This application claims priority to GB Patent Application No. 1303971.4, which was filed on 6 Mar. 2013, the teachings of which are incorporated herein by reference.
The present invention relates to superabsorbent materials useful in the manufacture of absorbent articles such as wound dressings, and in particular wound dressings for the treatment of chronic, non-healing wounds.
Absorbent fibres useful as components in advanced wound care dressings are known in the art, particularly fibres based on alginic acid, carboxymethylcellulose (CMC), carboxymethylchitosan, cellulose ethyl sulfonate (CES) and salts thereof. Fibrous wound dressings may typically absorb up to 20-25 g of wound exudate per 100 cm2 dressing. Heavily exuding wounds such as diabetic leg ulcers may exude 5-10 g of liquid per 10 cm2 per 24 h. A wound of say 80 cm2 would therefore overwhelm a 100 cm2 fibrous wound dressing within a few hours, necessitating change of the dressing. To partly overcome this, superabsorbent materials are often used in advanced wound care dressings.
Standard superabsorbent materials, such as those based upon polyacrylic acid and its salts, soften and lose their mechanical strength when they absorb fluid and become wet. This is particularly undesirable when the material is intended for use as wound dressing where it may be necessary to remove a used dressing in one piece before it is replaced. A loss of mechanical strength may lead to break up of the dressing which may lead to complications, pain and discomfort for the patient and an extension of treatment time.
Powdered superabsorbent materials are used, often in combination with a bulking agent such as cellulose fluff, in absorbent wound dressings such as Sorbion Sachet S (Sorbion Gmbh & Co, Germany) and Vliwasorb, (Lohmann and Rauscher Gmbh & Co, Austria). In these dressings the poor mechanical strength of the superabsorbent powder when wet is overcome by enclosing the material in a non-woven outer pouch. The pouch may be made of a textile material of a soft texture, for example a perforated or mesh-type hydrophobic fleece-type film such as polyethylene or polypropylene film or a natural-fibre fabric or fleece. Dressings such as the Sorbion Sachet S and Vliwasorb dressings are also not suitable for use in cavity wounds. Due to the very large absorbent capacity of these dressings, on absorbing wound exudate they swell to many times their original dimension, potentially causing pain and trauma to the patient and extending treatment times. Dressings containing a superabsorbent material in the form of a powder may also disadvantageously exhibit gel blocking where the surface of a superabsorbent particle gels, preventing fluid transfer and leaving the inside of the particle dry. This may reduce the overall absorbency of the dressing and may potentially lead to harmful maceration of the periwound skin. Due to the very large absorbent capacity of these dressings they lack flexibility when wet.
Other wound dressings such as Askina Absorb+ (B. Braun Melsungen AG) and Sorbsan Plus SA (Aspen Medical, UK) seek to overcome this by using a superabsorbent fibre instead of a powdered material. Both contain a fabric comprising cellulose fluff pulp, superabsorbent fibre and a thermoplastic bicomponent fibre. The thermoplastic bicomponent fibre is used to fuse together the individual filaments of superabsorbent fibre and fluff pulp which would otherwise be unusably weak when wet. The superabsorbent fibres used in Askina Absorb+ are contained within a non-woven outer pouch that, prima facie, is not dissimilar to the type used in products such as Sorbion Sachet A or Vliwasorb. The superabsorbent fibres used in Sorbsan Plus SA, present in a multilaminar construction of a fabric comprising cellulose fluff pulp, superabsorbent fibre and a thermoplastic bicomponent fibre, are needle bonded to a wound contacting calcium alginate layer. The backing layer may comprise two outer layers which are a blend of fluff pulp and low melt binder, and a core absorbency layer which is a blend of fluff pulp, gel-forming polymer superabsorbent fibres and low melt binder. However, due to their multiple layers these dressings are very thick and inflexible, having a typical weight of 250-300 g/m2. Because of the large amount of non absorbent thermoplastic fibre in the cellulose fluff pulp, superabsorbent fibre and thermoplastic bicomponent fibre containing fabric, the absorbency per gram is relatively low, comparable to or only slightly better than that of conventional fibrous wound dressings.
Cotton in GB0905341.4 seeks to provide a method for reinforcing superabsorbent materials. A layered arrangement is formed with a single inner absorbent layer sandwiched between two outer reinforcing layers. Cotton discloses that the application of high frequency mechanical vibrations to the layered arrangement is able to bring about the generation of localised heat by friction. Because the layered arrangement contains a thermoplastic material that fuses when heated, the heat generated causes the welding of those layers together to form a composite absorbent material. This method of reinforcing an absorbent material relies on ultrasonically welding together at least two different fabrics, at least one of which contains a thermoplastic synthetic fibre. Synthetic thermoplastic fibres are disadvantageous in that they do not absorb fluid and in this application are adding mass and cost to the absorbent article without adding to the capability to absorb fluid.
It is an object of the present invention to mitigate at least some of the problems described above.
According to a first aspect of the present invention, there is provided an absorbent material comprising a blend of a superabsorbent gel-forming fibre and a non gel-forming fibre, wherein the blend of fibres does not comprise a superabsorbent gel-forming fibre formed from a polysaccharide.
According to a second aspect of the present invention, there is provided an absorbent material comprising a blend of fibres, the blend of fibres consisting of a single type of superabsorbent gel-forming fibre and a non gel-forming fibre.
By the term ‘blend’ it will be appreciated that the superabsorbent gel-forming fibres and the non gel-forming fibres are intimately mixed so as to form a homogenous mixture of fibres.
It will be understood that the statements below apply equally to the first and second aspects of the invention, unless stated otherwise.
The superabsorbent gel-forming fibre may be formed from a superabsorbent polymer. It will be understood that a superabsorbent polymer is a polymer which is capable of absorbing water in an amount as much as 500 times its own weight. In some embodiments, the superabsorbent polymer is capable of absorbing water in an amount of more than 10, more than 20, more than 30, more than 40, more than 60 or more than 100 times its own weight. In some embodiments, the super-absorbent gel-forming fibre is capable of absorbing at least 15, at least 20, at least 30, at least 50, at least 75 or at least 100 g of liquid (e.g. water or saline) per g of fibre. In some embodiments, the super-absorbent polymer is capable of absorbing more than 20, more than 40, more than 60, more than 80 or more than 100 g of liquid (e.g. water or saline) per gram of fibre.
In some embodiments, the superabsorbent polymer is a synthetic polymer. Suitable synthetic polymers may be prepared from polymerizable, unsaturated, acid-containing monomers, such as unsaturated carboxylic acids and acid anhydrides, unsaturated sulfonic acids and combinations thereof. Useful unsaturated carboxylic acid and carboxylic acid anhydride monomers include, e.g., acrylic acid, methacrylic acid, ethacrylic acid, chloroacrylic acid, cyanoacrylic acid, crotonic acid, phenylacrylic acid, acrytoxypropionic acid, sorbic acid, chlorosorbic acid, angelic acid, cinnamic acid, p-chlorocinnamic acid, stearylacrylic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, tricarboxyethylene acid anhydride, maleic acid anhydride, and combinations thereof.
Useful unsaturated sulfonic acid monomers for the preparation of synthetic superabsorbent polymers include aliphatic and aromatic vinyl sulfonic acids (e.g., vinylsulfonic acid, allyl sulfonic acid, vinyl toluene sulfonic acid and styrene sulfonic acid), acrylic and methacrylic sulfonic acids (e.g., sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-methacryloxypropyl sulfonic acid and 2-acrylamide-2-methylpropane sulfonic acid), and combinations thereof.
In some embodiments, the superabsorbent polymer is selected from the group consisting of: polyacrylates or co-polymers thereof; polymers of anhydrides, such as poly(maleic anhydride), or co-polymers thereof; polymers with carboxylic acid groups or salts thereof, such as polymers of acrylic acid, maleic acid, methacrylic acid or derivatives thereof; polymers of acrylamide (e.g. polyacrylamide) or co-polymers thereof; polyethylene oxide (PEO); polyvinyl alcohol (PVOH); graft co-polymers; or mixtures thereof. Suitable polymers of acrylamide or copolymers thereof include polyacrylamide, polyAMPs (poly-acrylamido-2-methylpropane sulfonic acid) or its sodium salt, and acrylamide-co-acrylic acid.
In some embodiments, the superabsorbent polymer is a polyacrylate or copolymer thereof. Polyacrylates are a broad group of synthetic polymers derived from monomers which include esters of acrylic acid, for example poly(hydroxyl methacrylate), and salts of polymers of acrylic acid and derivatives thereof.
Suitable polyacrylates or copolymers thereof for use in the invention include sodium polyacrylate, sodium polymethacrylate, and co-polymers of acrylic acid with other monomers. Further examples include co-polymers of acrylic acid with vinyl pyrrolidone monomers, optionally with a diacrylate cross-linker, co-polymers of acrylic acid with maleic acid or hydrolysed maleic anhydride. Co-polymers may also comprise olefins, such as ethylene.
In some embodiments the polymers or co-polymers are cross-linked.
One example of polyacrylate fibres is ‘SAF’™, commercially available fibres sold by Technical Absorbent Limited (Grimsby, UK). SAF™ is formed from a cross-linked polymer of acrylic acid (AA) methylacrylate (MA) and a small quantity of special acrylate/methylacrylate monomer (SAMM) in which the acrylic acid is partially neutralised to the sodium salt of acrylic acid (AANa). SAF™ fibres are available in different staple lengths, linear density and with different degrees of cross linking to give different absorbency levels. Thus, in some embodiments the superabsorbent gel-forming fibre is SAF.
In some embodiments of the second aspect of the invention, the superabsorbent gel-forming fibre is formed from a graft polymer. Graft polymers are polymers grafted onto a backbone of another suitable polymer, such as a polysaccharide backbone. The graft polymer may be a homopolymer or a copolymer. Suitable polymers for the formation of graft polymers include polyacrylic acid or acrylamide-co-acrylic acid. These polymers may be grafted on to a backbone of chitosan, cellulose, starch, guar gum, carrageenan, alginate, or synthetic polymers such as PVOH.
In some embodiments of the second aspect of the invention, the superabsorbent gel-forming fibre is formed from a polysaccharide. Suitable polysaccharides include alginate (i.e. a salt of alginic acid), modified cellulose, modified chitosan, guar gum, carrageenan, pectin, starch or mixtures thereof. The term ‘modified’ will be understood as meaning that the polysaccharide molecules have been chemically modified, for example by covalent attachment of additional functional groups. Examples of modified cellulose include carboxymethylcellulose (CMC), cellulose ethyl sulfonate (CES) and cellulose ethyl sulfonate. Examples of modified chitosan include carboxymethylchitosan, ethyl sulfonated chitosan and carboxyethyl chitosan.
In some embodiments of the second aspect of the invention, the superabsorbent gel-forming fibre is not formed from modified cellulose. In some embodiments, the superabsorbent gel-forming fibre is not formed from CES. In some embodiments, the superabsorbent gel-forming fibre is not formed from alginate. In further embodiments, the superabsorbent gel-forming fibre is not formed from a polysaccharide.
In some embodiments, the non gel-forming fibre is a naturally occurring fibre, for example cotton. In other embodiments the non gel-forming fibres are semi-synthetic fibres, in particular semi-synthetic cellulose-based fibres such as rayon (otherwise known as ‘viscose’ or ‘viscose-rayon’) or lyocell fibres (formed from solvent spun non-modified cellulose). In other embodiments the non gel-forming fibres are (entirely) synthetic fibres such as nylon fibres (made from polyamides), acrylic fibres (made from polyacetonitriles), or fibres made from polyester or polyolefins (e.g. polypropylene, polyethylene), or co-polymers thereof.
In some particular embodiments, the non gel-forming fibres are lyocell fibres. These may be obtained by an organic solvent spinning process, for example using various amine oxides as solvents. In particular, N-methylmorpholine-N-oxide (“NMNO”) with water (about 12%) proves to be a particularly useful solvent. Examples of processes for preparing cellulose fibres are described in McCorsley et al., U.S. Pat. Nos. 4,142,913; 4,144,080; 4,211,574; 4,246,221; and 4,416,698, and others. Jurkovic et al., U.S. Pat. No. 5,252,284 and Michels et al., U.S. Pat. No. 5,417,909 deal especially with the geometry of extrusion nozzles for spinning cellulose dissolved in NMMO. Brandner et al., U.S. Pat. No. 4,426,228 is exemplary of a considerable number of patents that disclose the use of various compounds to act as stabilizers in order to prevent cellulose and/or solvent degradation in the heated NMMO solution. Franks et al., U.S. Pat. Nos. 4,145,532 and 4,196,282, deal with the difficulties of dissolving cellulose in amine oxide solvents and of achieving higher concentrations of cellulose. All of these patents are incorporated herein by reference. Lyocell fibres are commercially available under the brand name ‘TENCEL’® from Lenzing AG, Austria. Thus, in some embodiments the non gel-forming fibre is TENCEL.
The use of naturally occurring non gel-forming fibres, in particular semi-synthetic fibres such as those based on cellulose, is advantageous because these fibres provide strength while also being capable of absorbing liquid. In some embodiments, the material does not contain any (entirely) synthetic non gel-forming fibres (i.e. the blend of fibres consists of naturally occurring and/or semi-synthetic fibres only). These embodiments are particularly advantageous since there are no non absorbent fibres in the material, thereby maximising the absorbency per gram of material.
In some embodiments, the non gel-forming fibre (in fibre form) is capable of absorbing more than 0.5, more than 0.8, more than 1.0, more than 1.2, more than 1.5 or more than 2.0 g liquid per gram of fibre. In some embodiments, the non gel-forming fibre (in fibre form) is capable of absorbing approximately 1 g of liquid per g of fibre.
In some embodiments, the superabsorbent gel-forming fibre is a polyacrylate (e.g. SAF) and the non gel-forming fibre is a semi-synthetic fibre. In particular embodiments, the superabsorbent gel-forming fibre is polyacrylate (e.g. SAF) and the non gel-forming fibre is a lyocell fibre such as TENCEL.
In some embodiments, the absorbent material comprises at least 30%, at least 40%, at least 50%, at least 60%, at least 70% or at least 80% of the superabsorbent gel-forming fibre, by weight of the total fibre content of the material. In some embodiments, the absorbent material comprises no more than 90%, no more than 80%, no more than 70%, no more than 60%, no more than 50% or no more than 40% of the superabsorbent gel-forming fibre, by weight of the total fibre content of the material.
In some embodiments, the absorbent material comprises at least 10%, at least 20%, at least 30%, at least 40%, at least 50% or at least 60% of the non gel-forming fibre, by weight of the total fibre content of the material. In some embodiments, the absorbent material comprises no more than 70%, no more than 60%, no more than 50%, no more than 40%, no more than 30% or no more than 20% of the superabsorbent gel-forming fibre, by weight of the total fibre content of the material.
In further embodiments, the absorbent material comprises from 30 to 90% or from 40% to 60% of the superabsorbent gel-forming fibre and from 10 to 70% or from 60% to 40% of the non gel-forming fibre, by weight of the total fibre content of the material. In particular embodiments, the material comprises 50% the superabsorbent gel-forming fibre and 50% of the non gel-forming fibre.
In some embodiments, the absorbent material has a weight of no more than 500 g/m2, no more than 400 g/m2, no more than 300 g/m2, no more than 200 g/m2, no more than 150 g/m2, no more than 120 g/m2, no more than 100 g/m2, no more than 80 g/m2, no more than 60 g/m2, no more than 50 g/m2 or no more than 40 g/m2.
In some embodiments, the absorbent material has an absorbency of more than 18, more than 19, more than 20, more than 22, more than 24, more than 26 or more than 28 grams of liquid (water or saline) per gram of material.
The absorbent material of the invention may be in sheet form. In some embodiments, the material is non-woven. The material may be made by carding, air-laying and/or needle-bonding the fibres, or by or hydro-entangling the fibres using a non-aqueous solvent. In some embodiments, the absorbent material is made by a method comprising carding and, optionally, needle bonding the fibres. Such methods are well-known to those skilled in the art.
The absorbent material may comprise one or more optional ingredients such as preservatives, antimicrobial agents or other pharmacologically active agents. For example, antibiotics (e.g. penicillin), antimicrobial agents (such as silver, PHMB (polyhexamethylene biguanide)), antiseptic agents (e.g. povidone iodine), anti-inflammatory agents (such as hydrocortisone), or other agents (such as zinc oxide) may be included. Such optional agents may be applied to the absorbent material or article by spraying, coating, dipping or by any other method known to those skilled in the art.
According to a third aspect of the present invention there is provided an absorbent article comprising the absorbent material according to the first aspect of the invention.
Absorbent articles may include wound dressings, disposable sanitary articles such as nappies (diapers), disposable nappies and training pants, feminine care products, e.g., tampons, sanitary towels, or napkins and pant liners, and incontinence products. In particular embodiments, the present invention provides a wound dressing comprising the absorbent material in accordance with the first or second aspects of the invention.
In some embodiments, the wound dressing may be in the form of swabs, wound pads, wadding ribbons, sponges, nets and bandages.
The absorbent material of the first aspect of the invention may form one of a plurality of layers. Thus in some embodiments, the wound dressing is a multi-laminar dressing, which may comprise at least 2 or at least 3 layers. Multi-laminar dressings comprising the absorbent material of the invention are more flexible and more absorbent than commercially available multi-laminar dressings, and thus offer improved comfort for the patient. They are also more convenient to use since a single, multi-laminar dressing is simpler and quicker for a care giver to apply to a wound than multiple separate components.
In some embodiments, the wound dressing comprises a first layer comprising or consisting of the absorbent material of the first aspect of the present invention, and a second layer formed from any suitable material. The material of the second layer may be selected according to its desired function. For example, the second layer may provide absorbency, padding, water-proofing or support. A variety of suitable wound dressing materials are commercially available and will be known to those skilled in the art. In some embodiments, the second layer is formed from another, known, absorbent material (such as alginate), which advantageously increases the absorbency of the dressing. In further embodiments, the wound dressing comprises the absorbent material of the first aspect of the present invention bonded to a foam layer. The foam may be a hydrophilic foam such as that described in EP2498829.
In some embodiments, the wound dressing comprises three layers. In some particular embodiments, the wound dressing comprises two outer layers and an inner core, wherein the inner core comprises or consists of the absorbent material of the first aspect of the invention. The outer layers may comprise any suitable material, for example alginate, foam, CES, CMC, or cellulose fluff pulp and a suitable binder. The outer layers may form wound contacting layers. The three-layer combination is useful as a ribbon dressing for cavity wounds. By providing two wound contacting layers and a core layer formed from the absorbent material of the first aspect of the present invention, the absorbency of the dressing is increased compared to existing technology.
In some embodiments, the wound dressing additionally comprises a wound contact layer. The contact layer is the layer which comes into contact with the surface (e.g. of the skin or wound) to which the material is applied. The contact layer conveniently increases the absorbency of the material, and may also help to prevent the material from sticking to the surface. The contact layer may also offer further advantages including providing a moist environment and/or delivering therapeutics or other agents, for example agents conducive to wound healing.
In some embodiments, the wound contact layer is a non-woven or a perforated polymer film, which is applied to one or more surfaces of the dressing. In some embodiments, the wound contact layer comprises or consists of alginate, such as calcium or silver alginate.
In some embodiments, the wound contact layer comprises or consists of alginate, modified cellulosic fibres (such as carboxymethyl cellulose (CMC) or cellulose ethyl sulfonate (CES), hydrogels or foams (e.g. polyurethane, alginate, cellulosic or modified cellulosic foams). Suitable hydrogels may include cross-linked hydrophobic polymers. The polymers may be polysaccharides (e.g. alginates, gelatins, pectins) or synthetic polymers (e.g. polymers based on 2-acrylamido-2-methylpropane sulfonic acid (AMPS), PEG, PVP, PVOH etc.). Suitable hydrogels are commercially available, for example, from Lohmann & Rauscher.
In some embodiments, the wound contact layer comprises or consists of alginate. The alginate salt may comprise a monovalent cation or a multivalent cation, in particular a divalent cation provided that the divalent cation is not Mg2+. In some embodiments, the alginate is calcium alginate, sodium calcium alginate, sodium alginate, silver alginate, copper alginate or mixtures thereof. In some embodiments, the alginate is calcium alginate.
Alginate fibres with a range of M/G ratios (the ratio of D-mannuronate to L-guluronate) may be used. A suitable range of M content in the M:G ratio is 30:70 and more preferably 40:60.
The absorbent material of the invention may be attached or bonded to the other materials or layers (such as a wound contact layer) in a multi-laminar wound dressing by any suitable means, such as needle punching, thermal bonding, ultrasonic welding, sewing, stitch bonding, adhesive etc. Such techniques will be well known to those skilled in the art.
Embodiments of the present invention will now be described by way of example only.
SAF (Technical Absorbents, Grimsby, UK), was carded with TENCEL fibres (Lenzing Fibres, Grimsby, UK) using a sample card and cross folder to produce a carded web. This carded web was needle punched using a TexTex needle loom to give materials A, B and C. Absorbency was measured by weighing a 5 cm×5 cm piece of sample material (W1). Next, the sample was placed in Solution A (16.6 g NaCl and 0.74 g CaCl2.2H2O in 2 L water) at 37° C. for 30 minutes in a petri dish. Then, the square was lifted out of the petri-dish by holding the square by one corner, and the sample was allowed to drain for 30 seconds. The sample was then reweighed to obtain the end weight (W2). The fabric absorbency is given by ((W2−W1)/W1).
The retention value of the material was determined for each sample immediately following the absorbency test.
After recording the weight of the sample in the petri dish absorbency test, the sample was placed on blue paper roll (eight layers). A perspex sheet weighing 1358 g and considered to be equivalent to pressure equal to 40 mmHg was placed on top for 30 seconds and then removed. The sample was removed using forceps and weighed. The retention value was determined according to the formula ((W3−W1)/W1) where W3 is the wet weight after compression and W1 is the dry weight.
The absorbency and retention values were measured for the following materials and the results shown in Table 1 below:
It can be seen from the data above that at a ratio of 40:60 or 60:40 SAF:Tencel (by weight), both the absorbency and the retention values of the material were improved compared to calcium alginate and other commercial wound dressing products. It was surprisingly observed that at a ratio of 50:50 SAF:Tencel (by weight), both the absorbency and the retention values were significantly increased.
The tensile strength of materials A-F when wet was measured using the following protocol. The results are shown in Table 2 below.
It can be seen from the data in Table 2 that the wet tensile strength of the SAF: TENCEL blends (materials A, B and C) was significantly increased in both the machine direction and the cross direction compared to the known materials. The wet tensile strength of the 50:50 SAF:TENCEL blend was more than 3-fold greater in the machine direction, and more than 2.5-fold greater in the cross direction, than that of the commercial wound dressings (F and G). Surprisingly, the wet tensile strength of the 40:60 SAF:TENCEL blend in the machine direction was more than 4-fold greater than that of the commercial products and more than 10-fold greater than that of the calcium alginate.
Number | Date | Country | Kind |
---|---|---|---|
1303971.4 | Mar 2013 | GB | national |
Number | Name | Date | Kind |
---|---|---|---|
4142913 | McCorsley, III et al. | Mar 1979 | A |
4144080 | McCorsley, III | Mar 1979 | A |
4145532 | Franks et al. | Mar 1979 | A |
4196282 | Franks et al. | Apr 1980 | A |
4211574 | McCorsley, III et al. | Jul 1980 | A |
4246221 | McCorsley, III | Jan 1981 | A |
4416698 | McCorsley, III | Nov 1983 | A |
4426228 | Brandner et al. | Jan 1984 | A |
4865596 | Weisman et al. | Sep 1989 | A |
5252284 | Jurkovic et al. | Oct 1993 | A |
5311389 | Howey | May 1994 | A |
5366832 | Hayashi et al. | Nov 1994 | A |
5417909 | Michels et al. | May 1995 | A |
5599585 | Cohen | Feb 1997 | A |
5656355 | Cohen | Aug 1997 | A |
5814094 | Flick et al. | Sep 1998 | A |
5848995 | Walder | Dec 1998 | A |
5985301 | Nakamura et al. | Nov 1999 | A |
6087549 | Flick et al. | Jul 2000 | A |
6113636 | Ogle | Sep 2000 | A |
6190407 | Ogle | Feb 2001 | B1 |
6191335 | Robinson | Feb 2001 | B1 |
6194332 | Rock et al. | Feb 2001 | B1 |
6218910 | Miller | Apr 2001 | B1 |
6224898 | Balogh et al. | May 2001 | B1 |
6267782 | Ogle | Jul 2001 | B1 |
6281515 | Demeo et al. | Aug 2001 | B1 |
6459091 | Demeo et al. | Oct 2002 | B1 |
6501343 | Miller | Dec 2002 | B2 |
6576338 | Meijer et al. | Jun 2003 | B1 |
6582411 | Carstens | Jun 2003 | B1 |
6592888 | Jensen et al. | Jul 2003 | B1 |
6599523 | Cohen | Jul 2003 | B2 |
6602811 | Rock et al. | Aug 2003 | B1 |
6627785 | Cohen | Sep 2003 | B1 |
6630016 | Koslow | Oct 2003 | B2 |
6660172 | Koslow | Dec 2003 | B2 |
6686754 | Miller | Feb 2004 | B2 |
6692773 | Burrell et al. | Feb 2004 | B2 |
6716895 | Terry | Apr 2004 | B1 |
6719987 | Langford et al. | Apr 2004 | B2 |
6720006 | Hanke et al. | Apr 2004 | B2 |
6723350 | Bowlby et al. | Apr 2004 | B2 |
6723428 | Foss et al. | Apr 2004 | B1 |
6822034 | Bast et al. | Nov 2004 | B2 |
6828578 | Demeo et al. | Dec 2004 | B2 |
6835311 | Koslow | Dec 2004 | B2 |
6841244 | Foss et al. | Jan 2005 | B2 |
6841791 | Demeo et al. | Jan 2005 | B2 |
6861570 | Flick et al. | Mar 2005 | B1 |
6866704 | Koslow | Mar 2005 | B2 |
6872311 | Koslow | Mar 2005 | B2 |
6905711 | Tullo et al. | Jun 2005 | B1 |
6911437 | Cohen | Jun 2005 | B2 |
6913154 | Koslow | Jul 2005 | B2 |
6917210 | Miller | Jul 2005 | B2 |
6939568 | Burrell et al. | Sep 2005 | B2 |
6946196 | Foss et al. | Sep 2005 | B2 |
6949598 | Terry | Sep 2005 | B2 |
6953604 | Koslow | Oct 2005 | B2 |
6959820 | Koslow | Nov 2005 | B2 |
6979491 | Yan et al. | Dec 2005 | B2 |
6989156 | Gillis | Jan 2006 | B2 |
6989157 | Gillis et al. | Jan 2006 | B2 |
6998058 | Koslow | Feb 2006 | B2 |
7001617 | Burrell et al. | Feb 2006 | B2 |
7005556 | Flick et al. | Feb 2006 | B1 |
7008537 | Koslow | Mar 2006 | B2 |
7008647 | Burrell et al. | Mar 2006 | B2 |
7011753 | Koslow | Mar 2006 | B2 |
7019391 | Tran | Mar 2006 | B2 |
7078060 | Burrell et al. | Jul 2006 | B2 |
7087249 | Burrell et al. | Aug 2006 | B2 |
7118761 | Canada et al. | Oct 2006 | B2 |
7141518 | MacDonald et al. | Nov 2006 | B2 |
7144533 | Koslow | Dec 2006 | B2 |
7179849 | Terry | Feb 2007 | B2 |
7201925 | Gillis | Apr 2007 | B2 |
7214847 | Flick et al. | May 2007 | B1 |
7229689 | Qin et al. | Jun 2007 | B2 |
7230153 | Flick et al. | Jun 2007 | B2 |
7241388 | Koslow | Jul 2007 | B2 |
7255881 | Gillis et al. | Aug 2007 | B2 |
7276166 | Koslow | Oct 2007 | B2 |
7287650 | Koslow | Oct 2007 | B2 |
7291762 | Flick et al. | Nov 2007 | B2 |
7296691 | Koslow | Nov 2007 | B2 |
7300673 | Djokic | Nov 2007 | B2 |
7330369 | Tran | Feb 2008 | B2 |
7375417 | Tran | May 2008 | B2 |
7378156 | Terry | May 2008 | B2 |
7410650 | Lin | Aug 2008 | B2 |
7427416 | Gillis et al. | Sep 2008 | B2 |
7455854 | Gower et al. | Nov 2008 | B2 |
7462753 | Yu et al. | Dec 2008 | B2 |
7470437 | Burrell et al. | Dec 2008 | B2 |
7476889 | Demeo et al. | Jan 2009 | B2 |
7489537 | Tran | Feb 2009 | B2 |
7514248 | Gower et al. | Apr 2009 | B2 |
7514249 | Gower et al. | Apr 2009 | B2 |
7544496 | Gower et al. | Jun 2009 | B2 |
7547449 | Gower et al. | Jun 2009 | B2 |
7630227 | Tran | Dec 2009 | B2 |
7655112 | Koslow | Feb 2010 | B2 |
7671398 | Tran | Mar 2010 | B2 |
7687076 | Djokic | Mar 2010 | B2 |
7745509 | Burton et al. | Jun 2010 | B2 |
7775998 | Riesinger | Aug 2010 | B2 |
7842306 | Cowan et al. | Nov 2010 | B2 |
7862624 | Tran | Jan 2011 | B2 |
7864560 | Tran | Jan 2011 | B2 |
7951853 | Ismail et al. | May 2011 | B2 |
7959624 | Riesinger | Jun 2011 | B2 |
7989674 | Flick et al. | Aug 2011 | B2 |
7998504 | Djokic | Aug 2011 | B2 |
8021685 | Cowan et al. | Sep 2011 | B2 |
8034454 | Terry et al. | Oct 2011 | B2 |
8056733 | Koslow | Nov 2011 | B2 |
8084762 | Tran | Dec 2011 | B2 |
8093444 | Flick et al. | Jan 2012 | B2 |
8118791 | Flick et al. | Feb 2012 | B2 |
8118792 | Effing et al. | Feb 2012 | B2 |
8118793 | Effing et al. | Feb 2012 | B2 |
8123730 | Effing et al. | Feb 2012 | B2 |
8124826 | Greenhalgh et al. | Feb 2012 | B2 |
8183167 | Delattre et al. | May 2012 | B1 |
8187626 | Cohen | May 2012 | B2 |
8193267 | Burton et al. | Jun 2012 | B2 |
8217220 | Abbas et al. | Jul 2012 | B2 |
8283513 | Flick et al. | Oct 2012 | B2 |
8293964 | Flick et al. | Oct 2012 | B2 |
8334524 | Demeo et al. | Dec 2012 | B2 |
8343535 | Burd et al. | Jan 2013 | B2 |
8361553 | Karandikar | Jan 2013 | B2 |
8367089 | Wan et al. | Feb 2013 | B2 |
8394403 | Cowan et al. | Mar 2013 | B2 |
8449514 | Flick et al. | May 2013 | B2 |
8450716 | Tran | May 2013 | B2 |
8455710 | Flick et al. | Jun 2013 | B2 |
8461410 | Addison et al. | Jun 2013 | B2 |
8613363 | Koslow | Dec 2013 | B2 |
20010035800 | Miller | Nov 2001 | A1 |
20010055622 | Langford et al. | Dec 2001 | A1 |
20020012693 | Cohen | Jan 2002 | A1 |
20020043631 | Demeo et al. | Apr 2002 | A1 |
20020051824 | Burrell et al. | May 2002 | A1 |
20020064551 | Cohen | May 2002 | A1 |
20020082340 | Bast et al. | Jun 2002 | A1 |
20020099449 | Speitling et al. | Jul 2002 | A1 |
20020122832 | Hanke et al. | Sep 2002 | A1 |
20020172709 | Nielsen et al. | Nov 2002 | A1 |
20020182265 | Bowlby et al. | Dec 2002 | A1 |
20020192298 | Burrell et al. | Dec 2002 | A1 |
20030010939 | Demeo et al. | Jan 2003 | A1 |
20030021854 | Burrell et al. | Jan 2003 | A1 |
20030049300 | Terry | Mar 2003 | A1 |
20030054046 | Burrell et al. | Mar 2003 | A1 |
20030067316 | Miller | Apr 2003 | A1 |
20030072810 | Burrell | Apr 2003 | A1 |
20030086977 | Gillis | May 2003 | A1 |
20030099718 | Burrell et al. | May 2003 | A1 |
20030130638 | Baker | Jul 2003 | A1 |
20030140785 | Koslow | Jul 2003 | A1 |
20030141261 | Koslow | Jul 2003 | A1 |
20030153889 | Gibbs | Aug 2003 | A1 |
20030168401 | Koslow | Sep 2003 | A1 |
20030170314 | Burrell et al. | Sep 2003 | A1 |
20030170453 | Foss et al. | Sep 2003 | A1 |
20030177909 | Koslow | Sep 2003 | A1 |
20030180346 | Woods | Sep 2003 | A1 |
20030180378 | Gillis et al. | Sep 2003 | A1 |
20030180379 | Burrell et al. | Sep 2003 | A1 |
20030185889 | Cheng et al. | Oct 2003 | A1 |
20030185901 | Burrell et al. | Oct 2003 | A1 |
20030190851 | Yan et al. | Oct 2003 | A1 |
20030194444 | Burrell et al. | Oct 2003 | A1 |
20030196963 | Koslow | Oct 2003 | A1 |
20030196964 | Koslow | Oct 2003 | A1 |
20030200868 | Koslow | Oct 2003 | A1 |
20030201231 | Koslow | Oct 2003 | A1 |
20030203046 | Burrell et al. | Oct 2003 | A1 |
20030205529 | Koslow | Nov 2003 | A1 |
20030205530 | Koslow | Nov 2003 | A1 |
20030205531 | Koslow | Nov 2003 | A1 |
20030206944 | Cohen | Nov 2003 | A1 |
20030206966 | Burrell et al. | Nov 2003 | A1 |
20030213750 | Koslow | Nov 2003 | A1 |
20030232071 | Gower et al. | Dec 2003 | A1 |
20040001880 | Bowler et al. | Jan 2004 | A1 |
20040004196 | Demeo et al. | Jan 2004 | A1 |
20040030276 | Flick et al. | Feb 2004 | A1 |
20040031749 | Koslow | Feb 2004 | A1 |
20040038609 | Mayer | Feb 2004 | A1 |
20040049145 | Flick et al. | Mar 2004 | A1 |
20040084378 | Koslow | May 2004 | A1 |
20040116551 | Terry | Jun 2004 | A1 |
20040129112 | Gillis | Jul 2004 | A1 |
20040131562 | Gower et al. | Jul 2004 | A1 |
20040131698 | Gillis et al. | Jul 2004 | A1 |
20040140822 | Miller | Jul 2004 | A1 |
20040157073 | Bowlby et al. | Aug 2004 | A1 |
20040176312 | Gillis | Sep 2004 | A1 |
20040178142 | Koslow | Sep 2004 | A1 |
20040191329 | Burrell et al. | Sep 2004 | A1 |
20040191500 | Foss et al. | Sep 2004 | A1 |
20040197553 | Foss et al. | Oct 2004 | A1 |
20040202860 | Foss et al. | Oct 2004 | A1 |
20040209059 | Foss et al. | Oct 2004 | A1 |
20040214495 | Foss et al. | Oct 2004 | A1 |
20040229034 | Djokic | Nov 2004 | A1 |
20040234604 | Mecking et al. | Nov 2004 | A1 |
20040241213 | Bray | Dec 2004 | A1 |
20050003728 | Foss et al. | Jan 2005 | A1 |
20050008861 | Yadav et al. | Jan 2005 | A1 |
20050011827 | Koslow | Jan 2005 | A1 |
20050019568 | Foss et al. | Jan 2005 | A1 |
20050035327 | Canada et al. | Feb 2005 | A1 |
20050037057 | Schuette et al. | Feb 2005 | A1 |
20050037058 | Cowan et al. | Feb 2005 | A1 |
20050037680 | Canada et al. | Feb 2005 | A1 |
20050051487 | Koslow | Mar 2005 | A1 |
20050058835 | Bayston et al. | Mar 2005 | A1 |
20050064020 | Schuette et al. | Mar 2005 | A1 |
20050085144 | Fish et al. | Apr 2005 | A1 |
20050101213 | Foss et al. | May 2005 | A1 |
20050101900 | Qin et al. | May 2005 | A1 |
20050106390 | Foss et al. | May 2005 | A1 |
20050124724 | Burton et al. | Jun 2005 | A1 |
20050129624 | Burrell et al. | Jun 2005 | A1 |
20050136100 | Foss et al. | Jun 2005 | A1 |
20050136128 | Gillis et al. | Jun 2005 | A1 |
20050147657 | Canada et al. | Jul 2005 | A1 |
20050152990 | Gower et al. | Jul 2005 | A1 |
20050191355 | Foss et al. | Sep 2005 | A1 |
20050211930 | Demeo et al. | Sep 2005 | A1 |
20050218397 | Tran | Oct 2005 | A1 |
20050218398 | Tran | Oct 2005 | A1 |
20050228351 | Bourgeois et al. | Oct 2005 | A1 |
20050229328 | Tran | Oct 2005 | A1 |
20050230822 | Tran | Oct 2005 | A1 |
20050231855 | Tran | Oct 2005 | A1 |
20050244484 | Flick et al. | Nov 2005 | A1 |
20050271743 | Burrell et al. | Dec 2005 | A1 |
20060057191 | Wellinghoff | Mar 2006 | A1 |
20060083777 | Burrell et al. | Apr 2006 | A1 |
20060083792 | Gillis et al. | Apr 2006 | A1 |
20060115541 | Gillis et al. | Jun 2006 | A1 |
20060127462 | Cowan et al. | Jun 2006 | A1 |
20060141015 | Tessier et al. | Jun 2006 | A1 |
20060145326 | Tran | Jul 2006 | A1 |
20060149182 | Addison et al. | Jul 2006 | A1 |
20060159732 | Greenhalgh et al. | Jul 2006 | A1 |
20060160448 | Abraham et al. | Jul 2006 | A1 |
20060198209 | Tran | Sep 2006 | A1 |
20060202382 | Lin | Sep 2006 | A1 |
20060204580 | Cheng et al. | Sep 2006 | A1 |
20060204581 | Cheng et al. | Sep 2006 | A1 |
20060204591 | Burrell et al. | Sep 2006 | A1 |
20060240067 | Chartier et al. | Oct 2006 | A1 |
20060260674 | Tran | Nov 2006 | A1 |
20060264796 | Flick et al. | Nov 2006 | A1 |
20060283567 | Bauer et al. | Dec 2006 | A1 |
20070003603 | Cornell et al. | Jan 2007 | A1 |
20070009586 | Cohen | Jan 2007 | A1 |
20070051366 | Hannsman et al. | Mar 2007 | A1 |
20070060691 | Kim | Mar 2007 | A1 |
20070087023 | Ismail et al. | Apr 2007 | A1 |
20070098806 | Ismail et al. | May 2007 | A1 |
20070100269 | Greenhalgh et al. | May 2007 | A1 |
20070122462 | Chandra et al. | May 2007 | A1 |
20070134307 | Robb et al. | Jun 2007 | A1 |
20070148449 | Winterhalter | Jun 2007 | A1 |
20070179522 | Flick et al. | Aug 2007 | A1 |
20070207335 | Karandikar et al. | Sep 2007 | A1 |
20070218298 | Terry | Sep 2007 | A1 |
20070243380 | Hayhurst et al. | Oct 2007 | A1 |
20070259196 | Ruhle et al. | Nov 2007 | A1 |
20070275043 | Bradford et al. | Nov 2007 | A1 |
20070286895 | Bowler et al. | Dec 2007 | A1 |
20070293799 | Yu et al. | Dec 2007 | A1 |
20070298064 | Koslow | Dec 2007 | A1 |
20080004559 | Riesinger | Jan 2008 | A1 |
20080009812 | Riesinger | Jan 2008 | A1 |
20080014286 | Gillis et al. | Jan 2008 | A1 |
20080033506 | Flick et al. | Feb 2008 | A1 |
20080053922 | Bumin et al. | Mar 2008 | A1 |
20080064997 | Flick et al. | Mar 2008 | A1 |
20080075650 | Djokic | Mar 2008 | A1 |
20080075860 | Djokic | Mar 2008 | A1 |
20080096449 | Bourgeois et al. | Apr 2008 | A1 |
20080102122 | Khanolkar et al. | May 2008 | A1 |
20080114279 | Flick et al. | May 2008 | A1 |
20080119773 | Flick et al. | May 2008 | A1 |
20080125687 | Flick et al. | May 2008 | A1 |
20080199536 | Terry | Aug 2008 | A1 |
20080199623 | Terry | Aug 2008 | A1 |
20080213394 | Ismail et al. | Sep 2008 | A1 |
20080233161 | Djokic | Sep 2008 | A1 |
20080239791 | Tran | Oct 2008 | A1 |
20080241229 | Li et al. | Oct 2008 | A1 |
20080241795 | Block et al. | Oct 2008 | A1 |
20080249453 | Effing et al. | Oct 2008 | A1 |
20080249485 | Effing et al. | Oct 2008 | A1 |
20080249486 | Effing et al. | Oct 2008 | A1 |
20080286346 | Effing et al. | Nov 2008 | A1 |
20080299160 | Agboh et al. | Dec 2008 | A1 |
20090000007 | Demeo et al. | Jan 2009 | A1 |
20090004474 | Luo | Jan 2009 | A1 |
20090035342 | Cornell et al. | Feb 2009 | A1 |
20090081312 | Block et al. | Mar 2009 | A1 |
20090114857 | Demeo et al. | May 2009 | A1 |
20090116277 | Tran | May 2009 | A1 |
20090130160 | Dugan | May 2009 | A1 |
20090214771 | Kang et al. | Aug 2009 | A1 |
20090220560 | Wan et al. | Sep 2009 | A1 |
20090247973 | Yeh et al. | Oct 2009 | A1 |
20090252861 | Tessier et al. | Oct 2009 | A1 |
20090259157 | Thomas | Oct 2009 | A1 |
20090263468 | Abbott et al. | Oct 2009 | A1 |
20090275906 | Abbas et al. | Nov 2009 | A1 |
20090293882 | Terry | Dec 2009 | A1 |
20100003296 | Cheng et al. | Jan 2010 | A1 |
20100015208 | Kershaw et al. | Jan 2010 | A1 |
20100021552 | Hayes et al. | Jan 2010 | A1 |
20100042034 | Riesinger | Feb 2010 | A1 |
20100044289 | Koslow | Feb 2010 | A1 |
20100055157 | Gunn | Mar 2010 | A1 |
20100073995 | Tran | Mar 2010 | A1 |
20100098949 | Burton et al. | Apr 2010 | A1 |
20100113871 | Franken et al. | May 2010 | A1 |
20100124861 | Wendler | May 2010 | A1 |
20100155692 | Tran | Jun 2010 | A1 |
20100196448 | Burd et al. | Aug 2010 | A1 |
20100221311 | Cohen | Sep 2010 | A1 |
20100221312 | Cohen | Sep 2010 | A1 |
20100233245 | Narayana | Sep 2010 | A1 |
20100233273 | Burton et al. | Sep 2010 | A1 |
20100262096 | Hall | Oct 2010 | A1 |
20100291174 | Barcikowski et al. | Nov 2010 | A1 |
20100291184 | Clark et al. | Nov 2010 | A1 |
20110034894 | Riesinger | Feb 2011 | A1 |
20110040289 | Cowan et al. | Feb 2011 | A1 |
20110052698 | Benoit et al. | Mar 2011 | A1 |
20110091557 | Buckley et al. | Apr 2011 | A1 |
20110110141 | Tran | May 2011 | A1 |
20110110999 | Bogana et al. | May 2011 | A1 |
20110115512 | Miller | May 2011 | A1 |
20110123597 | Cohen | May 2011 | A1 |
20110135846 | Seino et al. | Jun 2011 | A1 |
20110142898 | Fan | Jun 2011 | A1 |
20110152843 | Lundahl et al. | Jun 2011 | A1 |
20110171321 | Luchsinger et al. | Jul 2011 | A1 |
20110189287 | Abbott et al. | Aug 2011 | A1 |
20110232653 | Imashiro et al. | Sep 2011 | A1 |
20110262556 | Brooks et al. | Oct 2011 | A1 |
20110272619 | Wang et al. | Nov 2011 | A1 |
20110275513 | Tian et al. | Nov 2011 | A1 |
20110280928 | Cowan et al. | Nov 2011 | A1 |
20110306699 | Whang et al. | Dec 2011 | A1 |
20110313373 | Riesinger | Dec 2011 | A1 |
20120034432 | Cotton | Feb 2012 | A1 |
20120064138 | Beveridge et al. | Mar 2012 | A1 |
20120091429 | Tran | Apr 2012 | A1 |
20120094120 | Foss et al. | Apr 2012 | A1 |
20120107592 | Griesser et al. | May 2012 | A1 |
20120143157 | Riesinger | Jun 2012 | A1 |
20120164449 | Foss | Jun 2012 | A1 |
20120183674 | Bonn-Savage et al. | Jul 2012 | A1 |
20120202043 | Bonn-Savage et al. | Aug 2012 | A1 |
20120222826 | Foss | Sep 2012 | A1 |
20120276205 | Weissman et al. | Nov 2012 | A1 |
20120282321 | Cohen | Nov 2012 | A1 |
20120299175 | Tran | Nov 2012 | A1 |
20130052256 | Smith | Feb 2013 | A1 |
20130066288 | Lin | Mar 2013 | A1 |
20130122321 | Karandikar et al. | May 2013 | A1 |
20130152309 | Bray | Jun 2013 | A1 |
20130163310 | Tran | Jun 2013 | A1 |
20130197460 | Shaw et al. | Aug 2013 | A1 |
20130211308 | Wan et al. | Aug 2013 | A1 |
20130216598 | Wang et al. | Aug 2013 | A1 |
20130217649 | Woods | Aug 2013 | A1 |
20130231640 | Chen et al. | Sep 2013 | A1 |
Number | Date | Country |
---|---|---|
19722932 | Dec 1998 | DE |
10309558 | Sep 2004 | DE |
202005010978 | Oct 2005 | DE |
102005031711 | Jun 2007 | DE |
202008004240 | Jul 2008 | DE |
102007025714 | Dec 2008 | DE |
10 2007 049430 | Apr 2009 | DE |
10 2007 063294 | Jul 2009 | DE |
102009036302 | Feb 2011 | DE |
202010014723 | Nov 2011 | DE |
0306262 | Mar 1989 | EP |
1656914 | May 2006 | EP |
1666077 | Jun 2006 | EP |
1947167 | Jul 2008 | EP |
2140958 | Jan 2010 | EP |
2498829 | Sep 2012 | EP |
2401879 | Nov 2004 | GB |
0905341.4 | Mar 2009 | GB |
2476133 | Jun 2011 | GB |
1303971.4 | Aug 2013 | GB |
WO 9831402 | Jul 1998 | WO |
WO 0106047 | Jan 2001 | WO |
WO 0138615 | May 2001 | WO |
WO 0141819 | Jun 2001 | WO |
WO 03046273 | Jun 2003 | WO |
WO 2005018769 | Mar 2005 | WO |
WO 2006021155 | Mar 2006 | WO |
WO 2007029597 | Mar 2007 | WO |
WO 2007046806 | Apr 2007 | WO |
WO 2007078203 | Jul 2007 | WO |
WO 2008010199 | Jan 2008 | WO |
WO 2008024426 | Feb 2008 | WO |
WO 2008098420 | Aug 2008 | WO |
WO 2008100163 | Aug 2008 | WO |
WO 2008101417 | Aug 2008 | WO |
WO 2009141278 | Nov 2009 | WO |
WO 2010123392 | Oct 2010 | WO |
WO 2011073697 | Jun 2011 | WO |
WO 2011076203 | Jun 2011 | WO |
WO 2011101857 | Aug 2011 | WO |
WO 2012075658 | Jun 2012 | WO |
WO 2012106983 | Aug 2012 | WO |
WO 2012127326 | Sep 2012 | WO |
WO 2013123507 | Aug 2013 | WO |
WO 2013123509 | Aug 2013 | WO |
Entry |
---|
ohioline.osu.edu, ohio state, p. 1. |
http://www.m2polymer.com/html/super—absorbent—fibers.html; Oct. 17, 2008 (see provided copy). |
http://www.m2polymer.com/pdf/Tech%20Sheet—Oasis%20SAF%206mm—M2PT.pdf; Nov. 11, 2015. |
Number | Date | Country | |
---|---|---|---|
20140257221 A1 | Sep 2014 | US |