WO2000016914A1 - Durably wettable liquid pervious webs prepared using a remote plasma polymerization process - Google Patents
Durably wettable liquid pervious webs prepared using a remote plasma polymerization process Download PDFInfo
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- WO2000016914A1 WO2000016914A1 PCT/US1999/021710 US9921710W WO0016914A1 WO 2000016914 A1 WO2000016914 A1 WO 2000016914A1 US 9921710 W US9921710 W US 9921710W WO 0016914 A1 WO0016914 A1 WO 0016914A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/62—Plasma-deposition of organic layers
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- 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. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
- D06M10/025—Corona discharge or low temperature plasma
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- 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. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
Definitions
- the present invention relates to a durably wettable, liquid pervious web that is particularly suitable as a topsheet for absorbent articles. More particularly, the invention relates to a polymeric film or nonwoven to which is applied a thm organic material onto at least one surface of the film or nonwoven.
- the thm organic coating is in the form of a polymer and is obtained by after-glow plasma-induced polymerization of a polymerizable unsaturated compound, preferably a polymerizable vinyl or isopropenyl compound, under specific plasma conditions.
- the invention further relates to a process for making the durably wettable liquid pervious web, and to articles containing the durably wettable, liquid pervious web as a topsheet.
- polymeric and nonwoven webs are common components of disposable absorbant articles, dryer sheets and the like. More particularly, macroscopically expanded, three-dimensional, polymeric films have been utilized as topsheet materials for disposable absorbent articles.
- macroscopically expanded when used to describe three-dimensional webs, refers to webs which have been caused to conform to the surface of a three-dimensional forming structure so that both surfaces thereof exhibit the three-dimensional pattern of the forming structure or webs that have an inherent three-dimensional pattern arising from their structure.
- planar when utilized herein to describe nonwovens and polyme ⁇ c films, refers to the overall condition of the web when viewed by the naked eye on a macroscopic scale.
- planar webs may include webs having fine-scale surface aberrations on one or both sides, the surface aberrations not being readily visible to the naked eye when the perpendicular distance between the viewer's eye and the plane of the web is about 12 inches or greater.
- Thompson describes a macroscopically expanded, three dimensional web (e.g., a topsheet) comprised of liquid impermeable material, but provided with a pattern of tapered capillaries, the capillaries having a base opening in the plane of the topsheet and an apex opening remote from the plane of the topsheet, the apex opening being in intimate contact with the absorbent pad utilized in the disposable absorbent article.
- the Thompson topsheet allows the free transfer of liquids from the wearer's body into the absorbent element of the device while inhibiting the reverse flow of these liquids. This provides a relatively much drier surface in contact with the user than had previously been obtainable.
- FIG. 1 Another macroscopically expanded, three-dimensional apertured plastic web well suited for use as a topsheet on absorbent articles such as sanitary napkins is disclosed in commonly assigned U.S. Patent No. 4,342,314 issued to Radel et al. on Aug. 3, 1982, the patent being hereby incorporated by reference herein.
- the macroscopically expanded, three-dimensional plastic web disclosed in the Radel patent exhibits a fiber-like appearance and tactile impression which has been favorably received by consumers when used as a wearer contacting surface.
- plastic webs of the aforementioned type can be made by applying a pressure to the web while it is supported on a three-dimensional forming structure until the web is macroscopically expanded to comply with the three-dimensional cross-section of the forming structure on which it is supported.
- the pressure differential is applied until such time as apertu ⁇ ng of the web in areas coinciding with the apertures m the forming structure has been completed.
- the above references generally obtain such a structure by surface treating the naturally hydrophobic polymeric web with a wetting agent.
- Surface treatment is generally accomplished by either spraying surfactant onto the web's surface or by dipping the web m a surfactant-contammg bath. Regardless of which of these methods is employed, surface treatment suffers from the inability to precisely control the location and level of treatment, as well as adverse effects caused by migration of significant amounts of surfactant into apertures and other components (e.g., absorbent core) when the web is used as a topsheet in an absorbent article.
- a durably wettable, liquid pervious web having improved durable wettability.
- This durable wettability is attained by applying a plasma-mduced hydrophihc coating onto at least one surface of a starting web, to render the resulting treated web durably hydrophihc.
- the plasma-induced coating is attained using an "after-glow” or "remote” plasma polymerization process.
- the present invention relates to a durably wettable, liquid pervious web that is particularly useful as a topsheet material for absorbent articles.
- the inventions relates to a durably wettable, liquid pervious web which comprises:
- an apertured web selected from the group consisting of polymeric films or nonwovens; and (n) a substantially continues hydrophihc coating, less than about 2.5 microns thick, on at least one surface of the web, wherein said hydrophihc coating is applied to the web by a remote plasma polymerization process; wherein at least one surface of the durably- wettable, liquid pervious web has a Post Agmg contact angle that is not more than about 60 degrees greater than the Pre Agmg contact angle.
- At least one surface of the treated web will have a Post Washing contact angle that is not more than about 60 degrees greater than the Pre Washing contact angle.
- both conditions will exist m a single treated web.
- the invention also relates to an absorbent article comprising a durably wettable, liquid pervious topsheet, the topsheet comprising a web and a hydrophihc coating on at least one surface of the web, wherein the hydrophihc coating is applied to the web by a remote plasma polymerization process.
- the topsheet of the article comprises the durably wettably, liquid pervious web of the present invention.
- the invention relates to a remote plasma polymerization process for making the durably wettable, liquid pervious webs described herein.
- the present invention relates to a durably wettable, liquid pervious web that is prepared by applying a hydrophihc coating to a starting polymeric film or nonwoven, using a radiation curing process.
- the term "web” refers to the starting substrate (i.e., a polymeric film or nonwoven) to which the hydrophihc coating is applied.
- the terms "durably wettable, liquid pervious web” or “treated web” refer to the final product - the polymer film or nonwoven having the durable hydrophihc coating.
- the term "liquid pervious” refers to the ability of a web or treated web to transport liquids from one surface of the web or treated web to the opposite surface of the web or treated web m a sufficiently efficient manner so as to allow the treated web to be used as a component of a disposable article.
- Webs may be inherently liquid pervious or may be made liquid pervious by application of a processing step, such as, apertu ⁇ ng.
- a processing step such as, apertu ⁇ ng.
- substantially contmuos means sufficiently contmuos to provide the hydrophihc or wettable properties as defined by the stated or claimed contact angle limitations.
- hydrophilicity and wettability are used interchangeably and refer to surfaces that are wettable by aqueous liquids (e.g., aqueous body liquids) deposited on these surfaces. Hydrophilicity and wettability are typically defined m terms of contact angle and the surface tension of the liquids and solids involved. This is discussed in detail m the American Chemical Society publication entitled Contact Angle, Wettability and Adhesion, edited by Robert F. Gould (Copyright 1964).
- a web surface is said to be wetted by a liquid (i.e., hydrophihc) when either the contact angle between the liquid and the web surface is less than 90°, or when the liquid tends to spread spontaneously across the surface of the web, both conditions normally coexisting.
- a surface is considered to be hydrophobic if the contact angle is greater than 90° and the liquid does not spread spontaneously across the surface of the web. In general, the lower the contact angle between the surface and the liquid, the more hydrophihc the surface.
- the durably wettable, liquid pervious webs of the present invention are "durably wettable", insofar as the hydrophihc character engendered to the otherwise more hydrophobic film is maintained over time and after exposure to liquids.
- hydrophihc polymer and surface-treated polymer systems such as corona discharge treatments, go through a "hydrophobic recovery” process.
- surface wettability tends to decay over time because thermodynamics favors the exposure of lower surface energy molecular chain segments at polymer surface.
- hydrophihc molecular segments reorient and embed themselves and expose hydrophobic segments at polymer surface.
- chemical crosshnkmg is induced at the polymer surface, the crosshnkmg tends to limit polymer chain mobility, thus significantly slowing the "hydrophobic recovery” process and therefore preserving polymer surface wettability over time. Since Applicants' invention provides for polymer chemical crosshnkmg, via a remote plasma polymerization process, a durably wettable, liquid pervious web can be produced.
- remote plasma and “after glow” each mean that monomer is injected outside of plasma zone or plasma glow and the substrate to be surface treated is placed outside of plasma glow, usually beneath the monomer injection opening.
- the benefit derived from placement outside the plasma zone is to avoid interaction of monomer molecules with the plasma electrons and ions which cause undesired monomer fragmentation. Since electrons and ions are short-lived species, they are confined mside the plasma glow.
- plasma zone and “plasma glow” each refer to the portion of volume inside a chamber, normally in between the electrodes, which is significantly brighter than the remaining volume due to visible glow. The visible glow is produced by plasma excited species that undergo electronic relaxation accompanied by light emission.
- Plasma is often referred to as the fourth state of matter.
- a solid e.g., a polymeric film
- the solid can undergo a transition to the liquid state. If further energy is applied, the liquid becomes a gas. If additional energy of the proper kind is applied, the gas dissociates and becomes plasma.
- plasma polymerization to produce a coating on a web which may also be called "plasma grafting", “plasma deposition” or “plasma coating”
- a suitable organic monomer or a mixture of monomers having polymerizable unsaturated groups is introduced into the plasma zone of the reactor where it is fragmented and/or activated forming further excited species in addition to the complex mixture of the activated plasma gases.
- the excited species and fragments of the monomer recombine upon contact with the web in an undefined way to a largely undefined structure which contains a complex variety of different groups and chemical bonds forming a highly crosslinked polymer deposit on the web. If 0 2 , N 2 or oxygen- or nitrogen-containing molecules are present, either within the plasma reactor during the plasma coating process, or on exposure of the plasma coated substrate to oxygen or air subsequent to the plasma process, the polymeric deposit will include a variety of polar groups.
- the web to be treated and the monomers to be reacted are located within the plasma zone during the polymerization process. While this technique has been found useful for preparing durably wettable webs that are useful as topsheets for absorbent articles (see co- pending U.S. Patent Application Serial No. 09/157845, filed September 21, 1998 by Y. P. Lee et al. and titled DURABLY WETTABLE, LIQUID PERVIOUS POLYMERIC WEBS), polymerization within the plasma zone does have certain drawbacks. For instance, the monomers may become undesirably fragmented prior to deposition on the film.
- the use of direct plasma polymerization limits to some degree the monomers that may be utilized.
- the treated webs of the present invention are prepared using "remote” or “after-glow” (these terms are used interchangeably herein) plasma polymerization and therefore the concern of excess fragmentation is mitigated.
- Remote plasma polymerization is a process in which polymerization is effected in the presence of the plasma, but wherein the web as well as the inlet for the monomer feed are located outside of, or remote from (typically below), the plasma zone. Fragmentation of the monomer molecules can be largely avoided in this process, as the monomer does not pass the zone of the highly reactive plasma gases.
- certain desirable monomers for forming the hydrophihc coating can be used in the present process, while they cannot be used where direct plasma polymerization is employed.
- the structure of the polymer deposited can be controlled within certain limits, undesired surface erosion of susceptible substrates can be avoided and the formation of the polymer deposits is predominantly based on radical reactions.
- Plasmas exist in a variety of forms.
- the plasma process useful herein is a remote, low pressure or vacuum process, which allows processing of the web at or near ambient temperature, i.e., about 20°C. This prevents thermal degradation of the web being processed and/or thermal distortion of the formed web that is being treated.
- active species in the form of electrons, free-radicals, ions and energetic neutrals are formed and collide with the surface of the web, e.g. a polymer, (which is placed outside the plasma chamber) breaking molecular bonds and creating new functional groups on the web's surface.
- active and energetic species also react in the gas phase, resulting in a thin coating being deposited on at least one surface of the web.
- Suitable plasma systems for use m the present invention incorporate a parallel plate electrode design where materials to be treated are exposed to the primary field of RF energy, but are not part of the circuitry.
- some form of gas delivery system designed to create a uniform laminar flow of process gas throughout the entire chamber volume is beneficial.
- the preferred plasma process utilizes a matching network to constantly tune the plasma impedance to the output impedance of the RF generator.
- Advanced plasma systems suitable for use in the present invention are available from HIMONT Plasma Science, Foster City, Calif, (a business unit of HIMONT U.S.A., Inc.), and incorporate an automatic matching type of network and provisions for error checking during the process.
- the low temperature plasma is generated in a gaseous atmosphere at reduced pressure of from about 0.001 to about 10 Torr, preferably from about 0.01 to about 5 Torr, more preferably from about 0.05 to about 1 Torr, and most preferably from about 0.05 to about 0.4 Torr.
- the electric power can be supplied to the equipment at a high radio frequency, from about 40 KHz to 3 GHz, preferably from 13 to 27 MHz, and most conveniently at about 14 MHz.
- the electric power delivered to the apparatus can vary over a range of from about 1 to about 10,600 watts; preferably from about 10 to about 1,000 watts, more preferably from about 50 to about 500 watts, most preferably from about 75 to about 250 watts.
- the power used is somewhat dependent on the chamber's working volume.
- the most preferred 75 to 250 watts is appropriate for HIMONT Plasma Science PS0500D gas plasma apparatus with a working volume of 5.0 cubic feet.
- the plasma treatment time varies from a few seconds to several minutes, preferably from about 20 seconds to about 30 minutes, most preferably from 60 seconds to about 20 minutes.
- treatment pressure, time and power are interrelated, rather than independent, variables.
- the effect of the level selected for each of these variables will determine the extent of web surface modification and/or coating thickness; also related are the chamber volume and geometry as well as the sample size and surface geometry.
- the selection of the level for these variables is well withm the ordinary skill of practitioners m the art to which this mvention pertains.
- the hydrophihc coating layer is deposited onto the surface of a suitable web (either previously apertured or unapertured) via remote plasma-mduced vapor deposition (i.e., polymerization) of a monomer or combination of monomers, such that a hydrophihc coating will be applied to the web.
- the monomer(s) which may be used to prepare the polymeric coatings by after-glow plasma-mduced polymerization may be any polymerizable unsaturated compound which can be evaporated and introduced into the after-glow zone of a plasma generating apparatus to contact the web provided therein.
- each R 2 is independently hydrogen or C,-C 10 alkyl, preferably C r C 5 alkyl, and each R 3 is independently an aliphatic hydrocarbon group of up to about 10 carbon atoms which is unsubstituted or is substituted by one or more polar groups such as carboxy, hydroxy, amino, and a (poly)ethylene oxide group or substituted by one or more sulfate, phosphate, sulfonate groups or mixtures of such groups.
- acrylic derivatives include acrylic acid, methacrylic acid, hydroxyethylmethacrylate (HEMA), methyllmethacrylate (MMA), dimethylammoethyl- methacrylate (DMAEMA), 2-hydroxyethylacrylate (HEA), N,N-d ⁇ methylacrylam ⁇ de (DMA), N-acryloylmorphohne (NAM) and ethylene glycol dimethacrylate (EGDMA).
- suitable vmyl ethers are methylvmyl ethers, ethylvmyl ether and methoxyethylvmyl ether.
- Suitable hydrophihc monomers also include ethylene glycol, ethylene oxide and propylene oxide. The monomers can be used individually or as mixtures of monomers.
- the monomer Prior to being introduced into the chamber, the monomer is heated to a temperature sufficient to vaporize the compound and to create sufficient vapor pressure such that the coating is deposited at a reasonable speed. Typically, the temperature will be from about 40° to about 100°C, more typically from about 40° to about 60°C.
- Oxygen in gaseous form and argon is optionally fed into the deposition chamber simultaneously with, but each with a separate feeding means and mass flow controller, the gaseous monomer compound.
- the 0 2 flow rate ranges from 5 standard cubic centimeter/minute ("seem") to 1200 seem, the gaseous monomer compound flow is from 1 seem to 250 seem, and Ar flow is from 1 seem to 150 seem.
- Argon is used to enhance the rate of deposition of the gaseous materials being employed and, therefore, it is preferable to use Argon in the process.
- monomer deposition may be achieved via the flash vaporization technique that is described in U.S. Patent No. 4,842,893 issued to Yializis on Apr. 29, 1988, the disclosure of which is incorporated by reference herein.
- the low temperature plasma is generated in a gaseous atmosphere at reduced pressure of from about 0.001 to about 10 Torr, preferably from about 0.01 to about 5 Torr, more preferably from about 0.05 to about 1 Torr, and most preferably from about 0.05 to about 0.4 Torr, depending on the process used and the web being treated.
- the web may be flat (two dimensional) or complex (three dimensional, including previously apertured films) prior to plasma deposition of the hydrophihc coating. That is, plasma polymerization may be conducted either before or after formation of the apertures of the web. In a preferred embodiment, plasma treatment will be conducted after aperture formation, so as to better preserve a uniform hydrophihc coating on the film's surface.
- the aforementioned advanced plasma systems available from HIMONT Plasma Science, such as the PS0500D reactor are equipped with a throttle valve, thereby making it possible to achieve a range of process pressures with the same gas flow rate.
- the plasma treatment time for obtaining the desired hydrophihc coatings is from about 0.1 minute to about 10 minutes, preferably from about 1.5 to about 4 minutes, most preferably from about 1.5 to about 2.5 minutes; and the RF power used to cause reaction of the vapor is preferably from about 10 to about 1,000 watts, more preferably from about 50 to about 500 watts, most preferably from about 75 to about 250 watts.
- the RF power employed ranges from about 100 to about 2500 watts and depends on the substrate being treated and the throughput requirements.
- the resulting hydrophihc coatings can be produced in different thicknesses, but typically is from about 0.01 to about 2.5 microns, preferably from about 0.5 to about 1 microns.
- the web is preferably positioned at a distance of from about 1 to about 40 cm below the plasma zone.
- the monomer inlet is preferably positioned at a distance of from about 1 to about 35 cm below the plasma zone.
- the web distance downstream from (i.e., below) the plasma zone is more preferably from about 2 to about 20 cm, and most preferably from about 3 to about 10 cm.
- the monomer inlet distance downstream from the plasma zone is preferably from about 2 to about 20 cm, and most preferably from about 3 to about 10 cm
- remote plasma polymerization of a polymerizable unsaturated compound m accordance with the invention is preferably carried out under the following plasma conditions.
- the polymeric coatings of the present invention which are obtainable by remote plasma- mduced polymerization of a polymerizable unsaturated compound on a web under the aforementioned conditions regarding the distance between web and plasma zone, as well as monomer inlet and plasma zone, are characterized - contrary to coatings obtained by m-glow (or direct) plasma-induced polymerization - by the fact that the repeating units of the polymer chains are to a large extent identical in structure to those repeating units obtained through a non-plasma radical polymerization of the respective unsaturated compound.
- repeating structural units typically exhibit the same structure as the polymer obtained by non-plasma radical polymerization of the same monomer.
- from about 2% to about 30%, more typically from about 2% to about 24%, still more typically from about 2% to about 18% of the remaining structural units serve as covalent linking groups to the treated web or as crosshnkmg sites between adjacent polymer chains.
- the uniform structure and the controllable relatively low degree of crosshnkmg of the coatings which is surprisingly achieved using remote plasma polymerization of a polymerizable unsaturated compound under the specific conditions of the position of substrate and monomer mlet constitutes a characteristic feature of the coatings which is responsible for the durable wettabihty of the treated webs.
- a specific advantage of the coatings is their strong adherence to the surface of the treated web which is obtained to a large degree independently from the nature of the web.
- the plasma induced hydrophihc coating exhibits a contact angle for water of less than about 90 degree, such that any water or aqueous-based liquid placed on the web will tend to spread spontaneously over the web's coated surface.
- the treated web may be further treated by exposure to a low temperature plasma gas composition (also referred to herein as a "surface modifying gas stream") or an energy source (also referred herein as "radiation curing”) such as an apparatus that emits, including but not limited to, infra red, electron beam, thermionic or ultra violet radiation. Apparatuses that are suitable as energy sources m the present invention are disclosed in U.S. Patent No. 4,842,893 issued to Yiahzis on Apr. 29, 1988, the disclosure of which is incorporated by reference herein.
- the gas stream preferably comprises N 2 0 and C0 2 , to enhance the durability of the hydrophihc coating.
- the plasma gas composition will comprise from about 80 to about 40 mol % N 2 0 and from about 20 to about 60 mol % C0 2 , preferably from about 70 to about 45 mol % N 2 0 and from about 30 to about 55 mol % C0 2 , most preferably from about 60 to about 45 mol % N 2 0 and from about 40 to about 55 mol % C0 2 , where the amount of N 2 0 and C0 2 in the mixture equals 100 to 10 mol %, for a time sufficient to modify the surface of the hydrophihc coating to enhance its durability.
- the radiation source is preferably a gas discharge electron beam gun.
- the gun directs a flow of electrons through a emitter window onto the monomer, thereby further curing the monomer, which enhances the durability of the hydrophihc coating. Curing is controlled by matching the electron beam voltage to the dielectric thickness of the monomer coating. For example, a 10 Kv electron voltage will penetrate about 1 micron of deposited monomer.
- the plasma process is generally practiced as follows.
- the web to be treated is placed into a vacuum chamber and the chamber pressure is reduced, typically to about 0.005 Torr.
- the process gas or gas mixture employed is introduced to the chamber and the chamber pressure is stabilized at a pressure of 0.04-0.4 Torr.
- the interior dimension of the work area is approximately 1.73 X 0.76 X 1.02 meters (width x height x depth) for a total working volume of 1.34 cubic meters.
- a suitable high frequency form of energy typically 13.56 MHz radio frequency energy, is used to create the plasma; m the system described, this is achieved with a total power input capacity of up to 2500 watts.
- the RF energy dissociates the gas, creating a plasma characterized by a distinctive glow.
- the bulk temperature of the gas is near ambient temperature, thus the reference to a cold gas plasma, a glow discharge, or a cold gas glow discharge.
- the electrons or ions created in the plasma bombard the web's surface, abstracting atoms or breaking bonds, creating free radicals. These free radicals are unstable and seek to satisfy a more stable state by reacting with free radicals or groups within the plasma gas, also establishing new moieties on the surface of the web.
- the energetic electrons in the glow discharge fragment the molecules in the gas phase, leading to complex chemical reactions that result in a thin hydrophihc coating being deposited on at least one surface of the web.
- an initial step is performed before plasma deposition of the hydrophihc coating.
- the purpose of this step is to clean the web surface to be treated to promote adhesion of the subsequently deposited thin hydrophihc coating. Cleaning may be accomplished by subjecting the web's surface to radiation (herein referred to as radiation cleaning) from an energy source including but not limited to, infra red, electron beam, thermionic and ultra violet radiation or by plasma cleaning.
- radiation cleaning an energy source including but not limited to, infra red, electron beam, thermionic and ultra violet radiation or by plasma cleaning.
- Apparatuses that are suitable as energy sources in the present invention are disclosed in U.S. Patent No. 4,842,893 issued to Yializis on Apr. 29, 1988, the disclosure of which is incorporated by reference herein.
- the radiation source is preferably a gas discharge electron beam gun.
- the gun directs a flow of electrons through a emitter window onto the web's surface, thereby abstracting atoms or breaking bonds, thus creating free radicals.
- These free radicals are unstable and seek to satisfy a more stable state thus they serve as bonding sites for the monomers that are used to produce the web's hydrophihc coating.
- Cleaning is controlled by matching the electron beam voltage to the dielectric thickness or depth of cleaning that is desired. For example, a 10 Kv electron voltage will penetrate to a film depth of about 1 micron.
- the gases are typically either Ar alone, 0 2 alone, or mixtures (e.g., 1:1) of Ar and 0 2 .
- Gas flow rates are typically in the range of 20-100 seem (standard cc/min), preferably 40-80 seem, and most preferably 50-60 seem.
- RF power is approximately 1100 watts, and process pressure is about 0.04 Torr.
- the next step is the plasma deposition of the hydrophihc coating, as described above and in more detail in the examples below.
- the materials useful as polymeric films to be plasma treated to provide a hydrophihc coating will be derived from thermoplastic polymers.
- the term "thermoplastic polymer" is used herein to mean any thermoplastic polymer which can be used for the preparation of films.
- thermoplastic polymers include, by way of illustration only, end-capped polyacetals, such as poly(oxymethylene) or polyformaldehyde, poly(trichloroacetaldehyde), poly(n-valeraldehyde), poly(acetaldehyde), poly(propionaldehyde), and the like; acrylic polymers, such as polyacrylamide, poly(acrylic acid), poly(methacrylic acid), poly(ethyl acrylate), poly(methyl methacrylate), and the like; fluorocarbon polymers, such as poly(tetrafluoroethylene), perfluorinated ethylene-propylene copolymers, ethylene- tetrafluoroethylene copolymers, poly(chlorotrifluoroethylene), ethylene-chlorotrifluoroethylene copolymers, poly(vinylidene fluoride), poly(vinyl fluoride), and the like; polyamides, such as poly(6-aminocaproic acid) or poly( ⁇
- Preferred polymers are polyolefins and polyesters, with polyolefins being more preferred. Even more preferred are those polyolefins which contain only hydrogen and carbon atoms and which are prepared by the addition polymerization of one or more unsaturated monomers.
- Examples of such polyolefins include, among others, polyethylene, polypropylene, poly(l- butene), poly(2-butene), poly( 1-pentene), poly(2-pentene), poly(3 -methyl- 1-pentene), poly(4- methyl- 1-pentene), 1,2-poly- 1,3-butadiene, l,4-poly-l,3-butadiene, polyisoprene, and the like.
- such term is meant to include blends of two or more polyolefins and random and block copolymers prepared from two or more different unsaturated monomers. Because of their commercial importance, the most preferred polyolefins are polyethylene and polypropylene.
- webs that can be used to produce the durably wettable, liquid pervious webs of the present invention include but are not limited to spun bonded, hydroentangled, needled and polymericly bound nonwovens.
- Suitable nonwoven webs are typically formed from organic textile fibers including but not limited to cotton, wool, wood, jute, viscous rayon, nylon, polyester, polyolefins, carbon, or mixtures thereof.
- Inorganic fibers such as glass and metal can be used alone or in combination or further combined with organic fibers .
- staple fibers fiber length varies from about 1/4 inch to about 2 or more inches.
- spun bonded webs the fiber lengths are indefinite.
- the staple fibers used in hydroentangled, needled and polymericly bound nonwovens are processed through conventional textile machinery.
- a carding machine may be used to form a continuous length of rather two-dimensional loosely associated fibers known as a carded web. These webs may be assembled to form a multiple layer or three-dimensional fibrous web of significant weight, e.g., from about several grams to thousands of grams per yard.
- the textile fibers are arrayed at various angles to the lengthwise axis of the web.
- the fibers are usually predominantly oriented in the machine direction and, on the other hand, isotropic webs may be formed such as by air-laying.
- the fibrous webs described above are typically impregnated with a polymeric binding agent (polymericly bound).
- the polymeric binders are applied as emulsions of acrylic, polyvinylacetate, or similar polymeric nature, and mixtures thereof.
- the fibers are unwoven and substantially haphazardly oriented and adhesively bonded together with polymeric binder.
- Hydroentangled and needled webs are distinct from polymericly bound webs as they rely principally on the physical entanglement of their fibers to provide web integrity.
- spun bond webs typically are composed of fibers of infinite length that are bound together through solvent or melt processes.
- the webs may be two-dimensional or may have an apertured three dimensional structure made in accordance with the teachings of the incorporated references discussed in the Background section, supra.
- the coatings are durable and increase the surface energy of the to render the resulting treated web more wettable.
- the coating is durable, in that it is maintained over time, even after exposure to water or other aqueous liquids.
- the webs of the present invention are described in one respect in terms of their ability to remain wettable over time and/or after exposure to liquids.
- the ability to remain wettable over time is assessed by measuring the treated web's Post Aging contact angle. This measurement involves storing the plasma treated web at 74° C for 16 hours, to artificially age the sample, before measuring contact angle.
- the ability to remain wettable after exposure to liquids is assessed by measuring the treated web's Post Washing contact angle. This measurement involves placing a 2 in. x 2 in. sample of treated web in a 250 ml water bath at 65° C for 90 sec with vigorous agitation prior to measuring contact angle. Procedures and devices for measuring contact angle between a liquid and a web surface are well known in the art. However, the treated web that Applicants' have disclosed is tested for surface water drop contact angle and surface energy according to the procedures specified by T565 pm-96 provisional method and ACCU DYNE TEST, Diversified Enterprises (based on ASTM D2578-84 technique). Contact angle values arc reported as the average of measurements on 5 samples.
- the treated web of the present invention will have a Post Aging contact angle that is not more than about 60 degrees greater than the treated web's Pre Aging contact angle (i.e., the contact angle as measured before storage at 74°C for 16 hours).
- the treated web will have a Post Aging contact angle that is not more than about 40 degrees, more preferably not more than about 20 degrees, still more preferably not more than about 10 degrees, greater than the Pre Aging contact angle.
- the treated web of the present invention will have a Post Washing contact angle that is not more than about 60 degrees greater than the treated web's Pre Washing contact angle (i.e., the contact angle as measured before the treated web is placed in a 250 ml water bath at 65° C for 90 sec with vigorous agitation).
- the treated web will preferably have a Post Washing contact angle that is not more than about 40 degrees, more preferably not more than about 20 degrees, still more preferably not more than about 10 degrees, greater than the Pre Washing contact angle.
- the treated web of the present invention will exhibit both the Post Aging and Post Washing requirements discussed above.
- the durably wettable, liquid pervious webs of the present invention will exhibit either (preferably both) a Post Aging or a Post Washing contact angle of less than about 90 degrees, preferably not more than about 70 degrees, more preferably not more than about 50 degrees, still more preferably not more than about 30 degrees, and most preferably not more than about 20 degrees.
- the term "absorbent article” refers generally to devices used to absorb and contain body exudates, and more specifically refers to devices which are placed against or in proximity to the body of the wearer to absorb and contain the various exudates discharged from the body.
- the term "absorbent article” is intended to include diapers, catamenial pads, tampons, sanitary napkins, incontinent pads, training pants and the like, as well as wipes, bandages and wound dressings.
- absorbent articles which are not intended to be laundered or otherwise restored or reused as an absorbent article (i.e., they are intended to be discarded after limited use, and, preferably, to be recycled, composted or otherwise disposed of an environmentally compatible manner).
- a "unitary" absorbent article refers to absorbent articles which are formed as a single structure or as separate parts united together to form a coordinated entity so that they do not require separate manipulative parts such as a separate holder and pad.
- absorbent articles will also comprise an absorbent core for retention of any absorbed body liquids
- Exemplary absorbent structures for use as the absorbent core in the present invention are described in U.S. Patent No. 4,950,264 issued to Osborn on August 21, 1990; U.S. Patent No. 4,610,678 issued to Weisman et al. on September 9, 1986; U.S. Patent No. 4,834,735 issued to Alemany et al. on May 30, 1989; European Patent Application No. 0 198 683, the Procter & Gamble Company, published October 22, 1986 m the name of Duenk et al.; U.S. Patent No.
- the absorbent core may further comprise the dual core system containing an acquisition/distribution core of chemically stiffened fibers positioned over an absorbent storage core as detailed m
- the disclosure of all of these patents is incorporated herein by reference.
- a preferred embodiment of a unitary disposable absorbent article made in accordance herewith is a catamenial pad, or sanitary napkm.
- sanitary napkin refers to an absorbent article which is worn by females adjacent to the pudendal region, generally external to the urogenital region, and which is intended to absorb and contain menstrual liquids and other vaginal discharges from the wearer's body (e.g., blood, menses, and urine).
- Interlabial devices which reside partially withm and partially external to the wearer's vestibule are also withm the scope of this invention.
- Suitable feminine hygiene articles are disclosed m U.S. Patent No. 4,556,146, issued to Swanson et al. on Dec. 3, 1985, U.S.
- the sanitary napkin has two flaps each of which are adjacent to and extend laterally from the side edge of the absorbent core.
- the flaps are configured to drape over the edges of the wearer's panties m the crotch region so that the flaps are disposed between the edges of the wearer's panties and the thighs.
- the flaps serve at least two purposes. First, the flaps help serve to prevent soiling of the wearer's body and panties by menstrual liquid, preferably by forming a double wall barrier along the edges of the panty. Second, the flaps are preferably provided with attachment means on their garment surface so that the flaps can be folded back under the panty and attached to the garment facing side of the panty.
- the flaps serve to keep the sanitary napkin properly positioned m the panty.
- the flaps can be constructed of various materials including materials similar to the topsheet, backsheet, tissue, or combination of these materials. Further, the flaps may be a separate element attached to the mam body of the napkin or can comprise extensions of the topsheet and backsheet (i.e., unitary).
- a number of sanitary napkins having flaps suitable or adaptable for use with the sanitary napkins of the present invention are disclosed in U.S. Patent No. 4,687,478 entitled “Shaped Sanitary Napkin With Flaps", which issued to Van Tilburg on August 18, 1987; and U.S. Patent No. 4,589,876 entitled “Sanitary Napkin", which issued to Van Tilburg on May 20, 1986. The disclosure of each of these patents is hereby incorporated herein by reference.
- an acquisition layer(s) may be positioned between the topsheet and the absorbent core.
- the acquisition layer may serve several functions including improving wickmg of exudates over and into the absorbent core. There are several reasons why the improved wickmg of exudates is important, including providing a more even distribution of the exudates throughout the absorbent core and allowing the sanitary napkin to be made relatively thm.
- the wickmg referred to herein may encompass the transportation of liquids m one, two or all directions (i.e., m the x-y plane and/or in the z-direction).
- the acquisition layer may be comprised of several different materials including nonwoven or woven webs of synthetic fibers including polyester, polypropylene, or polyethylene; natural fibers including cotton or cellulose; blends of such fibers; or any equivalent materials or combinations of materials.
- Examples of sanitary napkins having an acquisition layer and a topsheet are more fully described in U.S. Patent No 4,950,264 issued to Osborn and U.S. Patent Application Serial No. 07/810,774, "Absorbent Article Having Fused Layers", filed December 17, 1991 in the names of Cree, et al. The disclosures of each of these references are hereby incorporated herein by reference.
- the acquisition layer may be joined with the topsheet by any of the conventional means for joining webs together, most preferably by fusion bonds as is more fully described in the referenced Cree application.
- Catamenial pads may be constructed as follows Onto sihcone-coated release paper a spiral pattern of H2031 Fmdlay hot melt adhesive is applied at 0.04 glwP-. This adhesive layer is transferred onto the top (wearer-facmg) side of a secondary topsheet by rolling the secondary topsheet and coated release paper together with a hand roller.
- the secondary topsheet is formed of a nonwoven material known as Fort James Airlaid Tissue, Grade 817, commercially available from the Fort James Corp. of Green Bay, Wisconsin.
- a topsheet of the present invention is applied to the adhesive side of the secondary topsheet and the two are bonded by gently pressing them together with a hand roller. Two strips of one-quarter-inch double-sided tape are applied along both long edges of a polyethylene backsheet. The absorbent core is added to construct the complete absorbent structure.
- a diaper refers to a garment generally worn by infants and incontinent persons that is worn about the lower torso of the wearer. It should be understood, however, that the present invention is also applicable to other absorbent articles such as incontinent briefs, incontinent pads, training pants, diaper inserts, facial tissues, paper towels, and the like.
- a diaper of the present invention will comprise a topsheet comprising the durably wettable, liquid pervious web of the present invention; a liquid impervious backsheet joined with the topsheet; and an absorbent core positioned between the topsheet and the backsheet. Additional structural features such as elastic members and fastening means for securing the diaper in place upon a wearer (such as tape tab fasteners) may also be included.
- topsheet, the backsheet, and the absorbent core can be assembled in a variety of well known configurations, a preferred diaper configuration is described generally in U.S. Patent No. 3,860,003 (Buell), issued January 14, 1975, the disclosure of which is incorporated by reference.
- preferred configurations for disposable diapers herein are also disclosed in U.S. Patent No. 4,808,178 (Aziz et al.), issued February 28, 1989; U.S. Patent No. 4,695,278 (Lawson), issued September 22, 1987; and U.S. Patent No. 4,816,025 (Foreman), issued March 28, 1989, the disclosures of each of these patents hereby being incorporated herein by reference.
- Suitable incontinence articles for adult wearers are disclosed in U.S.
- the absorbent core of the diaper is positioned between the topsheet and the backsheet.
- the absorbent core can be manufactured in a wide variety of sizes and shapes (e.g., rectangular, hourglass, asymmetrical, etc.)
- the total absorbent capacity of the absorbent core should, however, be compatible with the design liquid loading for the intended use of the absorbent article or diaper. Further, the size and absorbent capacity of the absorbent core can vary to accommodate wearers ranging from infants through adults.
- the absorbent core may include a liquid distribution member.
- the absorbent core preferably further includes an acquisition layer or member in liquid communication with the liquid distribution member and located between the liquid distribution member and the topsheet.
- the acquisition layer or member may be comprised of several different materials including nonwoven or woven webs of synthetic fibers including polyester, polypropylene, or polyethylene, natural fibers including cotton or cellulose, blends of such fibers, or any equivalent materials or combinations of materials.
- the diaper will comprise elasticized leg cuffs.
- the elasticized leg cuffs can be constructed m a number of different configurations, including those described in U.S. Patent No. 3,860,003; U.S. Patent No. 4,909,803, issued to Aziz et al. on Mar. 20, 1990; U.S Patent No. 4,695,278, issued to Lawson on Sep. 22, 1987; and U.S. Patent No. 4,795,454, issued to Dragoo on Jan. 3, 1989, each being incorporated herein by reference.
- the diaper In use, the diaper is applied to a wearer by positioning the back waistband region under the wearer's back, and drawing the reminder of the diaper between the wearer's legs so that the front waistband region is positioned across the front of the wearer.
- the tape-tab or other fasteners are then secured preferably to outwardly facing areas of the diaper.
- Example 1 A test web of polyethylene film material (30 cm x 20 cm) is placed on the bottom (20 cm below the bottom electrode) of a vacuum chamber of plasma discharge unit (APS Inc Model D). The plasma chamber is evacuated. When the pressure mside the chamber reaches 20 mTorr, a carrier gas (Ar) is continuously introduced into the chamber at a constant rate (10 seem), so the pressure mside the chamber is maintained at 63 mTorr by the balance of continuous evacuation and introduction of carrier gas. While keeping the conditions described above, low temperature plasma is generated side the chamber for a period of 1 mm. by supplying a high frequency electric power of 100 W at a frequency 40 kHz to expose the surface of the film to the low temperature plasma.
- APS Inc Model D plasma discharge unit
- a monomer (acrylic acid) is introduced into the chamber at a constant rate to maintain constant pressure in the chamber (165 mTorr). While maintaining the conditions described above, low temperature plasma (100 W, 40 kHz) is generated mside the chamber for a period of 10 mm. After the treatment, the chamber is evacuated (30 mTorr) and flooded with atmospheric air. The treated web is tested for surface water drop contact angle and surface energy according to the procedures specified by T565 pm-96 provisional method and ACCU DYNE TEST, Diversified Enterprises (based on ASTM D2578-84 technique), to give the results shown in Table 1.
- Comparative Examples 2-4 This example presents the contact angle data (as shown in Table 2, to be compared with
- Table 1 for a polyethylene film exposed to a carrier gas (Ar) and a monomer (acrylic acid) without plasma discharge (Example 2), a film exposed to a carrier gas (Ar) and plasma discharge (100 W) for 11 mm (Example 3), and a film placed in between the electrodes (direct plasma) exposed to a carrier gas (Ar), a monomer (acrylic acid), and plasma discharge (100 W, 11 mm) (Example 4). From comparison with Table 1, it is seen that remote plasma provides a web that better retains its hydrophilicity after accelerated agmg, relative to a web prepare under various other conditions, including direct plasma polymerization.
- contact angle value is an average of 5 measurements
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002340449A CA2340449A1 (en) | 1998-09-21 | 1999-09-20 | Durably wettable liquid pervious webs prepared using a remote plasma polymerization process |
AU60512/99A AU6051299A (en) | 1998-09-21 | 1999-09-20 | Durably wettable liquid pervious webs prepared using a remote plasma polymerization process |
DE69912626T DE69912626D1 (en) | 1998-09-21 | 1999-09-20 | PERMANENTLY HUMIDIFIED, LIQUID, LIQUID, PRODUCED BY PLASMA POLYMERIZATION PROCESS |
EP99969356A EP1115506B1 (en) | 1998-09-21 | 1999-09-20 | Durably wettable liquid pervious webs prepared using a remote plasma polymerization process |
JP2000573867A JP4679725B2 (en) | 1998-09-21 | 1999-09-20 | A durable and wettable liquid permeable web made using an indirect plasma polymerization method |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15784098A | 1998-09-21 | 1998-09-21 | |
US09/157,840 | 1998-09-21 | ||
US38206799A | 1999-08-24 | 1999-08-24 | |
US09/382,067 | 1999-08-24 |
Publications (1)
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WO2000016914A1 true WO2000016914A1 (en) | 2000-03-30 |
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ID=26854523
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1999/021710 WO2000016914A1 (en) | 1998-09-21 | 1999-09-20 | Durably wettable liquid pervious webs prepared using a remote plasma polymerization process |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP1115506B1 (en) |
JP (1) | JP4679725B2 (en) |
AU (1) | AU6051299A (en) |
CA (1) | CA2340449A1 (en) |
DE (1) | DE69912626D1 (en) |
ES (1) | ES2209554T3 (en) |
WO (1) | WO2000016914A1 (en) |
Cited By (13)
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US6878419B2 (en) | 2001-12-14 | 2005-04-12 | 3M Innovative Properties Co. | Plasma treatment of porous materials |
WO2005065603A1 (en) * | 2004-01-09 | 2005-07-21 | Bio-Gate Ag | Dressing for a wound |
WO2005123891A2 (en) * | 2004-05-14 | 2005-12-29 | Reckitt Benckiser (Uk) Limited | Cleansing wipes having a covalently bound oleophilic coating, their use and processes for their manufacture |
US20060008592A1 (en) * | 2002-03-23 | 2006-01-12 | University Of Durham | Preparation of superabsorbent materials by plasma modification |
US7491433B2 (en) | 2002-06-26 | 2009-02-17 | E.I. Du Pont De Nemours And Company | Coated sheet materials and packages made therewith |
US7521587B2 (en) | 2002-09-30 | 2009-04-21 | The Procter & Gamble Company | Absorbent articles comprising hydrophilic nonwoven fabrics |
US7887889B2 (en) | 2001-12-14 | 2011-02-15 | 3M Innovative Properties Company | Plasma fluorination treatment of porous materials |
US7973345B2 (en) | 2007-05-31 | 2011-07-05 | Applied Materials, Inc. | Method of cleaning a patterning device, method of depositing a layer system on a substrate, system for cleaning a patterning device, and coating system for depositing a layer system on a substrate |
EP2444039A1 (en) | 2010-08-26 | 2012-04-25 | Medline Industries, Inc. | Disposable Absorbent Lift Device |
WO2014152227A1 (en) | 2013-03-15 | 2014-09-25 | Medline Industries, Inc. | Flexible disposable sheet with absorbent core |
EP3320986A1 (en) * | 2016-11-09 | 2018-05-16 | Europlasma NV | Hydrophilic, multifunctional ultra-thin coatings with excellent stability and durability |
CN115135711A (en) * | 2020-06-01 | 2022-09-30 | 住友橡胶工业株式会社 | Polymer composite material, rubber composition, and tire |
DE102022126536A1 (en) | 2021-10-13 | 2023-04-13 | Medline Industries, Lp | UNDERLAY WITH WET INDICATOR |
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DE102004033196A1 (en) * | 2004-07-09 | 2006-01-26 | Carl Freudenberg Kg | Functionalized nonwovens, process for their preparation and their use |
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JPS6284761A (en) * | 1985-10-11 | 1987-04-18 | 花王株式会社 | Absorbable article |
WO1997021497A1 (en) * | 1995-12-08 | 1997-06-19 | Novartis Ag | Plasma-induced polymer coatings |
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1999
- 1999-09-20 WO PCT/US1999/021710 patent/WO2000016914A1/en active IP Right Grant
- 1999-09-20 EP EP99969356A patent/EP1115506B1/en not_active Expired - Lifetime
- 1999-09-20 JP JP2000573867A patent/JP4679725B2/en not_active Expired - Fee Related
- 1999-09-20 AU AU60512/99A patent/AU6051299A/en not_active Abandoned
- 1999-09-20 DE DE69912626T patent/DE69912626D1/en not_active Expired - Lifetime
- 1999-09-20 ES ES99969356T patent/ES2209554T3/en not_active Expired - Lifetime
- 1999-09-20 CA CA002340449A patent/CA2340449A1/en not_active Abandoned
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US7125603B2 (en) | 2001-12-14 | 2006-10-24 | 3M Innovative Properties Company | Plasma treatment of porous materials |
US6878419B2 (en) | 2001-12-14 | 2005-04-12 | 3M Innovative Properties Co. | Plasma treatment of porous materials |
US7887889B2 (en) | 2001-12-14 | 2011-02-15 | 3M Innovative Properties Company | Plasma fluorination treatment of porous materials |
US9127363B2 (en) | 2001-12-14 | 2015-09-08 | 3M Innovative Properties Company | Fluorinated porous article |
US20060008592A1 (en) * | 2002-03-23 | 2006-01-12 | University Of Durham | Preparation of superabsorbent materials by plasma modification |
US7491433B2 (en) | 2002-06-26 | 2009-02-17 | E.I. Du Pont De Nemours And Company | Coated sheet materials and packages made therewith |
US7521587B2 (en) | 2002-09-30 | 2009-04-21 | The Procter & Gamble Company | Absorbent articles comprising hydrophilic nonwoven fabrics |
US7858157B2 (en) | 2002-09-30 | 2010-12-28 | The Procter & Gamble Company | Absorbent articles comprising hydrophilic nonwoven fabrics |
US7605298B2 (en) | 2004-01-09 | 2009-10-20 | Bio-Gate Ag | Wound covering |
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WO2005123891A3 (en) * | 2004-05-14 | 2006-06-15 | Reckitt Benckiser Uk Ltd | Cleansing wipes having a covalently bound oleophilic coating, their use and processes for their manufacture |
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AU2005254759B2 (en) * | 2004-05-14 | 2010-10-28 | Reckitt Benckiser (Uk) Limited | Cleansing wipes having a covalently bound oleophilic coating, their use and processes for their manufacture |
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US7973345B2 (en) | 2007-05-31 | 2011-07-05 | Applied Materials, Inc. | Method of cleaning a patterning device, method of depositing a layer system on a substrate, system for cleaning a patterning device, and coating system for depositing a layer system on a substrate |
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US9724256B2 (en) | 2010-08-26 | 2017-08-08 | Medline Industries, Inc. | Disposable absorbent lift device |
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US11090210B2 (en) | 2010-08-26 | 2021-08-17 | Medline Industries, Inc. | Disposable absorbent lift device |
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EP3320986A1 (en) * | 2016-11-09 | 2018-05-16 | Europlasma NV | Hydrophilic, multifunctional ultra-thin coatings with excellent stability and durability |
WO2018087192A1 (en) * | 2016-11-09 | 2018-05-17 | Europlasma Nv | Hydrophilic, multifunctional ultra-thin coatings with excellent stability and durability |
BE1025053B1 (en) * | 2016-11-09 | 2018-10-12 | Europlasma Nv | HYDROFILE, MULTIFUNCTIONAL ULTRA-THIN COATING WITH EXCELLENT STABILITY AND SUSTAINABILITY |
US11167311B2 (en) | 2016-11-09 | 2021-11-09 | Europlasma Nv | Hydrophilic, multifunctional ultra-thin coatings with excellent stability and durability |
CN115135711A (en) * | 2020-06-01 | 2022-09-30 | 住友橡胶工业株式会社 | Polymer composite material, rubber composition, and tire |
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NL2033068A (en) | 2021-10-13 | 2023-04-19 | Medline Ind Lp | Underpad with wetness indicator |
Also Published As
Publication number | Publication date |
---|---|
ES2209554T3 (en) | 2004-06-16 |
CA2340449A1 (en) | 2000-03-30 |
JP2002526567A (en) | 2002-08-20 |
JP4679725B2 (en) | 2011-04-27 |
DE69912626D1 (en) | 2003-12-11 |
EP1115506A1 (en) | 2001-07-18 |
AU6051299A (en) | 2000-04-10 |
EP1115506B1 (en) | 2003-11-05 |
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