Low gauge films and film/nonwoven laminates

Abstract
Disclosed herein is a low gauge, multilayer film which may be laminated to other materials such as, for example, fibrous nonwoven webs. The multilayer film may include one or more skin layers which in certain configurations comprise no more than about 15 percent of the overall thickness and in other configurations no more than about 10 percent of the overall thickness of the multilayer film. Such films and laminates have a wide variety of uses including, but not limited to, personal care absorbent products, articles of clothing and health care related items such as surgical drapes and gowns.
Description




FIELD OF INVENTION




The present invention is directed to low gauge, multi-layer films with skin layers that are extremely thin. In addition, the present invention is directed to such films laminated to other materials such as, for example, fibrous nonwoven webs.




BACKGROUND OF THE INVENTION




The present invention is directed to extremely thin multi-layer films and their use with laminates. Such materials have a wide variety of uses, especially in the areas of limited use and disposable items.




Many products today require highly engineered components and yet, at the same time, these products are required to be limited use or disposable items. By limited use or disposable, it is meant that the product and/or component is used only a small number of times or possibly only once before being discarded. Examples of such products include, but are not limited to, surgical and health care related products such as surgical drapes and gowns, disposable work wear such as coveralls and lab coats and a personal care absorbent products such as diapers, training pants, incontinence garments, sanitary napkins, bandages, wipes and the like. All of these products can and do utilize as components, films and fibrous nonwoven webs. While both materials are often used interchangeably, films tend to have greater barrier properties, especially to liquids while fibrous nonwovens webs have, among other things, better tactile, comfort and aesthetic properties. When these materials are used in limited use and/or disposable products, the impetus for maximizing engineered properties while reducing cost is extremely high. To this end, it is often desirable to use either a film or a nonwoven to achieve the desired results because the combination often becomes more expensive. In the area of films, there have been previous attempts to make multi-layer films with reduced thicknesses. See, for example, U.S. Pat. No. 5,261,899 to Vischer wherein a three layer film is made with a central layer that comprises from about 30 to 70% of the total thickness of the multi-layer film. One advantage in forming multi-layer films is that specific properties can be designed into the film, and, by making the films multi-layer the more costly ingredients can be relegated to the outer layers where they are most likely to be needed.




It is an object of the present invention to provide a multilayer film which can be engineered to provide specific properties while providing such properties in a very thin gauge. Another object of the present invention is to combine such low gauge films with other support layers such as layers of fibrous nonwoven webs to increase strength and provide aesthetic properties. The means by which such objectives are achieved can be more fully comprehended by a review of the following specification, drawings and claims.




SUMMARY OF THE INVENTION




The present invention is directed to multilayer films and multilayer film/nonwoven laminates. The films are made by conventional film forming techniques such as cast and blown coextrusion film forming processes. The films are created with a core layer made from an extrudable thermoplastic polymer with the core layer defining a first exterior surface and a second exterior surface. In the most basic configuration, a first skin layer is attached, usually simultaneously due to the coextrusion process, to the first exterior surface of the core layer to form a multilayer film. The multilayer film defines an overall thickness with the first skin layer defining a first skin thickness which comprises less than about 10 percent of the overall thickness of the multilayer film. This is due to the stretching of the extruded film to such a degree so as to thin the multilayer film to within the dimensions defined herein. As a result, the thickness of the first skin layer will not exceed about 2 micrometers. Given the extremely thin nature of the multilayer film, it may be desirable to laminate the multilayer film to another material such as a support layer. Suitable support layers include, but are not limited to, such materials as other films, fibrous nonwoven webs, woven materials, scrims, netting and combinations of the foregoing.




In other embodiments of the present invention, the core layer may have a first skin layer attached to the first exterior surface of the core layer and a second skin layer attached to the second exterior surface of the core layer. In such situations, the first skin and the second skin layer should have a combined thickness which does not exceed about 15 percent of the overall thickness and more desirably where neither the first skin thickness nor the second skin thickness exceeds more than about 7.5 percent of the overall thickness of the multilayer film. If desired, one or more of the layers may contain other additives such as, for example, a particulate filler. Most typically, such fillers will be primarily utilized in the core layer in, for example, a weight percent of at least about 60 percent, based upon the total weight of that particular layer.




It is also possible to make multilayer films which are breathable either through the use of specialized polymers which permit diffusion of gases through the layers and/or through the use of particulate fillers. Normally, to make such films breathable, they are stretched and/or crushed between compression rollers so as create voids in and around the particles to permit the transmission of water vapor and other gases. Typically such breathable multilayer films will have water vapor transmission rates of at least 300 grams per square meter per 24 hours.




Such films and laminates have a wide variety of uses including, but not limited to, applications in personal care absorbent articles including diapers, training pants, sanitary napkins, incontinence devices, bandages and the like. These same films and laminates also may be used in items such as surgical drapes and gowns as well as various articles of clothing either as the entire article or simply as a component thereof.











BRIEF DESCRIPTION OF THE DRAWINGS





FIG. 1

is a cross-sectional side view of a multilayer film according to the present invention. The right side of the film has been split apart to facilitate its description.





FIG. 2

is a cross-sectional side view of a multilayer film/nonwoven laminate according to the present invention.





FIG. 3

is a schematic side view of a process for forming a multilayer film according to the present invention and a multilayer film/nonwoven laminate according to the present invention.





FIG. 4

is a partially cut away top plan view of an exemplary personal care absorbent article, in this case a diaper, which may utilize a multilayer film and multilayer film/nonwoven laminate according to the present invention.











DETAILED DESCRIPTION OF THE INVENTION




The present invention is directed to multilayer films, that is, films having two or more layers as well as such films laminated to support layers such as, for example, fibrous nonwoven webs. Referring to

FIG. 1

, there is shown, not to scale, a multilayer film


10


which, for purposes of illustration, has been split apart at the right side of the drawing. The multilayer film


10


includes a core layer


12


made from an extrudable thermoplastic polymer such as a polyolefin or a blend of polyolefins. The core layer


12


has a first exterior surface


14


and a second exterior surface


16


. The core layer also has a core thickness


22


. Attached to the first exterior surface


14


of the core layer


12


is a first skin layer


18


which has a first skin thickness


24


. Attached to the second exterior surface


16


of the core layer


12


is an optional second skin layer


20


which has a second skin thickness


26


. In addition, the multilayer film


10


has an overall thickness


28


. Such multilayer films


10


can be formed by a wide variety of processes well known to those of ordinary skill in the film forming industry. Two particularly advantageous processes are cast film coextrusion processes and blown film coextrusion processes. In such processes, the two or three layers are formed simultaneously and exit the extruder in a multilayer form. Due to the extremely thin nature of the multilayer films according to the present invention such processes will most likely prove to be the most advantageous though it also may be possible to form multilayer films using separate extrusion processes. For more information regarding such processes, see, for example, U.S. Pat. Nos. 4,522,203; 4,494,629 and 4,734,324 which are incorporated herein by reference in their entirety.




An important feature of the present invention is the ability to utilize a more generic core layer


12


in conjunction with a much thinner and more specially designed skin layer such as the first skin layer


18


or a combination of two or more skin layers attached to either or both sides of the core layer


12


. Thus, it is possible to form multilayer films


10


with many layers of material. The core layer


12


as with the first skin layer


18


and optional second skin layer


20


may be formed from any polymers which are capable of being utilized in multilayer film constructions including, but not limited to, polyolefins including homopolymers, copolymers, and blends. To further reduce the cost of the core layer


12


one or more types of fillers may be added to the core layer polymer extrusion blend. Both organic and inorganic fillers may be used. The fillers should be selected so as to not chemically interfere with or adversely affect the extruded film. These fillers can be used to reduce the amount of polymer being used for the core layer


12


and/or to impart particular properties such as breathability and/or odor reduction. Examples of fillers can include, but are not limited to, calcium carbonate (CaCO


3


), various kinds of clay, silica (SiO


2


), alumina, barium sulfate, sodium carbonate, talc, magnesium sulfate, titanium dioxide, zeolites, aluminum sulfate, cellulose-type powders, diatomaceous earth, magnesium sulfate, magnesium carbonate, barium carbonate, kaolin, mica, carbon, calcium oxide, magnesium oxide, aluminum hydroxide, pulp powder, wood powder, cellulose derivatives, polymer particles, chitin and chitin derivatives.




The amount of filler that can be used resides within the discretion of the end-user, however, additions of from 0 to 80% by weight based upon the total weight of the core layer


12


are possible. Generally the fillers will be in particulate form and usually will have somewhat of a spherical shape with average particle sizes in the range of about 0.1 to about 7 microns. Furthermore, if sufficient filler is used in combination with sufficient stretching of the multilayer film


10


, then voids can be created around the particles contained within the core layer


12


thereby making the core layer breathable. High loadings, in excess of about 60 percent by weight of the core layer


12


when combined with stretching provides films which are breathable. Such breathable films will generally have Water Vapor Transmission Rates (WVTR) in excess of 300 grams per square meter per 24 hours.




The skin layers


18


and


20


will typically include extrudable thermoplastic polymers and/or additives which provide specialized properties to the multilayer film


10


. Thus, the first skin layer


18


and/or the second skin layer


20


may be made from polymers which give such properties as antimicrobial activity, water vapor transmission, adhesion and/or antiblocking properties. Thus, the particular polymer or polymers chosen for the skin layer


18


and


20


will depend upon the particular attributes desired. Examples of possible polymers that may be used alone or in combination include homopolymers, copolymers and blends of polyolefins as well as ethylene vinyl acetate (EVA), ethylene ethyl acrylate (EEA), ethylene acrylic acid (EAA), ethylene methyl acrylate (EMA), ethylene butyl acrylate (EBA), polyester (PET), nylon (PA), ethylene vinyl alcohol (EVOH), polystyrene (PS), polyurethane (PU) and olefinic thermoplastic elastomers which are multistep reactor products wherein an amorphous ethylene propylene random copolymer is molecularly dispersed in a predominately semicrystalline high polypropylene monomer/low ethylene monomer continuous matrix.




Oftentimes it may be desirable to laminate the multilayer film


10


to one or more substrates or support layers


30


such as is shown in FIG.


2


. The core layer may not have sufficient adhesive or attachment properties so as to make it bondable to the support layer


30


. As a result, the first skin layer


18


may be made from a polymer or polymers which exhibit higher adhesive properties and/or a lower tack point than the core layer


12


.




A desired result with respect to the material of the present invention is to achieve a very low overall film thickness and more importantly, skin layers which are only a small percentage of the overall thickness of the multilayer film


10


. As demonstrated by the examples below, based upon the overall thickness


28


of the multilayer film


10


, in two layer constructions the first skin thickness


24


of the first skin layer


18


should not exceed more than 10 percent of the overall thickness


28


. In three layer film constructions the combined thickness of the first skin layer


18


and second skin layer


20


should not exceed 15 percent of the overall thickness and generally, the first skin layer


18


should not exceed more than 7.5 percent of the overall skin thickness


28


. The same is also true with respect to the second skin layer


20


. As a result, the core thickness


22


comprises at least 85 percent of the overall thickness


28


and the first skin layer


18


and second skin layer


20


each generally will comprise no more than 7.5 percent of the overall thickness


28


. Generally, it has been possible to create thinned films with overall thicknesses


28


of 30 microns or less and in certain applications with skin layers that do not exceed two microns. This is made possible by first forming a multilayer film


10


and then stretching or orienting the film in the machine direction, as explained in greater detail below, such that the resultant multilayer film


10


has increased strength properties in the machine direction, i.e., the direction which is parallel to the direction of the film as it is taken off the film extrusion equipment.




The resultant film can, if desired, be laminated to one or more support layers


30


as are shown in FIG.


2


. The support layers


30


as shown in

FIG. 2

are fibrous nonwoven webs. The manufacture of such fibrous nonwoven webs is well known to those of ordinary skill in the art of nonwoven manufacturing. Such fibrous nonwoven webs can add additional properties to the multilayer film


10


such as, a more soft, cloth-like feel. This is particularly advantageous when the multilayer film


10


is being used as a barrier layer to liquids in such applications as outer covers for personal care absorbent articles and as barrier materials for hospital, surgical, and clean room applications such as, for example, surgical drapes, gowns and other forms of apparel. Attachment of the support layers


30


to the first skin layer


18


and second skin layer


20


may be by the use of a separate adhesive such as hot-melt and solvent based adhesives or through the use of heat and/or pressure as with heated bonding rolls. As a result, it may be desirable to design either or both the first skin layer


18


and the second skin layer


20


so as to have inherent adhesive properties to facilitate the lamination process.




A particularly advantageous support layer is a fibrous nonwoven web. Such webs may be formed from a number of processes including, but not limited to, spunbonding, meltblowing and bonded carded web processes. Meltblown fibers are formed by extruding molten thermoplastic material through a plurality of fine, usually circular, die capillaries as molten threads or filaments into a high velocity usually heated gas stream such as air, which attenuates the filaments of molten thermoplastic material to reduce their diameters. Thereafter, the meltblown fibers are carried by the high velocity usually heated gas stream and are deposited on a collecting surface to form a web of randomly dispersed meltblown fibers. The meltblown process is well-known and is described in various patents and publications, including NRL Report 4364, “Manufacture of Super-Fine Organic Fibers” by B. A. Wendt, E. L. Boone and C. D. Fluharty; NRL Report 5265, “An Improved Device For The Formation of Super-Fine Thermoplastic Fibers” by K. D. Lawrence, R. T. Lukas, J. A. Young; U.S. Pat. No. 3,676,242, issued Jul. 11, 1972, to Prentice; and U.S. Pat. No. 3,849,241, issued Nov. 19, 1974, to Buntin, et al. The foregoing references are incorporated herein by reference in their entirety.




Spunbond fibers are formed by extruding a molten thermoplastic material as filaments from a plurality of fine, usually circular, capillaries in a spinnerette with the diameter of the extruded filaments then being rapidly reduced, for example, by non-eductive or eductive fluid-drawing or other well-known spunbonding mechanisms. The production of spunbond nonwoven webs is illustrated in patents such as Appel et al., U.S. Pat. No. 4,340,563; Matsuki, et al, U.S. Pat. No. 3,802,817; Dorschner et al., U.S. Pat. No. 3,692,618; Kinney, U.S. Pat. Nos. 3,338,992 and 3,341,394; Levy, U.S. Pat. No. 3,276,944; Peterson, U.S. Pat. No. 3,502,538; Hartman, U.S. Pat. No. 3,502,763; Dobo et al., U.S. Pat. No. 3,542,615; and Harmon, Canadian Patent Number 803,714. All of the foregoing references are incorporated herein by reference in their entirety.




Multilayer support layers


30


also may be used. Examples of such materials can include, for example, spunbond/meltblown laminates and spunbond/meltblown/spunbond laminates such as are taught in Brock et al., U.S. Pat. No. 4,041,203 which is incorporated herein by reference in its entirety.




Bonded carded webs are made from staple fibers which are usually purchased in bales. The bales are placed in a picker which separates the fibers. Next the fibers are sent through a combing or carding unit which further breaks apart and aligns the staple fibers in the machine direction so as to form a machine direction-oriented fibrous nonwoven web. Once the web has been formed, it is then bonded by one or more of several bonding methods. One bonding method is powder bonding wherein a powdered adhesive is distributed throughout the web and then activated, usually by heating the web and adhesive with hot air. Another bonding method is pattern bonding wherein heated calender rolls or ultrasonic bonding equipment is used to bond the fibers together, usually in a localized bond pattern though the web can be bonded across its entire surface if so desired. When using bicomponent staple fibers, through-air bonding equipment is, for many applications, especially advantageous.




A process for forming the multilayer film


10


is shown in

FIG. 3

of the drawings. Referring to the figure, the multilayer film


10


is formed from a coextrusion film apparatus


40


such as a cast or blown unit as was previously described above. Typically the apparatus


40


will include two or more polymer extruders


41


. The multilayer film


10


is extruded into a pair of nip or chill rollers


42


one of which may be patterned so as to impart an embossed pattern to the newly formed film


10


. This is particularly advantageous to reduce the gloss of the film and give it a matte finish. Using a three layer film construction such as is shown in

FIG. 1

, typically the multilayer film


10


, as initially formed, will have an overall thickness


28


of approximately 40 microns or greater with the first skin layer


18


and the second skin layer


20


each having initial thicknesses of 3 microns or greater which collectively is approximately 15% of the overall initial thickness.




From the coextrusion film apparatus


40


the film


10


is directed to a film stretching unit


44


such as a machine direction orienter which is a commercially available device from vendors such as the Marshall and Williams Company of Providence, R.I. Such an apparatus


44


has a plurality of stretching rollers


46


which progressively stretch and thin the multilayer film


10


in the machine direction of the film which is the direction of travel of the film


10


through the process as shown in FIG.


3


. After exiting the film stretching unit


44


the film


10


should have a maximum thickness of approximately 30 microns and each of the skin layers should have a maximum thickness of no more than about 2 microns which in turn is collectively less than about 15 percent of the overall film and more desirably less than 10 percent of the overall film thickness.




If desired, the multilayer film


10


may be attached to one or more support layers


30


to form a multilayer film/nonwoven laminate


32


. Referring again to

FIG. 3

, a conventional fibrous nonwoven web forming apparatus


48


, such as a pair of spunbond machines, is used to form the support layer


30


. The long, essentially continuous fibers


50


are deposited onto a forming wire


52


as an unbonded web


54


and the unbonded web


54


is then sent through a pair of bonding rolls


56


to bond the fibers together and increase the tear strength of the resultant web support layer


30


. One or both of the rolls are often heated to aid in bonding. Typically, one of the rolls


56


is also patterned so as to impart a discrete bond pattern with a prescribed bond surface area to the web


30


. The other roll is usually a smooth anvil roll but this roll also may be patterned if so desired. Once the multilayer film


10


has been sufficiently thinned and oriented and the support layer


30


has been formed, the two layers are brought together and laminated to one another using a pair laminating rolls or other means


58


. As with the bonding rolls


56


, the laminating rolls


58


may be heated. Also, at least one of the rolls may be patterned to create a discrete bond pattern with a prescribed bond surface area for the resultant laminate


32


. Generally, the maximum bond point surface area for a given area of surface on one side of the laminate


32


will not exceed about 50 percent of the total surface area. There are a number of discrete bond patterns which may be used. See, for example, Brock et al., U.S. Pat. No. 4,041,203 which is incorporated herein by reference in its entirety. Once the laminate


32


exits the laminating rolls


58


, it may be wound up into a roll


60


for subsequent processing. Alternatively, the laminate


32


may continue in-line for further processing or conversion.




The process shown in

FIG. 3

also may be used to create a three layer laminate


32


such as is shown in

FIG. 2

of the drawings. The only modification to the previously described process is to feed a supply


62


of a second fibrous nonwoven web support layer


30


into the laminating rolls


58


on a side of the multilayer film


10


opposite that of the other fibrous nonwoven web support layer


30


. As shown in

FIG. 3

, the supply of support layer


30


is in the form of a preformed roll


62


. Alternatively, as with the other layers, the support layer


30


may be formed directly in-line. In either event, the second support layer


30


is fed into the laminating rolls


58


and is laminated to the multilayer film


10


in the same fashion as the other support layer


30


.




As has been stated previously, the multilayer film


10


and the laminate


32


may be used in a wide variety of applications not the least of which includes personal care absorbent articles such as diapers, training pants, incontinence devices and feminine hygiene products such as sanitary napkins. An exemplary article


80


, in this case a diaper, is shown in

FIG. 4

of the drawings. Referring to

FIG. 4

, most such personal care absorbent articles


80


include a liquid permeable top sheet or liner


82


, a back sheet or outercover


84


and an absorbent core


86


disposed between and contained by the top sheet


82


and back sheet


84


. Articles


80


such as diapers may also include some type of fastening means


88


such as adhesive fastening tapes or mechanical hook and loop type fasteners.




The multilayer film


10


by itself or in other forms such as the multilayer film/support layer laminate


32


may be used to form various portions of the article including, but not limited to, the top sheet


82


and the back sheet


84


. If the film is to be used as the liner


82


, it will most likely have to be apertured or otherwise made to be liquid permeable. When using a multilayer film/nonwoven laminate


32


as the outercover


84


, it is usually advantageous to place the nonwoven side facing out away from the user. In addition, in such embodiments it may be possible to utilize the nonwoven portion of the laminate


32


as the loop portion of the hook and loop combination.




Other uses for the multilayer film and multilayer film/support layer laminates according to the present invention include, but are not limited to, surgical drapes and gowns, wipers, barrier materials and articles of clothing or portions thereof including such items as workwear and lab coats.




Test Methods




The properties of the present invention were determined using a series of test procedures which are set forth below. These properties include film thicknesses, water vapor transmission rates and peel strengths.




Water Vapor Transmission Rate




The water vapor transmission rate (WVTR) for the sample materials was calculated in accordance with ASTM Standard E96-80. Circular samples measuring three inches in diameter were cut from each of the test materials and a control which was a piece of CELGARD® 2500 film from Hoechst Celanese Corporation of Sommerville, N.J. CELGARD® 2500 film is a microporous polypropylene film. Three samples were prepared for each material. The test dish was a number 60-1 Vapometer pan distributed by Thwing-Albert Instrument Company of Philadelphia, Pa. One hundred milliliters of water was poured into each Vapometer pan and individual samples of the test materials and control material were placed across the open tops of the individual pans. Screw-on flanges were tightened to form a seal along the edges of each pan, leaving the associated test material or control material exposed to the ambient atmosphere over a 6.5 centimeter diameter circle having an exposed area of approximately 33.17 square centimeters. The pans were placed in a forced air oven at 100° F. (32° C.). The oven was a constant temperature oven with external air circulating through it to prevent water vapor accumulation inside. A suitable forced air oven is, for example, a Blue M Power-O-Matic 60 oven distributed by Blue M Electric Company of Blue Island, Ill. After 24 hours, the pans were removed from the oven and weighed again. The preliminary test water vapor transmission rate values were calculated as follows:






Test


WVTR


=(grams weight loss over 24 hours)×315.5 g/m


2


/24 hrs






The relative humidity within the oven was not specifically controlled.




Under predetermined set conditions of 100° F. (32° C.) and ambient relative humidity, the WVTR for the CELGARD® 2500 control has been determined to be 5000 grams per square meter for 24 hours. Accordingly, the control sample was run with each test and the preliminary test values were corrected to set conditions using the following equation:








WVTR


=(Test


WVTR


/control


WVTR


)×5000 g/m


2


/24 hrs.) (g/m


2


/24 hrs)






Film/Film Layer Thicknesses




The overall thickness


28


, first skin thickness


24


, core thickness


22


and second skin thickness


26


were measured in cross-section by Field Emission Scanning Electron Microscopy (FESEM). Each film sample was submersed in liquid nitrogen and cut on impact with a razor blade. The freshly cut cross-section was mounted to a specimen stub in an upright position using copper tape. The samples were observed using an Hitachi S-800 Field Emission Scanning Electron Microscope at 5 and 10 keV. Scanning electron photomicrographs were taken at 2000×magnification to show the film structures for each sample. Three separate samples and corresponding pictures were prepared for each multilayer film. The 10.2 centimeter by 12.7 centimeter negatives were enlarged to 20.4 centimeter by 25.4 centimeter copies and the measurements were taken directly off these photographs. A reference 15 micron scale magnified at 2000× was superimposed on each photo. Five measurements for each of the layers was made on each of the three photos for each film sample thereby creating 15 datapoints or measurements for each thickness. Measurements were made for the first skin layer, the second skin layer and the core layer of each sample. The 15 measurements for each layer were combined and averaged to yield a thickness value in microns for each layer. The total thickness of the overall film was obtained by adding the average values for the core layer, first skin layer and second skin layer for each sample. The relative percentage of each skin layer was obtained by dividing the average thickness of the respective skin layer by the average overall thickness of the same sample and multiplying the result by 100 to yield percent.




180° T Peel Test




To test the bond strength between the film layer and the fibrous nonwoven comfort layer, a delamination or peel strength test was performed upon samples of the various materials. 10.2 centimeter (cm) by approximately 15.2 centimeter (cm) samples of the material were cut. To the film side of the samples there was applied a 10.2 cm by 15.2 cm piece of 3M 2308 masking tape. The sample were then rolled, tape side up, forward and backwards two times with a 22.2 kilogram roller weight. The samples were then manually delaminated at one of the short ends to produce edges which could be placed within the jaws of a Sintech®/2 Computer Integrated Testing System manufactured by MTS Systems Corporation of Eden Prairie, Minn. The jaw gap was set at a span of 100 millimeters and enough of the material was left in the laminated state so that the jaws could travel 65 millimeters. The sample was positioned in the jaws so that the sample would start delaminating before the jaws had been expanded 10 millimeters. The crosshead speed was set at 300 millimeters per minute and the data were then recorded between the 10 millimeter start point and the 65 millimeter end point. The data recorded indicated the peel strength or load necessary in grams to separate the two layers and the standard index in grams with a maximum, minimum and mean value.




EXAMPLES




All the example films were three layer films with the two outer or skin layers in each example being the same. All films were cast films and all the films were embossed prior to stretching to yield a matte finish on the films. In addition, all the films were laminated to a 17 gram per square meter (gsm) polypropylene spunbond web made from approximately 2 denier fibers. The spunbond web was prebonded with a point bond pattern having an overall bond area of approximately 15 percent.




Example 1




In Example 1 the core layer was, on a weight percent basis based upon the total weight of the layer, 65 percent ECC English China Supercoat™ calcium carbonate with a 1 micron average particle size and a 7 micron top cut. The calcium carbonate was obtained from ECCA Calcium Products, Inc. of Sylacauga, Ala. which is a division of ECC International. The core layer also included 15 percent Exxon 9302 Random Copolymer Polypropylene (RCP) from the Exxon Chemical Company of Houston, Tex., 15 percent Himont KS059 Catalloy polymer from Himont U.S.A. of Wilmington, Del. and 5 percent Quantum NA206 Low Density Polyethylene (LDPE) from Quantum Chemical Corporation of New York, N.Y. The Himont Catalloy polymer is an olefinic thermoplastic elastomer or TPO multistep reactor product wherein an amorphous ethylene propylene random copolymer is molecularly dispersed in a predominately semicrystalline high polypropylene monomer/low ethylene monomer continuous matrix.




The two outer or skin layers on opposite sides of the core layer comprised 15 percent Himont KS057 Catalloy polymer from Himont U.S.A., 20 percent Ampacet 10115 antiblock and 65 percent Exxon XC-101 (28 percent EMA copolymer). Ampacet 10115 antiblock comprises 20 weight percent Superfloss™ diatomaceous earth let down in 79.75 percent Chevron 2207 EMA and 0.25 percent aluminum stearate. Ampacet 10115 antiblock is available from Ampacet Corporation of Tarrytown, N.Y. Chevron 2207 EMA is available from the Chevron Chemical Corporation of San Ramon, Calif. and Exxon XC-101 is available from the Exxon Chemical Company of Houston, Tex.




The three layer film was extruded using cast extrusion equipment of the type described above. The exiting melt temperature for the skin layers was measured to be 196° C. and for the core was 223° C. The air gap (distance between the die and the nip chill roll) was 53 centimeters and the gauge of the resultant film was 38 micrometers (microns). The film was wound up on a roll and later sent through a Machine Direction Orienter (MDO) Model No. 7200 from the Marshall and Williams Company of Providence, Rhode Island. The MDO unit was preheated to 77° C. and the film was stretched 4× while at a temperature of 77° C. By saying the film was stretched 4× it is meant that, for example, a 1 meter long film would be stretched to a resultant length of 4 meters. The final measured thickness of the film was 16.08 microns and the basis weight was 17 grams per square meter (gsm). Each of the two skin layers comprised approximately 2.7 percent of the overall film thickness. As a result, the core layer represented 94.6 percent of the overall thickness. Using the film thickness measuring method described above, the two skin layers each had a film thickness of 0.44 microns and the core layer had a thickness of 15.2 microns.




The resultant film was then thermally laminated to the above-described spunbond layer using a patterned bonding roll having a temperature of approximately 77° C. and a smooth anvil roll at a temperature of approximately 54° C. with a nip pressure of 4,218 kilograms per meter (kg/m) while at a line speed of 152 meters per minute with and overall bond area of 15 percent based upon the surface area of one side of the film. The laminate was passed through the bonder in such a fashion that the spunbond layer was adjacent the pattern roll and the film layer was adjacent the smooth anvil roll. The resultant laminate had a Water Vapor Transmission Rate (WVTR) measured as described above of 2570 grams per square meter per 24 hours (2570 g/m


2


/24 hr or day). The laminate had a hydrohead of 70 centimeters and a peel strength of 48 grams.




Example 2




In Example 2 the core layer was, on a weight percent basis based upon the total weight of the layer, 65 percent ECC English China Supercoat™ calcium carbonate, 15 percent Exxon 9302 Random Copolymer Polypropylene (RCP), 15 percent Himont KS059 Catalloy polymer and 5 percent Quantum NA206 Low Density Polyethylene (LDPE).




The two outer or skin layers on opposite sides of the core layer comprised 15 percent Ampacet 10115 antiblock (20 percent diatomaceous earth antiblock let down in a 24 percent copolymer ethylene methyl acrylate (EMA)) concentrate or masterbatch and 85 percent Himont KS057 Catalloy polymer.




The three layer film was extruded using cast extrusion equipment of the type described above. The exiting melt temperature from the extruder for the skin layers was 188° C. and the melt temperature for the core layer was 223° C. The air gap (distance between the die heads and the forming nip) was 53 centimeters and the gauge of the resultant film was 35.5 microns. The film was wound up on a roll and later sent through the MDO unit which was preheated to 88° C. and the film was stretched 3× while at a temperature of 88° C. The final measured thickness of the film was 17.28 microns and the basis weight was 15 gsm. Each of the two skin layers comprised 2 percent of the overall film thickness. As a result, the core layer represented 96 percent of the overall thickness. Using the film thickness measuring method described above, the two skin layers each had a film thickness of 0.33 micrometers (microns) and the core layer had a thickness of 16.62 microns.




The resultant film was then thermally laminated to the above-described spunbond layer using a patterned bonding roll having a temperature of approximately 77° C. and a smooth anvil roll at a temperature of approximately 54° C. with a nip pressure of 4,218 kg/m while at a line speed of 152 meters per minute with and overall bond area of 15 to 18 percent based upon the surface area of one side of the film. The laminate was passed through the bonder in such a fashion that the spunbond layer was adjacent the pattern roll and the film layer was adjacent the anvil roll. The film had a Water Vapor Transmission Rate (WVTR) measured as described above of 925 grams per square meter per 24 hours and the laminate had a WVTR of 820 g/m


2


/24 hr. The laminate had a hydrohead of 113 centimeters and a peel strength of 62 grams.




Example 3




In example 3 the core layer was, on a weight percent basis based upon the total weight of the layer, 63 percent ECC English China Supercoat™ calcium carbonate, 19 percent Himont KS059 Catalloy polymer, 13 percent Shell 6D81 polypropylene from the Shell Chemical Company of Houston, Tex. and 5 percent Dow 4012 low density polyethylene (LDPE) from Dow Chemical U.S.A. of Midland, Mich. The two outer or skin layers on opposite sides of the core layer comprised 30 percent Himont KS057 Catalloy polymer, 20 percent Techmer S110128E62 antiblock/EVA concentrate or masterbatch from Techmer PM of Rancho Dominguez, Calif., 20 percent Exxon 760.36 EMA and 30 percent Lotryl 29MA03 Ester-Modified EMA copolymer from Elf Atochem N.A. of Philadelphia, Pa.




The three layer film was extruded using cast extrusion equipment. The exiting temperature from the extruder for the skin layers was 188° C. and for the core was 209° C. The air gap (distance between the die heads and the forming roll) was 66 centimeters and the gauge of the resultant film was 38 microns. The film was wound up on a roll and later sent through the MDO unit which was preheated to 71° C. and the film was stretched 4× while at a temperature of 71° C. and subsequently annealed at a temperature of approximately 85° C.




The final gauge of the film was 16.98 microns and the basis weight was 17 gsm. Each of the two skin layers comprised 3.7 percent of the overall film thickness. As a result, the core layer represented 92.6 percent of the overall thickness. Using the film thickness measuring method described above, the two skin layers each had a film thickness of 0.6 microns and the core layer had a thickness of 15.77 microns.




The resultant film was then thermally laminated to the above-described spunbond layer using a patterned bonding roll having a temperature of approximately 110° C. and a smooth anvil roll at a temperature of approximately 32° C. with a nip pressure of 4570 kg/m inch while at a line speed of 61 meters per minute with and overall bond area of 15 to 18 percent based upon the per unit surface area of one side of the film. The laminate was passed through the bonder in such a fashion that the spunbond layer was adjacent the pattern roll and the film layer was adjacent the anvil roll. The film had a Water Vapor Transmission Rate (WVTR) measured as described above of 1301 grams per square meter per 24 hours (1301 g/m


2


/24 hr) and the resultant laminate had a WVTR of 1184 g/m


2


/24 hr. The laminate had a hydrohead of 110 centimeters and a peel strength of 161 grams.




Example 4




In Example 4 the core layer was, on a weight percent basis based upon the total weight of the layer, 63 percent ECC English China Supercoat™ calcium carbonate, 19 percent Himont KS059 Catalloy polymer, 13 percent Shell 6D81 polypropylene and 5 percent Dow 4012 LDPE.




The two outer or skin layers on opposite sides of the core layer comprised 35 percent Himont KS057 Catalloy polymer, 20 percent Techmer S110128E62 antiblock/EVA concentrate/masterbatch and 45 percent Exxon 760.36 EMA.




The three layer film was extruded using cast extrusion equipment. The exiting temperature for the skin layers was 187° C. and for the core was 208° C. The air gap (distance between the die heads and the forming roll) was 66 centimeters and the gauge of the resultant film was 35.5 microns. The film was wound up on a roll and later sent through the MDO unit which was preheated to 71° C. and the film was stretched 4× while at a temperature of 71° C. and subsequently annealed at a temperature of approximately 85° C. The final measured thickness of the film was 15.96 microns and the basis weight was 15 gsm. Each of the two skin layers comprised 3.0 percent of the overall film thickness. As a result, the core layer represented 94.0 percent of the overall thickness. Using the film thickness measuring method described above, the two skin layers each had a film thickness of 0.48 microns and the core layer had a thickness of 15.0 microns.




The resultant film was then thermally laminated to the above-described spunbond layer using a patterned bonding roll having a temperature of approximately 110° C. and a smooth anvil roll at a temperature of approximately 66° C. with a nip pressure of 4570 kg/m while at a line speed of 61 meters per minute with and overall bond area of 15 to 18 percent based upon the per unit surface area of one side of the film. The laminate was passed through the bonder in such a fashion that the spunbond layer was adjacent the pattern roll and the film layer was adjacent the anvil roll. The resultant laminate had a WVTR of 1522 g/m


2


/24 hrs., a hydrohead of 89 centimeters and a peel strength of 148 grams.




Example 5




In Example 5 the core layer was, on a weight percent basis based upon the total weight of the layer, 65 percent ECC English China Supercoat™ calcium carbonate, 15 percent Himont KS059 Catalloy polymer, 15 percent Exxon 9302 Random Copolymer Polypropylene (RCP) and 5 percent Dow 4012 LDPE.




The two outer or skin layers on opposite sides of the core layer comprised 35 percent Himont KS057 Catalloy polymer, 20 percent Techmer S110128E62 antiblock/EVA concentrate/masterbatch and 45 percent Exxon 760.36 EMA.




The three layer film was extruded using cast extrusion equipment. The exiting temperature for the skin layers was 175° C. and for the core was 234° C. The air gap (distance between the die heads and the forming roll) was 33 centimeters and the gauge of the resultant film was 35.5 microns. The film was wound up on a roll and later sent through the MDO unit which was preheated to 77° C. and the film was stretched 4× while at a temperature of 77° C. and subsequently annealed at a temperature of approximately 75° C. The final measured thickness of the film was 16.92 microns and the basis weight was 15 gsm. Each of the two skin layers comprised 1.0 percent of the overall film thickness. As a result, the core layer represented 98.0 percent of the overall thickness. Using the film thickness measuring method described above, the two skin layers each had a film thickness of 1.75 microns and the core layer had a thickness of 16.57 microns.




The resultant film was then thermally laminated to the above-described spunbond layer using a patterned bonding roll having a temperature of approximately 73° C. and a smooth anvil roll at a temperature of approximately 51° C. with a nip pressure of 4218 kg/m while at a line speed of 152 meters per minute with and overall bond area of 15 to 18 percent based upon the per unit surface area of one side of the film. The laminate was passed through the bonder in such a fashion that the spunbond layer was adjacent the pattern roll and the film layer was adjacent the anvil roll. The resultant laminate had a WVTR of 1930 g/m


2


/24 hrs., a hydrohead of 66 centimeters and a peel strength of 116 grams.




As shown by the above examples of the present invention, very low thickness (less than 30 microns) multilayer films can be formed. In addition, such films can have very thin skin layers which can impart a wide variety of functionalities including making the film vapor permeable, liquid impermeable and adhesive in nature. Furthermore such films can be attached to other support layers such as nonwoven to form laminates.




Having thus described the invention in detail, it should be apparent that various modifications can be made in the present invention without departing from the spirit and scope of the following claims.



Claims
  • 1. A multilayer film, comprising:a liquid impermeable multilayer film having a thickness less than 30 microns and a WVTR of at least 300 g/m2/24 hours, said multilayer film comprising a core layer and first and second skin layers; said core layer comprising an extrudable thermoplastic polymer and a particulate filler wherein pores are located adjacent said filler; said first skin layer on a first side of the core layer, and having a thickness constituting less than about 7.5% of the thickness of the multilayer film; and said second skin layer on a second side of the core layer and having a thickness constituting less than about 7.5% of the thickness of the multilayer film; each of said first and second skin layers comprise a polymer selected from the group consisting of polyolefins, ethylene vinyl acetate, ethylene ethyl acrylate, ethylene acrylic acid, ethylene methyl acrylate, ethylene butyl acrylate, polyester, nylon, ethylene vinyl alcohol, polystyrene, polyurethane, olefinic thermoplastic elastomers of ethylene and propylene, and combinations thereof.
  • 2. The multilayer film of claim 1, wherein at least one of the first and second skin layers comprises a polymer selected from the group consisting of polyolefins, ethylene vinyl acetate, polystyrene, olefinic thermoplastic elastomers of ethylene and propylene, and combinations thereof.
  • 3. The multilayer film of claim 1, wherein each of the first and second skin layers comprises a polymer selected from the group consisting of polyolefins, ethylene vinyl acetate, polystyrene, olefinic thermoplastic elastomers of ethylene and propylene, and combinations thereof.
  • 4. The multilayer film of claim 1, wherein at least one of the first and second skin layers comprises a polyolefin and an olefinic thermoplastic elastomer, said elastomer being a multistep reactor product wherein an amorphous ethylene-propylene random copolymer is molecularly dispersed in a continuous matrix of a predominantly semi-crystalline copolymer of propylene monomer/ethylene monomer.
  • 5. The multilayer film of claim 1, wherein both of the skin layers comprise a polyolefin and an olefinic thermoplastic elastomer, said elastomer being a multistep reactor product wherein an amorphous ethylene-propylene random copolymer is molecularly dispersed in a continuous matrix of a predominantly semi-crystalline copolymer of propylene monomer/ethylene monomer.
  • 6. The multilayer film of claim 1, wherein at least one of the first and second skin layers comprises an ethylene vinyl acetate and an olefinic thermoplastic elastomer, the elastomer being a multistep reactor product wherein an amorphous ethylene-propylene random copolymer is molecularly dispersed in a continuous matrix of a predominately semi-crystalline copolymer of propylene monomer/ethylene monomer.
  • 7. The multilayer film of claim 1, wherein both of the skin layers comprise an ethylene vinyl acetate and an olefinic thermoplastic elastomer, the elastomer being a multistep reactor product wherein an amorphous ethylene-propylene random copolymer is molecularly dispersed in a continuous matrix of a predominately semi-crystalline copolymer of propylene monomer/ethylene monomer.
  • 8. The multilayer film of claim 1, wherein at least one of the first and second skin layers comprises a polyolefin and an ethylene vinyl acetate.
  • 9. The multilayer film of claim 1, wherein both of the skin layers comprise a polyolefin and an ethylene vinyl acetate.
  • 10. The multilayer film of claim 1, wherein at least one of the first and second skin layers comprises a polyolefin and a polystyrene.
  • 11. The multilayer film of claim 1, wherein both of the skin layers comprise a polyolefin and a polystyrene.
  • 12. The multilayer film of claim 1, wherein at least one of the first and second skin layers comprises an ethylene vinyl acetate and a polystyrene.
  • 13. The multilayer film of claim 1, wherein both skin layers comprise an ethylene vinyl acetate and a polystyrene.
  • 14. The multilayer film of claim 3 wherein said core layer comprises a polyethylene and wherein each of the skin layers has a thickness less than 2 microns.
  • 15. The multilayer film of claim 14, wherein the core layer comprises at least about 60% by weight particulate filler.
  • 16. The multilayer film of a claim 1 wherein said extrudable thermoplastic polymer of said core layer comprises an olefin polymer and further wherein said thermoplastic polymer of the first skin layer comprises a polyolefin and an ethylene copolymer selected from the group consisting of ethylene vinyl acetate, ethylene ethyl acrylate and ethylene methyl acrylate.
  • 17. The multilayer film of claim 16 wherein said thermoplastic polymer of the second skin layer comprises a polyethylene and an ethylene copolymer selected from the group consisting of ethylene vinyl acetate, ethylene ethyl acrylate and ethylene methyl acrylate.
  • 18. The multilayer film of claim 17 wherein each of said first and second skin layers has a film thickness less than 2 micrometers.
  • 19. The multilayer film of claim 18 wherein the extrudable thermoplastic polymer of said core layer comprises a polyethylene.
  • 20. The multilayer film of claim 19 wherein the core layer comprises at least about 60% by weight particulate filler.
  • 21. The multilayer film of claim 1 wherein said thermoplastic polymer of the first skin layer comprises a polyethylene and an ethylene copolymer selected from the group consisting of ethylene vinyl acetate, ethylene ethyl acrylate, ethylene methyl acrylate, ethylene butyl acrylate, ethylene acrylic acid and ethylene vinyl alcohol.
  • 22. The multilayer film of claim 21 wherein said thermoplastic polymer of the second skin layer comprises a polyethylene and an ethylene copolymer selected from the group consisting of ethylene vinyl acetate, ethylene ethyl acrylate, ethylene methyl acrylate, ethylene butyl acrylate, ethylene acrylic acid and ethylene vinyl alcohol.
  • 23. The multilayer film of claim 22 wherein each of said first and second skin layers has a film thickness less than 2 micrometers.
  • 24. The multilayer film of claim 23 wherein said extrudable thermoplastic polymer of said core layer comprises a polyethylene.
  • 25. The multilayer film of claim 24 wherein the filler comprises at least about 60% by weight of the core layer.
  • 26. A breathable laminate, comprising the multilayer film of claim 1 and a nonwoven fabric attached to said first skin layer.
  • 27. The breathable laminate of claim 26 wherein said nonwoven fabric comprises a nonwoven fabric of polyolefin fibers.
  • 28. The breathable laminate of claim 26 wherein said nonwoven fabric is thermally laminated to said multilayer film at a plurality of bond points.
  • 29. A breathable laminate, comprising the multilayer film of claim 1 and a first nonwoven fabric attached to said first skin layer and a second support fabric attached to said second skin layer.
  • 30. A breathable laminate, comprising the multilayer film of claim 17 and a nonwoven fabric attached to said first skin layer.
  • 31. A multilayer, stretch-thinned breathable film having an overall thickness not exceeding about 30 microns and a moisture vapor transmission rate in excess of 300 grams/m2/24 hours, comprising:a core layer including a mixture of an extrudable thermoplastic polymer and a particulate filler; and a skin layer on a side of the core layer, having a skin layer thickness; the skin layer thickness constituting less than about 10% of the overall thickness; the skin layer comprising a polymer selected from the group consisting of polyolefins, ethylene vinyl acetate, ethylene ethyl acrylate, ethylene acrylic acid, ethylene methyl acrylate, ethylene butyl acrylate, polyester, nylon, ethylene vinyl alcohol, polystyrene, polyurethane, olefinic thermoplastic polymers of ethylene and propylene, and combinations thereof.
  • 32. The multilayer film of claim 31, wherein the skin layer comprises a polymer selected from the group consisting of polyolefins, ethylene vinyl acetate, polystyrene, olefinic thermoplastic polymers of ethylene and propylene, and combinations thereof.
  • 33. The multilayer film of claim 31, wherein the skin layer comprises a polyolefin and an olefinic thermoplastic elastomer, the elastomer being a multistep reactor product wherein an amorphous ethylene-propylene random copolymer is molecularly dispersed in a continuous matrix of a predominately semi-crystalline copolymer of propylene monomer/ethylene monomer.
  • 34. The multilayer film of claim 33, wherein the skin layer comprises an ethylene vinyl acetate and an olefinic thermoplastic elastomer, the elastomer being a multistep reactor product wherein an amorphous ethylene-propylene random copolymer is molecularly dispersed in a continuous matrix of a predominately semi-crystalline copolymer of propylene monomer/ethylene monomer.
  • 35. The multilayer film of claim 31, wherein the skin layer comprises a polyolefin and an ethylene vinyl acetate.
  • 36. The multilayer film of claim 31, wherein the skin layer comprises a polyolefin and a polystyrene.
  • 37. The multilayer film of claim 31, wherein the skin layer comprises an ethylene vinyl acetate and a polystyrene.
  • 38. The multilayer film of claim 31, wherein the core layer comprises at least about 60% by weight particulate filler.
  • 39. A personal care absorbent article including a liquid permeable top sheet, a breathable back sheet and an absorbent core between the top sheet and the back sheet, the back sheet including the multilayer film of claim 1.
  • 40. A personal care absorbent article including a liquid permeable top sheet, a breathable back sheet and an absorbent core between the top sheet and the back sheet, the back sheet including the multilayer film of claim 3.
  • 41. A personal care absorbent article including a liquid permeable top sheet, a breathable back sheet and an absorbent core between the top sheet and the back sheet, the back sheet including the multilayer film of claim 17.
  • 42. A personal care absorbent article including a liquid permeable top sheet, a breathable back sheet and an absorbent core between the top sheet and the back sheet, the back sheet including the breathable laminate of claim 26.
  • 43. A personal care absorbent article including a liquid permeable top sheet, a breathable back sheet and an absorbent core between the top sheet and the back sheet, the back sheet including the breathable laminate of claim 29.
  • 44. A personal care absorbent article including a liquid permeable top sheet, a breathable back sheet and an absorbent core between the top sheet and the back sheet, the back sheet including the multilayer film of claim 30.
Parent Case Info

This application is a continuation of application Ser. No. 08/724,435 filed in the U.S. Patent and Trademark Office on Oct. 1, 1996, and now U.S. Pat. No. 6,075,179, which is a file wrapper continuation of application Ser. No. 08/359,986 filed in the U.S. Patent and Trademark Office on Dec. 20, 1994, now abandoned, all entitled Low Gauge Films and Film/Nonwoven Laminates. The entirety of the aforesaid applications are hereby incorporated by reference.

US Referenced Citations (190)
Number Name Date Kind
2527299 De Phillips Oct 1950 A
3276944 Levy Oct 1966 A
3338992 Kinney Aug 1967 A
3341394 Kinney Sep 1967 A
3502538 Petersen Mar 1970 A
3502763 Hartmann Mar 1970 A
3510344 Dunderdale May 1970 A
3542615 Dobo et al. Nov 1970 A
3645992 Elston Feb 1972 A
3676242 Prentice Jul 1972 A
3692618 Dorschner et al. Sep 1972 A
3802817 Matsuki et al. Apr 1974 A
3836423 Wagner et al. Sep 1974 A
3849241 Butin et al. Nov 1974 A
3894904 Cook Jul 1975 A
3973063 Clayton Aug 1976 A
4041203 Brock et al. Aug 1977 A
4087486 Fielding et al. May 1978 A
4104404 Bieler et al. Aug 1978 A
4147827 Breidt, Jr. et al. Apr 1979 A
4154885 Tecl et al. May 1979 A
4178401 Weinberg et al. Dec 1979 A
4185135 Huff Jan 1980 A
4190624 Alard et al. Feb 1980 A
4194041 Gore et al. Mar 1980 A
4196240 Lustig et al. Apr 1980 A
4197150 Breidt, Jr. et al. Apr 1980 A
4239826 Knott, II et al. Dec 1980 A
4252851 Lansbury et al. Feb 1981 A
4254175 Kubat et al. Mar 1981 A
4265954 Romanek May 1981 A
4275119 Weiner Jun 1981 A
4276330 Stanley et al. Jun 1981 A
4289832 Schwarz Sep 1981 A
4294889 Hashimoto Oct 1981 A
4296156 Lustig et al. Oct 1981 A
4297408 Stead et al. Oct 1981 A
4303708 Gebhardt et al. Dec 1981 A
4306559 Nishizawa et al. Dec 1981 A
4312964 Sekine et al. Jan 1982 A
4332845 Nawata et al. Jun 1982 A
4339495 Weiner Jul 1982 A
4340563 Appel et al. Jul 1982 A
4340641 Weiner Jul 1982 A
4341216 Obenour Jul 1982 A
4343848 Leonard, Jr. Aug 1982 A
4344999 Gohlke Aug 1982 A
4347844 Ohki et al. Sep 1982 A
4350655 Hoge Sep 1982 A
4352849 Mueller Oct 1982 A
4353945 Sampson Oct 1982 A
4364985 Tokuyama et al. Dec 1982 A
4376147 Byrne et al. Mar 1983 A
4377616 Ashcraft et al. Mar 1983 A
4384024 Mitchell et al. May 1983 A
4386129 Jacoby May 1983 A
4390385 Ferguson et al. Jun 1983 A
4399173 Anthony et al. Aug 1983 A
4407986 Nomura et al. Oct 1983 A
4410582 Tsunashima et al. Oct 1983 A
4430468 Schumacher Feb 1984 A
4433026 Molde Feb 1984 A
4434258 Schumacher et al. Feb 1984 A
4438175 Ashcraft et al. Mar 1984 A
4439478 Ferguson et al. Mar 1984 A
4443511 Worden et al. Apr 1984 A
4494629 Raeburn Jan 1985 A
4501797 Super et al. Feb 1985 A
4522203 Mays Jun 1985 A
4525407 Ness Jun 1985 A
4533509 Gust et al. Aug 1985 A
4533602 Nakamura et al. Aug 1985 A
4546029 Cancio et al. Oct 1985 A
4552714 Krueger et al. Nov 1985 A
4560598 Cowan Dec 1985 A
4582752 Duncan Apr 1986 A
4582753 Duncan Apr 1986 A
4585604 Okuyama et al. Apr 1986 A
4595629 Mays Jun 1986 A
4603174 Okada et al. Jul 1986 A
4606970 Sharps, Jr. Aug 1986 A
4613643 Nakamura et al. Sep 1986 A
4615922 Newsome et al. Oct 1986 A
4636424 Amemiya et al. Jan 1987 A
4672091 Berta Jun 1987 A
4681578 Anderson et al. Jul 1987 A
4681793 Linman et al. Jul 1987 A
4684568 Lou Aug 1987 A
4686257 Mitsuno et al. Aug 1987 A
4698372 Moss Oct 1987 A
4702954 Duncan Oct 1987 A
4704323 Duncan et al. Nov 1987 A
4705813 Ito et al. Nov 1987 A
4725481 Ostapchenko Feb 1988 A
4734324 Hill Mar 1988 A
4748070 Beehler May 1988 A
4758396 Crass et al. Jul 1988 A
4758462 Park et al. Jul 1988 A
4761324 Rautenberg et al. Aug 1988 A
4777073 Sheth Oct 1988 A
4780364 Wade et al. Oct 1988 A
4791144 Nagou et al. Dec 1988 A
4814124 Aoyama et al. Mar 1989 A
4816328 Saville et al. Mar 1989 A
4824718 Hwang Apr 1989 A
4829096 Kitamura et al. May 1989 A
4832886 Douglas May 1989 A
4833026 Kausch May 1989 A
4842741 Coughlin et al. Jun 1989 A
4857370 Overbergh et al. Aug 1989 A
4861652 Lippert et al. Aug 1989 A
4863792 Mrozinski Sep 1989 A
4879078 Antoon, Jr. Nov 1989 A
4902553 Hwang et al. Feb 1990 A
4908251 Imura et al. Mar 1990 A
4909971 Coughlin et al. Mar 1990 A
4910639 Schloegl et al. Mar 1990 A
4921653 Aoyama et al. May 1990 A
4923650 Antoon, Jr. et al. May 1990 A
4929303 Sheth May 1990 A
4935287 Johnson et al. Jun 1990 A
4960637 Biczenczuk Oct 1990 A
4965123 Swan et al. Oct 1990 A
4980227 Sekiguchi et al. Dec 1990 A
5006394 Baird Apr 1991 A
5008296 Antoon, Jr. et al. Apr 1991 A
5011698 Antoon, Jr. et al. Apr 1991 A
5019073 Roessler et al. May 1991 A
5026591 Henn et al. Jun 1991 A
5026592 Janocha et al. Jun 1991 A
5032450 Rechlicz et al. Jul 1991 A
5036551 Dailey et al. Aug 1991 A
5055338 Sheth et al. Oct 1991 A
5073316 Bizen et al. Dec 1991 A
5091236 Keller et al. Feb 1992 A
5110670 Janocha et al. May 1992 A
5110677 Barmore et al. May 1992 A
5116662 Morman May 1992 A
5126197 Schinkel et al. Jun 1992 A
5126198 Schinkel et al. Jun 1992 A
5143679 Weber et al. Sep 1992 A
5149332 Walton et al. Sep 1992 A
5164258 Shida et al. Nov 1992 A
5167652 Mueller Dec 1992 A
5169712 Tapp Dec 1992 A
5173235 Kamei et al. Dec 1992 A
5176953 Jacoby et al. Jan 1993 A
5204179 Baker et al. Apr 1993 A
5204429 Kaminsky et al. Apr 1993 A
5208098 Stover May 1993 A
5209884 Wood, Jr. May 1993 A
5212009 Peiffer et al. May 1993 A
5212246 Ogale May 1993 A
5218036 Kagawa et al. Jun 1993 A
5236963 Jacoby et al. Aug 1993 A
5244716 Thornton et al. Sep 1993 A
5250612 Hazlitt et al. Oct 1993 A
5261899 Visscher et al. Nov 1993 A
5263949 Karami et al. Nov 1993 A
5272236 Lai et al. Dec 1993 A
5277970 Schuhmann et al. Jan 1994 A
5278272 Lai et al. Jan 1994 A
5284540 Roth et al. Feb 1994 A
5300365 Ogale Apr 1994 A
5317035 Jacoby et al. May 1994 A
5318842 Ogale Jun 1994 A
5324576 Reed et al. Jun 1994 A
5326625 Schuhmann et al. Jul 1994 A
5331047 Giacobbe Jul 1994 A
5336552 Strack et al. Aug 1994 A
5340646 Morita et al. Aug 1994 A
5372882 Peiffer et al. Dec 1994 A
5376430 Swenson et al. Dec 1994 A
5382400 Pike et al. Jan 1995 A
5382461 Wu Jan 1995 A
5397635 Wood, Jr. Mar 1995 A
5409761 Langley Apr 1995 A
5422172 Wu Jun 1995 A
5445862 Kaneko et al. Aug 1995 A
5453318 Giacobbe Sep 1995 A
5470639 Gessner et al. Nov 1995 A
5472775 Obijeski et al. Dec 1995 A
5539124 Etherton et al. Jul 1996 A
5554775 Krishnamurti et al. Sep 1996 A
5571619 McAlpin et al. Nov 1996 A
5582923 Kale et al. Dec 1996 A
5605735 Zehner et al. Feb 1997 A
5616420 Yamaoka et al. Apr 1997 A
5624991 Harada et al. Apr 1997 A
5695868 McCormack Dec 1997 A
Foreign Referenced Citations (31)
Number Date Country
803714 Jan 1969 CA
3724510 Feb 1989 DE
0 061 238 Sep 1982 EP
0 221 726 May 1987 EP
0 247 897 Dec 1987 EP
0 259 128 Mar 1988 EP
0 265 544 May 1988 EP
0 329 377 Aug 1989 EP
0 330 019 Aug 1989 EP
0 347 745 Dec 1989 EP
0 395 204 Oct 1990 EP
0 456 044 Nov 1991 EP
0 233 704 Jul 1992 EP
0 505 027 Sep 1992 EP
0 712 892 May 1996 EP
1 452 424 Oct 1976 GB
1453649 Oct 1976 GB
1 453 649 Oct 1976 GB
1 557 920 Dec 1979 GB
2 223 446 Apr 1990 GB
2 267 459 Dec 1993 GB
50-076187 Jun 1975 JP
54-038344 Mar 1979 JP
01-079249 Mar 1989 JP
01-146733 Jun 1989 JP
01-271240 Oct 1989 JP
02-162008 Jun 1990 JP
03-198724 Aug 1991 JP
4-227260 Aug 1992 JP
9527005 Oct 1995 WO
9704955 Feb 1997 WO
Non-Patent Literature Citations (7)
Entry
Abstract of JP 05-230251.
“Don't Say ‘Metallocene,’ Say ‘Single-Site’”, by Jan. H. Schut, Plastics World, Apr. 1997, p. 27-32.
“Here's the Latest Score on Single Site Catalysts”, by Jan H. Schut, Plastics World, Apr., 1997, pp. 41-46.
“New LLDPEs Offer Combined Properties, Processing Edge”, Plastics World, Apr. 1997, p. 8.
Exxon PE Grades, May 1996 (chart).
NRL Report 4364 “Manufacture of Superfine Organic Fibers” by V.A. Wente, E.L. Boone and C.D. Fluharty.
NRL Report 5265 “An Improved Device for the Formation of Superfine, Thermoplastic Fibers” by K.D. Lawrence, R.T. Lukas and J.A. Young.
Continuations (2)
Number Date Country
Parent 08/724435 Oct 1996 US
Child 09/412040 US
Parent 08/359986 Dec 1994 US
Child 08/724435 US