is 1 to 10; - R 5 -Si (R 6) (R 7) -R 8 wherein R 5 is H or an alkyl group, e.g. -CH 3, and wherein R 6, R 7 and R 8 are each independently H or an alkyl group of up to 10 carbon atoms or an alkoxy group -O-Z, wherein Z is preferably -CtH 2 t + 1, where t is 1 to 10; or - CH 2 = C (R 9) C (O) -O- (CH 2) p -Si (R 10) (R 11) -R 12 wherein R 9 is H or an alkyl group, e.g. -CH3, where p is from 0 to 10, and wherein R10, R11 and R12 are each independently H or an alkyl group of up to 10 carbon atoms or an alkoxy group-OZ where Z is preferably -CtH2t + 1, where t is 1 to 10 is.
    [8]
    8. Fumigated footwear, with a fumigation level of a maximum of 20 mTorr, and / or the footwear in a vacuum chamber loaded with a number of pieces of footwear, said vacuum chamber having a fumigation level of a maximum of 50 mTorr, the footwear preferably having an upper material that is optional contains concealed elements which are arranged on the outer surface of the upper material.
    [9]
    Footwear containing a water and / or oil repellent coating deposited with a low pressure plasma polymerization deposition method according to claims 1 to 7, wherein said coating is deposited on the outer surface of the upper material of the footwear, as well as on the internal surfaces and the inner surfaces of the footwear.
    [10]
    Footwear with a water and / or oil-repellent coating deposited with a low-pressure plasma polymerization deposition method according to claims 1 to 7, wherein the footwear has a Drying time that is a maximum of 10% of the Drying time of the untreated footwear.
    [11]
    Footwear with a water and / or oil-repellent coating deposited with a low-pressure plasma polymerization deposition method according to claims 1 to 7, wherein the footwear has a Direct Weight Gain that is at most 20% of the Direct Weight Gain of the untreated footwear.
    [12]
    12. Method for obtaining a selectively treated footwear via a low pressure plasma polymerization deposition process, comprising shielding parts of the footwear for the deposition process, and / or separately treating parts of the footwear with this deposition process before the parts are assembled to the footwear.
    [13]
    A method of depositing a low pressure plasma polymerization coating on a footwear, wherein the low pressure plasma polymerization uses a monomer according to CuF2u + iCw X2wCR13Y-OCO-C (R14) = CH2 where u is 2 to 6, w 0 to Is 9, X and Y are H, F, Cl, Br or I, R 13 is H or alkyl or a substituted alkyl, e.g. an at least partially halo-substituted alkyl, and R 14 is H or alkyl or a substituted alkyl, e.g. an at least partially halo-substituted alkyl.
    [14]
    A method of depositing a low pressure plasma polymerization coating on a footwear, wherein the low pressure plasma polymerization uses an organosilane monomer according to - Y1-X-Y2 where X, O or NH is, Y1 -Si (Y3) (Y4) ) Y5 and Y2 is Si (Y3 ') (Y4') Y5 'wherein Y3, Y4, Y5, Y3', Y4 ', and Y5' are independently H or an alkyl group of up to 10 carbon atoms in length; wherein at most one of Y3, Y4 and Y5 is H, and at most one of Y3 ', Y4' and Y5 'is H; and the total number of carbon atoms is no more than 20; - cyclically according to - [Si (CH 3) q (H) 2-q-X-] n - wherein n is 2 to 10, wherein q is 0 to 2 and wherein the total number of carbon atoms is no more than 20; - CH 2 = C (R 1) -Si (R 2) (R 3) -R 4 wherein R 1 is H or an alkyl group, e.g. -CH 3, and wherein R 1, R 2 and R 3 are independently H, or an alkyl group of up to 10 carbon atoms or an alkoxy group -O-Z, wherein Z is preferably -CtH 2 t + 1, where t is 1 to 10; - R 5 -Si (R a) (R 7) -R 8 wherein R 5 is H or an alkyl group, e.g. -CH 3, and wherein R 6, R 7 and R 8 are each independently H or an alkyl group of up to 10 carbon atoms or an alkoxy group -O-Z, wherein Z is preferably -CtH 2 t + 1, where t is 1 to 10; or - CH 2 = C (R 9) C (O) -O- (CH 2) p -Si (R 10) (Ru) -R 12 wherein R 9 is H or an alkyl group, e.g. -CH 3, wherein p is from 0 to 10, and wherein R 10, R 11 and R 12 are each independently H or an alkyl group of up to 10 carbon atoms or an alkoxy group-O 2 where Z is preferably -CtH 2 t + 1, where t is 1 to 10 is. optionally wherein the organosilane monomer is introduced into the chamber by means of a carrier gas to ignite the plasma, and wherein the flow rate of carrier gas is about 1% to 50% of the monomer flow.
    [15]
    A low pressure plasma polymerization deposition apparatus for treating shoes in large volumes, comprising at least two pairs of electrodes, each pair comprising a grounded electrode and a radio frequency (RF) electrode to induce a plasma and to apply a plasma polymerized overlay on footwear that can be placed between the grounded and the RF electrodes of a pair, the distance between the grounded electrode and the RF electrode of a pair being greater than 50 mm and less than 500 mm, and where the distance between the grounded electrode of a first pair and the RF electrode of a second pair is greater than 1 mm and less than 50 mm, the device preferably having slots between each pair of electrodes, the slots preferably comprising ways of one or more placing multiple substrate holders at variable or different positions, even more preferably where the device has one or more substrate holders in a slot for storing contain footwear or the parts of the footwear to be treated.
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    同族专利:
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    引用文献:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    EP14189138.2|2014-10-16|
    EP14189138.2A|EP3009198B1|2014-10-16|2014-10-16|Method to produce an item of footwear with improved wearing comfort, and item of footwear produced according to this method|
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