WO1991002552A1 - Materiau superabsorbant, structure superabsorbante, article absorbant et procede de preparation de ces superabsorbants - Google Patents

Materiau superabsorbant, structure superabsorbante, article absorbant et procede de preparation de ces superabsorbants Download PDF

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Publication number
WO1991002552A1
WO1991002552A1 PCT/BR1990/000009 BR9000009W WO9102552A1 WO 1991002552 A1 WO1991002552 A1 WO 1991002552A1 BR 9000009 W BR9000009 W BR 9000009W WO 9102552 A1 WO9102552 A1 WO 9102552A1
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WO
WIPO (PCT)
Prior art keywords
superabsorbent
fact
accordance
sodium acrylate
absorbent
Prior art date
Application number
PCT/BR1990/000009
Other languages
English (en)
Inventor
José Antonio PEREIRA
Original Assignee
Johnson & Johnson Indústria E Comércio Ltda.
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
Application filed by Johnson & Johnson Indústria E Comércio Ltda. filed Critical Johnson & Johnson Indústria E Comércio Ltda.
Publication of WO1991002552A1 publication Critical patent/WO1991002552A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/125—Water, e.g. hydrated salts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Definitions

  • the present invention relates to expanded superabsorbent materials, and in particular to expanded superabsorbents for use in absorbent products such as sanitary napkins, catamenial tampons, diapers, dressings or the like, for the absorption of body fluids.
  • absorbent materials are currently known, and generally used in the forming of absorbent structures. For ex ⁇ ample, absorbent materials based on cellulose pulp are well known. Another type of absorbent material well known for its great capa ⁇ bility of absorbing liquids belongs to the class of naturally oc ⁇ curring absorbent materials and is known as sphagnum.
  • sphagnum a moss of the family sphagnaceae
  • the moss forms dense and extensive colonies, its vegetative propagation occurring by ramification and death of older parts of the plant.
  • the leaves are formed of living and dead cells.
  • the living cells are green and are called chlorocysts, ha ⁇ ving an assimilatory function.
  • the dead cells are colourless and are called lencocysts, and these have spiral ribs and pores which function as reservoirs for water and other aqueous liquids.
  • liquid used herein signifies water or any a- queous liquid to be absorbed.
  • Superabsorbent materials so-called due to their large capacity for absorption and retention of liquids, are generally polymeric materials whose polymeric chains have highly hydrophilic active sites.
  • Superabsorbent materials may be by nature entirely syn ⁇ thetic, or may be obtained from essentially natural polymers in whose chains are introduced highly hydrophilic groups.
  • Outstanding the class of superabsorbent polymers are, inter alia, the aerylate based polymers such as sodium polyacry- late.
  • su ⁇ perabsorbent polymers may include various other types of natural or synthetic polymers based on or modified by highly hydrophilic groups which are well known to those skilled in the art.
  • Table I shows, by way of illustration, the liquid absorption capacities of some absorbent materials cited above, when subjected to a pressure in the range of from 0.05 to 0.5 psi.
  • the apparatus used to evaluate this property was the GATS, with a 1% saline NaCl solution.
  • the present invention provides a superabsorbent material with improved liquid absorption properties and free of the disad- vantages shown by absorbent materials of improved properties here ⁇ in described.
  • a third aspect of the present invention is the provision of new absorbent articles including the absorbent struct ⁇ res cited above. Additionally the present invention deals with a process for the obtention of the said improved superabsorbent materials. More specifically, the present invention reveals a new superabsorbent material obtained from a superabsorbent material commercially available, which presents a combination of the effec- tive characteristics of the starting superabsorbent without simul ⁇ taneously presenting the disadvantages shown thereby.
  • the mechanism of absorption of natural sphagnumis is by a purely physical process.
  • the structure of sphagnum is microporous, the mircopores being principally responsible for its absorptive properties. This mircroporous structure functions by capillary ac ⁇ tion, providing penetrating paths for the liquid to be absorbed.
  • the liquid is stored in the reservoir cells present in the struc ⁇ ture of sphagnum.
  • the absorption mechanism of superabsorbent materials is entirely different, occurring by an essentially chemical process.
  • the highly hydrophilic groups present in the polymeric chains of superabsorbents are essentially those responsible for its high ab ⁇ sorption and retention capacity.
  • the liquid to be absorbed attaches itself chemically to the hydrophilic groups present in the polyme- ric structure, by means of electrostatic forces of the hydrogen bridge type.
  • hydrophilic groups pre ⁇ sent in the polymeric chains of superabsorbent materials make them extremely efficient in their capacity for absorbing and retaining liquids, these materials are generally restricted in their absorp ⁇ tion and distribution speeds.
  • the material aspect of the present invention resides in the fact that the properties of the superabsorbent material may be greatly improved by the modification of the original compact structure to a structure having micropores, such as those which e- xist in the structure of natural sphagnum.
  • the modification of the original compact structure of the superabsorbent material for obtaining an expanded structure in ac ⁇ cordance with the invention is obtained by the expansion of the said original compact structure.
  • the expanded superabsorbent poly- mer of the present invention has an absorption speed superior to that of the original compact polymer, " principally in the initial period of absorption.
  • the expanded su ⁇ perabsorbent polymer shows absorption rates approximately 2 to 3.5 times higher than the original compact structured polymer.
  • the expansion may be performed by any suitable expansion process, which provides an expanded final structure.
  • suitable expansion process which provides an expanded final structure.
  • thermoexpansion processes are used to perform the invention.
  • thermoexpansion processes the following are preferred: a) expansion by submitting the compact superabsorbent ma terial to thermotreatment in a microwave oven; and b) expansion by contacting the compact superabsorbent ma terial with an adequately heated surface.
  • the process of expansion which resulted in a highly sat ⁇ isfactory expanded structure was that of submitting the original superabsorbent material to thermotreatment in a microwave oven, and is thus the preferred expansion process of the invention.
  • the temperature of the thermotreatment may vary within a wide range from the softening temperature to a temperature lower than the corbonization temperature of the material.
  • the preferred expansion temperature generally ranges from about 160 to 3009C more preferably from about 180 to 2509C.
  • the expansion may be performed by a process which uses thermotreatment in association with a variation of pres_ sure.
  • This process here referred as "gun type” expansion, con sists in heating the superabsorbent compact material within a clo- sed tube, until a pressure in the range of approximately 8 to 200 lb/in 2 is achieved, approximatel 170 lb/in2. Thereafter the tube is opened so that the material contacts the atmosphere at a lower pressure, and the material is thereby expanded.
  • the expansion period is variable, and depends on the ini ⁇ tial and final temperatures, the original moisture content of the polymer to prevent sticking of the polymer particles to each other and to the apparatus, the moisture being preferably between 0.5 and 5% and not greater than 15%.
  • the preferred expansion time is between about 0.5 and about 30 minutes.
  • any polymeric mate ⁇ rial based on sodium aerylate and having a compact structure may be used as a superabsorbent material to be expanded.
  • polymeric material based on sodium acrylate signifies a polymeric material constituted by monome- ric units of acrylic acid (AA) and sodium acrylate (SA) .
  • the propor ⁇ tion of AA and SA in the polymeric materials to be expanded should be in the range of 40 to 60% by weight of AA and 60 to 40% by weight of SA.
  • polymeric materials having from 50 to 60% by weight of SA are used.
  • Polymeric material having a content of AA superior to these limits also permit expansion, but their particles become agglomerated during the heat treatment and thus impede the obtention of discrete expanded particles.
  • a particularly preferred superabsorbent material of the present invention is the superabsor bent polymer commercially known as Favor SAB, since the proportions of AA and SA monomers in the polymeric chain lies within the above ranges.
  • Any commercially available polymeric material based on sodium acrylate which does not have the cited proportions of AA to SA may also be expanded to provide the improved superabsorbent ma ⁇ terials of the present invention, provided that they are duly treated so that the proportion of AA and SA monomers lies within the ranges specified above.
  • This treatment consists essentially in transforming the AA groups present in the chain of the polymeric material into SA groups when the proportion of AA in the polymeric material is greater than 60% by weight, so that the quantitative ranges of AA and SA in the polymeric material to be expanded are within the limits established herein.
  • This treatment may perform with any suitable compound for transforming SA groups into AA groups, for example by using an acidic compound such as hidrochloric acid or any suitable compound for transforming ; groups into SA groups, such as a basic sodium compound.
  • an acidic compound such as hidrochloric acid or any suitable compound for transforming
  • groups into SA groups such as a basic sodium compound.
  • the chemical composition of various types of commercially availa ⁇ ble superabsorbents based on sodium acrylate are given: Type of Material Manufacturer %AA %SA Favor SAB STOCKHAUSEN • 50 - 57 50 - 43 Favor SAB 922 " 19 - 23 81 - 77
  • Arasorb 802 ARAKAWA 18 - 20 81 - 80
  • Arasorb 803 18 - 20 82 - 80
  • the only commer cially available material having a proportion of AA and SA within the limits of the quantitative ranges of the present invention is Favor SAB.
  • the other materials may be duly modified as already men tioned in order to obtain a polymeric material having proportions of AA and SA in the range of 60 to 40% by weight and 40 to 60% by weight respectively.
  • the superabsorbent expanded materials in accordance with present invention should have a final density in the range of 0.05 to 0.4 g/cm 3, preferably, in the range of 0.05 to 0.14 g/cm3.
  • Figure 1 is a photomicrograph of the structure of natural sphagnum, magnified 675 times
  • Figure 2 is a microphotograph of the structure of natural sphagnum magnified 675 times, showing the micropores
  • Figure 3 is a microphotograph of the compact structure of a super- absorbent polymer (sodium polyacrylate) magnified 54 times;
  • Figure 4 is a microphotograph os a superabsorbent polymer (sodium polyacrylate) expanded according to the present invention and magnified 54 times;
  • Figure 5 is a microphotograph of the structure of an unexpanded superabsorbent polymer (sodium polyacrylate) magnified
  • Figure 6 is a microphotograph of a superabsorbent polymer (sodium polyacrylate) expanded according to the present invention and magnified 270 times.
  • the superabsorbent materials of the invention may be use ⁇ either in isolation for the absorption of liquids, or in associa- tion with other materials to provide an absorbent structure.
  • the improved absorbent structures according to the inven ⁇ tion include the new superabsorbent material in association with a suitable absorbent support.
  • Such structures can comprise one or more layers or nucleous of said expanded superabsorbent material in association with one or more layers of an auxiliary material.
  • Gene ⁇ rally, wood pulp is used as the support.
  • the quantity of superabsor_ bent material necessary to form an effective absorbent structure depends on the specific nature of the structure to be produced, and is well known to those skilled in this art. Proportions of about 2% to 60%, preferably, 5% to 10% by weight of superabsorbent materials with respect to the weight of the support materials, preferably ground wood pulp, are satisfactory to provide such structure.
  • the absorbent structures above are suitable for forming absorbent articles such as disposable diapers, sanitary napkins, tampons and absorbent bandages or their like.
  • the articles thus formed have effective liquid absorption and retention properties, without simultaneously presenting the disadvantages of conventio ⁇ nal absorbent articles and the disadvantages presented by using the regular compact superabsorbent product without the expanded final structure.
  • the superabsorbent starting polymer used in the illustra ⁇ tive examples is that commercially known by the name "Favor SAB", whose characteristics are listed below: Chemical nature - Sodium polyacrylate Appearance - white powder Granin size - 160 to 500 microns Apparent density - 660 - 30 g/1 Flowability - very good
  • the expansion of the above material was performed in a microwave oven at 400 to 700 watts.
  • the expansion time varied from about 0,5 to 30 minutes at a temperature of from 180 to 2509C.
  • Test method 0.2 g of superabsorbent material is set in heat sealable paper bags, commonly used commercially for tea bags. The dry weight is exactly determined and after the bags are sealed each sample is imersed in a 1% sodium chloride solution for in ⁇ tervals of 5, 10, 30, 60 and 120 seconds. After allowance to drain until excess solution is lost each weight is noted again. The same procedure as above described is repeated without superabsorbent.
  • the absorption after each imersion is calculated from the difference of both weight and converted to grams of saline solution absorbed per gram of material.
  • Cylindrical packs in form of tubes are manually prepared with light-weight non-
  • Sample disks of ground wood pulp and ground wood pulp containing ⁇ egular and expanded Favor SAB were manually prepared in lab scale. They were mixed through a kitchen blender, vacuum compacted in a 9 cm diameter mould and pressed to a thickness be ⁇ tween 1.0 and 1.5 mm.
  • GATS apparatus 1% NaCl saline solution, pressure of 0.05 psi and orifice centralized in the plate.
  • the deatils above show an increase in absorption veloci- ty of the structure of the invention by about 2.5 times relative to the structure using normal Favor SAB (3.24g/min as opposed to - 8.4 g/min) .
  • the final absorbent structure was composed with the su ⁇ perabsorbent materials spread between the two layers of ground wood pulp. Samples:
  • GATS apparatus pressure of 0,05 psi, 1% sodium chloride solution, point source.
  • the advantages of the expan ded superabsorbent lie in the results of volume variation and ab ⁇ sorption velocity when compared to structures containing the same amount of superabsorbent, one being unexpanded the other being ex- panded.
  • the solution was poured in 3 consecutive discharges of 15 ml each, at intervals of 30 minutes.
  • the wetted absorbent structure is then cut in 6 equal sections (S 1 -S fi ) and the quantity is determined as well as the percentage of utilization of the absorbent structure.
  • Table VIII below indicates improved results of distri ⁇ bution and utilization in the structures containing the expanded Favor SAB over those ones containing the unexpanded regular Favor SAB.
  • the % of utilization is calculated as follows:
  • a 2 x 2 cm pad of ground wood pulp with PCAc skin was centrally disposed on the absorbent structure similar to that des_ cribed for Table VII.
  • the pumping power of the absorbent structure is then measured by weighing the quantity of solution each structure pum ⁇ ped from the 2 x 2 pad after each discharge.
  • Example "X” This example illustrates the chemical modification of a commercially available sodium acrylate based polymer to obtain a proportion of AA and SA monomers within the operative ranges according to the present invention.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Hematology (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Absorbent Articles And Supports Therefor (AREA)

Abstract

L'invention se rapporte à un matériau superabsorbant ayant des propriétés améliorées, qui se compose d'un polymère superabsorbant dont la structure d'origine a été modifiée par expansion, de façon à obtenir une structure finale expansée. Un tel matériau est très efficace pour la formation de structures absorbantes et d'articles absorbants. L'invention décrit en outre un procédé de préparation de ces matériaux superabsorbants.
PCT/BR1990/000009 1989-08-23 1990-08-22 Materiau superabsorbant, structure superabsorbante, article absorbant et procede de preparation de ces superabsorbants WO1991002552A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BR898904238A BR8904238A (pt) 1989-08-23 1989-08-23 Material superabsorvente,estrutura absorvente,artigo absorvente e processo para preparacao do dito material superabsrovente
BRPI8904238 1989-08-23

Publications (1)

Publication Number Publication Date
WO1991002552A1 true WO1991002552A1 (fr) 1991-03-07

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PCT/BR1990/000009 WO1991002552A1 (fr) 1989-08-23 1990-08-22 Materiau superabsorbant, structure superabsorbante, article absorbant et procede de preparation de ces superabsorbants

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JP (1) JPH05504072A (fr)
AU (1) AU6272090A (fr)
BR (1) BR8904238A (fr)
CA (1) CA2064871A1 (fr)
DE (1) DE4091474T (fr)
WO (1) WO1991002552A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0530517A1 (fr) * 1991-08-15 1993-03-10 Kimberly-Clark Corporation Procédé de traitement de matériaux super-absorbants insolubles dans l'eau
US5206205A (en) * 1991-08-15 1993-04-27 Kimberly-Clark Corporation Thermal treatment of superabsorbents to enhance their rate of absorbency under load
US5247072A (en) * 1991-10-25 1993-09-21 Kimberly-Clark Corporation Carboxyalkyl polysaccharides having improved absorbent properties and process for the preparation thereof
US5328935A (en) * 1993-03-26 1994-07-12 The Procter & Gamble Company Method of makig a superabsorbent polymer foam
US5338766A (en) * 1993-03-26 1994-08-16 The Procter & Gamble Company Superabsorbent polymer foam
US5550189A (en) * 1992-04-17 1996-08-27 Kimberly-Clark Corporation Modified polysaccharides having improved absorbent properties and process for the preparation thereof
WO2010083785A1 (fr) * 2009-01-26 2010-07-29 Hornak Jozef Couverture de protection paragrêle
EP2238956A1 (fr) 2009-04-10 2010-10-13 The Procter & Gamble Company Noyau absorbant

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA92308B (en) 1991-09-11 1992-10-28 Kimberly Clark Co Thin absorbent article having rapid uptake of liquid

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0049944A1 (fr) * 1980-08-25 1982-04-21 Johnson & Johnson Produits absorbants, procédé et compositions pour l'immobilisation de produits absorbants particulaires
EP0295438A2 (fr) * 1987-05-14 1988-12-21 JOHNSON & JOHNSON MEDICAL, INC. Composition superabsorbante et procédé
EP0347241A2 (fr) * 1988-06-16 1989-12-20 Mitsubishi Petrochemical Co., Ltd. Procédé de préparation d'un polymère absorbant de l'eau
US4902721A (en) * 1987-05-04 1990-02-20 The Dow Chemical Company Foamable thermoplastic polymers and a method for foaming

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0049944A1 (fr) * 1980-08-25 1982-04-21 Johnson & Johnson Produits absorbants, procédé et compositions pour l'immobilisation de produits absorbants particulaires
US4902721A (en) * 1987-05-04 1990-02-20 The Dow Chemical Company Foamable thermoplastic polymers and a method for foaming
EP0295438A2 (fr) * 1987-05-14 1988-12-21 JOHNSON & JOHNSON MEDICAL, INC. Composition superabsorbante et procédé
EP0347241A2 (fr) * 1988-06-16 1989-12-20 Mitsubishi Petrochemical Co., Ltd. Procédé de préparation d'un polymère absorbant de l'eau

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0530517A1 (fr) * 1991-08-15 1993-03-10 Kimberly-Clark Corporation Procédé de traitement de matériaux super-absorbants insolubles dans l'eau
US5206205A (en) * 1991-08-15 1993-04-27 Kimberly-Clark Corporation Thermal treatment of superabsorbents to enhance their rate of absorbency under load
AU651233B2 (en) * 1991-08-15 1994-07-14 Kimberly-Clark Worldwide, Inc. Thermal treatment of superabsorbents to enhance their rate of absorbency under load
US5247072A (en) * 1991-10-25 1993-09-21 Kimberly-Clark Corporation Carboxyalkyl polysaccharides having improved absorbent properties and process for the preparation thereof
US5550189A (en) * 1992-04-17 1996-08-27 Kimberly-Clark Corporation Modified polysaccharides having improved absorbent properties and process for the preparation thereof
US5451452A (en) * 1993-03-26 1995-09-19 The Procter & Gamble Company Absorbent members and articles containing superabsorbent polymer foam
US5338766A (en) * 1993-03-26 1994-08-16 The Procter & Gamble Company Superabsorbent polymer foam
US5506035A (en) * 1993-03-26 1996-04-09 The Procter & Gamble Company Superabsorbent polymer foam
US5328935A (en) * 1993-03-26 1994-07-12 The Procter & Gamble Company Method of makig a superabsorbent polymer foam
WO2010083785A1 (fr) * 2009-01-26 2010-07-29 Hornak Jozef Couverture de protection paragrêle
EP2238956A1 (fr) 2009-04-10 2010-10-13 The Procter & Gamble Company Noyau absorbant
EP2238957A1 (fr) 2009-04-10 2010-10-13 The Procter & Gamble Company Noyau absorbant
WO2010118272A1 (fr) 2009-04-10 2010-10-14 The Procter & Gamble Company Noyau absorbant

Also Published As

Publication number Publication date
JPH05504072A (ja) 1993-07-01
AU6272090A (en) 1991-04-03
DE4091474T (fr) 1992-08-27
BR8904238A (pt) 1991-02-26
CA2064871A1 (fr) 1991-02-24

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