WO1994010957A1 - A method for the manufacturing of an absorbent structure and an absorbent article comprising an absorbent structure manufactured according to this method - Google Patents

A method for the manufacturing of an absorbent structure and an absorbent article comprising an absorbent structure manufactured according to this method Download PDF

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Publication number
WO1994010957A1
WO1994010957A1 PCT/SE1993/000975 SE9300975W WO9410957A1 WO 1994010957 A1 WO1994010957 A1 WO 1994010957A1 SE 9300975 W SE9300975 W SE 9300975W WO 9410957 A1 WO9410957 A1 WO 9410957A1
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WO
WIPO (PCT)
Prior art keywords
absorbent
absorbent article
fibres
layer
density
Prior art date
Application number
PCT/SE1993/000975
Other languages
French (fr)
Inventor
Eje Österdahl
Original Assignee
Mölnlycke AB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=20387840&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1994010957(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to SK654-95A priority Critical patent/SK282204B6/en
Priority to JP51201194A priority patent/JP3589462B2/en
Priority to DK94900340T priority patent/DK0773765T3/en
Priority to AT94900340T priority patent/ATE189594T1/en
Priority to DE69327854T priority patent/DE69327854T2/en
Application filed by Mölnlycke AB filed Critical Mölnlycke AB
Priority to EP94900340A priority patent/EP0773765B1/en
Priority to AU55360/94A priority patent/AU681870B2/en
Priority to PL93309009A priority patent/PL173293B1/en
Publication of WO1994010957A1 publication Critical patent/WO1994010957A1/en
Priority to NO951916A priority patent/NO305972B1/en
Priority to FI952409A priority patent/FI117467B/en
Priority to GR20000400651T priority patent/GR3032954T3/en

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Classifications

    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/425Cellulose series
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/15Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/28Polysaccharides or their derivatives
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H13/00Other non-woven fabrics
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/15Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/15203Properties of the article, e.g. stiffness or absorbency
    • A61F2013/15284Properties of the article, e.g. stiffness or absorbency characterized by quantifiable properties
    • A61F2013/15292Resistance, i.e. modulus or strength
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/15Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/15203Properties of the article, e.g. stiffness or absorbency
    • A61F2013/15284Properties of the article, e.g. stiffness or absorbency characterized by quantifiable properties
    • A61F2013/15357Stiffness, e.g. Taber rigidity
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/15Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/15203Properties of the article, e.g. stiffness or absorbency
    • A61F2013/15284Properties of the article, e.g. stiffness or absorbency characterized by quantifiable properties
    • A61F2013/15406Basis weight
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/15Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/15203Properties of the article, e.g. stiffness or absorbency
    • A61F2013/15284Properties of the article, e.g. stiffness or absorbency characterized by quantifiable properties
    • A61F2013/15422Density
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/15Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/15203Properties of the article, e.g. stiffness or absorbency
    • A61F2013/15284Properties of the article, e.g. stiffness or absorbency characterized by quantifiable properties
    • A61F2013/15463Absorbency
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/15Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/15203Properties of the article, e.g. stiffness or absorbency
    • A61F2013/15284Properties of the article, e.g. stiffness or absorbency characterized by quantifiable properties
    • A61F2013/15487Capillary properties, e.g. wicking
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/15Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/84Accessories, not otherwise provided for, for absorbent pads
    • A61F2013/8488Accessories, not otherwise provided for, for absorbent pads including testing apparatus

Definitions

  • the present invention relates to a method for manufacturing an absorbent structure in an absorbent article, such as a sanitary napkin, a tampon, a panty protector, an incontinence guard, a diaper, a bed protector, a wound or sore dressing, a saliva absorbent, and like articles.
  • an absorbent article such as a sanitary napkin, a tampon, a panty protector, an incontinence guard, a diaper, a bed protector, a wound or sore dressing, a saliva absorbent, and like articles.
  • absorbent articles of this kind are known to the art.
  • the absorbent bodies of such articles are typically produced by dry- defibering and fluffing cellulose pulp in roll, bale or sheet form for. instance, to form a pulp mat, sometimes admixed with so-called superabsorbents in the pulp mat, these superab ⁇ orbent ⁇ being polymers which are capable of absorbing many times their own weight of water or body fluid.
  • the pulp body is often compressed so as to enhance its fluid wicking ability and also in order to reduce the bulk of the pulp body and therewith obtain an article which is as compact as possible.
  • the absorbent body may also include other constituents, for instance constituents which will improve its fluid aquisition properties or its fluid- wicking properties, or to increase its coherent strength, i.e. its coherency, and its ability to withstand deformation in use.
  • rewctting i.e. the transference of body fluid that has already been absorbed back into contact with the wearer ' s skin as a result of external forces, for instance when the wearer sits down. It is generally desired that the surface of the article that lies proximal to the wearer will remain as dry as possible.
  • the article shall be thin and soft, so that it can be worn as discretely as possible.
  • the compressed absorbent body of the absorbent article is softened to achieve the desired softness.
  • One method to soften an absorbent sheet is described in European Patent Application EP 0 360 472, where the compressed absorbent material is worked between partially cutting rollers and thereby gaining softness. This method however leads among other things to decreased strength in the softened material.
  • Flash-dried fibres of paper pulp which may consist of thermomcchanical pulp, chemi-thermomechanical pulp CTMP, or chemical paper pulp, sulphite or sulphate pulp with a dry solids content of about 80%, is delivered by means of an air stream in a controlled flow to a forming head arranged above a forming wire and there formed into a web that has a surface weight of 300-1500 g/m2 and a density of 550-1000 kg/m3. Air is sucked away through a suction box placed beneath the wire. The moisture content in the process shall be 5-30%.
  • the web is pre-pressed to a density of 550-1000 kg/m3 in order to slightly reduce the bulk of the web, prior to the final pressing stage.
  • the pressed web thus has a mechanical strength which enables it to be rolled-up or handled in sheet form for storage and transportation purposes.
  • the web can be readily defibred and is intended to be converted into fluff for use in the manufacture of absorbent bodies or pads for diapers, sanitary napkins and like articles.
  • the object of the present invention is to provide in an absorbent article of the aforede scribed kind an absorbent structure which exhibits extremely good absorption properties, both with respect to its ability to quickly take up fluid and also its ability to spread the fluid throughout the material.
  • the material will preferably have low rewetting tendencies and will also be capable of being made very thin. It is also desirable, among other things from the aspect of flexibility, to be able to use both dry-formed roll pulp and conventional fluff pulp as a starting material and achieve equivalent article properties.
  • This object is achieved in accordance with the present invention by, in immediate conjunction with the manufacture of the absorbent article, compressing an air-laid web of cellulose fibres, subsequent to conventional defibcring and fluffing of the web, to a dry-formed sheet having a surface weight of between 30-2000 g/m2 and a first density of between 0.2-1 g/cm3, and then softening the sheet mechanically to a second density which is lower than the original density and therewith delaminating the sheet, so that the resultant structure forme a plurality of partially separated thin fibre layers which in themselves have a density corresponding to the first density.
  • Figure 1 illustrates the absorption properties of a dry-formed CTMP- material subsequent to being worked between rolls at different roll spacings. Conventionally formed and compressed pulp mats of CTMP- pulp and chemical pulp respectively were used as references.
  • Figure 2 illustrates the absorption properties of dry-formed CTMP- material subsequent to being softened. Conventionally formed and compressed mats comprised of CTMP-pulp and of chemical pulp respectively were used as references.
  • Figure 3 illustrates the absorption properties of a complete absorbent article manufactured with dry-formed CTMP in the core. Conventionally manufactured products of corresponding compositions were used as references.
  • Figure 4 illustrates the fluid aquisition time of a complete absorbent article manufactured with dry-formed CTMP in the core. Conventionally manufactured products of corresponding compositions were used as references.
  • Figure 5 illustrates the degree of utilization of a complete absorbent article manufactured with dry-formed CTMP in the core. Conventionally manufactured products of corresponding compositions were used as references.
  • Figure 6 illustrates the absorption properties of an absorbent structure produced from dry-formed CTMP, both with and without a superabsorbent admixture. Conventionally manufactured pulp cores both with and without a superabsorbent admixture were used as references.
  • Figure 7 illustrates the rewetting of a complete absorbent article produced with dry-formed CTMH in the core. Conventionally manufactured products of cor-responding compositions were used as references.
  • Figure 8 illustrates the respective rewetting of an unsoftened and a softened absorbent structure which had absorbed blood and which was produced with dry-formed CTMP in the core, both with and without a superabsorbent admixture.
  • Figure 9 illustrates the rewetting of a complete absorbent article which had absorbed blood and which was produced with dry-formed CTMP in the core. Conventionally manufactured products of corresponding composition were used as references.
  • Figures 10-14 illustrate schematically the composition of various exemplifying embodiments of ' ventive absorbent articles.
  • Figure 15 illustrates the structure of a cross section of the material in unsoftened condition.
  • Figure 16 illustrates the structure of a cross section of the material in softened condition.
  • important properties of a material used in the manufacture of a hygiene article are its absorbent capacity, absorption rate, fluid-dispersion capacity, drainage capacity, fluid retention capacity, rewetting tendency, softness and smoothness.
  • the fluids concerned are urine, menstruation blood, blood, fluid matter from wounds and sores, rinsing fluid and saliva.
  • the object of the present invention is to provide in an absorbent article, such as a sanitary napkin, tampon, panty protector, incontinence guard, diaper, bed protector, wound dressings, saliva absorbents and the like, an absorbent structure which exhibits highly effective absorption properties, both with regard to its fluid-aqui ⁇ ition rate and in its ability to disperse the fluid throughout the material.
  • the material will also preferably have low rewetting tendencies and capable of being made very thin.
  • Untreated, dry-formed roll pulp has very good absorption properties, fluid-wicking properties and swelling properties, and it has been found possible to use this material as an absorbent material directly in hygiene articles without defibering the material. In the case of certain absorbent articles, it is beneficial to soften the material in some way or another. A method of softening the material mechanically is described below. Conventional fluff pulp does not normally possess these properties. It is desirable, among other things from the aspect of flexibility, to be able to use both dry-formed roll pulp and conventional fluff pulp as starting materials and, nevertheless, achieve the same good properties as those achieved with a product manufactured from dry-formed roll pulp.
  • pulp for instance a wet-formed or dry-formed product manufactured from mechanical pulp or chemi-thermomcchanical pulp (CTMP) or a corresponding product manufactured from sulphite or sulphate pulp, so-called chemical cellulose pulp.
  • CMP chemi-thermomcchanical pulp
  • chemical cellulose pulp a product manufactured from sulphite or sulphate pulp
  • Cellulose fibres which have been stiffened chemically may also be used.
  • Curl value can be measured according to the method described by B.D. Jordan, N.G. Nguyen in Papper och Tra, 4/1986, page 313.
  • the material can be given a softness which renders the material liighly suitable for use as an absorbent material in the majority of hygiene articles, by working dry-formed roll pulp between rolls, for instance between corrugated rolls.
  • the material can be brought to different degrees of softness for different product applications, by working the material between different types of rolls, different patterns in the rolls and at different roll spacings.
  • Dry-formed roll pulp exhibits very good product properties when softened in this way, and the earlier mentioned good absorption properties are not influenced by the softening process to any great extent.
  • the material is delaminated in the softening process as illustrated in figures 15 and 16.
  • the unsoftened material has normally an even high density throughout the whole the thickness of the material (61).
  • the material is delaminated so as to form a plurality of partially separated (63), thin fibre layers (62).
  • Softening and delamination of the material reduces its total density to some extent, although the original density is essentially retained in each individual layer. Because a very high density is retained in the individual layers, the good fluid wicking properties of the material are retained despite the increase in bulk obtained in conjunction with the softening process.
  • the total bulk is increased by up to 300%, normally 1-100%, as a result of the softening process, depending on the method used and the extent to which the material is softened.
  • the aforesaid material softening method is given solely by way of example and that corresponding results can be achieved with the aid of other methods.
  • the material could eventually be softened by means of ultrasonic energy, microwaves, by moisturizing the material or with the aid of chemical additives.
  • Method 1 Absorption Properties Up an Inclined Plane
  • a rectangular test body was punched from the material and a line was drawn transversely across the test body at a point 11 cm from one short end of the body.
  • a fluid container was placed adjacent laboratory scales and both the scales and the container were adjusted to a horizontal position.
  • a plexiglass plate was placed on the scales at a 30_ slope, with one free edge of the plate extending slightly down into the container.
  • a line had been drawn transversely across the plate at a point 11 cm from the lower edge of said plate.
  • Test fluid (0.9% NaCl- solution) was poured into the container, until 20 mm of the plexiglass plate was located beneath the surface of the liquid.
  • test body was secured on the plexiglass plate so that the line drawn on the test body coincided with the line drawn on the plate while, at the same time, folding away the lower part of the test body so as to prevent it from coming into contact with the test liquid.
  • a clock was started at the same time as the test body was laid onto the plate, with the test body extended down into the solution to the same extent as the plate. The increase in weight of the test body with time was recorded.
  • test product was secured in a fixture.
  • Test fluid (0.9% NaCl-solution) was delivered to the wetting point of the product over a period of 60 minutes at the rate at which the fluid was absorbed.
  • the amount of fluid absorbed was measured continuously and the total amount of fluid absorbed by the product constitutes the utilized absorption capacity of the test product.
  • the test product was then placed in a fluid bath, in which it had the maximum opportunity of absorbing test fluid.
  • the test product was then again weighed and the total absorption capacity calculated.
  • the degree of utilization is constituted by the quotient between the utilized absorption capacity of the test product and the total absorption capacity.
  • sample fluid (0.9% NaCl-solution), each comprising 28 ml, were delivered at 20-minute intervals. The time measurement was continued until all fluid had been absorbed. The extent to which the fluid had dispersed in the diaper was noted after each batch. Subsequent to delivering the last batch of fluid, filter paper was placed over the wetting point and loaded with a weight of 1.1 kg for 15 seconds. The filter paper was weighed both before and after applying the load and rewetting was recorded.
  • a diaper intended for a given child weight range was weighed and then placed on a flat support surface.
  • An adapted quantity of test fluid (0.9% NaCl-solution, 100 ml for a diaper intended for a child weight range of 7-15 kg) was delivered to the wetting point of the diaper.
  • a further l ⁇ ml of fluid was delivered after 20 minutes.
  • a filter paper was placed over the wetting point and loaded with a weight of 1..1 kg for 15 seconds.
  • the filter paper was weighed both before and after applying the load and the result was recorded as a first rewetting instance.
  • another 100 ml of fluid was delivered and when all fluid had been absorbed, the procedure was repeated with a fresh filter paper and the result recorded as a second rewetting instance.
  • test body 65 x 200 mm, was punched from the material.
  • 5 ml test fluid (0.9% NaCl-solution) were delivered to the wetting point on the Lest body. Dispersion of the fluid was measured after about 30 minutes.
  • a further 5 ml of test fluid (0.9% NaCl-solution) were then delivered to the wetting point and fluid dispersion was measured after about a further 30 minutes.
  • eight filter papers were placed over the wetting point and loaded with a weight of 4.875 kg for 15 seconds. The filter papers were weighed both before and after applying the load and rewet ⁇ ng was recorded.
  • Softening With the intention of investigating how the material was affected at different softening roll spacings when softening the material, a material was tested under different softening conditions. For instance, in the case of a dry-formed CTMP-material having a surface weight of 900 g/m2 and a density of 0.63 g/cm3, a suitable roll spacing is 1.7-2.4 mm during the softening process. The material is not influenced to any great extent at roll ⁇ pacings which lie within this range.
  • Figure 1 illustrates the absorption properties at different roll spacings. The results were determined in accordance with Method 1.
  • a Material according to the invention roll spacing 1.7 mm.
  • D Material according to the invention roll spacing 2.0 mm, softened twice.
  • E Material according to the invention roll spacing 2.0 mm, softened four times.
  • F CTMP-pulp density 0J25 g/cm3.
  • G Chemical sulphate pulp density 0.125 g cm3.
  • test products were prepared in the form of conventional children's diapers which comprised a T-shaped absorbent body (T-core) and a rectangular absorbent body (R-core), where the rectangular absorbent body in the test products was manufactured from a CTMP- material in accordance with the invention.
  • T-core T-shaped absorbent body
  • R-core rectangular absorbent body
  • the T-shaped absorbent body (T-core) and the rectangular absorbent body (R-core) were comprised of conventional defibred CTMP and chemical pulp.
  • superabsorbent material in an absorbent body will influence the absorption properties of the body.
  • Superab ⁇ orbent material can be incorporated in the absorbent body in different ways, for instance it may be admixed with the body material, laid in layers in the body, or disposed in some other way. This admixture of superabsorbent material can be effected in conjunction with manufacturing the dry-formed material, although it may also be effected during some other part of the manufacturing process.
  • the absorption properties were compared with an inventive CTMP- material to which no superabsorbent material had been added and also with corresponding pulp cores comprised of conventional defibred CTMP and chemical pulp. The results of this comparison are shown in Figure 6. The results were determined in accordance with Method 1.
  • a Inventive material 350 g/m2.
  • Dry-formed roll pulp will normally have sufficient mat strength for the product applications intended here. If the network strength of certain product applications should be found insufficient, the network strength can be increased by reinforcing the structure in some suitable manner, by adding reinforcing fibres, binding fibres or binding agent to the cellulose fibre mixture. The network strength can also be increased by incorporating a reinforcing layer of, for instance, plastic, non-woven, not or threads in the absorbent structure, or by fastening a reinforcing layer or an outer sheet on one or both sides of the material.
  • a suitable density is 0.2-1.0 g/cm3, preferably 0.25-0.9 g/cm3 and most preferably 0.3-0.85 g/cm3.
  • a suitable surface weight is between 30-2000 g/m2, preferably 50-1500 g/m2 and most preferably 100-1000 g/cm2.
  • FIG 10 illustrates a diaper constructed in accordance with one embodiment of the invention.
  • the diaper includes, in a conventional manner, an absorbent body 11 which is enclosed between a fluid- permeable top sheet 12, which conveniently comprises a soft non- woven material, a perforated plastic film or the like and which is intended to lie proximal to the wearer in use, and a fluid-impermeable bottom sheet 13.
  • the sheets 12 and 13 have parts which extend beyond the absorbent body 11 and the sheets are joined together at these protruding parts.
  • the bottom sheet 13 is comprised of a suitable plastic material, for instance polyethylene. It will be understood, however, that other known materials can be used for the top and bottom sheets, within the scope of the invention.
  • the absorbent body is comprised of two or more layers, an upper aquisition layer 14 and one or two lower wicking layers and storage layers 15 and 16.
  • the inventive material can be used either as an aquisition layer 14, a wicking layer 15 or a storage layer 16 or as several of these layers.
  • Those layers in which inventive material is not used can include types of other materials, for instance conventional cellulose fibre material.
  • the purpose of the aquisition layer 14 is to rapidly receive a given quantity of fluid. This fluid shall solely be held loosely in the fibre structure and quickly drained therefrom.
  • the aquisition layer 14 is comprised of dry-formed material in accordance with the invention and is comprised of a relatively open fibre structure of relatively low density and contains 0-10% superabsorbent material.
  • the superabsorbent material in the aquisition layer 14 will preferably have a high gel strength, so that an open three-dimensional fibre structure will be retained in this layer after becoming wet.
  • a suitable density range for the aquisition layer 14 is 0.20-0.80 g/cm3.
  • a suitable surface weight range for the aquisition layer 14 is 50-1200 g m2.
  • the main purpose of the wicking layer 15 is to transport the fluid received in the aquisition layer 14 effectively to the storage layer 16 located beneath the wicking layer 15 and to ensure that the greatest possible part of the storage layer 16 is utilized for absorption purposes.
  • the wicking layer 15 therefore has a relatively low superabsorbent content.
  • a suitable superabsorbent content in the case of the wicking layer 15 is 0-20%, while a suitable density range is 0.25-1.0 g cm3.
  • a suitable surface weight range in the case of the wicking layer 15 is 50- 1500 g m2.
  • the purpose of the storage layer 16 is to absorb and bind the fluid which is dispersed to the storage layer 16 through the wicking layer 15.
  • the storage layer 16 may therefore have a relatively high superabsorbent content and a relatively high density. Suitable density values are 0.25-1.0 g/cm3, while a suitable superabsorbent content is 40-70%.
  • a suitable surface weight range in the case of the storage layer 16 is 100-1500 g/m2.
  • the wicking layer 15 and the storage layer 16 may optionally be combined to form a single layer.
  • the single layer will have a relatively high superabsorbent content and a relatively high density. Suitable density values are 0.25-1.0 g/cm3, while a suitable superabsorbent content is 20-70%.
  • a suitable surface weight range in the case of a combined wicking and storage layer is 100-2000 g m2.
  • the superabsorbent content of the layer can be varied throughout the product, so as to obtain a superabsorbent gradient in the depth, length and/or the breadth direction of the product.
  • the various layers may have different forms and sizes.
  • the absorbent structure is combined with some form of elastication, inter alia in the crotch region of the product, in order to improve product efficiency.
  • FIG 11 illustrates an exemplifying embodiment of an inventive sanitary napkin.
  • the napkin comprises, in a conventional manner, an absorbent body 21 which is enclosed between a fluid-permeable top sheet 22, which is suitably comprised of perforated plastic film or like material and which lies proximal to the wearer in use, and a fluid- impermeable bottom sheet 23.
  • a thin fluid-permeable layer 27, for instance of non- woven material, may be placed between the absorbent body 21 and the top sheet 22.
  • the sheets 22 and 23 have parts which protrude beyond the absorbent body 21 and the sheets are mutually joined at these protruding parts.
  • the bottom sheet 23 is comprised of a suitable plastic material, for instance polyethylene. It will be understood, however, that other known materials may be used for the top and the bottom sheets within the scope of the invention.
  • the absorbent body 21 is comprised of one single layer. This layer may consist of a dry-formed material according to the invention which contains from 0-10% superabsorbent material. A suitable density range in the case of the absorbent body 21 is 0.6-0.9 g cm3, while a suitable surface weight is 200-300 g/m2. When the absorbent body is comprised of a CTMP-material or some other material having a yellowish or brownish colour, a covering layer of chemical pulp white in colour may be applied to the top of the absorbent body.
  • Figure 12 illustrates an exemplifying embodiment of an inventive tampon.
  • the tampon is comprised of an inventive absorbent material which has been rolled to a cylinder- like form 31.
  • a string 38 is placed in the centre of the cylinder 31, in a conventional manner, and the cylinder 1 is compressed to the desired thickness and shape, in a
  • the absorbent material Prior to being compressed and shaped, the absorbent material will suitably have a density range of 0.4-0.9 g/cm3 and a surface weight of 200-600 g/m2.
  • FIG 13 illustrates an exemplifying embodiment of an inventive wound or sore dressing.
  • the dressing includes, in a conventional manner, an absorbent body 41 which is enclosed between a fluid- permeable top sheet 42, which is suitably comprised of a soft non- woven material, a perforated plastic film or the like, and which is intended to lie proximal to the wearer in use, and a fluid-repellent bottom sheet 43.
  • the sheets 42 and 43 have parts which protrude beyond the absorbent body 41 and are joined together at these protruding parts.
  • the bottom sheet 43 is comprised of a suitable fluid- repellent material, for instance a non- woven material that has been made hydrophobic. It will be understood, however, that the top and bottom sheets may comprise other known materials, within the scope of the invention.
  • the absorbent body 41 is comprised of only one single layer.
  • This layer may consist of inventive dry-formed material and may be constructed with a relatively open fibre structure of relatively low density and with a superabsorbent content of 0-10%.
  • a suitable density range in respect of the absorbent body 41 is 0.20-0.50 g/cm3 and a suitable surface weight is 200-700 g/m2.
  • FIG 14 illustrates an exemplifying embodiment of an inventive saliva absorbent.
  • the saliva absorbent includes, in a conventional manner, an absorbent body 51 which is enclosed between a fluid- permeable top sheet 52, which is suitably comprised of a perforated plastic film or like material and which is intended to lie proximal to the wearer when used, and a fluid-impermeable bottom sheet 53.
  • the bottom sheet 53 is comprised of a suitable plastic material, for instance polyethylene. It will be understood, however, that the top sheet 52 and the bottom sheet 53 may be comprised of other known materials within the scope of the invention.
  • the absorbent body 51 is comprised solely of one single layer.
  • This layer may be comprised of inventive dry-formed material and has a relatively high density and a superabsorbent content of 20-70%.
  • a suitable density range in respect of the absorbent body 51 is 0.40-0.80 g/cm3.

Abstract

A method for manufacturing an absorbent structure in an absorbent article, such as a sanitary napkin, a tampon, a panty protector, an incontinence guard, a diaper, a bed protector, a wound or sore dressing, a saliva absorbent and like article. The absorbent structure includes a dry-formed sheet which includes cellulose fibres and which has a density of between 0.2-1 g/cm3 and a surface weight between 30-2000 g/m2. The sheet is formed by compressing a web of cellulose fibres and is produced in immediate conjunction with the manufacture of an absorbent article of the aforesaid kind, after conventional defibration and fluffing. The material is softened prior to being used as an absorbent material. The material has good fluid wicking properties and swelling properties effective for the function of the product. A high degree of surface dryness is obtained, among other things. In addition to cellulose fibres, the absorbent structure may also include superabsorbent material and/or binding fibres, among other things. The pulp mat is very thin, therewith obviating the need to further compress the mat in the product.

Description

A METHOD FOR THE MANUFACTURING OF AN ABSORBENT STRUCTURE AND AN ABSORBENT ARTICLE COMPRISING AN ABSORBENT STRUCTURE MANUFACTURED ACCORDING TO THIS METHOD.
Background
The present invention relates to a method for manufacturing an absorbent structure in an absorbent article, such as a sanitary napkin, a tampon, a panty protector, an incontinence guard, a diaper, a bed protector, a wound or sore dressing, a saliva absorbent, and like articles.
Many types of absorbent articles of this kind are known to the art. The absorbent bodies of such articles are typically produced by dry- defibering and fluffing cellulose pulp in roll, bale or sheet form for. instance, to form a pulp mat, sometimes admixed with so-called superabsorbents in the pulp mat, these superabβorbentβ being polymers which are capable of absorbing many times their own weight of water or body fluid.
The pulp body is often compressed so as to enhance its fluid wicking ability and also in order to reduce the bulk of the pulp body and therewith obtain an article which is as compact as possible.
The absorbent body may also include other constituents, for instance constituents which will improve its fluid aquisition properties or its fluid- wicking properties, or to increase its coherent strength, i.e. its coherency, and its ability to withstand deformation in use.
One serious drawback with products of this nature is found in the total absorption capacity of the articles and also in the fact that the articles will often leak long before their total absorption capacity has been fully utilized. Among other things, this is because the body fluid discharged by the wearer is unable to penetrate into the absorption material and to spread to hitherto unused areas of the article quickly enough, but instead leaks from the sides of the sanitary napkin, diaper or incontinence guard. The ability of the materials used in the article to disperse the absorbed fluid throughout the entire absorbent body is thus highly important.
Another problem resides in so-called rewctting, i.e. the transference of body fluid that has already been absorbed back into contact with the wearer's skin as a result of external forces, for instance when the wearer sits down. It is generally desired that the surface of the article that lies proximal to the wearer will remain as dry as possible.
Another desideratum with regard to the majority of hygiene products is that the article shall be thin and soft, so that it can be worn as discretely as possible. For some purposes the compressed absorbent body of the absorbent article is softened to achieve the desired softness. One method to soften an absorbent sheet is described in European Patent Application EP 0 360 472, where the compressed absorbent material is worked between partially cutting rollers and thereby gaining softness. This method however leads among other things to decreased strength in the softened material.
It is known from International Patent Application WO 90/05808 to produce a pulp web which is later deflbred, so-called dry-formed roll pulp. Flash-dried fibres of paper pulp, which may consist of thermomcchanical pulp, chemi-thermomechanical pulp CTMP, or chemical paper pulp, sulphite or sulphate pulp with a dry solids content of about 80%, is delivered by means of an air stream in a controlled flow to a forming head arranged above a forming wire and there formed into a web that has a surface weight of 300-1500 g/m2 and a density of 550-1000 kg/m3. Air is sucked away through a suction box placed beneath the wire. The moisture content in the process shall be 5-30%.
The web is pre-pressed to a density of 550-1000 kg/m3 in order to slightly reduce the bulk of the web, prior to the final pressing stage. The pressed web thus has a mechanical strength which enables it to be rolled-up or handled in sheet form for storage and transportation purposes. The web can be readily defibred and is intended to be converted into fluff for use in the manufacture of absorbent bodies or pads for diapers, sanitary napkins and like articles. Sn-rηpiflj-y g the Invention
The object of the present invention is to provide in an absorbent article of the aforede scribed kind an absorbent structure which exhibits extremely good absorption properties, both with respect to its ability to quickly take up fluid and also its ability to spread the fluid throughout the material. The material will preferably have low rewetting tendencies and will also be capable of being made very thin. It is also desirable, among other things from the aspect of flexibility, to be able to use both dry-formed roll pulp and conventional fluff pulp as a starting material and achieve equivalent article properties.
This object is achieved in accordance with the present invention by, in immediate conjunction with the manufacture of the absorbent article, compressing an air-laid web of cellulose fibres, subsequent to conventional defibcring and fluffing of the web, to a dry-formed sheet having a surface weight of between 30-2000 g/m2 and a first density of between 0.2-1 g/cm3, and then softening the sheet mechanically to a second density which is lower than the original density and therewith delaminating the sheet, so that the resultant structure forme a plurality of partially separated thin fibre layers which in themselves have a density corresponding to the first density.
Brief Description of tha Drawings
The invention will now be described in more detail with reference to a number of exemplifying embodiments thereof and also with reference to the accompanying drawings, in which:
Figure 1 illustrates the absorption properties of a dry-formed CTMP- material subsequent to being worked between rolls at different roll spacings. Conventionally formed and compressed pulp mats of CTMP- pulp and chemical pulp respectively were used as references.
Figure 2 illustrates the absorption properties of dry-formed CTMP- material subsequent to being softened. Conventionally formed and compressed mats comprised of CTMP-pulp and of chemical pulp respectively were used as references. Figure 3 illustrates the absorption properties of a complete absorbent article manufactured with dry-formed CTMP in the core. Conventionally manufactured products of corresponding compositions were used as references.
Figure 4 illustrates the fluid aquisition time of a complete absorbent article manufactured with dry-formed CTMP in the core. Conventionally manufactured products of corresponding compositions were used as references.
Figure 5 illustrates the degree of utilization of a complete absorbent article manufactured with dry-formed CTMP in the core. Conventionally manufactured products of corresponding compositions were used as references.
Figure 6 illustrates the absorption properties of an absorbent structure produced from dry-formed CTMP, both with and without a superabsorbent admixture. Conventionally manufactured pulp cores both with and without a superabsorbent admixture were used as references.
Figure 7 illustrates the rewetting of a complete absorbent article produced with dry-formed CTMH in the core. Conventionally manufactured products of cor-responding compositions were used as references.
Figure 8 illustrates the respective rewetting of an unsoftened and a softened absorbent structure which had absorbed blood and which was produced with dry-formed CTMP in the core, both with and without a superabsorbent admixture.
Figure 9 illustrates the rewetting of a complete absorbent article which had absorbed blood and which was produced with dry-formed CTMP in the core. Conventionally manufactured products of corresponding composition were used as references. Figures 10-14 illustrate schematically the composition of various exemplifying embodiments of' ventive absorbent articles.
Figure 15 illustrates the structure of a cross section of the material in unsoftened condition.
Figure 16 illustrates the structure of a cross section of the material in softened condition.
Description pt the Invention
As before mentioned, important properties of a material used in the manufacture of a hygiene article are its absorbent capacity, absorption rate, fluid-dispersion capacity, drainage capacity, fluid retention capacity, rewetting tendency, softness and smoothness.
The fluids concerned are urine, menstruation blood, blood, fluid matter from wounds and sores, rinsing fluid and saliva.
The object of the present invention is to provide in an absorbent article, such as a sanitary napkin, tampon, panty protector, incontinence guard, diaper, bed protector, wound dressings, saliva absorbents and the like, an absorbent structure which exhibits highly effective absorption properties, both with regard to its fluid-aquiθition rate and in its ability to disperse the fluid throughout the material. The material will also preferably have low rewetting tendencies and capable of being made very thin.
Untreated, dry-formed roll pulp has very good absorption properties, fluid-wicking properties and swelling properties, and it has been found possible to use this material as an absorbent material directly in hygiene articles without defibering the material. In the case of certain absorbent articles, it is beneficial to soften the material in some way or another. A method of softening the material mechanically is described below. Conventional fluff pulp does not normally possess these properties. It is desirable, among other things from the aspect of flexibility, to be able to use both dry-formed roll pulp and conventional fluff pulp as starting materials and, nevertheless, achieve the same good properties as those achieved with a product manufactured from dry-formed roll pulp.
This is achieved with the aid of the present invention, by compressing an air-laid web of cellulose fibres in immediate conjunction with the manufacture of said absorbent article and subsequent to conventional defibration and fluffing, into a dry-formed sheet having a surface weight of between 30-2000 g/m2 and a first density of between 0.2-1.0 g/cm3, and softening the sheet mechanically to a second density which is lower than the first density and herewith delaminate the sheet so that the structure forms a plurality of partially separated thin fibre layers which in themselves have a density which corresponds to the first density.
When practicing the present invention using conventional defibration and fluffing, there may be used different kinds of pulp, for instance a wet-formed or dry-formed product manufactured from mechanical pulp or chemi-thermomcchanical pulp (CTMP) or a corresponding product manufactured from sulphite or sulphate pulp, so-called chemical cellulose pulp. Cellulose fibres which have been stiffened chemically may also be used.
In the case of certain absorbent articles, it is suitable to soften the material used in some way or another. A method of softening the material mechanically is described below.
Cellulose pulp fibres have a so-called curl value which defines the degree of crookedness of the fibre. Curl value can be measured according to the method described by B.D. Jordan, N.G. Nguyen in Papper och Tra, 4/1986, page 313.
Softening of the Material
The material can be given a softness which renders the material liighly suitable for use as an absorbent material in the majority of hygiene articles, by working dry-formed roll pulp between rolls, for instance between corrugated rolls. The material can be brought to different degrees of softness for different product applications, by working the material between different types of rolls, different patterns in the rolls and at different roll spacings.
Dry-formed roll pulp exhibits very good product properties when softened in this way, and the earlier mentioned good absorption properties are not influenced by the softening process to any great extent.
The material is delaminated in the softening process as illustrated in figures 15 and 16. The unsoftened material has normally an even high density throughout the whole the thickness of the material (61). As a result of the softening process the material is delaminated so as to form a plurality of partially separated (63), thin fibre layers (62). Softening and delamination of the material reduces its total density to some extent, although the original density is essentially retained in each individual layer. Because a very high density is retained in the individual layers, the good fluid wicking properties of the material are retained despite the increase in bulk obtained in conjunction with the softening process. The total bulk is increased by up to 300%, normally 1-100%, as a result of the softening process, depending on the method used and the extent to which the material is softened.
It will be understood that the aforesaid material softening method is given solely by way of example and that corresponding results can be achieved with the aid of other methods. For instance, the material could eventually be softened by means of ultrasonic energy, microwaves, by moisturizing the material or with the aid of chemical additives.
Investigation of Material Properties
The test equipment described below was used to evaluate the absorption properties.
Method 1. Absorption Properties Up an Inclined Plane A rectangular test body was punched from the material and a line was drawn transversely across the test body at a point 11 cm from one short end of the body. A fluid container was placed adjacent laboratory scales and both the scales and the container were adjusted to a horizontal position. A plexiglass plate was placed on the scales at a 30_ slope, with one free edge of the plate extending slightly down into the container. A line had been drawn transversely across the plate at a point 11 cm from the lower edge of said plate. Test fluid (0.9% NaCl- solution) was poured into the container, until 20 mm of the plexiglass plate was located beneath the surface of the liquid. The test body was secured on the plexiglass plate so that the line drawn on the test body coincided with the line drawn on the plate while, at the same time, folding away the lower part of the test body so as to prevent it from coming into contact with the test liquid. A clock was started at the same time as the test body was laid onto the plate, with the test body extended down into the solution to the same extent as the plate. The increase in weight of the test body with time was recorded.
Method 2. Measuring Absorption Capacity and Degree of Utilization
A test product was secured in a fixture. Test fluid (0.9% NaCl-solution) was delivered to the wetting point of the product over a period of 60 minutes at the rate at which the fluid was absorbed. The amount of fluid absorbed was measured continuously and the total amount of fluid absorbed by the product constitutes the utilized absorption capacity of the test product. The test product was then placed in a fluid bath, in which it had the maximum opportunity of absorbing test fluid. The test product was then again weighed and the total absorption capacity calculated. The degree of utilization is constituted by the quotient between the utilized absorption capacity of the test product and the total absorption capacity.
Method 3. Determining Rewetting. Fluid Wicking and Aouisition Time
Four batches of sample fluid (0.9% NaCl-solution), each comprising 28 ml, were delivered at 20-minute intervals. The time measurement was continued until all fluid had been absorbed. The extent to which the fluid had dispersed in the diaper was noted after each batch. Subsequent to delivering the last batch of fluid, filter paper was placed over the wetting point and loaded with a weight of 1.1 kg for 15 seconds. The filter paper was weighed both before and after applying the load and rewetting was recorded.
Method 4. Dfttermininr Rewetting
A diaper intended for a given child weight range was weighed and then placed on a flat support surface. An adapted quantity of test fluid (0.9% NaCl-solution, 100 ml for a diaper intended for a child weight range of 7-15 kg) was delivered to the wetting point of the diaper. A further lϋϋ ml of fluid was delivered after 20 minutes. When all fluid had been absorbed, a filter paper was placed over the wetting point and loaded with a weight of 1..1 kg for 15 seconds. The filter paper was weighed both before and after applying the load and the result was recorded as a first rewetting instance. After a further 20 minutes, another 100 ml of fluid was delivered and when all fluid had been absorbed, the procedure was repeated with a fresh filter paper and the result recorded as a second rewetting instance.
Method 5. Determining Blood Absorption
A test body, 65 x 200 mm, was punched from the material. 5 ml test fluid (0.9% NaCl-solution) were delivered to the wetting point on the Lest body. Dispersion of the fluid was measured after about 30 minutes. A further 5 ml of test fluid (0.9% NaCl-solution) were then delivered to the wetting point and fluid dispersion was measured after about a further 30 minutes. Subsequent to the last delivery, eight filter papers were placed over the wetting point and loaded with a weight of 4.875 kg for 15 seconds. The filter papers were weighed both before and after applying the load and rewetϋng was recorded.
Test Results
Softening With the intention of investigating how the material was affected at different softening roll spacings when softening the material, a material was tested under different softening conditions. For instance, in the case of a dry-formed CTMP-material having a surface weight of 900 g/m2 and a density of 0.63 g/cm3, a suitable roll spacing is 1.7-2.4 mm during the softening process. The material is not influenced to any great extent at roll βpacings which lie within this range. Figure 1 illustrates the absorption properties at different roll spacings. The results were determined in accordance with Method 1.
A Material according to the invention, roll spacing 1.7 mm.
B Material according to the invention, roll spacing 2.0 mm.
C Material according to the invention, roll spacing 2.4 mm.
D Material according to the invention, roll spacing 2.0 mm, softened twice. E Material according to the invention, roll spacing 2.0 mm, softened four times. F CTMP-pulp, density 0J25 g/cm3. G Chemical sulphate pulp, density 0.125 g cm3.
Absorption Properties of Absorbent Structures
The absorption properties of an inventive CTMP-material having a surface weight of 900 g/m2 and a density of 0.63 g/cm3 compared with those of corresponding pulp cores produced from conventionally defibred and web-formed CTMP and corresponding chemical pulp are shown in Figure 2. In the absence of superabsorbent material, the absorption capacity is about 9 g of fluid for each gram of absorbent material. The results were determined in accordance with Method 1. A Material according to the invention. B CTMP-pulp, density 0J25 g/cm3. C Chemical sulphate pulp, density 0.125 g/cm3.
Product Properties of a Complete Absorbent Article
With the intention of studying other properties of complete absorbent articles, test products were prepared in the form of conventional children's diapers which comprised a T-shaped absorbent body (T-core) and a rectangular absorbent body (R-core), where the rectangular absorbent body in the test products was manufactured from a CTMP- material in accordance with the invention. In the conventional products, the T-shaped absorbent body (T-core) and the rectangular absorbent body (R-core) were comprised of conventional defibred CTMP and chemical pulp.
Measuring the Absorption Capacity
Products which comprised an inventive CTMP-material exhibited an absorption in grams which was equal to the reference products having corresponding pulp cores comprised of conventionally defibred and web- formed CTMP and chemical pulp. The results are set forth in Figure 3. The results were determined in accordance with Method 2. A Reference diaper Libero Girl. B Reference diaper Libero Boy. C Child diaper comprising inventive material.
Measuring Fluid Aquisition Time
Products in which the R-core comprised an inventive CTMP-material exhibited a shorter fluid aquisition time than the reference product. This implies that an inventive CTMP-material in the R-core is able to drain the T-core more effectively. The results are set forth in Figure 4. The results were determined in accordance with Method 3. A Reference diaper Libero Girl. B Reference diaper Libero Boy. C Child diaper comprising inventive material.
Measuring the Utilization of the Absorbent Body
A comparison between the degree of utilization of the absorbent body in an absorbent article which contained an inventive CTMP-material and a corresponding absorbent article which contained conventional CTMP and chemical pulp showed that the degree of utilization is about equal, although slightly on the plus side for an inventive CTMP- material. The results are set forth in Figure 5. The results were determined in accordance with Method 2. A Reference diaper Libero Girl. B Reference diaper Libero Boy.
C Child diaper comprising inventive material.
Admixing Superabsorbent Material
The presence of superabsorbent material in an absorbent body will influence the absorption properties of the body. Superabβorbent material can be incorporated in the absorbent body in different ways, for instance it may be admixed with the body material, laid in layers in the body, or disposed in some other way. This admixture of superabsorbent material can be effected in conjunction with manufacturing the dry-formed material, although it may also be effected during some other part of the manufacturing process. The absorption properties were compared with an inventive CTMP- material to which no superabsorbent material had been added and also with corresponding pulp cores comprised of conventional defibred CTMP and chemical pulp. The results of this comparison are shown in Figure 6. The results were determined in accordance with Method 1. A Chemical sulphate pulp containing 30% superabsorbent and having a density of 0.125 g/cm3. B Inventive material containing 30% superabsorbent. C Reference diaper containing 30% superabsorbent. D Inventive material containing no superabsorbent.
Measurements of Rewettinp
Products which comprised an inventive CTMP-material in the R-core exhibited better rewetting values than the reference product. This also implies that an inventive CTMP-material in the R-core is able to drain the T-core more effectively. The results are set forth in Figure 7. The results were determined in accordance with Method 4. A Reference diaper Libero Girl. B Reference diaper Libero Boy. C Child diaper comprising inventive material.
Measurements of Rewetting. Specific for Blood Absorption In the case of blood absorption, products comprising an inventive softened CTMP-material showed better rewetting values than non- softened products. The results also showed that in respect of blood absorption products which lacked superabsorbent material exhibited lower rewetting values than material which contained superabsorbent material. Material which lacks superabsorbent material also disperses blood much more effectively. The results are set forth in Figures 8 and 9. The reference products comprised two different products frequently found on the market. The results were determined in accordance with Method 5. The prerequisites for this effect are that at least one layer of the pulp mat is free from superabsorbent material, and this does not therefore exclude the presence of such material in other parts of the absorbent article.
Figure 8
A Inventive material 350 g/m2.
B Inventive material 350 g/m2, softened.
C Inventive material 350 g/m2 + 5% superabsorbent.
D Inventive material 350 g/m2 + 5% superabsorbent, softened.
Figure 9
A Reference product 1.
B Reference product 2.
C Product containing inventive material.
Network Strength
Dry-formed roll pulp will normally have sufficient mat strength for the product applications intended here. If the network strength of certain product applications should be found insufficient, the network strength can be increased by reinforcing the structure in some suitable manner, by adding reinforcing fibres, binding fibres or binding agent to the cellulose fibre mixture. The network strength can also be increased by incorporating a reinforcing layer of, for instance, plastic, non-woven, not or threads in the absorbent structure, or by fastening a reinforcing layer or an outer sheet on one or both sides of the material.
Density and Surface Weight The softened pulp mat is still very thin, and consequently it is unnecessary in many cases to further compress the mat prior to its use in an absorbent article. A suitable density is 0.2-1.0 g/cm3, preferably 0.25-0.9 g/cm3 and most preferably 0.3-0.85 g/cm3. A suitable surface weight is between 30-2000 g/m2, preferably 50-1500 g/m2 and most preferably 100-1000 g/cm2. When calculating the density, the thickness of the material was measured with the aid of a Mitutoyo thickness meter.
Description of a First Exemplifying Embodiment
Figure 10 illustrates a diaper constructed in accordance with one embodiment of the invention. The diaper includes, in a conventional manner, an absorbent body 11 which is enclosed between a fluid- permeable top sheet 12, which conveniently comprises a soft non- woven material, a perforated plastic film or the like and which is intended to lie proximal to the wearer in use, and a fluid-impermeable bottom sheet 13. The sheets 12 and 13 have parts which extend beyond the absorbent body 11 and the sheets are joined together at these protruding parts. The bottom sheet 13 is comprised of a suitable plastic material, for instance polyethylene. It will be understood, however, that other known materials can be used for the top and bottom sheets, within the scope of the invention.
The absorbent body is comprised of two or more layers, an upper aquisition layer 14 and one or two lower wicking layers and storage layers 15 and 16. The inventive material can be used either as an aquisition layer 14, a wicking layer 15 or a storage layer 16 or as several of these layers. Those layers in which inventive material is not used can include types of other materials, for instance conventional cellulose fibre material.
The purpose of the aquisition layer 14 is to rapidly receive a given quantity of fluid. This fluid shall solely be held loosely in the fibre structure and quickly drained therefrom. The aquisition layer 14 is comprised of dry-formed material in accordance with the invention and is comprised of a relatively open fibre structure of relatively low density and contains 0-10% superabsorbent material. The superabsorbent material in the aquisition layer 14 will preferably have a high gel strength, so that an open three-dimensional fibre structure will be retained in this layer after becoming wet. A suitable density range for the aquisition layer 14 is 0.20-0.80 g/cm3. A suitable surface weight range for the aquisition layer 14 is 50-1200 g m2.
The main purpose of the wicking layer 15 is to transport the fluid received in the aquisition layer 14 effectively to the storage layer 16 located beneath the wicking layer 15 and to ensure that the greatest possible part of the storage layer 16 is utilized for absorption purposes. The wicking layer 15 therefore has a relatively low superabsorbent content. A suitable superabsorbent content in the case of the wicking layer 15 is 0-20%, while a suitable density range is 0.25-1.0 g cm3. A suitable surface weight range in the case of the wicking layer 15 is 50- 1500 g m2.
The purpose of the storage layer 16 is to absorb and bind the fluid which is dispersed to the storage layer 16 through the wicking layer 15. The storage layer 16 may therefore have a relatively high superabsorbent content and a relatively high density. Suitable density values are 0.25-1.0 g/cm3, while a suitable superabsorbent content is 40-70%. A suitable surface weight range in the case of the storage layer 16 is 100-1500 g/m2.
The wicking layer 15 and the storage layer 16 may optionally be combined to form a single layer. In this case, the single layer will have a relatively high superabsorbent content and a relatively high density. Suitable density values are 0.25-1.0 g/cm3, while a suitable superabsorbent content is 20-70%. A suitable surface weight range in the case of a combined wicking and storage layer is 100-2000 g m2.
When the wicking layer 15 and the storage layer 16 are combined in a single layer, the superabsorbent content of the layer can be varied throughout the product, so as to obtain a superabsorbent gradient in the depth, length and/or the breadth direction of the product. The various layers may have different forms and sizes. Normally, the absorbent structure is combined with some form of elastication, inter alia in the crotch region of the product, in order to improve product efficiency.
Description of a Second Exemplifying Embodimen
Figure 11 illustrates an exemplifying embodiment of an inventive sanitary napkin. The napkin comprises, in a conventional manner, an absorbent body 21 which is enclosed between a fluid-permeable top sheet 22, which is suitably comprised of perforated plastic film or like material and which lies proximal to the wearer in use, and a fluid- impermeable bottom sheet 23. A thin fluid-permeable layer 27, for instance of non- woven material, may be placed between the absorbent body 21 and the top sheet 22. The sheets 22 and 23 have parts which protrude beyond the absorbent body 21 and the sheets are mutually joined at these protruding parts. The bottom sheet 23 is comprised of a suitable plastic material, for instance polyethylene. It will be understood, however, that other known materials may be used for the top and the bottom sheets within the scope of the invention.
The absorbent body 21 is comprised of one single layer. This layer may consist of a dry-formed material according to the invention which contains from 0-10% superabsorbent material. A suitable density range in the case of the absorbent body 21 is 0.6-0.9 g cm3, while a suitable surface weight is 200-300 g/m2. When the absorbent body is comprised of a CTMP-material or some other material having a yellowish or brownish colour, a covering layer of chemical pulp white in colour may be applied to the top of the absorbent body.
Description of a Third Exemplifying Embodiment
Figure 12 illustrates an exemplifying embodiment of an inventive tampon. The tampon is comprised of an inventive absorbent material which has been rolled to a cylinder- like form 31. In conjunction with rolling the absorbent material into its cylindrical shape, a string 38 is placed in the centre of the cylinder 31, in a conventional manner, and the cylinder 1 is compressed to the desired thickness and shape, in a
1 G conventional manner. Prior to being compressed and shaped, the absorbent material will suitably have a density range of 0.4-0.9 g/cm3 and a surface weight of 200-600 g/m2.
Description of a Fourth Exemplifying Embodiment
Figure 13 illustrates an exemplifying embodiment of an inventive wound or sore dressing. The dressing includes, in a conventional manner, an absorbent body 41 which is enclosed between a fluid- permeable top sheet 42, which is suitably comprised of a soft non- woven material, a perforated plastic film or the like, and which is intended to lie proximal to the wearer in use, and a fluid-repellent bottom sheet 43. The sheets 42 and 43 have parts which protrude beyond the absorbent body 41 and are joined together at these protruding parts. The bottom sheet 43 is comprised of a suitable fluid- repellent material, for instance a non- woven material that has been made hydrophobic. It will be understood, however, that the top and bottom sheets may comprise other known materials, within the scope of the invention.
The absorbent body 41 is comprised of only one single layer. This layer may consist of inventive dry-formed material and may be constructed with a relatively open fibre structure of relatively low density and with a superabsorbent content of 0-10%. A suitable density range in respect of the absorbent body 41 is 0.20-0.50 g/cm3 and a suitable surface weight is 200-700 g/m2.
Description of a Fifth Exemplifying Embodiment
Figure 14 illustrates an exemplifying embodiment of an inventive saliva absorbent. The saliva absorbent includes, in a conventional manner, an absorbent body 51 which is enclosed between a fluid- permeable top sheet 52, which is suitably comprised of a perforated plastic film or like material and which is intended to lie proximal to the wearer when used, and a fluid-impermeable bottom sheet 53. The bottom sheet 53 is comprised of a suitable plastic material, for instance polyethylene. It will be understood, however, that the top sheet 52 and the bottom sheet 53 may be comprised of other known materials within the scope of the invention.
The absorbent body 51 is comprised solely of one single layer. This layer may be comprised of inventive dry-formed material and has a relatively high density and a superabsorbent content of 20-70%. A suitable density range in respect of the absorbent body 51 is 0.40-0.80 g/cm3.
It will be understood that the invention is not restricted to the illustrated and described exemplifying embodiments thereof and that other embodiments arc conceivable within the scope of the following Claims.

Claims

_______B_S.
1. A method of producing an absorbent structure in an absorbent article, such as a diaper, sanitary napkin, panty protector, incontinence guard, bed protector, wound or sore dressing, saliva absorbent and the like, characterized in that an air-laid web of cellulose fibres is compressed into a dry-formed sheet having a first density of between 0.2-1.0 g/cm3 and that the compressed sheet is mechanically softened to a second density which is lower than the original, first density while delaminating the sheet so as to form a plurality of partially separated thin fibre layers which in themselves exhibit a density which corresponds to the first density.
2. A method of producing an absorbent structure according to claim 1 characterized in that the softening in carried out by bending the dry formed sheet over one or several edges or rollers.
3 A method of producing an absorbent structure according to claim 1 characterized in that the softening in carried out by working the dry formed sheet between rollers with engraved patterns.
4 An absorbent structure in an absorbent article, such as a diaper, sanitary napkin, panty protector, incontinence guard, bed protector, wound or sore dressing, saliva absorbent and like articles produced in accordance with the method of Claim 1, characterized in that the structure contains 5-100% cellulose fibre and also includes a plurality of thin, partially separated fibre layers; and in that after being softened, the structure exhibits a density reduction of between 0-75% and a surface weight of between 30-2000 g/m2; and in that the thin, partially separated fibre layers exhibit in themselves a density of between 0.2-1.0 g/cm3.
5. An absorbent structure according to Claim 4, characterized in that the density is between 0.25-0.9 g/cm3, preferably 0.3-0.85 g/cm3.
6. An absorbent structure according to Claim 4 or 5, characterized in that the density reduction after softening is between 1-50%.
7. An absorbent structure according to Claim 4, characterized in that the surface weight is between 30-2000 g/m2, preferably 50-1500 gm2 and most preferably 100-1000 gm2.
8. An absorbent structure according to Claims 4-7, characterized in that the cellulose fibres are mainly comprised of flash-dried cellulose fibres.
9. An absorbent structure according to Claims 4-7, characterized in that the cellulose fibres are mainly comprised of conventional fluff-pulp fibres.
10. An absorbent structure according to one or more of the preceding Claims, characterized in that the cellulose fibres are mainly comprised of fibres of chemi-thermomechanically produced pulp.
11. An absorbent structure according to Claim 6, characterized in that the chemi-thermomechanical pulp fibres have a curl value of between 0.20 and 0.40.
12. An absorbent structure according to one or more of Claims 1-8, char cterized in that the cellulose fibres are comprised mainly of fibres of chemically produced pulp.
13. An absorbent structure according to one or more of the preceding Claims, characterized in that at least an amount of the fibres are chemically stiffened cellulose fibres.
14. An absorbent structure according to one or more of the preceding Claims, characterized in that in that the structure contains between 0.5-70% superabsorbent material, preferably between 2-50%, and most preferably between 5-30%, calculated on the total weight of the structure in a dry state.
15. An absorbent structure according to one or more of the preceding Claims, characterized in that the structure has a moisture content of between 3-20%, preferably between 4-18% and most preferably between 11-16%, calculated on the total weight of the structure.
16. An absorbent structure according to one or more of the preceding Claims, characterized in that the structure includes reinforcing means, for instance binding agent, reinforcing fibre or thermoplastic binding fibres.
17. An absorbent structure according to one or more of the preceding Claims, chara cteri ze d in that the structure includes a reinforcing layer of, e.g., non-woven, tissue, plastic or net.
18. An absorbent article, such as a diaper, sanitary napkin, panty protector, incontinence guard, bed protector, dressing, saliva absorbent and like articles, comprising a fluid-permeable top sheet, an essentially fluid-impermeable bottom sheet and an absorbent body arranged between said sheets, characterized in that the absorbent body includes an absorbent structure according to one or more of Claims 2- 17.
19. An absorbent article according to Claim 18, in which the absorbent body includes at least two layers, a aquisition layer and one or more wicking and/or storage layers, wherein the aquisition layer is intended to rapidly take up fluid and disperse said fluid to the fluid- wi eking/ storing layer or layers, characterized in that the aquisition layer is comprised of a dry-formed sheet comprising cellulose fibres and having a density of between 0.20-0.80 g/cm3 and a surface weight of between 50-1500 g/m2 and include a plurality of thin, partially separated fibre layers.
20. An absorbent article according to Claim 19, characterized in that the cellulose fibres are mainly comprised of fibres of chemi-thermomechanically produced pulp.
1. An absorbent article according to Claim 20, characterized in that the absorbent structure is covered with a layer of chemical pulp on one side thereof.
22. An absorbent article according to one or more of Claims 20 and 21, characterized in that the cellulose fibres are mainly comprised of flash-dried cellulose fibres.
23. An absorbent article according to one or more of Claims 19-22, characterized in that least an amount of the fibres in the aquisition layer arc chemically stiffened cellulose fibres
24. An absorbent article according to one or more of Claims 19-23, characterized in that the aquisition layer has a density of between 0.20-0.70 g/cm3, preferably between 0.30-0.60 g/cm3.
25. An absorbent article according to one or more of Claims 19-24, characterized in that the fluid-aquisition layer has a surface weight of between 50-1200 g/m2, preferably between 80-1000 gm2.
26. An absorbent article according to Claim 18, in which the absorbent body includes two or three layers, a aquisition layer and one or two wicking and storage layers, wherein the aquisition layer is intended to rapidly take up fluid and disperse fluid to the wicking layer, characterized in that the wicking layer is comprised of a dry- formed sheet containing cellulose fibres and having a density of between 0.25-1.0 g/cm3 and a surface weight of between 50-1500 g/m2, and further includes a plurality of thin, partially separated fibre layers.
27. An absorbent article according to Claim 26, characterized in that the wicking/storage layer is comprised mainly of fibres of chemi-thermomechanically produced pulp.
28. An absorbent article according to Claim 26, characterized in that cellulose fibres are comprised mainly of flash-dried cellulose fibres.
29. An absorbent article according to Claim 26, characterized in that the wicking layer is comprised mainly of fibres of chemically produced pulp.
30. An absorbent article according to one or more of Claims 26-29, characterized in that the wicking layer has a density of between 0.3-1.0 g/cm3, preferably between 0.3-0.9 g/cm3.
31. An absorbent article according to one or more of Claims 26-30, characterized in that the wicking layer includes between 0-40%, preferably between 5-20% superabsorbent material.
32. An absorbent article according to Claim 18, in which the absorbent body comprises two or three layers, a aquisition layer and one or two wicking and storage layers, wherein the aquisition layer is intended to rapidly take up fluid and disperse fluid to the wicking layer for further transportation to the storage layer, characterized in that the storage layer is comprised of a dry-formed sheet which contains cellulose fibres and which has a density of between 0.25-1.0 g/cm<3 and a surface weight of between 50-1500 g/m2, and further includes a plurality of thin, partially, separated fibre layers.
33. An absorbent article according to Claim 32, characterized in that the cellulose fibres are mainly comprised of fibres of chemi-thermomcchanically produced pulp.
34. An absorbent article according to Claim 33, characterized in that the cellulose fibres are mainly comprised of flash-dried cellulose fibres.
35. An absorbent article according to one or more of Claims 32-34, characterized in that the storage layer has a density of between 0.3-0.9 g/cm3, preferably between 0.4-0.8 g/cm3.
36. An absorbent article according to one or more of Claims 32-35, characterized in that the storage layer has a surface weight of between 80-1200 g/m2, preferably 100-1000 g/m2.
37. An absorbent article according to one or more of Claims 32-36, characterized in that the storage layer includes between 20- 70%, preferably between 25-60% and most preferably between 30-50% superabsorbent material.
38. An absorbent article according to Claim 18, intended for the absorbent of blood, such as a sanitary napkin, panty protector or wound or sore dressing, characterized in that the absorbent structure mainly includes fibres of chemi-thermomechanically produced pulp; and in that the absorbent structure further includes between 0-15% superabsorbent material calculated on the total dry weight of the structure.
39. An absorbent article according to Claim 38, characterized in that the absorbent structure contains no superabsorbent material.
40. An absorbent article according to any one of Claims 38 and 39, characterized in that one side of the absorbent structure is covered with a layer of chemical pulp.
41. An absorbent article intended for the absorption of blood, such as a tampon or like article, characterized in that the article includes an absorbent structure according to one or more of Claims 2-
17.
42. An absorbent article according to Claim 41, characterized in that the absorbent structure is mainly comprised of fibres of chemi-thermomechanically produced pulp; and in that the absorbent structure includes between 0-15% superabsorbent material, calculated on the total weight of the structure in a dry state.
43. An absorbent article according to Claim 42, ch aracterized in that the absorbent structure contains no superabsorbent material
PCT/SE1993/000975 1992-11-17 1993-11-15 A method for the manufacturing of an absorbent structure and an absorbent article comprising an absorbent structure manufactured according to this method WO1994010957A1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
PL93309009A PL173293B1 (en) 1992-11-17 1993-11-15 Method of making a moisture absorbing element and moisture absorbing product incorporating such element
JP51201194A JP3589462B2 (en) 1992-11-17 1993-11-15 Method for producing absorbent structure and absorbent article comprising absorbent structure produced by this method
DK94900340T DK0773765T3 (en) 1992-11-17 1993-11-15 A process for making an absorbent structure and an absorbent article comprising an absorbent structure f
AT94900340T ATE189594T1 (en) 1992-11-17 1993-11-15 METHOD FOR PRODUCING AN ABSORBENT STRUCTURE AND ARTICLES HAVING A STRUCTURE PRODUCED ACCORDING TO THIS METHOD
DE69327854T DE69327854T2 (en) 1992-11-17 1993-11-15 METHOD FOR PRODUCING AN ABSORBING STRUCTURE AND ARTICLE WITH A STRUCTURE PRODUCED ACCORDING TO THIS METHOD
SK654-95A SK282204B6 (en) 1992-11-17 1993-11-15 Method for the manufacturing of an absorbent structure and an absorbent article
EP94900340A EP0773765B1 (en) 1992-11-17 1993-11-15 A method for the manufacturing of an absorbent structure and an absorbent article comprising an absorbent structure manufactured according to this method
AU55360/94A AU681870B2 (en) 1992-11-17 1993-11-15 A method for the manufacturing of an absorbent structure andan absorbent article comprising an absorbent structure manufactured according to this method
NO951916A NO305972B1 (en) 1992-11-17 1995-05-15 Absorbent structure and process for making such a structure
FI952409A FI117467B (en) 1992-11-17 1995-05-17 Process for producing absorbent structure and absorbent articles comprising the structure prepared by the process
GR20000400651T GR3032954T3 (en) 1992-11-17 2000-03-10 A method for the manufacturing of an absorbent structure and an absorbent article comprising an absorbent structure manufactured according to this method

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SE9203446A SE509037C2 (en) 1992-11-17 1992-11-17 Absorbent structure and method of manufacture
SE9203446-1 1992-11-17

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JP (1) JP3589462B2 (en)
AT (1) ATE189594T1 (en)
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CA (1) CA2149513A1 (en)
CO (1) CO4180497A1 (en)
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DE (1) DE69327854T2 (en)
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ES (1) ES2144043T3 (en)
FI (1) FI117467B (en)
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GR (1) GR3032954T3 (en)
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HUT71659A (en) 1996-01-29
NO951916D0 (en) 1995-05-15
HU9501425D0 (en) 1995-07-28
CZ124895A3 (en) 1995-11-15
HU218567B (en) 2000-10-28
ZA938244B (en) 1994-06-08
EP0773765A1 (en) 1997-05-21
CZ285874B6 (en) 1999-11-17
CA2149513A1 (en) 1994-05-26
AU5536094A (en) 1994-06-08
SK65495A3 (en) 1995-11-08
SE509037C2 (en) 1998-11-30
PL173293B1 (en) 1998-02-27
GB9322992D0 (en) 1994-01-05
JPH08503397A (en) 1996-04-16
AU681870B2 (en) 1997-09-11
ATE189594T1 (en) 2000-02-15
PT773765E (en) 2000-07-31
CO4180497A1 (en) 1995-06-07
TNSN93126A1 (en) 1994-03-17
NO951916L (en) 1995-05-15
DK0773765T3 (en) 2000-05-15
NO305972B1 (en) 1999-08-30
SE9203446D0 (en) 1992-11-17
EP0773765B1 (en) 2000-02-09
PL309009A1 (en) 1995-09-18
FI117467B (en) 2006-10-31
GB2272459B (en) 1997-01-22
US5634915A (en) 1997-06-03
DE69327854T2 (en) 2000-05-25
DE69327854D1 (en) 2000-03-16
NZ257927A (en) 1996-10-28
JP3589462B2 (en) 2004-11-17
GR3032954T3 (en) 2000-07-31
FI952409A (en) 1995-05-17
SE9203446L (en) 1994-05-18
GB2272459A (en) 1994-05-18
ES2144043T3 (en) 2000-06-01
SK282204B6 (en) 2001-12-03
FI952409A0 (en) 1995-05-17

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