CA2228606A1 - Method of corona treating a hydrophobic sheet material - Google Patents
Method of corona treating a hydrophobic sheet material Download PDFInfo
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- CA2228606A1 CA2228606A1 CA 2228606 CA2228606A CA2228606A1 CA 2228606 A1 CA2228606 A1 CA 2228606A1 CA 2228606 CA2228606 CA 2228606 CA 2228606 A CA2228606 A CA 2228606A CA 2228606 A1 CA2228606 A1 CA 2228606A1
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- sheet material
- corona discharge
- treated
- nonwoven web
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/10—Surface shaping of articles, e.g. embossing; Apparatus therefor by electric discharge treatment
-
- 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
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Textile Engineering (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
A method of preventing localized arcing to ground during treatment of a sheet material in a corona discharge field generated by a corona discharge apparatus having at least two electrodes, which method involves passing the sheet material to be treated through the corona discharge field, in which the sheet material to be treated is electrically isolated from the electrodes. When the corona discharge apparatus has a bare metal electrode and a dielectric-covered electrode, the sheet material to be treated is passed through the corona discharge field as a layer of a multilayered composite having at least three layers, in which at least one of the layers is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode. The method may be employed to treat a hydrophobic sheet material having a porosity, in which case the hydrophobic sheet material is passed through a corona discharge field generated by a corona discharge apparatus having a bare metal electrode and a dielectric covered electrode under conditions adapted to render the porous sheet wettable. The hydrophobic sheet material is a layer of a multilayered composite having at least three layers, in which at least one layer is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode and one of the at least three layers is a nonconductive, nonporous sheet material.
Description
W O 97/11834 PCTrUS96/13227 METHOD OF CORONA TREATING
A HYDROPHOBIC SHEET MATERIAL
Background of the Invention The present invention relates to a sheet material, such as a porous sheet material.
Polymers are used extensively to make a variety of products which include blown and cast films, extruded sheets, injection molded articles, foams, blow molded 10 articles, extruded pipe, monofilaments, and fibrous materials such as nonwoven webs.
Some of the polymers. such as polyoiefins, have no functionality (i.e., reactive groups) and are naturally hydrophobic, and for many uses these properties are either a positive attribute or at least not a disadvantage.
There are a number of uses for polymers, however, where their hydro-15 phobic/nonfunctional nature either limits their usefulness or requires some effort tomodify the surface characteristics of the shaped articles made therefrom. By way of example, polyolefins, such as polyethylene and polypropylene, are used to manufacture polymeric fabrics which are employed in the construction of such disposable absorbent articles as diapers, feminine care products, incontinence 2 o products, training pants, wipes, and the like. Such polymeric fabrics often are nonwoven webs prepared by, for example, such processes as meltblowing, cofomming, and spunbonding. Frequently, such polymeric fabrics need to be wettable by water.
Wettability can be obtained by spraying or otherwise coating Ii.e., surface treating or topically treating) the fabric with a surfactant solution during or after its formation, and 25 then drying the web, Some of the more common topically applied surfactants are nonionic surfactants, such as polyethoxylated octylphenols and condensation products of propylene oxide with propylene glycol, by way of iilustration only. These surfactants are effective in rendering normally hydrophobic polymeric fabrics wettable. However, 30 the surfactant is readily removed from the fabric, often after only a single exposure to an aqueous liquid.
Hydrophobic polymers also have been rendered wettabie by passing the porous hydrophobic sheet material through a corona discharge field. A corona discharge field also has been used to improve ink adhesion on a surface of a film: to 35 improve the adhesion of one fiim to another; or to introduce functional or ionic groups -on the surfaces of the fibers of filter media, films, and the like. In some cases, a film has been rendered porous or more porous by exposing the film to a corona discharge field. Because arcing is an intrinsic phenomenon associated with a corona discharge field, localized arcing is a frequent and common occurrence. However, localized 5 arcing results in the formation of pinholes in the materiai being treated. This result often is either desired or not a disadvantage. Localized arcing is a problem, though, when porous materials are utilized and it is desired that the porosity of the material not be altered by the corona discharge treatment.
Notwithstanding past improvements in rendering a polymeric fibrous material 10 wettable or introducing functional or ionic groups on the surfaces of the fibers of filter media and films, there still are opportunities for improvements in these areas. This is particularly true where it is desired to treat a porous sheet material in a corona discharge field without altering the porosity of the sheet material.
Summary of the Invention The present invention addresses some of the difficulties and problems discussed above by providing a method of preventing localized arcing to ground during treatment of a sheet material in a corona discharge field generated by a corona 20 discharge apparatus having at least two electrodes, which method involves passing the sheet material to be treated through the corona discharge field, in which the sheet material to be treated is electrically isolated from the electrodes.
When the corona discharge apparatus has a bare metal electrode and a dielectric-covered electrode, the sheet material to be treated is passed through the 25 corona discharge field as a layer of a multilayered composite having at least three layers, in which at least one of the layers is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode.
The method may be employed to treat a hydrophobic sheet material having a porosity, in which case the hydrophobic sheet material is passed through a corona 3 o discharge field generated by a corona discharge apparatus having a bare metal electrode and a dielectric covered electrode under conditions adapted to render the porous sheet wettable. The hydrophobic sheet material is a layer of a multilayered composite having at least three layers, in which at least one layer is a nonconductive sheet material situated between the sheet material to be treated and the bare metal 35 electrode and one of the at least three layers is a nonconductive, nonporous sheet W O 97/11834 ' PCTnJS96/13227 material. For example, the at least one layer which is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode also may be nonporous.
In general, the sheet material may be any sheet material capable of being treated in a corona discharge field. The sheet material may be nonporous or porous.
For example, the sheet material may be a film. As another example, the sheet material may be a fibrous web. The fibrous web may be woven or nonwoven. Examples of nonwoven fibrous webs include meltblown. coformed. and spunbonded nonwoven webs.
The sheet material may be made of any desired material which is capable of being treated in a corona discharge field. For example. the sheet material may be made from a synthetic polymer, such as a polyolefin. Particularly desired polyolefins include polypropylene and polyethylene.
Detailed Description of the Invention As used herein, the term "corona discharge field" is employed with its usual meaning. Such field may be generated by any means known to those having ordinaryskill in the art.
The term "nonconductive" with reference to a sheet material is used herein to mean that the sheet material will not conduct electricity.
As used herein, the term "wettable" means wettable by water, e.g., the spontaneous absorption of water by a porous material such as a nonwoven web.
As stated earlier, the present invention provides a method of preventing 25 localized arcing to ground during treatment of a sheet material in a corona discharge field generated by a corona discharge apparatus having at least two electrodes. The method involves passing the sheet material to be treated through the corona discharge field, in which the sheet material to be treated is electrically isolated from the electrodes.
The sheet material may be any sheet material capable of being treated in a corona discharge field. The sheet material may be nonporous or porous. For example, the sheet material may be a film. As another example, the sheet material may be a fibrous web. The fibrous web may be woven or nonwoven. Examples of nonwoven fibrous webs include, by way of illustration only, meltblown, coformed, spunbonded, 35 air-laid, wet-laid, and bonded carded nonwoven webs.
A nonwoven web desirably will be formed by such well-known processes as meltblowing, coforming, spunbonding, and the like. By way of iliustration only, such processes are exemplified by the following references, each of which is incorporated herein by reference: r s (a) meltblowing references include, by way of example, U.S. Patent Nos.3,016,599 to R. W. Perry, Jr., 3,704,198 to J. S. Prentice, 3,755,527 to J. P. Keller et al 3,849,241 to R. R. Butin et al., 3,978,185 to R. R. Butin et al., and 4,663,220 to T. J. Wisneski et al. See, also, V. A. Wente, "Superfine Thermoplastic Fibers", Industrial and Enqineerina Chemistrv, Vol. 48,~No. 8, pp. 1342-1346 (1956); V. A. Wente et al., "Manufacture of Superfine Organic Fibers", Navy Research Laboratory, Washington, D.C., NRL Report 4364 (111437), dated May 25, 1954, United States Department of Commerce. Office of Technical Services: and Robert R. Butin and Dwight T. Lohkamp. "Melt Blowing - A One-Step Web Process for New Nonwoven Products", Journal of the Technical Association of the Pulo and PaPer Industrv, Vol. 56, No.4, pp. 74-77 (1973):
(b) coforming references (i.e., references disclosing a meltblowing process in which fibers or particles are commingled with the meltblown fibers as they are formed) include U.S. Patent Nos. 4,100,324 to R. A. Anderson et al. and 4,118,531 to E. R. Hauser:
and (c) spunbonding references include, among others, U.S. Patent Nos. 3.341,394 to Kinney, 3,655,862 to Dorschner et al., 3,692,618 to Dorschner et al., 3,705,068 to Dobo et al., 3,802,817 to Matsuki et al., 3,853,651 to Porte, 4,064,605 to Akiyama et al., 4,091,140 to Harmon, 4,100,319 to Schwartz, 4,340.563 to Appel and Morman, 4,405.297 to Appel and Morman, 4,434,204 to Hartman et al., 4,627,811 to Greiser and Wagner, and 4,644,045 to Fowells.
The sheet material may be made of any desired material which is capable of being treated in a corona discharge field. For example, the sheet material typically may be made from a synthetic polymer. which may be a thermosetting or thermoplas-tic polymer.
Examples of thermosetting polymers include, by way of illustration only, alkyd resins, such as phthalic anhydride-glycerol resins, maleic acid-glycerol resins, adipic acid-glycerol resins, and phthalic anhydride-pentaerythritol resins: allylic resins, in which such monomers as diallyl phthalate, diallyl isophthalate diallyl maleate. and diallyl chlorendate serve as nonvolatile cross-linking agents in polyester compounds: amino resins. such as aniline-formaldehyde resins, ethylene urea-formaldehyde resins, dicyan-diamide-formaldehyde resins. melamine-fommaldehyde resins, sulfonamide-formaldehyde resins, and urea-fommaldehyde resins; epoxy resins, such as cross-linked epichlorohydrin-bisphenol A resins; phenolic resins. such as phenol-formaldehyde resins, including Novolacs and resols: and thermosetting polyesters, silicones, and urethanes.
Examples of thermoplastic polymers include, by way of illustration only, end-capped polyacetals, such as poly(oxymethylene) or polyformaldehyde, polyltrichloroacetaldehyde), poly(n-valeraldehyde), poly(acetaldehyde), po-ly(propionaldehyde), and the like; acrylic polymers, such as polyacrylamide, poly(acrylic acid), poly(methacrylic acid), poly(ethyl acrylate), poly(methyl methacrylate), poiyacrylonitrile, and the like: fluorocarbon polymers, such as 10 poly(tetrafluoroethylene), perfluorinated ethylene-propylene copolymers, ethylene-tetrafluoroethylene copolymers, poly(chlorotrifluoroethylene), ethylene-chlorotrifiuoroethylene copolymers, poly(vinylidene fluoride), poly(vinyl fluoride), and the like: polyamides, such as poly(6-aminocaproic acid) or poly(E-caprolactam), poly-(hexamethylene adipamide), poly(hexamethylene sebacamide), poly(l l-amino-15 undecanoic acid), and the like: polyu~u",:-ics, such as poly(imino-1,3-phenylenei-minoisophthaloyl) or poly(m-phenylene isophthalamide), and the like: parylenes, such as poly-e-xylylene, poly(chloro-e-xylylene), and the like: polyaryl ethers, such as poly(oxy-2,6-dimethyl-1,4-phenylene) or poly(e-phenylene oxidej, and the like: polyaryl sulfones, such as poly(oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1,4-phenylene-20 isopropylidene-1,4-phenylene), poly(sulfonyl-1,4-phenyleneoxy-1,4-phenylenesulfonyl-4,4'-biphenylene), and the like: polycarbonates, such as poly(bisphenol A) or poly(carbonyldioxy- 1 ,4-phenyleneisopropylidene- 1 ,4-phenylene), and the like;polyesters, such as poly(ethylene terephthalate), poly(tetramethylene terephthalate), poly(cyclohexylene-1,4-dimethylene terephthalate) or polyloxymethylene-1,4-25 cyclohexylenemethyleneoxyterephthaloyl), and the like: polyaryl sulfides, such as poly(e-phenylene sulfide) or poly(thio-1,4-phenylene), and the like: polyimides, such as poly(pyromellitimido-1,4-phenylene), and the like; polyolefins, such as polyethylene, polypropylene, poly( 1 -butene), poly(2-butene), poly( l-pentene), poly(2-pentene), poly(3-methyl-1-pentene), poly(4-methyl-1-pentene), and the like; vinyl polymers, such 30 as poly(vinyl acetate), poly(vinylidene chloride), poly(vinyl chloride), and the like;
diene polymers, such as 1,2-poly-1,3-butadiene, 1,4-poly-1,3-butadiene, polyisoprene, polychloroprene, and the like; polystyrenes; copolymers of the foregoing, such as acrylonitrile-butadiene-styrene (ABS) copolymers, and the like: and the like.
In some embodiments, the sheet material may be made of a synthetic 35 hydrophobic polymer. Hydrophobic polymers in general give contact angles with W O 97/11834 PCTrUS96/13227 water of at least about 60~ and typically have surface free energies of less than about 45 dynes cm ~ (mjoule m-2). Examples of such polymers include, by way of illustration only, aromatic polyesters, polyolefins, polytetrafluoroethylene, poly(methyl methacry-late), poly(vinylidene fluoride), polyamides, and polystyrenes.
s Aromatic polyesters include, by way of example only, poly(ethylene terephthalate), poly(tetramethylene terephthalate), poly(cyclohexane-1,4-dimethylene terephthalate), and thermotropic liquid crystalline such as the copolymers of hydroxybenzoic acid and hydroxynaphthoic acid.
Examples of polyolefins include, again by way of illustration only, polyethylene, polypropylene, poly(1-butene), poly(2-butene), poly(1-pentene), poly(2-pentene),poly(3-methyl-1-pentene), poly(4-methyl-1-pentene), and the like. In addition, 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 and15 polypropylene.
Polyamides include, by way of example only, poly(6-aminocaproic acid) (nylon 6), polyfhexamethylene sebacamide) (nylon 6,10), and poly(octamethylene suberamide) (nylon 8,8) .
As already stated, the sheet material to be treated must be electrically isolated 20 from the electrodes of the corona discharge apparatus. This may be accomplished by any means. For example, both electrodes may be covered with a dielectric sleeve. As another example, one electrode may be covered with a dielectric sleeve and one electrode may be covered with a nonconductive fiim which may be renewable.
Other means will be readily apparent to those having ordinary skill in the art.
When the corona discharge apparatus has a bare metal electrode and a dielectric-covered electrode, the sheet material to be treated may be passec! through the corona discharge field as a layer of a multilayered composite having at least three layers, in which at least one of the layers is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode. If desired, 30 the nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode also may be nonporous.
The method may be employed to treat a hydrophobic sheet material having a porosity, in which case the hydrophobic sheet material is passed through a corona discharge field generated by a corona discharge apparatus having a bare metal 35 electrode and a dielectric covered electrode under conditions adapted to render the porous sheet wettable. The hydrophobic sheet material is a layer of a multilayered composite having at least three layers, in which at least one layer is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode and one of the at least three layers is a nonconductive, nonporous sheet material. For example, the at least one layer which is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode also may be nonporous.
The present invention is further described by the examples which follow. Such examples, howeve~r, are not to be construed as limiting in any way either the spirit or 0 the scope of the present invention.
Materials In the examples, the following materials were used:
Polypropylene film: 2-mil (about û,05-mmJ thickness (Type XP715S/P, Lot #468û5, Edison Plastics Co., Newport News, Virginia).
Polyethylene Film: 1-mil (about û.025-mm) thickness (standard linear low densitypolyethylene film).
Polytetrafluoroethylene film: 2-mil (about û.û5-mm) thickness (Fisher Scientific, Atlanta, Georgia).
Celgard(~ 25ûO Microporous polypropylene film: Hoechst Celanese, Charlotte, 2 o North Carolina.
Manila Paperboard: 11-mil (about 0.3-mm) thickness (No. 2-152C, Smead Inc,, Hastings, Minnesota). The paperboard is believed to be porous, although no tests were run to verify or define such porosity.
Aluminum Foil: 1-mil (about û.û25-mm~ thickness (Reynolds Metals Company, Richmond, Virginia).
Corona Discharqe Treater A corona discharge field was generated by means of a Corotec Laboratory Corona Treating Station (Corotec Corporation, Collinsville, Connecticut) equipped with a CXC-5 power supply. The Corotec Laboratory Corona Treating Station generated ahigh voltage alternating current corona discharge. The voltage of the discharge (peak to peak) ranged from 7 kV to 1û kV and the frequency ranged from 19 kHz to 20 ~ kHz. The treater utilized two horizontally positioned, counter-rotating aluminum rolls as the electrodes. The bottom roll was grounded and its surface was covered by a 2-mm thick dielectric sleeve. The top roll was bare aluminum metal. The nip point formed by 35 the two rolls provided a minimum gap of 2 mm. The actual gap between the electrodes during the treatment of a material was the sum of the thicknesses of the materials being passed through the gap and the 2-mm thick dielectric cover on the lower electrode. The line speed was fixed at 12 ft/min ~about 6 cm/secJ. The power dissipated in the gap during corona discharge was indicated by an integral power5 meter.
The corona energy density was a quantitative measure of power dissipated across the widttl of the electrodes per unit area of material being treated. This is simply expressed by dividing the output power of the power supply by the width of the anode (ft) and ttle line speed (ft/s). Energy density was assumed to be a cumulative function 10 of the number of passes through the discharge. Typically. materials were passed through the discharge from I to 1 û times. Table 1 lists energy density per pass for typical output power used in the examples.
Table 1 Corona Energy Densities Output Powera Er~çrqY Densitvb lOO 500 (5.38) 200 1000 ( 10.8) 300 1500 (16.2) 400 2000 (21.5) 5002500 ( 26 . 9 ) aln watts or joule sec-'.
bln watt sec ft 2 (kjoule m '~).
Critical Surface Tension of Wettinq A critical surface tension of wetting was determined for each sample treated using a Wetting Tension Test Kit, Model STT 11 - 1 (Pillar Technologies, Inc., Hartland, Wisconsin Michigan~). The critical surface tension of wetting was taken as the surface 30 tension of the Pillar test kit fluid which was spontaneously absorbed into a porous substrates. The Wetting Tension Kit conforms to ASTM Standard D2578-67.
Surface Analysis The surfaces of treated samples were analyzed by electron spectroscopy for chemical analysis lESCA). All analyses were carried out with a Surface Science 35 Instruments M-Probe ESCA Spectrometer. Spectral collections were performed with W O 97/11834 PCT~US96/13227 monochromatic aluminum x-ray excitation of an 800 square micrometer area of eachsample. Differential charging of samples was compensated for by using a low energy ( 1 eV) flux of electrons from an electron flood gun.
Example 1 Corona Discharge Treatment of Polypropylene Meltblown Nonwoven Webs Samples of 0~5 ounce per square yard or osy (about 17 grams per square meter or gsm) polypropyiene meltblown nonwoven webs were corona discharge treated at corona energy densities per pass ranging from 500 to 2500 watt sec ft-2 (about 5.38 to 26.9 kjoule m-2). Each meltblown sample was mounted as a multilayered structure in which 1 to 5 layers of material were overlayed or stacked to form a composite sample for corona treatment. No adhesive was applied between layers of the laminates: thus, after corona discharge treatment, the layers were easily separable.
The multilayered composites are referred to or described layer by layer, beginning with the layer closest to the top or bare metal electrode of the Treating Station and ending with the layer closest to the bottom electrode of the treater, i.e., the electrode covered with the dielectric sleeve. While in the examples a maximum of 2 0 five layers were used, this number of layers should not be construed as limiting in any way either the spirit or the scope of the invention.
The multilayered composite were corona discharge treated by feeding the materials through the nip formed between the upper and lower electrodes of the Treating Station. The severity of treatment was varied by increasing the corona output power and by increasing the number of passes through the discharge field at a fixed corona energy density.
The numerous composite configurations examined are summarized in Table 2.
Included in Table 2 are data indicating the observance of pinholes in the coronatreated material and the critical surface tension for wetting (CSTW) of the treated meltblown nonwoven web for each configuration examined. The CSTW was evaluated on both the top and bottom sides of each fabric. In no case was the CSTW of the top ~ side (the side closest to the bare metal electrode of the Treating Station~ found to be different from that observed on the bottom side (the side closest to the dielectric-Y covered electrode of the Treating Station). All samples were passed through the corona discharge field a total of ten times at a fixed corona energy density of 1500 W O 97/11834 PCTrUS96/13227 watt sec ft 2 (about 16.2 kjoule m-2). The following abbreviations are employed in all tables:
PPF = Polypropylene film MB = Polypropylene meltblown nonwoven web MPB = Manila paperboard Tc~ble 2 Summary of Results for Corona Treatment of Nonwoven Webs in Multilayeled Composites ComPosite Descrir~tion Pinholes CSTWa Wettable MB Yes 58 No MB/PPF Yes 72 Yes PPF/MB Yes 72 Yes 15MB/PPF/PPF Yes 72 Yes PPF/MB/PPF No 72 Yes PPF/PPF/MB yesb 72 Yes MB/MPB Ye~ 58 No MPB/MB ye5c /2 Yes 20MB/MPB/MPB Yes 60 No MPB/MB/MPB No ~8 No MPB/MPB/MB No 62 No MB/PPF/MPB yesb 72 Yes MPB/PPF/MB No 72 Yes 25MB/MPB/PPF Yes 72 Yes PPF/MPB/MB No 72 Yes PPF/MB/MPB No 72 Yes MPB/MB/PPF No 72 Yes Table 2, Continued Colt" o~ile Descril~tion Pinholes CSTWa Wettable PPF/MB/PPF/MPB No 60 No MPB/PPF/MB/PPF No 60 No '' aCritical suRace tension of wetting in dynes cm-' (mjoule m-2).
bVery few.
cVery large.
From the series of experiments summarized in Table 2, several conclusion can be drawn:
lal isolation of the meltblown nonwoven web from the upper bare electrode was essential to prevent pinholes from forming in the web:
(b) hole sizes appeared to be controlled by the material which acts as a carrier sheet for the nonwoven web:
(c) the total composite thickness had a pronounced effect on the wettability of the treated nonwoven web: and (d) the optimal sample configuration which yields a pinhole-free and water-20 wettable material was MPBtMB/PPF, i.e., manila paperboard/meltblown nonwovenweb/polypropylene film.
Treatment Sidedness The results of ESCA determinations on the surfaces of meltblown nonwoven web sampies corona treated in the PPF/MB/MPB and MPB/MB/PPF configurations are 2 5 summarized in Table 3. Each sample was corona treated at a corona energy density of l 500 Watt sec ft-2 (about l 6.2 kjoule m 2~ per pass for l O passes.
W O 97/11834 PCT~US96/13227 Table 3 ESCA Analyses of Corona Treated Meltblown Nonwoven Webs s Element Alomic Percent SampleCarbon Oxyaen Controla100 PPF/MB/MPB ( top) 88 . 5 11.5 PPF/MBtMPB ~bottom) 89. 5 10. 5 10 MPB/MBIPPF (top) 88.711.3 MPB/MB/PPF ~bottom~ 90 . 3 9 . 7 aNoncorona treated MB.
The surface analysis data summarized in Table 3 illustrate quantitatively the lack 15 of sidedness to the nonwoven web following corona treatment in the multilayered composite configuration.
Effect of Corona Power The effect of output power of the corona treater on the CSTW and the surface composition of the meltblown nonwoven web was evaluated using the MPB/MB/PPF
20 configuration described above. The surface composition was determined by ESCAanalysis of the nonwoven web after treatment and is herein expressed as the ratio of the atomic percent of oxygen to that of carbon ~O/C ratio). In all cases the samples were passed through the corona discharge field a total of five times. The results are summarized in Table 4.
Table 4 Summary of the EFFect of Output Power Corona Powera ~/C RatiobCSTWC Wettable 100 9.û 56 No 2ûO 11.5 56 No 300 12.6 60 No 400 17.6 62 No 500 14.5 62 No aln watts or joule sec-l.
W O 97/11834 PCTnUS96/13227 bThe calculated O/C ratio times 100.
aCritical surface tension of wetting in dynes cm-' (mjoule m-2).
As can be seen from the table, both the surface O/C ratio and the CSTW
increased with increasing corona power. Except for the O/C ratio at 400 watts or joule sec-', the increases in both the O/C ratio and CSTW appear to be roughly linear at output power rating increases above 100 watts or joule sec-E
EFfect cf Corona Treatment Severitv The effect of corona treatment severity (time) was evaluated by increasing the number of passes through a corona discharge field at fixed power. In this case the corona power was set at 300 watts or joule sec-', corresponding to a corona energy density of 1 5ûû watt sec ft 2 (about 16.2 kjoule m ~l per pass. The results are summarized in Table 5.
Table 5 Summary of the Effect of Number of Passes Number Passes O/C Ratio~ CSTWb Wettable 1 6.5 56 No 3 12. 8 56 No 16. 8 60 No 8 17.1 64 No 15. 9 72 Yes ~The calculated O/C ratio times 100.
bCritical surface tension of wetting in dynes cm-' mjoule m-21.
According to the data in the table, the CSTW increased with the number of passes through the corona field, although fewer than about five passes had little apparent effect on the CSTW value. The surface O/C ratio, however, appeared to reach a maximum after about 5 passes, .~
Example 2 Conductive versus Dielectric Film Layers W O 97/11834 ' PCT~US96/13227 in the Multilayered Composite The corona treatment of the polypropylene meltblown nonwoven web was examined as a function of the electrical conductivity of the film layer used in the 5 preparation of the multilayered composite. A l-mil ~about 0.025-mm) thick aluminum foil was used as a conductive film and several polymer films were evaluated as dielectric film layers. The corona treatment conditions were 1500 watt sec ft-2 (about 16.2 ~kjoule m-2) per pass and 10 passes.
Conductive Film Three samples of the meltblown nonwoven web were treated in multilayered composites which included an aluminum foil conductive film iayer. In the first, a section of the meltblown web was mounted on manila paperboard with poly-propylene film covering one half and aluminum foil the other. The sample was constructed such that, as the sample passed through the corona field, half of the 15 electrode pair would "see" the polypropylene film and the other half would "see" the aluminum foil. Thus, the juncture between the two types of film was parallel to the direction of motion of the composite through the corona discharge apparatus.
After treatment. both sides of the meltblown nonwoven web had a CSTW value of 60 dynes cm ' ~mjoule m-2), while only the aluminum foil side had pinholes. A second 2 0 experiment in which the same sample configuration was used except that the sample was constructed such that the aluminum foil and polypropylene film halves were treated sequentially. The results were the same. A third sample was prepared wherein a second polypropylene film layer was added between the manila paperboard and the nonwoven web. In this case, no pin holes were observed in either the aluminum foil 25 covered or polypropylene film covered sides, and the CSTW value was the same on each side.
W O 97/11834 PCT~US96/132Z7 Nonconductive Film Other examples of nonconductive films used as layers in multilayered composites included polytetrafluoroethylene IPTFE), polyethylene (PE~, and Celgard(9 25ûû microporous polypropylene. The sample configuration was MPB/MB/Nonconduc-tive Film.
No pinholes were observed in nonwoven webs treated using composites constructed with the PTFE or the PE film. Both samples had CTSW values of 72 dynes cm-' (mjoule m-2). Corona treatment of the sample utilizing the Celgard~9) 25û0 microporous polypropylene yielded a nonwoven web which was badly pinholed. In 0 addition, the treatment uniformity was poor. Some areas had a CSTW value of 72 dynes cm-' (mjoule m-2), while others had a CSTW value of 60 dynes cm-~ (mjoule m-2).
This illustrates the need for a nonporous nonconductive film layer in the multilayered composite subjected to the corona discharge field in order to prevent the formation of pinholes in the nonwoven web while producing a web which is wettable.
Example 3 Corona Discharge Treatment of Microporous Film The corona discharge treatment of microporous films was demor,,lluled using sample of Celgard~ 25ûû microporous polypropylene film. The microporous film wastreated in a manner similar to that described in Example l . The corona treatment conditions were l 50û watt sec ft-2 per pass and l0 passes. The Celgard film was treated either by itself or as a multilayered composite with PP film, PE film, and PTFE film.
Treatment of the Celgard~ 250û microporous polypropylene film by itself produced a material with pinholes over greater than 90 percent of its surface. The introduction of a nonconductive film such as PP film on top of the Celgard film prevented pinhole formation and yielded a material with a CSTW value of 72 dynescm-' Imjoule m-2). Identical results were obtained when treating with either the PTFE or PE films as covers.
3 0 Example 4 Corona Discharge Treatment of Nonwoven Webs The broad applicability of the multilayered composite approach to controlling pinhole formation during corona treatment of nonwoven webs was further demor,,l,ul~d by examining higher basis weight polypropylene meltblown webs and a series of nonwoven webs made from polyethylene. The corona treatment conditions were 1500 watt sec ft-2 per pass and 10 passes. The MPB/Nonwoven Web/PPF sample configuration was used For each nonwoven web. The nonwoven webs studied were as follows:
s A - 1.0 osy (about 34 gsm~ polypropylene meltblown nonwoven web.
B - l.û osy ~about 34 gsm) polypropylene spunbonded nonwoven web.
C - 1.6 osy (about 54 gsm) polyethylene meltblown nonwoven 0 web.
D - 6 osy labout 204 gsm) polyethylene meltblown nonwoven web.
The results of these studies are summarized in Table 6.
Table 6 Corona Treatment of Various Nonwoven Webs SamPle PinholesCSTWa Wettable A Nb 62 N!o 2 0 B No 58 No C No 72 Yes D No 58 No ~Critical surface tension of wetting in dynes cm-~ (mjoule m-2).
While the specification has been described in detail with respect to specific embodiments thereof, it will be appreciated that those skilled in the art. upon attaining an understanding of the foregoing, may readily conceive of alterations to, variations of, and equivalents to these embodiments.
A HYDROPHOBIC SHEET MATERIAL
Background of the Invention The present invention relates to a sheet material, such as a porous sheet material.
Polymers are used extensively to make a variety of products which include blown and cast films, extruded sheets, injection molded articles, foams, blow molded 10 articles, extruded pipe, monofilaments, and fibrous materials such as nonwoven webs.
Some of the polymers. such as polyoiefins, have no functionality (i.e., reactive groups) and are naturally hydrophobic, and for many uses these properties are either a positive attribute or at least not a disadvantage.
There are a number of uses for polymers, however, where their hydro-15 phobic/nonfunctional nature either limits their usefulness or requires some effort tomodify the surface characteristics of the shaped articles made therefrom. By way of example, polyolefins, such as polyethylene and polypropylene, are used to manufacture polymeric fabrics which are employed in the construction of such disposable absorbent articles as diapers, feminine care products, incontinence 2 o products, training pants, wipes, and the like. Such polymeric fabrics often are nonwoven webs prepared by, for example, such processes as meltblowing, cofomming, and spunbonding. Frequently, such polymeric fabrics need to be wettable by water.
Wettability can be obtained by spraying or otherwise coating Ii.e., surface treating or topically treating) the fabric with a surfactant solution during or after its formation, and 25 then drying the web, Some of the more common topically applied surfactants are nonionic surfactants, such as polyethoxylated octylphenols and condensation products of propylene oxide with propylene glycol, by way of iilustration only. These surfactants are effective in rendering normally hydrophobic polymeric fabrics wettable. However, 30 the surfactant is readily removed from the fabric, often after only a single exposure to an aqueous liquid.
Hydrophobic polymers also have been rendered wettabie by passing the porous hydrophobic sheet material through a corona discharge field. A corona discharge field also has been used to improve ink adhesion on a surface of a film: to 35 improve the adhesion of one fiim to another; or to introduce functional or ionic groups -on the surfaces of the fibers of filter media, films, and the like. In some cases, a film has been rendered porous or more porous by exposing the film to a corona discharge field. Because arcing is an intrinsic phenomenon associated with a corona discharge field, localized arcing is a frequent and common occurrence. However, localized 5 arcing results in the formation of pinholes in the materiai being treated. This result often is either desired or not a disadvantage. Localized arcing is a problem, though, when porous materials are utilized and it is desired that the porosity of the material not be altered by the corona discharge treatment.
Notwithstanding past improvements in rendering a polymeric fibrous material 10 wettable or introducing functional or ionic groups on the surfaces of the fibers of filter media and films, there still are opportunities for improvements in these areas. This is particularly true where it is desired to treat a porous sheet material in a corona discharge field without altering the porosity of the sheet material.
Summary of the Invention The present invention addresses some of the difficulties and problems discussed above by providing a method of preventing localized arcing to ground during treatment of a sheet material in a corona discharge field generated by a corona 20 discharge apparatus having at least two electrodes, which method involves passing the sheet material to be treated through the corona discharge field, in which the sheet material to be treated is electrically isolated from the electrodes.
When the corona discharge apparatus has a bare metal electrode and a dielectric-covered electrode, the sheet material to be treated is passed through the 25 corona discharge field as a layer of a multilayered composite having at least three layers, in which at least one of the layers is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode.
The method may be employed to treat a hydrophobic sheet material having a porosity, in which case the hydrophobic sheet material is passed through a corona 3 o discharge field generated by a corona discharge apparatus having a bare metal electrode and a dielectric covered electrode under conditions adapted to render the porous sheet wettable. The hydrophobic sheet material is a layer of a multilayered composite having at least three layers, in which at least one layer is a nonconductive sheet material situated between the sheet material to be treated and the bare metal 35 electrode and one of the at least three layers is a nonconductive, nonporous sheet W O 97/11834 ' PCTnJS96/13227 material. For example, the at least one layer which is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode also may be nonporous.
In general, the sheet material may be any sheet material capable of being treated in a corona discharge field. The sheet material may be nonporous or porous.
For example, the sheet material may be a film. As another example, the sheet material may be a fibrous web. The fibrous web may be woven or nonwoven. Examples of nonwoven fibrous webs include meltblown. coformed. and spunbonded nonwoven webs.
The sheet material may be made of any desired material which is capable of being treated in a corona discharge field. For example. the sheet material may be made from a synthetic polymer, such as a polyolefin. Particularly desired polyolefins include polypropylene and polyethylene.
Detailed Description of the Invention As used herein, the term "corona discharge field" is employed with its usual meaning. Such field may be generated by any means known to those having ordinaryskill in the art.
The term "nonconductive" with reference to a sheet material is used herein to mean that the sheet material will not conduct electricity.
As used herein, the term "wettable" means wettable by water, e.g., the spontaneous absorption of water by a porous material such as a nonwoven web.
As stated earlier, the present invention provides a method of preventing 25 localized arcing to ground during treatment of a sheet material in a corona discharge field generated by a corona discharge apparatus having at least two electrodes. The method involves passing the sheet material to be treated through the corona discharge field, in which the sheet material to be treated is electrically isolated from the electrodes.
The sheet material may be any sheet material capable of being treated in a corona discharge field. The sheet material may be nonporous or porous. For example, the sheet material may be a film. As another example, the sheet material may be a fibrous web. The fibrous web may be woven or nonwoven. Examples of nonwoven fibrous webs include, by way of illustration only, meltblown, coformed, spunbonded, 35 air-laid, wet-laid, and bonded carded nonwoven webs.
A nonwoven web desirably will be formed by such well-known processes as meltblowing, coforming, spunbonding, and the like. By way of iliustration only, such processes are exemplified by the following references, each of which is incorporated herein by reference: r s (a) meltblowing references include, by way of example, U.S. Patent Nos.3,016,599 to R. W. Perry, Jr., 3,704,198 to J. S. Prentice, 3,755,527 to J. P. Keller et al 3,849,241 to R. R. Butin et al., 3,978,185 to R. R. Butin et al., and 4,663,220 to T. J. Wisneski et al. See, also, V. A. Wente, "Superfine Thermoplastic Fibers", Industrial and Enqineerina Chemistrv, Vol. 48,~No. 8, pp. 1342-1346 (1956); V. A. Wente et al., "Manufacture of Superfine Organic Fibers", Navy Research Laboratory, Washington, D.C., NRL Report 4364 (111437), dated May 25, 1954, United States Department of Commerce. Office of Technical Services: and Robert R. Butin and Dwight T. Lohkamp. "Melt Blowing - A One-Step Web Process for New Nonwoven Products", Journal of the Technical Association of the Pulo and PaPer Industrv, Vol. 56, No.4, pp. 74-77 (1973):
(b) coforming references (i.e., references disclosing a meltblowing process in which fibers or particles are commingled with the meltblown fibers as they are formed) include U.S. Patent Nos. 4,100,324 to R. A. Anderson et al. and 4,118,531 to E. R. Hauser:
and (c) spunbonding references include, among others, U.S. Patent Nos. 3.341,394 to Kinney, 3,655,862 to Dorschner et al., 3,692,618 to Dorschner et al., 3,705,068 to Dobo et al., 3,802,817 to Matsuki et al., 3,853,651 to Porte, 4,064,605 to Akiyama et al., 4,091,140 to Harmon, 4,100,319 to Schwartz, 4,340.563 to Appel and Morman, 4,405.297 to Appel and Morman, 4,434,204 to Hartman et al., 4,627,811 to Greiser and Wagner, and 4,644,045 to Fowells.
The sheet material may be made of any desired material which is capable of being treated in a corona discharge field. For example, the sheet material typically may be made from a synthetic polymer. which may be a thermosetting or thermoplas-tic polymer.
Examples of thermosetting polymers include, by way of illustration only, alkyd resins, such as phthalic anhydride-glycerol resins, maleic acid-glycerol resins, adipic acid-glycerol resins, and phthalic anhydride-pentaerythritol resins: allylic resins, in which such monomers as diallyl phthalate, diallyl isophthalate diallyl maleate. and diallyl chlorendate serve as nonvolatile cross-linking agents in polyester compounds: amino resins. such as aniline-formaldehyde resins, ethylene urea-formaldehyde resins, dicyan-diamide-formaldehyde resins. melamine-fommaldehyde resins, sulfonamide-formaldehyde resins, and urea-fommaldehyde resins; epoxy resins, such as cross-linked epichlorohydrin-bisphenol A resins; phenolic resins. such as phenol-formaldehyde resins, including Novolacs and resols: and thermosetting polyesters, silicones, and urethanes.
Examples of thermoplastic polymers include, by way of illustration only, end-capped polyacetals, such as poly(oxymethylene) or polyformaldehyde, polyltrichloroacetaldehyde), poly(n-valeraldehyde), poly(acetaldehyde), po-ly(propionaldehyde), and the like; acrylic polymers, such as polyacrylamide, poly(acrylic acid), poly(methacrylic acid), poly(ethyl acrylate), poly(methyl methacrylate), poiyacrylonitrile, and the like: fluorocarbon polymers, such as 10 poly(tetrafluoroethylene), perfluorinated ethylene-propylene copolymers, ethylene-tetrafluoroethylene copolymers, poly(chlorotrifluoroethylene), ethylene-chlorotrifiuoroethylene copolymers, poly(vinylidene fluoride), poly(vinyl fluoride), and the like: polyamides, such as poly(6-aminocaproic acid) or poly(E-caprolactam), poly-(hexamethylene adipamide), poly(hexamethylene sebacamide), poly(l l-amino-15 undecanoic acid), and the like: polyu~u",:-ics, such as poly(imino-1,3-phenylenei-minoisophthaloyl) or poly(m-phenylene isophthalamide), and the like: parylenes, such as poly-e-xylylene, poly(chloro-e-xylylene), and the like: polyaryl ethers, such as poly(oxy-2,6-dimethyl-1,4-phenylene) or poly(e-phenylene oxidej, and the like: polyaryl sulfones, such as poly(oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1,4-phenylene-20 isopropylidene-1,4-phenylene), poly(sulfonyl-1,4-phenyleneoxy-1,4-phenylenesulfonyl-4,4'-biphenylene), and the like: polycarbonates, such as poly(bisphenol A) or poly(carbonyldioxy- 1 ,4-phenyleneisopropylidene- 1 ,4-phenylene), and the like;polyesters, such as poly(ethylene terephthalate), poly(tetramethylene terephthalate), poly(cyclohexylene-1,4-dimethylene terephthalate) or polyloxymethylene-1,4-25 cyclohexylenemethyleneoxyterephthaloyl), and the like: polyaryl sulfides, such as poly(e-phenylene sulfide) or poly(thio-1,4-phenylene), and the like: polyimides, such as poly(pyromellitimido-1,4-phenylene), and the like; polyolefins, such as polyethylene, polypropylene, poly( 1 -butene), poly(2-butene), poly( l-pentene), poly(2-pentene), poly(3-methyl-1-pentene), poly(4-methyl-1-pentene), and the like; vinyl polymers, such 30 as poly(vinyl acetate), poly(vinylidene chloride), poly(vinyl chloride), and the like;
diene polymers, such as 1,2-poly-1,3-butadiene, 1,4-poly-1,3-butadiene, polyisoprene, polychloroprene, and the like; polystyrenes; copolymers of the foregoing, such as acrylonitrile-butadiene-styrene (ABS) copolymers, and the like: and the like.
In some embodiments, the sheet material may be made of a synthetic 35 hydrophobic polymer. Hydrophobic polymers in general give contact angles with W O 97/11834 PCTrUS96/13227 water of at least about 60~ and typically have surface free energies of less than about 45 dynes cm ~ (mjoule m-2). Examples of such polymers include, by way of illustration only, aromatic polyesters, polyolefins, polytetrafluoroethylene, poly(methyl methacry-late), poly(vinylidene fluoride), polyamides, and polystyrenes.
s Aromatic polyesters include, by way of example only, poly(ethylene terephthalate), poly(tetramethylene terephthalate), poly(cyclohexane-1,4-dimethylene terephthalate), and thermotropic liquid crystalline such as the copolymers of hydroxybenzoic acid and hydroxynaphthoic acid.
Examples of polyolefins include, again by way of illustration only, polyethylene, polypropylene, poly(1-butene), poly(2-butene), poly(1-pentene), poly(2-pentene),poly(3-methyl-1-pentene), poly(4-methyl-1-pentene), and the like. In addition, 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 and15 polypropylene.
Polyamides include, by way of example only, poly(6-aminocaproic acid) (nylon 6), polyfhexamethylene sebacamide) (nylon 6,10), and poly(octamethylene suberamide) (nylon 8,8) .
As already stated, the sheet material to be treated must be electrically isolated 20 from the electrodes of the corona discharge apparatus. This may be accomplished by any means. For example, both electrodes may be covered with a dielectric sleeve. As another example, one electrode may be covered with a dielectric sleeve and one electrode may be covered with a nonconductive fiim which may be renewable.
Other means will be readily apparent to those having ordinary skill in the art.
When the corona discharge apparatus has a bare metal electrode and a dielectric-covered electrode, the sheet material to be treated may be passec! through the corona discharge field as a layer of a multilayered composite having at least three layers, in which at least one of the layers is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode. If desired, 30 the nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode also may be nonporous.
The method may be employed to treat a hydrophobic sheet material having a porosity, in which case the hydrophobic sheet material is passed through a corona discharge field generated by a corona discharge apparatus having a bare metal 35 electrode and a dielectric covered electrode under conditions adapted to render the porous sheet wettable. The hydrophobic sheet material is a layer of a multilayered composite having at least three layers, in which at least one layer is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode and one of the at least three layers is a nonconductive, nonporous sheet material. For example, the at least one layer which is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode also may be nonporous.
The present invention is further described by the examples which follow. Such examples, howeve~r, are not to be construed as limiting in any way either the spirit or 0 the scope of the present invention.
Materials In the examples, the following materials were used:
Polypropylene film: 2-mil (about û,05-mmJ thickness (Type XP715S/P, Lot #468û5, Edison Plastics Co., Newport News, Virginia).
Polyethylene Film: 1-mil (about û.025-mm) thickness (standard linear low densitypolyethylene film).
Polytetrafluoroethylene film: 2-mil (about û.û5-mm) thickness (Fisher Scientific, Atlanta, Georgia).
Celgard(~ 25ûO Microporous polypropylene film: Hoechst Celanese, Charlotte, 2 o North Carolina.
Manila Paperboard: 11-mil (about 0.3-mm) thickness (No. 2-152C, Smead Inc,, Hastings, Minnesota). The paperboard is believed to be porous, although no tests were run to verify or define such porosity.
Aluminum Foil: 1-mil (about û.û25-mm~ thickness (Reynolds Metals Company, Richmond, Virginia).
Corona Discharqe Treater A corona discharge field was generated by means of a Corotec Laboratory Corona Treating Station (Corotec Corporation, Collinsville, Connecticut) equipped with a CXC-5 power supply. The Corotec Laboratory Corona Treating Station generated ahigh voltage alternating current corona discharge. The voltage of the discharge (peak to peak) ranged from 7 kV to 1û kV and the frequency ranged from 19 kHz to 20 ~ kHz. The treater utilized two horizontally positioned, counter-rotating aluminum rolls as the electrodes. The bottom roll was grounded and its surface was covered by a 2-mm thick dielectric sleeve. The top roll was bare aluminum metal. The nip point formed by 35 the two rolls provided a minimum gap of 2 mm. The actual gap between the electrodes during the treatment of a material was the sum of the thicknesses of the materials being passed through the gap and the 2-mm thick dielectric cover on the lower electrode. The line speed was fixed at 12 ft/min ~about 6 cm/secJ. The power dissipated in the gap during corona discharge was indicated by an integral power5 meter.
The corona energy density was a quantitative measure of power dissipated across the widttl of the electrodes per unit area of material being treated. This is simply expressed by dividing the output power of the power supply by the width of the anode (ft) and ttle line speed (ft/s). Energy density was assumed to be a cumulative function 10 of the number of passes through the discharge. Typically. materials were passed through the discharge from I to 1 û times. Table 1 lists energy density per pass for typical output power used in the examples.
Table 1 Corona Energy Densities Output Powera Er~çrqY Densitvb lOO 500 (5.38) 200 1000 ( 10.8) 300 1500 (16.2) 400 2000 (21.5) 5002500 ( 26 . 9 ) aln watts or joule sec-'.
bln watt sec ft 2 (kjoule m '~).
Critical Surface Tension of Wettinq A critical surface tension of wetting was determined for each sample treated using a Wetting Tension Test Kit, Model STT 11 - 1 (Pillar Technologies, Inc., Hartland, Wisconsin Michigan~). The critical surface tension of wetting was taken as the surface 30 tension of the Pillar test kit fluid which was spontaneously absorbed into a porous substrates. The Wetting Tension Kit conforms to ASTM Standard D2578-67.
Surface Analysis The surfaces of treated samples were analyzed by electron spectroscopy for chemical analysis lESCA). All analyses were carried out with a Surface Science 35 Instruments M-Probe ESCA Spectrometer. Spectral collections were performed with W O 97/11834 PCT~US96/13227 monochromatic aluminum x-ray excitation of an 800 square micrometer area of eachsample. Differential charging of samples was compensated for by using a low energy ( 1 eV) flux of electrons from an electron flood gun.
Example 1 Corona Discharge Treatment of Polypropylene Meltblown Nonwoven Webs Samples of 0~5 ounce per square yard or osy (about 17 grams per square meter or gsm) polypropyiene meltblown nonwoven webs were corona discharge treated at corona energy densities per pass ranging from 500 to 2500 watt sec ft-2 (about 5.38 to 26.9 kjoule m-2). Each meltblown sample was mounted as a multilayered structure in which 1 to 5 layers of material were overlayed or stacked to form a composite sample for corona treatment. No adhesive was applied between layers of the laminates: thus, after corona discharge treatment, the layers were easily separable.
The multilayered composites are referred to or described layer by layer, beginning with the layer closest to the top or bare metal electrode of the Treating Station and ending with the layer closest to the bottom electrode of the treater, i.e., the electrode covered with the dielectric sleeve. While in the examples a maximum of 2 0 five layers were used, this number of layers should not be construed as limiting in any way either the spirit or the scope of the invention.
The multilayered composite were corona discharge treated by feeding the materials through the nip formed between the upper and lower electrodes of the Treating Station. The severity of treatment was varied by increasing the corona output power and by increasing the number of passes through the discharge field at a fixed corona energy density.
The numerous composite configurations examined are summarized in Table 2.
Included in Table 2 are data indicating the observance of pinholes in the coronatreated material and the critical surface tension for wetting (CSTW) of the treated meltblown nonwoven web for each configuration examined. The CSTW was evaluated on both the top and bottom sides of each fabric. In no case was the CSTW of the top ~ side (the side closest to the bare metal electrode of the Treating Station~ found to be different from that observed on the bottom side (the side closest to the dielectric-Y covered electrode of the Treating Station). All samples were passed through the corona discharge field a total of ten times at a fixed corona energy density of 1500 W O 97/11834 PCTrUS96/13227 watt sec ft 2 (about 16.2 kjoule m-2). The following abbreviations are employed in all tables:
PPF = Polypropylene film MB = Polypropylene meltblown nonwoven web MPB = Manila paperboard Tc~ble 2 Summary of Results for Corona Treatment of Nonwoven Webs in Multilayeled Composites ComPosite Descrir~tion Pinholes CSTWa Wettable MB Yes 58 No MB/PPF Yes 72 Yes PPF/MB Yes 72 Yes 15MB/PPF/PPF Yes 72 Yes PPF/MB/PPF No 72 Yes PPF/PPF/MB yesb 72 Yes MB/MPB Ye~ 58 No MPB/MB ye5c /2 Yes 20MB/MPB/MPB Yes 60 No MPB/MB/MPB No ~8 No MPB/MPB/MB No 62 No MB/PPF/MPB yesb 72 Yes MPB/PPF/MB No 72 Yes 25MB/MPB/PPF Yes 72 Yes PPF/MPB/MB No 72 Yes PPF/MB/MPB No 72 Yes MPB/MB/PPF No 72 Yes Table 2, Continued Colt" o~ile Descril~tion Pinholes CSTWa Wettable PPF/MB/PPF/MPB No 60 No MPB/PPF/MB/PPF No 60 No '' aCritical suRace tension of wetting in dynes cm-' (mjoule m-2).
bVery few.
cVery large.
From the series of experiments summarized in Table 2, several conclusion can be drawn:
lal isolation of the meltblown nonwoven web from the upper bare electrode was essential to prevent pinholes from forming in the web:
(b) hole sizes appeared to be controlled by the material which acts as a carrier sheet for the nonwoven web:
(c) the total composite thickness had a pronounced effect on the wettability of the treated nonwoven web: and (d) the optimal sample configuration which yields a pinhole-free and water-20 wettable material was MPBtMB/PPF, i.e., manila paperboard/meltblown nonwovenweb/polypropylene film.
Treatment Sidedness The results of ESCA determinations on the surfaces of meltblown nonwoven web sampies corona treated in the PPF/MB/MPB and MPB/MB/PPF configurations are 2 5 summarized in Table 3. Each sample was corona treated at a corona energy density of l 500 Watt sec ft-2 (about l 6.2 kjoule m 2~ per pass for l O passes.
W O 97/11834 PCT~US96/13227 Table 3 ESCA Analyses of Corona Treated Meltblown Nonwoven Webs s Element Alomic Percent SampleCarbon Oxyaen Controla100 PPF/MB/MPB ( top) 88 . 5 11.5 PPF/MBtMPB ~bottom) 89. 5 10. 5 10 MPB/MBIPPF (top) 88.711.3 MPB/MB/PPF ~bottom~ 90 . 3 9 . 7 aNoncorona treated MB.
The surface analysis data summarized in Table 3 illustrate quantitatively the lack 15 of sidedness to the nonwoven web following corona treatment in the multilayered composite configuration.
Effect of Corona Power The effect of output power of the corona treater on the CSTW and the surface composition of the meltblown nonwoven web was evaluated using the MPB/MB/PPF
20 configuration described above. The surface composition was determined by ESCAanalysis of the nonwoven web after treatment and is herein expressed as the ratio of the atomic percent of oxygen to that of carbon ~O/C ratio). In all cases the samples were passed through the corona discharge field a total of five times. The results are summarized in Table 4.
Table 4 Summary of the EFFect of Output Power Corona Powera ~/C RatiobCSTWC Wettable 100 9.û 56 No 2ûO 11.5 56 No 300 12.6 60 No 400 17.6 62 No 500 14.5 62 No aln watts or joule sec-l.
W O 97/11834 PCTnUS96/13227 bThe calculated O/C ratio times 100.
aCritical surface tension of wetting in dynes cm-' (mjoule m-2).
As can be seen from the table, both the surface O/C ratio and the CSTW
increased with increasing corona power. Except for the O/C ratio at 400 watts or joule sec-', the increases in both the O/C ratio and CSTW appear to be roughly linear at output power rating increases above 100 watts or joule sec-E
EFfect cf Corona Treatment Severitv The effect of corona treatment severity (time) was evaluated by increasing the number of passes through a corona discharge field at fixed power. In this case the corona power was set at 300 watts or joule sec-', corresponding to a corona energy density of 1 5ûû watt sec ft 2 (about 16.2 kjoule m ~l per pass. The results are summarized in Table 5.
Table 5 Summary of the Effect of Number of Passes Number Passes O/C Ratio~ CSTWb Wettable 1 6.5 56 No 3 12. 8 56 No 16. 8 60 No 8 17.1 64 No 15. 9 72 Yes ~The calculated O/C ratio times 100.
bCritical surface tension of wetting in dynes cm-' mjoule m-21.
According to the data in the table, the CSTW increased with the number of passes through the corona field, although fewer than about five passes had little apparent effect on the CSTW value. The surface O/C ratio, however, appeared to reach a maximum after about 5 passes, .~
Example 2 Conductive versus Dielectric Film Layers W O 97/11834 ' PCT~US96/13227 in the Multilayered Composite The corona treatment of the polypropylene meltblown nonwoven web was examined as a function of the electrical conductivity of the film layer used in the 5 preparation of the multilayered composite. A l-mil ~about 0.025-mm) thick aluminum foil was used as a conductive film and several polymer films were evaluated as dielectric film layers. The corona treatment conditions were 1500 watt sec ft-2 (about 16.2 ~kjoule m-2) per pass and 10 passes.
Conductive Film Three samples of the meltblown nonwoven web were treated in multilayered composites which included an aluminum foil conductive film iayer. In the first, a section of the meltblown web was mounted on manila paperboard with poly-propylene film covering one half and aluminum foil the other. The sample was constructed such that, as the sample passed through the corona field, half of the 15 electrode pair would "see" the polypropylene film and the other half would "see" the aluminum foil. Thus, the juncture between the two types of film was parallel to the direction of motion of the composite through the corona discharge apparatus.
After treatment. both sides of the meltblown nonwoven web had a CSTW value of 60 dynes cm ' ~mjoule m-2), while only the aluminum foil side had pinholes. A second 2 0 experiment in which the same sample configuration was used except that the sample was constructed such that the aluminum foil and polypropylene film halves were treated sequentially. The results were the same. A third sample was prepared wherein a second polypropylene film layer was added between the manila paperboard and the nonwoven web. In this case, no pin holes were observed in either the aluminum foil 25 covered or polypropylene film covered sides, and the CSTW value was the same on each side.
W O 97/11834 PCT~US96/132Z7 Nonconductive Film Other examples of nonconductive films used as layers in multilayered composites included polytetrafluoroethylene IPTFE), polyethylene (PE~, and Celgard(9 25ûû microporous polypropylene. The sample configuration was MPB/MB/Nonconduc-tive Film.
No pinholes were observed in nonwoven webs treated using composites constructed with the PTFE or the PE film. Both samples had CTSW values of 72 dynes cm-' (mjoule m-2). Corona treatment of the sample utilizing the Celgard~9) 25û0 microporous polypropylene yielded a nonwoven web which was badly pinholed. In 0 addition, the treatment uniformity was poor. Some areas had a CSTW value of 72 dynes cm-' (mjoule m-2), while others had a CSTW value of 60 dynes cm-~ (mjoule m-2).
This illustrates the need for a nonporous nonconductive film layer in the multilayered composite subjected to the corona discharge field in order to prevent the formation of pinholes in the nonwoven web while producing a web which is wettable.
Example 3 Corona Discharge Treatment of Microporous Film The corona discharge treatment of microporous films was demor,,lluled using sample of Celgard~ 25ûû microporous polypropylene film. The microporous film wastreated in a manner similar to that described in Example l . The corona treatment conditions were l 50û watt sec ft-2 per pass and l0 passes. The Celgard film was treated either by itself or as a multilayered composite with PP film, PE film, and PTFE film.
Treatment of the Celgard~ 250û microporous polypropylene film by itself produced a material with pinholes over greater than 90 percent of its surface. The introduction of a nonconductive film such as PP film on top of the Celgard film prevented pinhole formation and yielded a material with a CSTW value of 72 dynescm-' Imjoule m-2). Identical results were obtained when treating with either the PTFE or PE films as covers.
3 0 Example 4 Corona Discharge Treatment of Nonwoven Webs The broad applicability of the multilayered composite approach to controlling pinhole formation during corona treatment of nonwoven webs was further demor,,l,ul~d by examining higher basis weight polypropylene meltblown webs and a series of nonwoven webs made from polyethylene. The corona treatment conditions were 1500 watt sec ft-2 per pass and 10 passes. The MPB/Nonwoven Web/PPF sample configuration was used For each nonwoven web. The nonwoven webs studied were as follows:
s A - 1.0 osy (about 34 gsm~ polypropylene meltblown nonwoven web.
B - l.û osy ~about 34 gsm) polypropylene spunbonded nonwoven web.
C - 1.6 osy (about 54 gsm) polyethylene meltblown nonwoven 0 web.
D - 6 osy labout 204 gsm) polyethylene meltblown nonwoven web.
The results of these studies are summarized in Table 6.
Table 6 Corona Treatment of Various Nonwoven Webs SamPle PinholesCSTWa Wettable A Nb 62 N!o 2 0 B No 58 No C No 72 Yes D No 58 No ~Critical surface tension of wetting in dynes cm-~ (mjoule m-2).
While the specification has been described in detail with respect to specific embodiments thereof, it will be appreciated that those skilled in the art. upon attaining an understanding of the foregoing, may readily conceive of alterations to, variations of, and equivalents to these embodiments.
Claims (23)
1. A method of preventing localized arcing to ground during treatment of a sheet material in a corona discharge field generated by a corona discharge apparatus having at least two electrodes, which method comprises:
passing the sheet material to be treated through the corona discharge field, in which the sheet material to be treated is electrically isolated from said electrodes.
passing the sheet material to be treated through the corona discharge field, in which the sheet material to be treated is electrically isolated from said electrodes.
2. The method of claim 1, in which the sheet material is a film.
3. The method of claim 1, in which the sheet material is a fibrous web.
4. The method of claim 3, in which the fibrous web is a nonwoven web.
5. A method of preventing localized arcing to ground during treatment of a sheet material in a corona discharge field generated by a corona discharge apparatus having a bare metal electrode and a dielectric-covered electrode, which method comprises:
passing the sheet material to be treated through the corona discharge field as alayer of a multilayered composite having at least three layers, in which at least one of the layers is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode.
passing the sheet material to be treated through the corona discharge field as alayer of a multilayered composite having at least three layers, in which at least one of the layers is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode.
6. The method of claim 5, in which the sheet material is a film.
7. The method of claim 5, in which the sheet material is porous.
8. The method of claim 7, in which the sheet material is a fibrous web.
9. The method of claim 8, in which the fibrous web is a nonwoven web.
10. The method of claim 9, in which the nonwoven web is a meltblown nonwoven web.
11. The method of claim 9, in which the nonwoven web is a spunbonded nonwoven web.
12. The method of claim 9, in which the nonwoven web is a polyolefin nonwoven web.
13. The method of claim 12, in which the polyolefin is polypropylene or polyethylene.
14. A method of treating a hydrophobic sheet material having a porosity which comprises:
passing the porous hydrophobic sheet material:
through a corona discharge field generated by a corona discharge apparatus having a bare metal electrode and a dielectric covered electrode;
under conditions adapted to render the porous sheet wettable;
and as a layer of a multilayered composite having at least three layers, in which at least one layer is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode and one of the at least three layers is a nonconductive, nonporous sheet material;
thereby preventing the porosity of the hydrophobic sheet material from being altered.
passing the porous hydrophobic sheet material:
through a corona discharge field generated by a corona discharge apparatus having a bare metal electrode and a dielectric covered electrode;
under conditions adapted to render the porous sheet wettable;
and as a layer of a multilayered composite having at least three layers, in which at least one layer is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode and one of the at least three layers is a nonconductive, nonporous sheet material;
thereby preventing the porosity of the hydrophobic sheet material from being altered.
15. The method of claim 14, in which the sheet material is a film.
16. The method of claim 14, in which the sheet material is porous.
17. The method of claim 16, in which the sheet material is a fibrous web.
18. The method of claim 17, in which the fibrous web is a nonwoven web.
19. The method of claim 18, in which the nonwoven web is a meltblown nonwoven web.
20. The method of claim 18, in which the nonwoven web is a spunbonded nonwoven web.
21. The method of claim 18, in which the nonwoven web is a polyolefin nonwoven web.
22. The method of claim 21. in which the polyolefin is polypropylene or polyethylene.
23. The method of claim 14, in which the at least one layer which is a nonconductive sheet material situated between the sheet material to be treated and the bare metal electrode also is nonporous.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US453495P | 1995-09-29 | 1995-09-29 | |
| US60/004,534 | 1995-09-29 | ||
| US08/645,435 US5688465A (en) | 1996-05-13 | 1996-05-13 | Method of corona treating a hydrophobic sheet material |
| US08/645,435 | 1996-05-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2228606A1 true CA2228606A1 (en) | 1997-04-03 |
Family
ID=26673126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2228606 Abandoned CA2228606A1 (en) | 1995-09-29 | 1996-08-16 | Method of corona treating a hydrophobic sheet material |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU6725196A (en) |
| CA (1) | CA2228606A1 (en) |
| WO (1) | WO1997011834A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7700500B2 (en) | 2002-12-23 | 2010-04-20 | Kimberly-Clark Worldwide, Inc. | Durable hydrophilic treatment for a biodegradable polymeric substrate |
| KR101222273B1 (en) * | 2004-05-20 | 2013-01-15 | 소프탈 일렉트로닉 게엠베하 | Continuous and semi-continuous treatment of textile materials integrating corona discharge |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3067119A (en) * | 1960-02-11 | 1962-12-04 | American Viscose Corp | Surface treatment of films |
| BE635191A (en) * | 1962-08-16 | |||
| US3779882A (en) * | 1971-04-01 | 1973-12-18 | Union Carbide Corp | Electrode method for the surface treatment of thermoplastic materials |
| DE2559139A1 (en) * | 1975-12-30 | 1977-07-14 | Windmoeller & Hoelscher | DEVICE FOR TREATMENT OF TUBE FABRIC |
| US4375718A (en) * | 1981-03-12 | 1983-03-08 | Surgikos, Inc. | Method of making fibrous electrets |
| DE3115958C2 (en) * | 1981-04-22 | 1983-12-29 | Hahne, Ernst August, 4123 Allschwill | "Process for moistening a flexible, web-shaped carrier material provided with a coating that has solidified by drying |
| JPS58222118A (en) * | 1982-06-17 | 1983-12-23 | Mitsubishi Paper Mills Ltd | Method and apparatus for corona discharge treatment |
| US4588537A (en) * | 1983-02-04 | 1986-05-13 | Minnesota Mining And Manufacturing Company | Method for manufacturing an electret filter medium |
-
1996
- 1996-08-16 CA CA 2228606 patent/CA2228606A1/en not_active Abandoned
- 1996-08-16 WO PCT/US1996/013227 patent/WO1997011834A1/en active Application Filing
- 1996-08-16 AU AU67251/96A patent/AU6725196A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO1997011834A1 (en) | 1997-04-03 |
| AU6725196A (en) | 1997-04-17 |
| MX9801521A (en) | 1998-05-31 |
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