EP3645776A1 - Nonwoven article and method of making the same - Google Patents

Nonwoven article and method of making the same

Info

Publication number
EP3645776A1
EP3645776A1 EP18749509.8A EP18749509A EP3645776A1 EP 3645776 A1 EP3645776 A1 EP 3645776A1 EP 18749509 A EP18749509 A EP 18749509A EP 3645776 A1 EP3645776 A1 EP 3645776A1
Authority
EP
European Patent Office
Prior art keywords
nonwoven
particle coating
fiber web
thermally
softenable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP18749509.8A
Other languages
German (de)
French (fr)
Other versions
EP3645776B1 (en
Inventor
Megan A. CREIGHTON
Emily S. Goenner
Raymond P. Johnston
Morgan A. PRIOLO
Joel A. Getschel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Publication of EP3645776A1 publication Critical patent/EP3645776A1/en
Application granted granted Critical
Publication of EP3645776B1 publication Critical patent/EP3645776B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, e.g. by ultrasonic waves, corona discharge, irradiation, electric currents or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/005—Laser beam treatment
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/407—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties containing absorbing substances, e.g. activated carbon
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
    • D04H1/5412—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres sheath-core
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides

Definitions

  • the present disclosure broadly relates to methods for improving the durability of particle coatings on nonwoven fiber webs, and articles preparable thereby.
  • Coatings of powders (e.g., graphite) on nonwoven fiber webs are widely known; however, the powders are typically loosely bound to the fibers and are prone to falling off.
  • Various methods have been devised to overcome this problem, including: 1) use of a curable resin applied to the fibers prior to powder coating, and that when cured securely binds the powder to the fibers; 2) in those cases where the nonwoven fiber web is durable enough, the powder may be rubbed onto it in a process known as triboadhesion; and 3) the powders can be selected to contain binder components that can fuse to the fibers on heating.
  • each of these techniques has disadvantages if a particle coating consisting essentially of inorganic particles is desired.
  • the presence of binder components in approaches 1) and 3) would be unacceptable in such a situation, and durability of particle coatings made by approach 2) is generally problematic as particle coatings are typically prone to damage by methods such as abrasion and/or rinsing with solvent.
  • the present disclosure provides an easy method to enhance the durability of particle coatings that involves instantaneous heating by exposure to pulsed electromagnetic radiation having at least one wavelength in the range of 200 nm to 1000 nm.
  • pulsed electromagnetic radiation having at least one wavelength in the range of 200 nm to 1000 nm.
  • the present inventors believe that the modulated electromagnetic radiation hitting the particles in the particle coating is converted to heat that is localized adjacent to the particles thereby softening the adjacent fibers and increasing adhesion between those fibers and the particles.
  • the present disclosure provides a method of making a nonwoven article, the method comprising exposing a particle coating disposed on a thermally-softenable nonwoven fiber web to pulsed electromagnetic radiation having at least one wavelength in the range of 200 to 1000 nanometers, wherein the particle coating comprises loosely bound distinct particles that are not chemically bonded to each other and are not retained in a binder material other than the thermally-softenable nonwoven fiber web, and wherein the pulsed electromagnetic radiation has sufficient fluence and pulse width to increase bonding force between at least a portion of the loosely bound distinct particles and the thermally- softenable nonwoven fiber web.
  • the present disclosure provides a nonwoven article made according to the foregoing method of the present disclosure.
  • the present disclosure provides a nonwoven article comprising a thermally- softenable nonwoven fiber web having a particle coating disposed thereon, wherein the particle coating comprises distinct particles that are not chemically bonded to each other and are not retained in a binder material other than the thermally-softenable nonwoven fiber web, and wherein the particle coating is at least 60 percent retained after a one minute immersion in isopropanol at 22°C.
  • visible light refers to electromagnetic radiation having a wavelength of 400 to 700 nanometers (nm).
  • powder refers to a free-flowing collection of minute particles.
  • pulsed electromagnetic radiation refers to electromagnetic radiation that is modulated to become a series of discrete spikes with increased intensity.
  • the spikes may be relative to a background level of electromagnetic radiation that is negligible or zero, or the background level may be at a higher level that is substantially ineffective to increase adhesion of particles in the particle coating to the fiber.
  • thermo-softenable means softenable upon heating.
  • particle coating refers to a coating of minute particles which may or may not be free- flowing.
  • Fig. 1 is an enlarged schematic side view of an exemplary article 100 according to the present disclosure.
  • the present disclosure provides an easy method to enhance the durability of particle coatings on nonwoven fiber webs using instantaneous heating by exposure to a modulated source of electromagnetic radiation.
  • exemplary article 100 comprises a thermally-softenable nonwoven fiber web 110 having a particle coating 120 disposed thereon.
  • Particle coatings on thermally-softenable nonwoven (e.g., thermoplastic) fiber webs can be carried out by various known methods including, for example, exposure to an aerosolized particle cloud, contact with a powder bed, coating with a solvent-based particle dispersion coating followed by evaporation of solvent, and/or powder-rubbed (rubbing dry particles against a substrate to form a coating of the powder particles). Examples of powder-rubbing methods can be found in U. S. Pat. Nos.
  • Useful particle coatings comprise minute loosely bound particles capable of absorbing at least one wavelength of the pulsed electromagnetic radiation, preferably corresponding to a majority of the energy of the pulsed electromagnetic radiation. Suitable particles are preferably at least substantially unaffected by electromagnetic radiation, but are moderate to strong absorbers of it. This is desirable to maximize the light (electromagnetic radiation) to heat conversion yield without altering the chemical nature of the particles .
  • Exemplary suitable particles include graphite, clays, hexagonal boron nitride, pigments, inorganic oxides (e.g., alumina, calcia, silica, ceria, zinc oxide, or titania), metal(s), organic polymeric particles (e.g., polytetrafluoroethylene, polyvinylidene difluoride), carbides (e.g., silicon carbide), flame retardants (e.g., aluminum trihydrate, aluminum hydroxide, magnesium hydroxide, sodium hexametaphosphate, organic phosphonates and phosphates and ester thereof), carbonates (e.g., calcium carbonate, magnesium carbonate, sodium carbonate), dry biological powders (e.g., spores, bacteria), and combinations thereof.
  • organic polymeric particles e.g., polytetrafluoroethylene, polyvinylidene difluoride
  • carbides e.g., silicon carbide
  • flame retardants e.g., aluminum trihydrate
  • the particles have an average particle size of 0.1 to 100 micrometers, more preferably 1 to 50 micrometers, and more preferably 1 to 25 micrometers, although this is not a requirement.
  • Graphite and hexagonal boron nitride are particularly preferred in many applications
  • the particle coating Prior to exposure to the electromagnetic radiation the particle coating comprises loosely bound distinct particles that are not chemically bonded to each other, and are not retained in a binder material other than the thermally-softenable nonwoven fiber web itself.
  • the thermally-softenable nonwoven fiber web preferably comprises thermoplastic fibers, although non-thermoplastic fibers may be used alone or in combination with thermoplastic fibers, for example.
  • the fibers of the thermally-softenable nonwoven fiber web are non- tacky and/or non-thermosetting, although this is not a requirement.
  • thermally-softenable nonwoven fiber webs include meltspun fiber webs, blown microfiber webs, needletacked staple fiber webs, thermally bonded airlaid webs, and spunlace webs.
  • the thermally-softenable nonwoven fiber web may be made by any suitable nonwoven fiber web making process. Examples include meltspun, blown microfiber (BMF), air-laid processes, wet-laid processes, and spunlace. These and other methods will be known to those of skill in the art.
  • thermally-softenable nonwoven fiber web comprising thermally-softenable fibers are commercially available.
  • the thermally-softenable nonwoven fiber web may be of any basis weight and may be densely compacted or lofty and open, for example.
  • thermoplastic polymers materials that may be used to make nonwoven fiber web comprising thermoplastic fibers are disclosed in U. S. Pat. Nos.
  • thermoplastic fiber web have a higher melting core and a lower melting sheath.
  • the higher melting core should preferably be at least 25°C.
  • the pulsed electromagnetic radiation may come from any source(s) capable of generating sufficient fluence and pulse duration to effect sufficient heating of the nonwoven fiber web to cause the particle coating to bind more tightly to it.
  • At least three types of sources may be effective for this purpose: flashlamps, lasers, and shuttered lamps.
  • flashlamps lasers
  • shuttered lamps The selection of appropriate sources will typically be influenced by desired process conditions such as, for example, line speed, line width, spectral output, and cost.
  • the pulsed electromagnetic radiation is generated using a flashlamp.
  • a flashlamp xenon and krypton flashlamps are the most common. Both provide a broad continuous output over the wavelength range 200 to 1000 nanometers, however the krypton flashlamps have higher relative output intensity in the 750-900 nm wavelength range as compared to xenon flashlamps which have more relative output in the 300 to 750 nm wavelength range.
  • xenon flashlamps are preferred for most applications, and especially those involving graphite particles.
  • Many suitable xenon and krypton flashlamps are commercially available from vendors such as Excelitas Technologies Corp. of Waltham, Massachusetts and Heraeus of Hanau, Germany.
  • the pulsed electromagnetic radiation can be generated using a pulsed laser.
  • Suitable lasers may include, for example, excimer lasers (e.g., XeF (351 nm), XeCl (308 nm), and KrF (248 nm)), solid state lasers (e.g., ruby 694 nm)), and nitrogen lasers (337.1 nm).
  • the pulsed electromagnetic radiation is generated using a continuous light source and a shutter (preferably a rotating aperture/shutter to reduce overheating of the shutter).
  • Suitable light sources may include high-pressure mercury lamps, xenon lamps, and metal-halide lamps.
  • the electromagnetic radiation spectrum is preferably most intense at wavelength(s) that are strongly absorbed by the particles, although this is not a requirement.
  • the electromagnetic radiation spectrum is preferably most intense in spectral regions in which the particles are least reflective, although this is not a requirement.
  • the source of pulsed electromagnetic radiation is capable of generating a high fluence (energy density) with high intensity (high power per unit area), although this is not a requirement.
  • high fluence energy density
  • intensity high power per unit area
  • the pulse duration is preferably short; e.g., less than 10 milliseconds, less than 1 millisecond, less than 100 microseconds, less than 10 microseconds, or even less than 1 microsecond, although this is not a requirement.
  • the pulsed electromagnetic radiation preferably be powerful, but the exposure area is preferably large and the pulse repetition rate is preferably fast (e.g., 100 to 500 Hz).
  • the resultant exposed particle-coated nonwoven fiber web may be immersed in a solvent such as, e.g., isopropanol for a fixed interval (e.g., 1, 2, 3, 4, or even 5 minutes, or longer) at about 22°C (e.g., room temperature), and then removed, dried, and weighed. Weight loss of powder can then be determined by subtraction.
  • the solvent should be selected such that it does not dissolve the nonwoven fiber web.
  • the particulate coating of the nonwoven article is sufficiently bonded to the nonwoven fiber web so that after one minute of immersion in isopropanol at 22°C at least 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or even at least 90 percent of the particulate coating remains bonded to the nonwoven fiber web.
  • the present disclosure provides a method of making a nonwoven article, the method comprising exposing a particle coating disposed on a thermally-softenable nonwoven fiber web to pulsed electromagnetic radiation having at least one wavelength in the range of 200 to 1000 nanometers, wherein the particle coating comprises loosely bound distinct particles that are not chemically bonded to each other and are not retained in a binder material other than the thermally- softenable nonwoven fiber web, and wherein the pulsed electromagnetic radiation has sufficient fluence and pulse width to increase bonding force between at least a portion of the loosely bound distinct particles and the thermally-softenable nonwoven fiber web.
  • the present disclosure provides a method according to the first embodiment, wherein the particle coating comprises at least one of graphite or hexagonal boron nitride.
  • the present disclosure provides a method according to the first or second embodiment, wherein the particle coating consists essentially of graphite.
  • the present disclosure provides a method according to any one of the first to third embodiments, wherein the pulsed electromagnetic radiation is generated using a flashlamp.
  • the present disclosure provides a method according to any one of the first to third embodiments, wherein the pulsed electromagnetic radiation is generated using a pulsed laser.
  • the present disclosure provides a method according to any one of the first to third embodiments, wherein the pulsed electromagnetic radiation is generated using a continuous light source and a shutter.
  • the present disclosure provides a method according to any one of the first to sixth embodiments, wherein the thermally-softenable nonwoven fiber web comprises fibers having a higher melting core and a lower melting sheath.
  • the present disclosure provides a nonwoven article made according to any one of the first to seventh embodiments of the present disclosure.
  • the present disclosure provides a nonwoven article comprising a thermally-softenable nonwoven fiber web having a particle coating disposed thereon, wherein the particle coating comprises distinct particles that are not chemically bonded to each other and are not retained in a binder material other than the thermally-softenable nonwoven fiber web, and wherein the particle coating is at least 60 percent retained after a one minute immersion in isopropanol at 22°C.
  • the present disclosure provides a nonwoven article according to the ninth embodiment, wherein the particle coating comprises at least one of graphite or hexagonal boron nitride.
  • the present disclosure provides a nonwoven article according to the ninth or tenth embodiment, wherein the particle coating consists essentially of graphite.
  • the present disclosure provides a nonwoven article according to any one of the ninth to eleventh embodiments, wherein the particle coating is at least 90 percent retained after the one minute immersion in isopropanol at 22°C.
  • the present disclosure provides a nonwoven article according to any one of the ninth to twelfth embodiments, wherein the thermally-softenable nonwoven fiber web comprises fibers having a higher melting core and a lower melting sheath.
  • graphite coatings were applied on PE nonwoven substrates by placing a strip of nonwoven approximately 1.5 inches (3.8 cm) by 10 inches (25.4 cm) in dimension and a small amount of MICRO850 in a sealable plastic bag. The bag was then sealed and shaken, until the PE nonwoven was visibly covered in graphite. The nonwoven was then removed, and excess graphite particles were removed by blowing with compressed nitrogen at a pressure of 40 pounds per square inch.
  • the relative amount of graphite coating deposited on the PE nonwoven film was determined by measuring the weight of the sample before and after the process.
  • Nonwoven samples were completely immersed (i.e., submerged) in a bath of IP A at room temperature (22°C) and stirred by hand for 1 minute. The samples were then removed and spread onto a clean surface in a chemical hood and allowed to dry completely.
  • CEX-A and EX-1 to EX- 12 were graphite coated PE nonwoven substrates prepared as described above.
  • the substrate was not subjected to IPL and was a control sample.
  • EX-1 to EX-11 were prepared by subjecting the samples to an intense pulsed light irradiation (IPL).
  • the source used was a Xe flashlamp, commercially obtained from Xenon Corporation, Wilmington, Massachusetts, as a SINTERON S-2100 Xe flashlamp equipped with Type C bulb. Samples were placed beneath a quartz plate for the irradiation process.
  • the substrate was treated 1 time at a pulse rate of 1 Hz and an energy density of 0.1 J/cm 2 .
  • the substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
  • the substrate was treated 3 times at a pulse rate of 1 Hz and an energy density of 0.1 J/cm 2 .
  • the substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
  • the substrate was treated 5 times at a pulse rate of 1 Hz and an energy density of 0.1 J/cm 2 .
  • the substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
  • the substrate was treated 1 time at a pulse rate of 1 Hz and an energy density of 0.2 J/cm 2 .
  • the substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
  • the substrate was treated 3 times at a pulse rate of 1 Hz and an energy density of 0.2 J/cm 2 .
  • the substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
  • the substrate was treated 5 times at a pulse rate of 1 Hz and an energy density of 0.2 J/cm 2 .
  • the substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
  • the substrate was treated 1 time at a pulse rate of 1 Hz and an energy density of 0.3 J/cm 2 .
  • the substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
  • the substrate was treated 3 times at a pulse rate of 1 Hz and an energy density of 0.3 J/cm 2 .
  • the substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
  • the substrate was treated 5 times at a pulse rate of 1 Hz and an energy density of 0.3 J/cm 2 .
  • the substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
  • the substrate was treated 1 time at a pulse rate of 1 Hz and an energy density of 0.4 J/cm 2 . The substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
  • the substrate was treated 3 times at a pulse rate of 1 Hz and an energy density of 0.4 J/cm 2 . The substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Procédé comprenant l'exposition d'un revêtement de particules disposé sur une bande de fibres non tissées comprenant des fibres ramollies thermiquement à un rayonnement électromagnétique pulsé ayant au moins une longueur d'onde dans la plage de 200 nm à 1000 nm. Le revêtement de particules comprend des particules distinctes qui ne sont pas liées chimiquement les unes aux autres, et ne sont pas retenues dans un matériau liant autre que les fibres ramollies thermiquement. L'invention concerne également des articles non tissés comprenant une bande de fibres non tissées ramollies thermiquement ayant un revêtement de particules disposé sur celle-ci. Le revêtement de particules comprend des particules distinctes qui ne sont pas liées chimiquement les unes aux autres et ne sont pas retenues dans un matériau liant autre que la bande de fibres non tissées ramollies thermiquement. Le revêtement de particules est maintenu au moins à 60 pour cent après une immersion d'une minute dans de l'isopropanol à 22 °C.A method comprising exposing a particle coating disposed on a nonwoven fiber web comprising thermally softened fibers to pulsed electromagnetic radiation having at least one wavelength in the range of 200 nm to 1000 nm. The particle coating comprises discrete particles that are not chemically bonded to one another, and are not retained in a binder material other than thermally softened fibers. The invention also relates to nonwoven articles comprising a strip of heat-softened nonwoven fibers having a particle coating disposed thereon. The particle coating comprises discrete particles that are not chemically bonded to one another and are not retained in a binder material other than the thermally softened nonwoven fiber web. The particle coating is maintained at least 60 percent after one minute immersion in isopropanol at 22 ° C.

Description

NONWOVEN ARTICLE AND METHOD OF MAKING THE SAME
TECHNICAL FIELD
The present disclosure broadly relates to methods for improving the durability of particle coatings on nonwoven fiber webs, and articles preparable thereby.
BACKGROUND
Coatings of powders (e.g., graphite) on nonwoven fiber webs are widely known; however, the powders are typically loosely bound to the fibers and are prone to falling off. Various methods have been devised to overcome this problem, including: 1) use of a curable resin applied to the fibers prior to powder coating, and that when cured securely binds the powder to the fibers; 2) in those cases where the nonwoven fiber web is durable enough, the powder may be rubbed onto it in a process known as triboadhesion; and 3) the powders can be selected to contain binder components that can fuse to the fibers on heating.
However, each of these techniques has disadvantages if a particle coating consisting essentially of inorganic particles is desired. For example, the presence of binder components in approaches 1) and 3) would be unacceptable in such a situation, and durability of particle coatings made by approach 2) is generally problematic as particle coatings are typically prone to damage by methods such as abrasion and/or rinsing with solvent.
SUMMARY
Advantageously, the present disclosure provides an easy method to enhance the durability of particle coatings that involves instantaneous heating by exposure to pulsed electromagnetic radiation having at least one wavelength in the range of 200 nm to 1000 nm. Without wishing to be bound by theory, the present inventors believe that the modulated electromagnetic radiation hitting the particles in the particle coating is converted to heat that is localized adjacent to the particles thereby softening the adjacent fibers and increasing adhesion between those fibers and the particles.
In a first aspect, the present disclosure provides a method of making a nonwoven article, the method comprising exposing a particle coating disposed on a thermally-softenable nonwoven fiber web to pulsed electromagnetic radiation having at least one wavelength in the range of 200 to 1000 nanometers, wherein the particle coating comprises loosely bound distinct particles that are not chemically bonded to each other and are not retained in a binder material other than the thermally-softenable nonwoven fiber web, and wherein the pulsed electromagnetic radiation has sufficient fluence and pulse width to increase bonding force between at least a portion of the loosely bound distinct particles and the thermally- softenable nonwoven fiber web.
By this technique, durability of the particle coating is improved, while alternative heating methods were prone to damaging (e.g., warping) the thermally-softenable nonwoven fiber web.
Accordingly, in a second aspect, the present disclosure provides a nonwoven article made according to the foregoing method of the present disclosure.
In a third aspect, the present disclosure provides a nonwoven article comprising a thermally- softenable nonwoven fiber web having a particle coating disposed thereon, wherein the particle coating comprises distinct particles that are not chemically bonded to each other and are not retained in a binder material other than the thermally-softenable nonwoven fiber web, and wherein the particle coating is at least 60 percent retained after a one minute immersion in isopropanol at 22°C.
As used herein:
The term "visible light" refers to electromagnetic radiation having a wavelength of 400 to 700 nanometers (nm).
The term "powder" refers to a free-flowing collection of minute particles.
The term "pulsed electromagnetic radiation" refers to electromagnetic radiation that is modulated to become a series of discrete spikes with increased intensity. The spikes may be relative to a background level of electromagnetic radiation that is negligible or zero, or the background level may be at a higher level that is substantially ineffective to increase adhesion of particles in the particle coating to the fiber.
The term "thermally-softenable" means softenable upon heating.
The term "particle coating" refers to a coating of minute particles which may or may not be free- flowing.
Features and advantages of the present disclosure will be further understood upon consideration of the detailed description as well as the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is an enlarged schematic side view of an exemplary article 100 according to the present disclosure.
It should be understood that numerous other modifications and embodiments can be devised by those skilled in the art, which fall within the scope and spirit of the principles of the disclosure.
DETAILED DESCRIPTION
Advantageously, the present disclosure provides an easy method to enhance the durability of particle coatings on nonwoven fiber webs using instantaneous heating by exposure to a modulated source of electromagnetic radiation.
Referring now to Fig. 1, exemplary article 100 comprises a thermally-softenable nonwoven fiber web 110 having a particle coating 120 disposed thereon.
Particle coatings on thermally-softenable nonwoven (e.g., thermoplastic) fiber webs can be carried out by various known methods including, for example, exposure to an aerosolized particle cloud, contact with a powder bed, coating with a solvent-based particle dispersion coating followed by evaporation of solvent, and/or powder-rubbed (rubbing dry particles against a substrate to form a coating of the powder particles). Examples of powder-rubbing methods can be found in U. S. Pat. Nos.
6,511,701 B l (Divigalpitiya et al), 6,025,014 (Stango), and 4,741,918 (Nagybaczon et al.). The remaining methods will be familiar to those of ordinary skill in the art.
Useful particle coatings comprise minute loosely bound particles capable of absorbing at least one wavelength of the pulsed electromagnetic radiation, preferably corresponding to a majority of the energy of the pulsed electromagnetic radiation. Suitable particles are preferably at least substantially unaffected by electromagnetic radiation, but are moderate to strong absorbers of it. This is desirable to maximize the light (electromagnetic radiation) to heat conversion yield without altering the chemical nature of the particles .
Exemplary suitable particles include graphite, clays, hexagonal boron nitride, pigments, inorganic oxides (e.g., alumina, calcia, silica, ceria, zinc oxide, or titania), metal(s), organic polymeric particles (e.g., polytetrafluoroethylene, polyvinylidene difluoride), carbides (e.g., silicon carbide), flame retardants (e.g., aluminum trihydrate, aluminum hydroxide, magnesium hydroxide, sodium hexametaphosphate, organic phosphonates and phosphates and ester thereof), carbonates (e.g., calcium carbonate, magnesium carbonate, sodium carbonate), dry biological powders (e.g., spores, bacteria), and combinations thereof. Preferably, the particles have an average particle size of 0.1 to 100 micrometers, more preferably 1 to 50 micrometers, and more preferably 1 to 25 micrometers, although this is not a requirement. Graphite and hexagonal boron nitride are particularly preferred in many applications
Prior to exposure to the electromagnetic radiation the particle coating comprises loosely bound distinct particles that are not chemically bonded to each other, and are not retained in a binder material other than the thermally-softenable nonwoven fiber web itself.
The thermally-softenable nonwoven fiber web preferably comprises thermoplastic fibers, although non-thermoplastic fibers may be used alone or in combination with thermoplastic fibers, for example. In preferred embodiments, the fibers of the thermally-softenable nonwoven fiber web are non- tacky and/or non-thermosetting, although this is not a requirement.
Exemplary suitable thermally-softenable nonwoven fiber webs include meltspun fiber webs, blown microfiber webs, needletacked staple fiber webs, thermally bonded airlaid webs, and spunlace webs. The thermally-softenable nonwoven fiber web may be made by any suitable nonwoven fiber web making process. Examples include meltspun, blown microfiber (BMF), air-laid processes, wet-laid processes, and spunlace. These and other methods will be known to those of skill in the art.
Alternatively, a wide array of nonwoven fiber web comprising thermally-softenable fibers are commercially available. The thermally-softenable nonwoven fiber web may be of any basis weight and may be densely compacted or lofty and open, for example.
Some examples of thermoplastic polymers that may be suitable for fiber-forming include polycarbonates, polyesters, polyamides, polyurethanes, polyacrylics (e.g., polyacrylonitrile), block copolymers such as styrene-butadiene-styrene and styrene-isoprene-styrene block copolymers, polyolefins such as polyethylene, polypropylene, polybutylene, and poly(4-methyl-l-pentene), and combinations of such resins. Examples of thermoplastic polymers materials that may be used to make nonwoven fiber web comprising thermoplastic fibers are disclosed in U. S. Pat. Nos. 5,706,804 (Baumann et al.), 4,419,993 (Peterson), Re 28,102 (Mayhew), 5,472,481 (Jones et al.), 5,411,576 (Jones et al.), and 5,908,598 (Rousseau et al). In some preferred methods, at least a portion of the fibers in the
thermoplastic fiber web have a higher melting core and a lower melting sheath. In such cases, the higher melting core should preferably be at least 25°C.
The pulsed electromagnetic radiation may come from any source(s) capable of generating sufficient fluence and pulse duration to effect sufficient heating of the nonwoven fiber web to cause the particle coating to bind more tightly to it. At least three types of sources may be effective for this purpose: flashlamps, lasers, and shuttered lamps. The selection of appropriate sources will typically be influenced by desired process conditions such as, for example, line speed, line width, spectral output, and cost.
Preferably, the pulsed electromagnetic radiation is generated using a flashlamp. Of these, xenon and krypton flashlamps are the most common. Both provide a broad continuous output over the wavelength range 200 to 1000 nanometers, however the krypton flashlamps have higher relative output intensity in the 750-900 nm wavelength range as compared to xenon flashlamps which have more relative output in the 300 to 750 nm wavelength range. In general, xenon flashlamps are preferred for most applications, and especially those involving graphite particles. Many suitable xenon and krypton flashlamps are commercially available from vendors such as Excelitas Technologies Corp. of Waltham, Massachusetts and Heraeus of Hanau, Germany.
In another embodiment, the pulsed electromagnetic radiation can be generated using a pulsed laser. Suitable lasers may include, for example, excimer lasers (e.g., XeF (351 nm), XeCl (308 nm), and KrF (248 nm)), solid state lasers (e.g., ruby 694 nm)), and nitrogen lasers (337.1 nm).
In yet another embodiment, the pulsed electromagnetic radiation is generated using a continuous light source and a shutter (preferably a rotating aperture/shutter to reduce overheating of the shutter). Suitable light sources may include high-pressure mercury lamps, xenon lamps, and metal-halide lamps.
For maximum efficiency, the electromagnetic radiation spectrum is preferably most intense at wavelength(s) that are strongly absorbed by the particles, although this is not a requirement. Likewise, in the case of reflective particles, the electromagnetic radiation spectrum is preferably most intense in spectral regions in which the particles are least reflective, although this is not a requirement.
Preferably, the source of pulsed electromagnetic radiation is capable of generating a high fluence (energy density) with high intensity (high power per unit area), although this is not a requirement. These conditions assure that the sufficient heat is absorbed to effect increased adhesion of the particles to the fibers. However, the combination of intensity and fluence should not be so great/high as to cause ablation, excessive degradation, or volatilization of fibers in the nonwoven fiber web. Selection of appropriate conditions is within the capability of one of ordinary skill in the art. To minimize heating of interior portions of the fibers that cannot interact with the particles on the nonwoven fiber web, the pulse duration is preferably short; e.g., less than 10 milliseconds, less than 1 millisecond, less than 100 microseconds, less than 10 microseconds, or even less than 1 microsecond, although this is not a requirement.
To achieve high line speed in continuous manufacturing processes, not only should the pulsed electromagnetic radiation preferably be powerful, but the exposure area is preferably large and the pulse repetition rate is preferably fast (e.g., 100 to 500 Hz).
In order to evaluate durability, the resultant exposed particle-coated nonwoven fiber web may be immersed in a solvent such as, e.g., isopropanol for a fixed interval (e.g., 1, 2, 3, 4, or even 5 minutes, or longer) at about 22°C (e.g., room temperature), and then removed, dried, and weighed. Weight loss of powder can then be determined by subtraction. The solvent should be selected such that it does not dissolve the nonwoven fiber web.
Preferably, the particulate coating of the nonwoven article is sufficiently bonded to the nonwoven fiber web so that after one minute of immersion in isopropanol at 22°C at least 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or even at least 90 percent of the particulate coating remains bonded to the nonwoven fiber web.
SELECT EMBODIMENTS OF THE PRESENT DISCLOSURE
In a first embodiment, the present disclosure provides a method of making a nonwoven article, the method comprising exposing a particle coating disposed on a thermally-softenable nonwoven fiber web to pulsed electromagnetic radiation having at least one wavelength in the range of 200 to 1000 nanometers, wherein the particle coating comprises loosely bound distinct particles that are not chemically bonded to each other and are not retained in a binder material other than the thermally- softenable nonwoven fiber web, and wherein the pulsed electromagnetic radiation has sufficient fluence and pulse width to increase bonding force between at least a portion of the loosely bound distinct particles and the thermally-softenable nonwoven fiber web.
In a second embodiment, the present disclosure provides a method according to the first embodiment, wherein the particle coating comprises at least one of graphite or hexagonal boron nitride.
In a third embodiment, the present disclosure provides a method according to the first or second embodiment, wherein the particle coating consists essentially of graphite.
In a fourth embodiment, the present disclosure provides a method according to any one of the first to third embodiments, wherein the pulsed electromagnetic radiation is generated using a flashlamp.
In a fifth embodiment, the present disclosure provides a method according to any one of the first to third embodiments, wherein the pulsed electromagnetic radiation is generated using a pulsed laser.
In a sixth embodiment, the present disclosure provides a method according to any one of the first to third embodiments, wherein the pulsed electromagnetic radiation is generated using a continuous light source and a shutter. In a seventh embodiment, the present disclosure provides a method according to any one of the first to sixth embodiments, wherein the thermally-softenable nonwoven fiber web comprises fibers having a higher melting core and a lower melting sheath.
In an eighth embodiment, the present disclosure provides a nonwoven article made according to any one of the first to seventh embodiments of the present disclosure.
In a ninth embodiment, the present disclosure provides a nonwoven article comprising a thermally-softenable nonwoven fiber web having a particle coating disposed thereon, wherein the particle coating comprises distinct particles that are not chemically bonded to each other and are not retained in a binder material other than the thermally-softenable nonwoven fiber web, and wherein the particle coating is at least 60 percent retained after a one minute immersion in isopropanol at 22°C.
In a tenth embodiment, the present disclosure provides a nonwoven article according to the ninth embodiment, wherein the particle coating comprises at least one of graphite or hexagonal boron nitride.
In an eleventh embodiment, the present disclosure provides a nonwoven article according to the ninth or tenth embodiment, wherein the particle coating consists essentially of graphite.
In a twelfth embodiment, the present disclosure provides a nonwoven article according to any one of the ninth to eleventh embodiments, wherein the particle coating is at least 90 percent retained after the one minute immersion in isopropanol at 22°C.
In a thirteenth embodiment, the present disclosure provides a nonwoven article according to any one of the ninth to twelfth embodiments, wherein the thermally-softenable nonwoven fiber web comprises fibers having a higher melting core and a lower melting sheath.
Objects and advantages of this disclosure are further illustrated by the following non-limiting examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this disclosure. EXAMPLES
Unless otherwise noted, all parts, percentages, ratios, etc. in the Examples and the rest of the specification are by weight. All reagents used in the examples were obtained, or are available, from general chemical suppliers such as, for example, Sigma-Aldrich Company, Saint Louis, Missouri, or may be synthesized by conventional methods. MATERIALS USED IN THE EXAMPLES
GENERAL METHOD FOR COATING GRAPHITE ONTO SUBSTRATES
To make Examples and Comparative Examples described below, graphite coatings were applied on PE nonwoven substrates by placing a strip of nonwoven approximately 1.5 inches (3.8 cm) by 10 inches (25.4 cm) in dimension and a small amount of MICRO850 in a sealable plastic bag. The bag was then sealed and shaken, until the PE nonwoven was visibly covered in graphite. The nonwoven was then removed, and excess graphite particles were removed by blowing with compressed nitrogen at a pressure of 40 pounds per square inch.
The relative amount of graphite coating deposited on the PE nonwoven film was determined by measuring the weight of the sample before and after the process.
GENERAL METHODS FOR DETERMINING DURABILITY
The samples prepared according to Examples and Comparative Examples described below, were tested for durability (resilience of coatings).
Nonwoven samples were completely immersed (i.e., submerged) in a bath of IP A at room temperature (22°C) and stirred by hand for 1 minute. The samples were then removed and spread onto a clean surface in a chemical hood and allowed to dry completely.
All reported percentages of graphite retained (%R) were calculations from the following equation:
o/oR = 100 M^ ~ M^
M9,i
Where Mg i is the mass of graphite on the nonwoven just prior to immersion in isopropanol, and M is the mass of graphite remaining on the nonwoven after the wash step. EXAMPLES 1-11 (EX-1 to EX- 11) and COMPARATIVE EXAMPLE A (CEX-A) CEX-A and EX-1 to EX- 12 were graphite coated PE nonwoven substrates prepared as described above. For CEX-A, the substrate was not subjected to IPL and was a control sample. EX-1 to EX-11 were prepared by subjecting the samples to an intense pulsed light irradiation (IPL). In all cases of IPL, the source used was a Xe flashlamp, commercially obtained from Xenon Corporation, Wilmington, Massachusetts, as a SINTERON S-2100 Xe flashlamp equipped with Type C bulb. Samples were placed beneath a quartz plate for the irradiation process.
For EX-1, the substrate was treated 1 time at a pulse rate of 1 Hz and an energy density of 0.1 J/cm2. The substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
For EX-2, the substrate was treated 3 times at a pulse rate of 1 Hz and an energy density of 0.1 J/cm2. The substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
For EX-3, the substrate was treated 5 times at a pulse rate of 1 Hz and an energy density of 0.1 J/cm2. The substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
For EX-4, the substrate was treated 1 time at a pulse rate of 1 Hz and an energy density of 0.2 J/cm2. The substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
For EX-5, the substrate was treated 3 times at a pulse rate of 1 Hz and an energy density of 0.2 J/cm2. The substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
For EX-6, the substrate was treated 5 times at a pulse rate of 1 Hz and an energy density of 0.2 J/cm2. The substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
For EX-7, the substrate was treated 1 time at a pulse rate of 1 Hz and an energy density of 0.3 J/cm2. The substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
For EX-8, the substrate was treated 3 times at a pulse rate of 1 Hz and an energy density of 0.3 J/cm2. The substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
For EX-9, the substrate was treated 5 times at a pulse rate of 1 Hz and an energy density of 0.3 J/cm2. The substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
For EX- 10, the substrate was treated 1 time at a pulse rate of 1 Hz and an energy density of 0.4 J/cm2. The substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate. For EX-11, the substrate was treated 3 times at a pulse rate of 1 Hz and an energy density of 0.4 J/cm2. The substrate was then removed and flipped over, and the treatment was repeated on the backside of the substrate.
Table 1, below, reports the IPL effects on PE nonwoven and the measured fraction (f) of the graphite coating retained.
TABLE 1
COMPARATIVE EXAMPLES B-D (CEX-B to CEX-D) For CEX-B to CEX-D, samples of nonwoven PE were subjected to heating in a Model 725G Isotemp laboratory oven (Fisher Scientific, Hampton, New Hampshire). Samples were placed on an aluminum tray in a preheated oven for the specified amount of time. Results are reported in Table 2, below.
TABLE 2
All cited references, patents, and patent applications in the above application for letters patent are herein incorporated by reference in their entirety in a consistent manner. In the event of inconsistencies or contradictions between portions of the incorporated references and this application, the information in the preceding description shall control. The preceding description, given in order to enable one of ordinary skill in the art to practice the claimed disclosure, is not to be construed as limiting the scope of the disclosure, which is defined by the claims and all equivalents thereto.

Claims

What is claimed is:
1. A method of making a nonwoven article, the method comprising exposing a particle coating disposed on a thermally-softenable nonwoven fiber web to pulsed electromagnetic radiation having at least one wavelength in the range of 200 to 1000 nanometers, wherein the particle coating comprises loosely bound distinct particles that are not chemically bonded to each other and are not retained in a binder material other than the thermally-softenable nonwoven fiber web, and wherein the pulsed electromagnetic radiation has sufficient fluence and pulse width to increase bonding force between at least a portion of the loosely bound distinct particles and the thermally-softenable nonwoven fiber web.
2. The method of claim 1, wherein the particle coating comprises at least one of graphite or hexagonal boron nitride.
3. The method of claim 1 or 2, wherein the particle coating consists essentially of graphite.
4. The method of any one of claims 1 to 3, wherein the pulsed electromagnetic radiation is generated using a flashlamp.
5. The method of any one of claims 1 to 3, wherein the pulsed electromagnetic radiation is generated using a pulsed laser.
6. The method of any one of claims 1 to 3, wherein the pulsed electromagnetic radiation is generated using a continuous light source and a shutter.
7. The method of any one of claims 1 to 6, wherein the thermally-softenable nonwoven fiber web comprises fibers having a higher melting core and a lower melting sheath.
8. A nonwoven article made according to the method of any one of claims 1 to 7.
9. A nonwoven article comprising a thermally-softenable nonwoven fiber web having a particle coating disposed thereon, wherein the particle coating comprises distinct particles that are not chemically bonded to each other and are not retained in a binder material other than the thermally-softenable nonwoven fiber web, and wherein the particle coating is at least 60 percent retained after a one minute immersion in isopropanol at 22°C.
10. The nonwoven article of claim 9, wherein the particle coating comprises at least one of graphite or hexagonal boron nitride.
11. The nonwoven article of claim 9 or 10, wherein the particle coating consists essentially of graphite.
12. The nonwoven article of any one of claims 9 to 11, wherein the particle coating is at least 90 percent retained after the one minute immersion in isopropanol at 22°C.
13. The nonwoven article of any one of claims 9 to 12, wherein the thermally-softenable nonwoven fiber web comprises fibers having a higher melting core and a lower melting sheath.
EP18749509.8A 2017-06-29 2018-06-26 Nonwoven article and method of making the same Active EP3645776B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762526711P 2017-06-29 2017-06-29
PCT/IB2018/054716 WO2019003115A1 (en) 2017-06-29 2018-06-26 Nonwoven article and method of making the same

Publications (2)

Publication Number Publication Date
EP3645776A1 true EP3645776A1 (en) 2020-05-06
EP3645776B1 EP3645776B1 (en) 2021-08-25

Family

ID=63080211

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18749509.8A Active EP3645776B1 (en) 2017-06-29 2018-06-26 Nonwoven article and method of making the same

Country Status (5)

Country Link
US (1) US20200157734A1 (en)
EP (1) EP3645776B1 (en)
KR (1) KR102492536B1 (en)
CN (1) CN110799687B (en)
WO (1) WO2019003115A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019003056A1 (en) 2017-06-29 2019-01-03 3M Innovative Properties Company Article and methods of making the same
CN113584724B (en) * 2021-07-28 2023-03-17 五邑大学 Non-woven material net fixing method and electric needling net fixing device
CN220564848U (en) 2022-05-16 2024-03-08 耐克创新有限合伙公司 Nonwoven fabrics, composite nonwoven fabrics and apparel products

Family Cites Families (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US28102A (en) 1860-05-01 Stove-gkrate
US4419993A (en) 1981-12-10 1983-12-13 Minnesota Mining & Manufacturing Company Anti-fogging surgical mask
GB8401838D0 (en) 1984-01-24 1984-02-29 Tribohesion Ltd Coating process
DE3679316D1 (en) * 1985-11-14 1991-06-20 Deutsches Textilforschzentrum FIBER, FILAMENT, YARN AND / OR THIS OR THIS PROPERTY AREA AND / OR PULL-UP AND METHOD FOR PRODUCING THE SAME OR. THE SAME.
US5318650A (en) * 1990-06-05 1994-06-07 E. I. Du Pont De Nemours And Company Bonded fibrous articles
US5154969A (en) * 1990-06-05 1992-10-13 E. I. Du Pont De Nemours And Company Bonded fibrous articles
US5134032A (en) * 1991-02-25 1992-07-28 General Electric Company Abrasive particle and rotary seal therewith
SG49833A1 (en) * 1993-03-24 1998-06-15 Du Pont Wet-laid sheet material and composites thereof
AU669420B2 (en) 1993-03-26 1996-06-06 Minnesota Mining And Manufacturing Company Oily mist resistant electret filter media
US5908598A (en) 1995-08-14 1999-06-01 Minnesota Mining And Manufacturing Company Fibrous webs having enhanced electret properties
US5706804A (en) 1996-10-01 1998-01-13 Minnesota Mining And Manufacturing Company Liquid resistant face mask having surface energy reducing agent on an intermediate layer therein
JP3877842B2 (en) * 1997-03-05 2007-02-07 ユニチカ株式会社 Method for producing female material for hook-and-loop fastener
US5827368A (en) 1997-06-02 1998-10-27 Marquette University Device for depositing a layer of material on a surface
US6511701B1 (en) 2000-05-09 2003-01-28 3M Innovative Properties Company Coatings and methods
US20030119394A1 (en) * 2001-12-21 2003-06-26 Sridhar Ranganathan Nonwoven web with coated superabsorbent
BRPI0821677A2 (en) * 2007-12-31 2015-06-16 3M Innovative Properties Co Composite non-woven fibrous blankets having continuous particulate phase and methods for preparing and using same
GB0818186D0 (en) * 2008-10-06 2008-11-12 3M Innovative Properties Co Scouring material comprising natural fibres
PL2561128T3 (en) * 2010-04-22 2015-08-31 3M Innovative Properties Co Nonwoven fibrous webs containing chemically active particulates and methods of making and using same
BR112012026835A2 (en) * 2010-04-30 2015-09-22 Procter & Gamble nonwoven that has durable hydrophilic coating
WO2012006300A1 (en) * 2010-07-07 2012-01-12 3M Innovative Properties Company Patterned air-laid nonwoven fibrous webs and methods of making and using same
US20120065283A1 (en) * 2010-09-14 2012-03-15 Sabic Innovative Plastics Ip B.V. Reinforced thermoplastic articles, compositions for the manufacture of the articles, methods of manufacture, and articles formed therefrom
JP2012214965A (en) * 2011-03-29 2012-11-08 Sanyo Chem Ind Ltd Binder for inorganic fiber nonwoven cloth
CN103781956B (en) * 2011-06-30 2016-09-28 3M创新有限公司 Non-woven electret fiber net and preparation method thereof
GB2498265B (en) * 2012-01-04 2015-04-08 Procter & Gamble Fibrous structures comprising particles and methods for making same
CN103474610A (en) * 2013-09-29 2013-12-25 天津工业大学 Method for preparing composite lithium-ion battery separator through electrostatic spinning/electrostatic spraying
CN103640308A (en) * 2013-11-27 2014-03-19 怡星(无锡)汽车内饰件有限公司 Processing technology of non-woven fabric composite material for automotive interior
CN106029302B (en) * 2014-02-14 2019-08-13 3M创新有限公司 Abrasive articles and methods of use thereof
WO2015141495A1 (en) * 2014-03-19 2015-09-24 Ｊｘ日鉱日石エネルギー株式会社 Method for manufacturing ultrafine fiber
WO2016053830A1 (en) * 2014-10-01 2016-04-07 3M Innovative Properties Company Articles including fibrous substrates and porous polymeric particles and methods of making same
CN105463704A (en) * 2015-12-31 2016-04-06 福建恒安集团有限公司 Moisture absorbing article

Also Published As

Publication number Publication date
US20200157734A1 (en) 2020-05-21
KR20200024163A (en) 2020-03-06
EP3645776B1 (en) 2021-08-25
KR102492536B1 (en) 2023-01-27
CN110799687A (en) 2020-02-14
CN110799687B (en) 2022-04-08
WO2019003115A1 (en) 2019-01-03

Similar Documents

Publication Publication Date Title
EP3645776A1 (en) Nonwoven article and method of making the same
Tsukamoto et al. Periodic microstructures produced by femtosecond laser irradiation on titanium plate
Zhang et al. Removal mechanisms of nanosecond pulsed laser cleaning of blue and red polyurethane paint
CA2303233A1 (en) Laser marking method
JPS62230832A (en) Treatment of molded surface with ultraviolet laser
CN101746154B (en) Method of marking or inscribing a workpiece
D’couto et al. Heat transfer and material removal in pulsed excimer‐laser‐induced ablation: Pulsewidth dependence
Seifert et al. Self-organized structure formation on the bottom of femtosecond laser ablation craters in glass
Rode et al. Ultrafast laser ablation for restoration of heritage objects
EP3645769B1 (en) Method of making an article
JP3427273B2 (en) How to clean and remove contaminated concrete surfaces
Tsunemi et al. Paint removal from aluminum and composite substrate of aircraft by laser ablation using TEA CO2 lasers
JP2024523192A (en) Laser nanostructuring for highly transparent anti-fog glass
Abdul Razab et al. Estimation of threshold fluence, absorption coefficient and thermal loading of car coated substrate in laser paint removal
JPH02225347A (en) How to mark glass
Böhme et al. Ultra-short laser processing of transparent material at the interface to liquid
JP3862924B2 (en) Optical film laminate
JPH04318074A (en) Temporarily protecting coating film composition
Dyer et al. VUV F2 laser ablation of sodium chloride
Böhme et al. Backside etching of fused silica with ultra-short laser pulses at the interface to absorbing liquid
Cama et al. Cleaning surfaces from food residues with pulsed laser
PEETHANª et al. Superhydrophobic Surfaces
JP2010519050A (en) Surface drawing or marking method
AU2003237299B2 (en) Method of coating cutting edges
RU2000102840A (en) METHOD FOR PROFILING REFLECTIVE AND CHEMICAL RESISTANT MATERIALS

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20200107

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20201117

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20210318

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Ref country code: AT

Ref legal event code: REF

Ref document number: 1423904

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210915

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018022458

Country of ref document: DE

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210825

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1423904

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210825

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211125

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211125

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211227

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211126

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018022458

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

26N No opposition filed

Effective date: 20220527

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20220630

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20220626

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220626

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220630

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220626

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220630

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220626

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20180626

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210825

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20250520

Year of fee payment: 8