EP3359713B1 - Fibre composite - Google Patents

Fibre composite Download PDF

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Publication number
EP3359713B1
EP3359713B1 EP16781175.1A EP16781175A EP3359713B1 EP 3359713 B1 EP3359713 B1 EP 3359713B1 EP 16781175 A EP16781175 A EP 16781175A EP 3359713 B1 EP3359713 B1 EP 3359713B1
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EP
European Patent Office
Prior art keywords
fibre
polyurethane
range
particulate
skin
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EP16781175.1A
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German (de)
English (en)
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EP3359713A1 (fr
Inventor
Parikshit GOSWAMI
Timothy Smith
Andrew HEBDEN
Stephen Russell
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University of Huddersfield
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University of Huddersfield
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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/04—Pigments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • D01D5/0985—Melt spinning methods with simultaneous stretching by means of a flowing gas (e.g. melt-blowing)
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes

Definitions

  • the invention relates to a polyurethane fibre/web, in particular to composite fibres/webs of polyurethane and a particulate, together with uses and processes for manufacture.
  • the invention relates to the provision of non-slip products, for instance, but not limited to, for applications in which silicone bands are currently used.
  • silicone bands include hosiery (hold-ups for instance), and intimate apparel (for instance brassieres and shapewear), where silicon bands are provided to prevent the garment shifting out of place during wear.
  • hold ups are only possible as a product because of the silicone band replacing the suspender belt which would otherwise retain the stocking on the leg.
  • Further applications include sportswear (such as swimwear and strap tops) and medical clothing applications (for instance compression garments or supports, such as knee or ankle supports).
  • silicone bands can cause allergies in some wearers, can lack flexibility leading to discomfort, and are not easily coloured.
  • the lack of breathability and concerns about silicone leaching can deter some consumers from wearing products including silicone bands.
  • the invention is intended to overcome or ameliorate at least some aspects of this problem.
  • a polyurethane and particulate composite fibre of mean particle diameter in the range 50nm - 50 ⁇ m as defined in the appended claims. It has been found that adding metal particulates (particles) to a polyurethane fibre modifies the friction properties of the fibre, generally resulting in an increase in the frictional coefficient relative to prior art polyurethane fibres and, as a result, in a web which has good non-slip/gripping properties, even where moisture is present, such as water, perspiration or other aqueous solutions so that the skin is wet. Further the webs have excellent shape recovery properties, preventing sagging of the garment in use, and loss of fit over time.
  • the particulate modifies the friction co-efficient of the fibre, making it suitable for use in non-slip applications.
  • modify is intended to mean that the friction co-efficient of the fibre is modified by at least ⁇ 1.8% relative to the value for any substrate when compared to present commercial polyurethane containing products (i.e. polyurethane without particulate matter).
  • the friction coefficient will be increased, for instance by at least ⁇ 1.8%, although often the modification will be far greater, for instance ⁇ 20%, or ⁇ 50% or even ⁇ 100%; often the modification will be an increase.
  • the particulate is selected from a metal, such as silver, copper, gold, titanium, zinc, iron, aluminium or combinations thereof. Silver will often be used to enhance the antimicrobial properties of the fibre. Additionally, pigment particulates may be used, as these can colour the fibre in addition to modifying the friction properties thereof. Further, inorganic compounds such as silica (such as Celite), calcium phosphate (such as ivory black), ceramic or glass microparticles may be added also as these are inexpensive, safe on the skin, nontoxic and have been shown to give high friction values. Polymeric particles may also be added, for instance polyethylene or cellulose acetate particles for the same reasons.
  • silver particles in the size range 5 - 10 ⁇ m has been found to offer particularly high static friction coefficients, as has silver in the range 0.5 - 1 ⁇ m, this latter particle size being especially effective when used at low levels, such as in the range 1 - 3 wt% or around 2 wt%.
  • the fibre will comprise in the range 1-25 wt% particulate, often in the range 2 - 10 wt%. At these ranges the particulate has been found to increase the friction coefficient of the fibre and resulting web, without, it is believed, reducing overall fibre strength significantly.
  • the range 2 - 10 wt% particles has been found to be particularly effective at providing a web which had good non-slip properties.
  • the particulate comprises particles of mean particle size in the range 50nm - 50 ⁇ m, often in the range 0.5 - 25 ⁇ m, in the range 0.5 - 10 ⁇ m or in the range 0.7 - 1.5 ⁇ m.
  • Particle size is important as it is believed that this offers one of the advantages over known technologies, in that particle sizes in this range offer a web with a very fine surface topography, such that the particles can settle in the grooves of the skin, providing intimate contact, without loss of comfort.
  • This micro-scale contact is much more effective at preventing slipping of the web across the skin than the macro-scale friction based contact provided by silicone band technologies.
  • the particles will be in the micro- or sub-micro scale rather than the nano-scale to ensure that toxicity is avoided.
  • the term "diameter” is intended to refer to the width of the fibre or particle across the largest part of its cross-section.
  • the fibre will be of mean diameter in the range 0.05 - 20 ⁇ m, often in the range 0.2 - 15 ⁇ m, or 1.5 - 5 ⁇ m.
  • the diameter of the fibre can be controlled through careful selection of the manufacturing method, for instance, melt blowing processes generally produce fibres of larger diameter than electrospinning techniques. Fibres of the diameters described above have been found to offer increased contact with the skin, because of the large surface area relative to fibres of larger diameters.
  • fibres with diameters in this range also allows for more particulate to be present at the surface of the fibre, improving the friction properties of the fibre relative to fibres of larger diameters.
  • An advantage of these techniques is that they inherently produce fibres with a range of diameters. This allows them to interact more effectively with the skin, as the range of fibre diameters is well suited to interacting with the range of groove sizes found in the skin.
  • a ratio of particle size to mean fibre diameter is in the range 0.05:1 - 2:5 This is desirable because at such ratios the friction with the skin is excellent.
  • a web comprising a plurality of fibres according to the first aspect of the invention.
  • a web according to the second aspect of the invention may be for non-slip applications, applications where fabric breathability is important and/or antimicrobial applications among others.
  • the web may be used in hosiery (hold-ups for instance), and intimate apparel (for instance brassieres and shapewear).
  • Further applications include sportswear (such as swimwear and strap tops) and medical clothing applications (for instance compression garments or supports, such as knee or ankle supports).
  • sportswear such as swimwear and strap tops
  • medical clothing applications for instance compression garments or supports, such as knee or ankle supports.
  • a particular advantage of the invention is that the fibres offer their friction modification properties regardless of whether the substrate, for instance skin, is wet or dry. This makes them particularly suitable for use in swimwear and sportswear applications.
  • a method of making a fibre according to the first aspect of the invention comprising forming the polyurethane and particulate composite fibre using a technique selected from but not limited to electrospinning or melt blowing. Often electrospinning will be used, such that the webs produced will be electrospun. Electrospinning offers the advantage that the fibre diameters are smaller than other methods, including melt-blowing. It is often the case that the fibre is sufficiently thin to interact with the grooves of the skin, working with the particulate to modify the friction co-efficient of the web. Often the method will comprise:
  • the particulate modifies the friction coefficient of the fibre.
  • the particulate comprises 1 - 25 wt% of the fibre, and the particulate is a metal selected from silver, copper, gold, titanium, zinc, iron, aluminium or combinations thereof.
  • the particulate comprises particles of mean particle size in the range 50nm - 50 ⁇ m.
  • the particulate comprises particles of multimodal, in some cases, bimodal particle size distribution.
  • the fibre will be of mean diameter in the range 0.2 - 20 ⁇ m, and a ratio of particle size to mean fibre diameter is in the range 0.05:1-2:5.
  • Polyurethane (Selectophore TM , at the desired wt%) was dissolved in DMF:THF (15 ml, 60:40 (v:v)) with stirring over 24 hours.
  • the particulate was added as defined in Table 1 below, slowly with stirring and allowed to disperse over the period of an hour.
  • a 10 wt% solution of Selectophore TM polyurethane was prepared using a 60:40 DMF:THF solvent ratio.
  • Selectophore TM polyurethane (1.5 g) was added to 15 ml of the solvent mixture with stirring and left to dissolve overnight.
  • Once dissolved particle/pigment additive was then added to the solution with continuous stirring for 10 minutes (according to Table 1), the solution was then added to the 10 ml syringe and electrospun for approximately 4 hours.
  • the aluminium foil collection plate was periodically rotated 90 degrees resulting in more uniform fibre coverage. The syringe and needles were wiped clean using tissue and then washed using acetone, followed by distilled water.
  • Friction Test The friction coefficient was determined in accordance with European Standard EN ISO 8295:2004. Applied force (F p ) of 1.96N via an 80g sled, and a 120g weight for a total weight of 200g. The speed was 100 mm/min. Sample size was 90 x 755mm.
  • F s represents the static friction force (N) measured by the machine and is always proportional to the static friction coefficient.
  • the static friction force arises from the interlocking of surface irregularities between the polyurethane sample and the test surface. As a force is applied horizontally to the test sample this interlocking force will increase to prevent any relative movement of the sled. This force increases until a threshold force is reached where motion of the sled begins. It is this threshold point of motion which defines the static force.
  • lipid films as well as surface structure of the skin will all affect frictional behaviour when in contact with textiles. For example, moist skin has an elevated frictional coefficient and dry skin has lower frictional coefficient. Age has been seen to have little effect on the frictional coefficient of human skin, while the anatomical region the skin is located has a large influence. Regarding gender; skin viscoelasticity was found to be comparable however, the friction of female skin shows significantly higher moisture sensitivity than that of men. It should be noted that as pig skin is a natural product, test results will vary from batch to batch. Therefore, each set of comparative tests were carried out on a single sample of pig skin to ensure the validity of the test. However, absolute values of static friction would be expected to (and have been observed to) vary slightly with each pig skin sample.
  • Webs The tested webs were electrospun polyurethane with added particulates.
  • Scanning Electron Microscopy The structure and morphology of the electrospun fibre mats produced were examined by scanning electron microscopy (SEM; Carl Zeiss EVO) at the Leeds Electron Microscopy and Spectroscopy (LEMAS) centre. SEM images were taken at different magnifications for all electrospun fibres for comparison.
  • Fibre Analysis Media Cybernetics Image Pro Analyser Plus was used to analyse images captured via SEM. The software was used to measure fibre diameters of samples; a minimum of 75 fibre diameters were recorded for each sample and digitised in order to obtain values for the mean, maximum and minimum fibre diameters for each sample.
  • Breathability tests were carried out following the BS 7209:1990 standard for 20 hours in a climate controlled laboratory (temperature 20 ⁇ 2 °C and relative humidity 65 ⁇ 5 %). Test samples were placed over a weighed amount of distilled water and the water allowed to evaporate slowly (through the fabric) prior to reweighing after a set time. This calculation of water loss can be applied to the following equation which allows the relative breathability of the fabric to be assessed.
  • WVP 24 ⁇ m At WVP is the water vapour permeability (g/m 2 /day), ⁇ m is the change in mass of water in grams, A is the area of the test material in m 2 and t equals the time in hours for the experiment.
  • the WVP index is a breathability ratio which compares the test samples to the reference fabric.
  • I WVP S WVP R ⁇ 100
  • I is the water vapour permeability index of the material
  • WVP s is water vapour permeability of a particular test sample
  • WVP R is the water vapour permeability value calculated for the polyester reference fabric.
  • the friction test was applied to a medium weight cotton weave fabric (100% plain cotton optic white 150cm CD12) as a skin substitute. It is known that for a fabric to adhere to the skin, a static force (N) of at least 2.0 and a friction coefficient ( ⁇ S) of at least 1.1 be observed.
  • N static force
  • ⁇ S friction coefficient
  • Table 2 Electrospun Fibre Composition Static Force (N) Friction Coefficient ( ⁇ S) Polyurethane 2.01 1.03 2 wt% silver particles of size range 0.5 - 1 ⁇ m 1.97 1.01 10 wt% silver particles of size range 0.5 - 1 ⁇ m 2.70 1.38 10 wt% ivory black particles 2.29 1.17
  • the friction test was also applied to a cotton gauze (CX202 cotton gauze L/State 96cm, CC28).
  • the gauze is a lighter weight muslin style fabric in which the fibre surfaces are sized so that they are smoother. It would be expected that a lower friction be observed in these tests.
  • the results are shown in Table 3 and Figure 4 .
  • inventive samples with silver particles have good friction properties indicating utility in non-slip apparel applications.
  • Porcine (pig) skin models are a useful tool to predict human interactions with compounds because both human and porcine skin have a spare hair coat, a thick well differentiated epidermis, a dermis that has a well-differentiated papillary body and a large content of elastic tissue, alongside similar size, distribution and communication of the dermal blood vessels.
  • the porcine and human skin differ in the type of sweat glands present in majority (apocrine vs. eccrine). In humans, apocrine glands are located mainly in the armpits, genital area and around the nipples, the prevalence of apocrine glands in porcine skin samples makes porcine skin an excellent model for human skin in these areas.
  • Table 4 (data for graph of Figure 5a) Electrospun Fibre Composition Static Force (N) Static Coefficient ( ⁇ S) Polyurethane 3.17 1.62 2 wt% silver particles of size range 0.5 - 1 ⁇ m 3.82 1.95 10 wt% silver particles of size range 0.5 - 1 ⁇ m 1.82 0.93 10 wt% silver particles of size range 0.7 - 1.3 ⁇ m 2.18 1.11 10 wt% silver particles of size range 5 - 8 ⁇ m 4.49 2.29 10 % Celite 0.02 - 0.1 mm 2.88 1.47 Silicone 2.28 1.16
  • Table 5 (data for graph of Figure 5b) Electrospun Fibre Composition Static force (N) Static coefficient ( ⁇ S) polyurethane only 4.74 2.42 10% Ag 4.0 -7.0 ⁇ m 5.06 2.58 2% Celite 0.02 - 0.1 mm 2.25 1.15 5% Celite 0.02 - 0.1 mm 2.5
  • the static friction observed is significantly higher than the minimum values for skin adherence, for instance 10% silver at 5 - 8 ⁇ m provides an excellent static friction coefficient.
  • the Figure 5c clearly shows that the fibres can outperform both conventional silicone systems and (specifically a woven elastane, Nylon and polyurethane system in which the polyurethane is present in the warp only). polyurethane systems. This series of tests also showed that pigment particles can also successfully form composite fibres, and that the pigment particles can also be sufficient, when used alone with polyurethane, to increase the friction properties of the web.
  • Figure 6a and the table above shows that the samples in this test performed well, compared to the silicone product of the prior art ("silicone") indicating that this material can provide higher friction in wet conditions.
  • the main contributing factor to the good frictional resistance in wet conditions is believed to be the porous nature of the electrospun material.
  • the water present on the skin surface is able to leach into the membrane (between the fibres) effectively removing some surface water and allowing the membrane to interact with the skin surface.
  • Figure 6b shows that for the same pig skin sample, that performance in the wet is superior to that in the dry.
  • the static friction values between all these samples are less variable than the dry tests. This supports the argument that it is the porosity of the material and not the added particles that leads predominantly to the high friction values in wet conditions.
  • the web has an antimicrobial effect on contact with the bacteria. There is no zone of inhibition around the web, indicating that there is no leaching of the particles from the web.
  • Electrospun fibrous polyurethane webs can be produced whilst simultaneously incorporating colour into the product in a single step, which provides a significant economic advantage in production relative to known multi-step methods.
  • Table 11 shows the results of the WVP testing: Table 11 WVP (g/m 2 /day) WVP Index (I) Polyester reference material 907.76 100.00 10% Electrospun polyurethane only 969.57 106.81 10% Electrospun PU with Ag 5.0 - 8.0 ⁇ m 874.76 96.36 10% Electrospun PU with Celite 0.02 - 0.1 mm only 941.28 103.69 Melt blown polyurethane only (75g/m 2 ) 992.36 109.32 Melt blown polyurethane only (94g/m 2 ) 974.81 107.39 Melt blown 1% Ag 5.0 - 8.0 ⁇ m 944.95 104.10
  • the samples are at least as breathable, and generally more so, than the polyester reference sample.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Nonwoven Fabrics (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (12)

  1. Fibre composite comprenant du polyuréthane et un particulat métallique,
    le métal étant sélectionné parmi l'argent, le cuivre, l'or, le titane, le zinc, le fer, l'aluminium ou des combinaisons de ceux-ci dans lesquelles le particulat a un diamètre moyen de particule dans la plage de 50 nm - 50 µm.
  2. Fibre selon la revendication 1, dans laquelle le particulat modifie le coefficient de friction de la fibre.
  3. Fibre selon la revendication 1 ou la revendication 2, comprenant du particulat dans la plage de 0,1 à 25% en poids.
  4. Fibre selon l'une quelconque des revendications précédentes, dans laquelle le particulat comprend des particules d'une taille moyenne de particule dans la plage 0,05 à 10 µm.
  5. Fibre selon l'une quelconque des revendications précédentes, dans laquelle le particulat comprend des particules dont la taille suit une distribution multimodale.
  6. Fibre selon l'une quelconque des revendications précédentes, d'un diamètre moyen dans la plage de 0,1 à 20 µm.
  7. Fibre selon l'une quelconque des revendications précédentes, dans laquelle un ratio de la taille de particule par rapport au diamètre de fibre moyenne se situe dans la plage 0,05:1 - 2:5.
  8. Nappe comprenant une pluralité de fibres selon l'une quelconque des revendications précédentes.
  9. Utilisation d'une toile selon la revendication 8, pour des applications anti-dérapantes.
  10. Utilisation d'une toile selon la revendication 9, pour des applications anti-dérapantes en présence d'eau.
  11. Utilisation d'une toile selon la revendication 8, pour des applications antimicrobiennes.
  12. Procédé de fabrication d'une fibre selon l'une quelconque des revendications 1 à 7, comprenant la formation de la fibre composite de polyuréthane et de particulat en utilisant une technique sélectionnée à partir de mais sans s'y limiter l'électrofilage ou le soufflage à l'état fondu.
EP16781175.1A 2015-10-08 2016-10-06 Fibre composite Active EP3359713B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB1517791.8A GB201517791D0 (en) 2015-10-08 2015-10-08 Composite fibre
PCT/GB2016/053112 WO2017060709A1 (fr) 2015-10-08 2016-10-06 Fibre composite

Publications (2)

Publication Number Publication Date
EP3359713A1 EP3359713A1 (fr) 2018-08-15
EP3359713B1 true EP3359713B1 (fr) 2022-01-26

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US (1) US20180291529A1 (fr)
EP (1) EP3359713B1 (fr)
JP (1) JP7046369B2 (fr)
CN (1) CN108138368B (fr)
CA (1) CA3001263A1 (fr)
DK (1) DK3359713T3 (fr)
ES (1) ES2910275T3 (fr)
GB (1) GB201517791D0 (fr)
PT (1) PT3359713T (fr)
WO (1) WO2017060709A1 (fr)

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US11572638B2 (en) 2017-07-01 2023-02-07 China Petroleum & Chemical Corporation Spider-silk-like polymer fiber, preparation method therefor and use thereof
CN108936891B (zh) * 2018-09-20 2020-10-13 厦门传福堂药业有限公司 一种除螨抗菌无纺布医用口罩
CN109112841A (zh) * 2018-09-20 2019-01-01 合肥巧织纺织科技有限公司 一种防霉抗油厨师服面料
CN111519266A (zh) * 2019-02-01 2020-08-11 钱远强 用于抗微生物的热熔纤维及其制备方法
CN110004508B (zh) * 2019-04-26 2021-09-17 广州增城市大发塑胶颜料有限公司 一种熔纺氨纶色母粒及其制备方法

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JPH11323662A (ja) * 1998-05-11 1999-11-26 Du Pont Toray Co Ltd ポリウレタン系弾性繊維

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JP7046369B2 (ja) 2022-04-04
JP2018535331A (ja) 2018-11-29
DK3359713T3 (da) 2022-04-11
CN108138368A (zh) 2018-06-08
CN108138368B (zh) 2021-08-06
PT3359713T (pt) 2022-03-30
EP3359713A1 (fr) 2018-08-15
US20180291529A1 (en) 2018-10-11
ES2910275T3 (es) 2022-05-12
CA3001263A1 (fr) 2017-04-13
WO2017060709A1 (fr) 2017-04-13

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