JP2005537852A - Sensing and absorbing articles - Google Patents

Abstract

A disposable sensing absorbent structure for detecting wetting is provided that includes at least one absorbent layer and at least one sensing means comprising a magnetoelastic film. Such absorbent structures provide a means and method for monitoring conditions, such as wetting, at least one bioanalyte and / or at least one chemical analyte in an absorbent article. Changes in conditions such as wetting can reflect events such as urination or feces. Also included is a method for detecting wet, at least one bioanalyte and / or at least one chemical analyte using a sensing and absorbing structure according to the present invention.

Description

  The present invention relates to a sensing and absorbing structure comprising at least one absorbing layer and at least one sensing means including a magnetoelastic film. The present invention also provides a sensing and absorption system and method for detecting at least one bioanalyte and / or at least one chemical analyte in the absorption structure.

Disposable absorbent articles Absorbent articles such as diapers for infants and adults, sanitary napkins and adult incontinence pants are well known and widely used in the industry. Most such products are used on a single use basis. Such single use standards for disposable products have led to the development of a broad class of different products that meet specific conditions, such as the care of infants and toddlers and adults suffering from incontinence. The main purpose of such absorbent articles is generally to absorb, retain and separate body excreta, ie urine, feces or blood.

Event Detection Certain groups of absorbent articles can react to events such as urination or defecation after absorption onto or into the product. The reaction can be once after the event has occurred, for example based on wet or temperature measurements. Event cues can provide feedback to the user or nursing assistant for the event to occur for ease of handling for the user or caregiver / nurse.

  US 5348761 describes a moisture / wet detection sensor that utilizes a swellable plastic with a conductive additive. The sensor swells in response to moisture in action, which in turn increases the resistance of the sensor. All examples show connecting wires attached to electrodes for monitoring moisture / wetting.

Chemical Detection One group of absorbent articles known in the industry includes chemical reaction means, or sensors, for detecting various chemicals, such as pH or ions, glucose, etc. in body excreta such as feces or urine. Detection of such chemicals will provide feedback to the user or nursing assistant that an event has occurred. Most chemical sensors utilize color changes, for example, to allow detection of pH or various ions. Such color change monitoring also often requires a user, such as an elderly incontinence patient or infant, to be physically displaced, for example by facing one side.
In addition, chemical compounds that impart color changes are often toxic or irritating to the skin. Therefore, the incorporation of such compounds in the absorbent article is hardly evaluated for environmental aspects as well as user health.

Biodetection Another group of absorbent articles includes means for detecting proteins, hormones, microorganisms such as bacteria or viruses, glucose, or bacterial toxins. Some of these also detect and target potentially pathogenic microorganisms such as bacteria, viruses, fungi, and parasites such as protozoa. Detection of such biomolecules, such as microorganisms, provides an indication of potential health and / or nutritional status and can detect events such as urination or defecation.

  WO 00/00233 discloses a disposable article adapted to a wearer that includes a biosensor having a biorecognition element to detect bioanalytes in body excreta.

  WO 98/27417 describes a biosensor device for detecting and quantifying an analyte present in a medium. The analyte is detected by an image generated as a diffraction pattern.

Magnetoelastic Sensors Magnetoelastic sensors are described by Grimes et al. (Biomedical Microdevices, 2: 51-60, 1999).

  When a magnetic field is applied to, for example, a ferromagnetic material, the material dimensions change. This effect is called magnetostriction. The size of the material dimensional change is governed by the magnetostriction constant.

  When exposed to an externally applied magnetic pulse, the material generates a magnetic flux with a characteristic resonant frequency. The magnetic flux can be detected remotely by a pickup coil. The change in resonance frequency can be monitored to measure or detect a number of environmental parameters. Measurements of temperature, pressure, and velocity using this method are described in Grimes et al. (Biomedical Microdevices, 2: 51-60, 1999). In situ measurements of glucose levels can be made by the inclusion of glucose reactants that change the polymer.

  The reaction from the material can also be measured by exciting the material with a continuous magnetic field having a frequency corresponding to the magnetoacoustic resonance frequency. The response from the material is maximal at this resonance frequency. It is also possible to excite the material with a continuous magnetic field having a frequency close to the magnetoacoustic resonance frequency in the pulses and measure the weakened magnetic response from the material between the pulses.

Magnetoacoustic Effect When a magnetic material is excited by a magnetic field, it stores magnetic energy in a magnetoelastic manner. When the magnetic field is cut off, the material exhibits a weakened vibration with a special frequency that is the magnetoacoustic resonance frequency.

General problems with sensors in absorbent articles Sensors contained in absorbent articles are preferably inexpensive to allow single use of the absorbent article. They also need to be reliable and able to withstand certain environments found in very special environments such as diapers.

  The sensor must also be safe for the user and nursing assistant. That is, it is necessary not to provoke skin irritation or toxic effects on either. Furthermore, it is recommended that the sensor be environmentally friendly so that such absorbent products can be disposed of without any restrictions on waste handling. Environment-related issues are becoming increasingly important to our society today and are being petitioned and implemented by international environmental regulators and national governments.

  Some of the sensors described above require direct physical connection to the sensor and / or the incorporation of electronic circuitry. This is inconvenient for the user in many ways, it does not allow for remote detection and monitoring, which limits the usefulness of the sensor in several ways. Electronic circuits require that a power supply be incorporated into the absorbent article, which creates health problems for the user or nursing assistant. Furthermore, it is bulky to incorporate into an absorbent article. Also, the incorporation of one or more batteries into a disposable product becomes an environmental obstacle. This is because batteries require special recycling procedures.

  Event monitoring should be made simple that the user or nursing assistant can easily understand the body excretion status without having to physically displace the user in any way.

  US Pat. No. 5,821,129 discloses a sensor that enables remote continuous magnetic chemical detection of various chemical species, for example in exhaust pipes, waterways, chemical baths or body implants.

  WO 0079497 describes the use of a radio frequency resonance circuit sensing device and its use for the detection of fluid leakage from a container or body, for example fluid discharge from a person suffering from urine and / or fecal incontinence. The sensor device uses a coil that can receive bodily fluids and react, for example, by shorting in a “single hit” event after urination.

  Thus, in light of the above-mentioned problems, monitoring conditions in absorbent articles that reflect user conditions in an easily detected, inexpensive and disposable manner and avoid problems associated with prior art means and methods. It would be highly desirable to develop means and methods for doing so. In this regard, the present invention addresses this need and interest.

  In light of the above-mentioned previously known drawbacks when monitoring conditions in absorbent articles, the present invention is a sensitive absorbent structure that can be easily monitored, provides information about the condition of absorbent articles in an inexpensive and disposable manner. I will provide a. In one example, the state of the absorbent article reflects the state of the user.

  One object of the present invention is to provide a sensitive absorbent article for detecting wetting.

  One further object of the present invention is to provide a sensitive absorbent article for detecting at least one biological analyte and / or at least one chemical analyte.

  The present invention thus provides an absorbent structure comprising at least one absorbent layer and at least one sensing means comprising a magnetoelastic film.

  The absorption structure according to the invention is a structure in which at least one layer contains 0-95% of superabsorbent material.

  The magnetoelastic film in the absorbing structure according to the present invention vibrates at the magnetoacoustic resonance frequency after the magnetoelastic film is excited by the magnetic field and when the magnetic field is cut off.

  Furthermore, the at least one sensing means in the absorbent structure according to the invention may be 1 to 20 sensing means.

  The magnetoelastic film in the absorbing structure according to the present invention is a thin film, and the film is selected from the group consisting of magnetostrictive materials such as magnetoelastic materials, soft magnetoelastic materials, amorphous magnetoelastic materials, and mixtures thereof. .

  The invention also includes a diaper, a pant-type diaper, an incontinence garment, a sanitary napkin, a wipe, a towel, a tissue, a bed, comprising an absorbent structure according to the invention, a body fluid permeable sheet, and an essentially body fluid impermeable bottom sheet Absorbent articles such as protectors, wound dressings, or similar products are provided.

  In another aspect, the present invention provides an absorption structure according to the present invention that is optionally part of an absorbent article according to the present invention, an excitation coil that generates a magnetic field to magnetize the magnetoelastic film, and optionally a magnetoacoustic resonance frequency. A sensing and absorption system is provided that includes a handheld unit that includes a pick-up coil for detection.

In a further aspect, a method for detecting wetness, at least one bioanalyte and / or at least one chemical analyte is provided. Such a method includes the following steps:
a) providing an absorbent structure according to the invention, an absorbent article according to the invention, or a system according to the invention;
b) applying a magnetic field;
c) exciting the magnetoelastic film of at least one sensing means in the absorbing structure;
d) turn off the magnetic field;
e) record the magnetoacoustic resonance frequency;
f) repeat steps b) -e) if desired; and g) detect changes in magnetoacoustic resonance frequency to detect wet / moisture / humidity, at least one organism and / or chemical analyte in the absorbing structure. .

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows an absorbent structure 11 according to the present invention suitable for an absorbent article such as a diaper. Absorbent structure 11 may include a soft non-woven material, a perforated plastic film, etc., as in the prior art, and a body fluid permeable layer 12 intended to lie close to the wearer during use, and a body fluid impermeable bottom. Surrounded by the sheet 13. The sheets 12 and 13 have portions that may extend beyond the absorber 11. The absorbent structure shown in FIGS. 1a and 1b has at least one sensing means 17 comprising a magnetoelastic film placed in different positions in FIGS. 1a and b.

  FIG. 2 shows a magnetoelastic film, an excitation coil, and a pickup coil. The magnetoelastic film is magnetized by an excitation coil having a pulsed magnetic field. The magnetic film is magnetized and the reaction from the film is detected by a pickup coil.

  FIG. 3 shows an experimental configuration for detecting the magnetoacoustic effect. The external coil is an excitation coil. The internal coil is a pickup coil positioned around the METGLAS® film. The central coil is used to cancel the magnetic field from the excitation coil.

  FIGS. 4a-f show five different examples for sensors that detect magnetic, METGLAS® film, wet, at least one bioanalyte and / or at least one chemical analyte.

  FIG. 5 shows a diagram of a handheld unit that may be used to excite the magnetoelastic film, detect the reaction from the film, and provide results to the user. It includes a signal generator that generates a signal that is sent to the excitation coil, and a detection circuit that receives and detects the signal from the pickup coil. The presentation unit presents the results to the user in an appropriate way.

  6A-C show a diaper comprising an absorbent structure according to the present invention, a front part, a rear part, and a crotch part between the front part and the rear part.

  FIG. 6A is a diaper having one sensing means 20 in the absorbent structure.

  FIG. 6B is a diaper having five sensing means 20 placed on various parts of the absorbent structure.

  FIG. 6C is a diaper having four sensing means 20 in the front part of the absorbent structure.

  FIG. 7A is a perspective view of a simplified example of an unassembled pant-type diaper having a single sensing means 35 placed on an absorbent structure.

  FIG. 7B is a perspective view of a simplified example of a pant-type diaper in the assembled state or ready to be worn.

  FIG. 7C shows the same as FIG. 7A, but with four sensing means 35 placed on the absorbing structure.

  FIG. 8 shows a cut-away view of the tampon structure to show the sensing means 39 placed in the tampon absorption structure.

  FIG. 9 shows a wipe having a plurality of individual sheets.

  FIG. 10 shows an absorption sensing unit.

  FIG. 11 shows an experimental configuration in an experiment having a circular excitation coil and an 8-shaped pickup coil.

  FIG. 12 shows a diaper placed in an experimental configuration. The pickup coil is directly under the diaper (not visible).

FIG. 13 shows the frequency shift from 5.93 × 10 ⁴ Hz to 5.75 × 10 ⁴ Hz when synthetic urine is detected by a wet sensor coated with polyvinylpyrrolidone (PVP).

FIG. 14 shows the frequency shift from 5.83 × 10 ⁴ Hz to 5.69 × 10 ⁴ Hz when synthetic urine is detected by a wet sensor coated with cross-linked polyvinyl alcohol (PVOH).

FIG. 15 shows the frequency shift from 5.71 × 10 ⁴ Hz to 5.63 × 10 ⁴ Hz when synthetic urine is detected by a wet sensor coated with sodium chloride (NaCl).

FIG. 16 shows the frequency shift from 5.81 × 10 ⁴ Hz to 5.74 × 10 ⁴ Hz when the AA means is attached to the absorbent structure 27 cm from the center front of the liquid-impermeable bottom sheet.

  FIG. 17 shows the frequency shift from two different sensors placed at various positions on the absorbing structure.

FIG. 18 shows the frequency shift from 5.76 × 10 ⁴ Hz to 5.66 × 10 ⁴ Hz when using the sensor without Metglas film containment.

FIG. 19 shows the frequency shift from 6.00 × 10 ⁴ Hz to 5.95 × 10 ⁴ Hz when using the sensor without a permanent magnet.

  FIG. 20 shows the frequency shift from 58680 Hz to 58480 Hz when using Metglas coated with a cationic polymer.

  FIG. 21 shows the frequency shift from 58140 Hz to 57980 Hz when using Metglas coated with a colloidal suspension.

  FIG. 22 shows the frequency shift from 57899 Hz to 58060 Hz when using Metglas coated with a hydrophobic polymer.

  FIG. 23 shows the frequency shift from 58665 Hz to 58428 Hz when using Metglas coated with a cationic polymer.

  FIG. 24 shows a close-up of the central part of the experimental setup showing the configuration of the U-shaped excitation / detection coil 2 of the devices 1 and 8 under test.

  FIG. 25 shows an overview of the experimental configuration of Experiment 7-11. The device 1 under test is placed horizontally in the center of the configuration. Below the sample 1 is a figure 8 pickup / detect and excitation coil 2 configuration. The outermost coil pair is a Helmholtz coil 3 used to apply a homogeneous magnetic field. The concentric coil pair 4 in the Helmholtz coil 3 was not used for these measurements. The magnetoelastic detection unit 5 can be seen under the coil. The magnetoelastic detection unit is connected 6 to the excitation / detection coil 2.

Definitions As used herein, the term “absorbent article” relates to means for absorbing, retaining and containing body excretion or exudate. The means is placed against or near the wearer's body to absorb, retain and contain various body excretion or body exudates from the body.

  The term “disposable” is intended herein to mean an absorbent article that is not intended to be washed, restored or reused as an absorbent article. Such absorbent articles are intended to be discarded after a single use. Single use does not exclude that the product is recycled, composted or otherwise disposed of in an environmentally compatible manner.

  The term “sensor” is intended herein to mean a means capable of detecting an event or a parameter associated with an event. Parameters associated with an event are measurable signals associated with the occurrence of the event within the skeleton of the system, such as signals generated by excreta, a wearer, or components thereof. Sensors include anything that responds to one or more specific inputs.

  The term “sensing” is intended here to mean a means and method capable of detecting an event or a parameter associated with an event, for example by a sensing means.

  The term “wet” is intended here to mean a state that is wet, humid, damp or moisture, or that contains or is covered by a liquid.

  The term “diaper” is intended herein to mean an absorbent article generally worn around the lower torso by infants, toddlers and incontinent persons.

  The term “user” is intended here to mean a) the user of the absorbent article or b) the nursing assistant of the user of the absorbent article.

  The term “magnetostriction” relates to the general phenomenon for magnetic materials. Magnetostriction means that when a magnetic material is magnetized, the dimensions of the material change. The size of the dimensional change depends on the temperature of the material, the magnetization, and of course the material properties. Magnetostriction is due to the interaction between the atomic magnetic moments of the material.

  The term “magnetoacoustic resonance frequency” relates to the vibration frequency. Such a frequency occurs when the magnetic material is excited by a magnetic field and stores magnetic energy in a magnetoelastic manner. When the magnetic field is turned off, the material exhibits a damped vibration with a specific frequency referred to as the magnetoacoustic resonance frequency.

  The term “bioanalyte” or “biomolecule” is intended herein to mean a biologically derived material.

Absorbent structure In normal use, the absorbent structure of absorbent articles such as diapers, pants-type diapers, incontinence garments, sanitary napkins, bed protectors, wound dressings are body excretion or exudates such as urine, feces, blood, menstrual blood Acts to absorb, retain and separate bodily fluid materials, rinses and saliva from wounds.

  As revealed above, the present invention relates to a sensing and absorbing structure, in which the sensing portion is easily monitored, in a cheap and disposable manner, in or after a urination event that reflects the state of the absorbing structure. Means and methods for monitoring conditions by measuring wetness or moisture will be realized. Changes in conditions such as wetting or humidity may reflect events such as urination or defecation events. Easily monitored means include remote access to conditions, such as wet conditions, without moving the user in any way, and continuous monitoring of conditions, such as wet conditions, nutritional conditions and / or health conditions over time May be realized.

  According to the present invention there is provided an absorbent structure comprising at least one absorbent layer and at least one sensing means comprising a magnetoelastic film.

  In a further example, the at least one absorbent layer includes an acquisition layer, a storage layer, and optionally one or more wicking layers. The acquisition layer is intended to take in bodily fluids, suck up and disperse the bodily fluids in the storage layer.

  In one example, the absorbent structure is a disposable absorbent structure.

  Another example includes an absorbent structure in which at least one of the layers comprises 0-100% superabsorbent material.

  In further examples, the layer may comprise 0-95%, 20-100%, 0-30%, 20-90%, or 30-40% superabsorbent material.

Absorbent structure for use in a diaper product or bed protector One example of the present invention includes an absorbent structure according to the present invention, wherein the absorbent layer includes at least one acquisition layer and at least one storage layer. Such absorbent structures may be included in diapers, pant diapers, incontinence clothing, sanitary napkins and similar products.

  FIGS. 1 a and b show two examples of an absorbent structure 11 according to the present invention suitable for an absorbent article such as a diaper. Absorbent structure 11 may include a soft non-woven material, a perforated plastic film, etc., as in the prior art, and a body fluid permeable layer 12 intended to lie close to the wearer during use, and a body fluid impermeable bottom. Enclosed between sheets 13. Sheets 12 and 13 have portions that may extend beyond absorber 11. These sheets are joined together at these overhangs. The lower sheet 13 is made of a suitable plastic material such as polyethylene, for example, a laminate, a laminate between nonwoven fabric and polypropylene, or a laminate between polyolefin and nonwoven fabric. It may be filled with an organic filler. However, it will be understood that other known materials for the upper and lower sheets may be used within the scope of the present invention.

The absorbent structure is composed of two or more layers, an upper acquisition layer 14, one or more wicking layers 15, and one or more storage layers 16. These layers may be composed of conventional cellulose fiber materials. The purpose of the acquisition layer is to receive a certain amount of bodily fluids or solids, or mixtures thereof, bodily excretion or exudates, such as urine, feces, blood, menstrual blood, bodily fluid substances from wounds, rinses and saliva That is. Body fluid is held loosely in the fiber structure and is quickly drained therefrom. The acquisition layer is composed of dry-formed and wet-formed materials according to the present invention, is composed of a low density open structure, and may contain 0-30% superabsorbent material (SAP). The SAP in the acquisition layer 14 preferably has a high gel strength, so that an open three-dimensional fiber structure will be retained in this layer after wetting. A preferred density range for the acquisition layer 14 is 0.30-1.0 g / cm ³ . A suitable weight range per unit area for the acquisition layer 14 is 20-1200 g / m ² .

The primary purpose of the wicking layer is to effectively transfer body fluid received in the acquisition layer 14 to the storage layer 16 located below the wicking layer 15, with the bulk of the storage layer 16 being utilized for absorption purposes. Is to make sure. The wicking layer therefore has a relatively low superabsorbent content. In the case of the wicking layer 15, the preferred superabsorbent content may be 0-20% and the preferred density range may be 0.18-1.0 g / cm ³ . A suitable weight per unit area for the wicking layer 15 may be 50-1500 g / m ² .

The purpose of the storage layer 16 is to absorb and bind body fluid, which is dispersed in the storage layer 16 through the wicking layer 15. Therefore, the storage layer 16 may have a high density. A suitable density value may be 0.18-1.0 g / cm ³ and a suitable superabsorbent content may be 20-100%. In a further example, a suitable superabsorbent content may be 30-40%. A suitable weight range per unit area in the case of the storage layer 16 is 100-1500 g / m ² .

The wicking layer 15 and the storage layer 16 may be combined to form a single layer if desired. In this case, the single layer will have a high superabsorbent content and a high density. A suitable density value may be 0.125-1.0 g / cm ³ , while a suitable superabsorbent content may be 20-90%. A preferred weight range per unit area when the wicking layer and storage layer are combined is 100-2000 g / m ² .

  When the wicking layer 15 and storage layer 16 are combined, the superabsorbent content of the layer can be varied throughout the product to obtain a superabsorbent gradient in the depth, length and / or width direction of the product. .

  The absorbent structure may include several layers, such as one layer or two, three or more layers.

  The various layers may have different shapes and sizes. Usually, the absorbent structure is combined with an elastic body in the form of the crotch region of the product, for example a diaper, in order to improve production efficiency.

  According to the present invention there is provided an absorbent structure comprising at least one absorbent layer and at least one sensing means 17 comprising a magnetoelastic film. In FIGS. 1a and 1b, the position of at least one sensing means 17 is shown. In the two examples shown, the sensors are placed at various depths in the absorbing structure. Furthermore, other positions and numbers of sensors are also contemplated within the scope of the present invention and are discussed further below.

Absorbent structure used for bed protectors, wipes, towels or tissues One example according to the present invention is an absorbent structure, wherein at least one absorbent layer comprises at least one dry layer, the layers optionally comprising a plurality of It includes individual sheets and joining means for joining the individual sheets. The multiple sheets allow the manufacture of exact desired thicknesses such as wipes, towels, bed protectors and tissues that may vary from case to case according to different specific applications.

  FIG. 9 shows an example of an absorbent structure according to the invention comprising at least one sensing means for detecting wetting, wherein at least one absorbent layer comprises at least one dry layer. The figure shows a cloth for removing unwanted substances from an object by wiping, said cloth comprising an absorbent structure according to the invention having a plurality of individual sheets and a coupling means for joining the individual sheets together .

  The fabric may be a wipe for home or commercial use, or industrial or sanitary use. Further, the fabric may be an oil wipe useful for wiping oil, a solvent wipe useful for solvent cleaning, a wet wipe useful for wet wiping, or a material suitable or undesirable for hygiene or household applications Other wipes suitable for removing may be used.

  Suitable wipes for hygiene or housekeeping applications may be housework items such as sanitary wipes, kitchen towels, napkins or industrial wipes.

  The undesirable substances are fluids such as household or industrial spills, high viscosity liquids, water, oils, solvents, chemicals, particles, dust, dirt such as grease, stains, dirt or any type of household soil. May be.

  The object is an object that requires the removal of undesirable substances, such as the whole body or a part of the body, such as hands, faces, feet, etc., such as machines, vehicles, printing plates, tools, floors, walls, furniture, tables, etc. It may be part or surface.

  “Removing unwanted material from an object by wiping” means removing unwanted material from the object by wiping, rubbing, rubbing, stroking, etc. using the cloth.

  Each individual sheet may comprise a suitable natural or synthetic material such as, for example, woven or non-woven type, tissue, and the sheet may be homogenously or heterogeneously shaped from the fibers described below.

  The individual sheets are, for example, polyamide, polyester, polypropylene, polyethylene or copolymers thereof, or thermoplastic fibers, core-sheath composite fibers comprising a polypropylene core and a polyethylene sheath, copolyester fibers or unstretched polypropylene fibers, or continuous filaments, For example, it may comprise polyethylene terephthalate continuous filaments, or polyurethane, polyurea, cellulose or cotton fibers, peat, or polylactide. Further, the individual sheets may include two or some of the components listed herein or mixtures thereof.

  The joining means for joining the individual sheets together may include, for example, techniques from conventional layer bonding or conventional bonding techniques, such as hot or cold bonding systems, and the use of spot or strip bonding.

  According to an example of the invention, the plurality of individual sheets may have matching edges, and the plurality of individual sheets may be joined together by the joining means at the edges.

  In another example of the invention, the plurality of individual sheets may be joined together by the joining means in spots or strips.

  All bonding variations as disclosed herein may be achieved by using techniques from conventional layer bonding or conventional bonding techniques, such as hot or cold bonding systems, and spot or strip bonding.

  The individual sheets may comprise a non-woven material, where the non-woven material may be made, for example, by meltblowing, spunbonding or carding, the non-woven material being for example fluid jet entanglement or other entanglement, super Further processing may be performed by sonication or embossing. The nonwoven material may be made from natural fibers, wood pulp fibers, cotton fibers or linen fibers or other artificial cellulosic fibers such as viscose or rayon, for example synthetic fibers such as polymer fibers or thermoplastic polymer fibers.

  In a further fabric according to the invention, the individual sheets may comprise a tissue material, wherein the tissue material covers a fibrous material based on cellulose in combination with cellulose or synthetic fibers.

  Individual sheets may be heterogeneous. A sheet is said to be heterogeneous when the sheet consists of more than one material, where the material may have different properties. Each foreign individual sheet may include, for example, an absorbent layer and a liquid barrier layer, where the absorbent layer of the exposed individual sheet may constitute the exterior of the fabric. The liquid barrier layer may be a liquid impermeable layer and may include, for example, a thermoplastic film.

  FIG. 9 shows an absorbent structure 1, which comprises a plurality of individual sheets 2 and a body 3. The individual sheets 2 have matching edges, and the matching edges have coupling means 4 for joining the individual sheets 2 together. Each of the individual sheets 2 includes an absorbent layer 5 and a liquid barrier layer 6. Furthermore, in FIG. 9, a single individual sheet 7 that has been partially removed from the fabric 1 is also shown.

  According to the invention, at least one sensing means is placed on the absorbent structure. The sensing means may be placed on any of the at least one absorption layer. The exact positioning of the sensor depends on the specific application of the wipe, tissue, towel or similar product and how the material to be removed is to be absorbed. Thus, each example must be considered individually when placing the sensor in an optimal manner with respect to both the exact location of the sensor and the number of sensors.

Sensing means for detecting wetness, at least one biological analyte and / or at least one chemical analyte For example, when a magnetic field is applied to a ferromagnetic material, the dimensions of the material change as a result of the magnetostriction. The size of the material dimensional change is governed by the magnetostriction constant.

  When a magnetic material is excited by a magnetic field, it stores magnetic energy in a magnetoelastic manner. When the magnetic field is cut off, the material exhibits vibrations damped at a specific frequency, the magnetoacoustic resonance frequency. These vibrations produce a time-varying magnetic flux that can be detected remotely by a pickup coil.

Magnetostriction has many materials such as iron, nickel, cobalt, rare earth metals, and various alloys such as iron-nickel alloys, ferrites such as spinel ferrite (Fe ₃ O ₄ , MnFe ₂ O ₄ ), silicon iron alloys, And many other various alloys can be observed.

  Further examples may use soft magnetic materials, alloys or mixtures thereof.

A still further example is that amorphous magnetic materials, alloys or mixtures thereof may be used because it is very easy for amorphous magnetic materials to be magnetically saturated and exhibit small magnetic anisotropy. In alloy amorphous magnetic materials, there is also magnetostriction, and the amount of magnetostriction depends on the exact composition of the alloy. Examples of amorphous alloys are Fe ₄₀ Ni ₃₈ Mo ₄ B ₁₈ , such as Metglas 282MB® (Honeywell Amorphous Metals, Pittsburg, PA, USA) (FeCO) ₈₀ B ₂₀ , (CoNi) ₈₀ B ₂₀ , (FeNi ) is a metglase such as ₈₀ B _20.

  One example uses METGLAS (R) from Honeywell (Honeywell Amorphous Metals, Pittsburg, PA, USA) as a magnetoelastic material such as METGLAS (R) 2826MB.

  One way to further enhance the magnetostrictive effect is to include a magnetic bias field. FIG. 4e shows an example of such a bias field that includes two electrodes. The two electrodes in FIG. 4e are made of Cu and Al, respectively. An example of the present invention includes such a magnetic bias field. The magnetic bias field has an optimal magnetic bias field that provides an optimal magnetoacoustic effect and further provides an optimal signal from the magnetoacoustic effect (Grimes et al., Sensors and Actuators, B71: 112-117, 2000). In one example, the magnetic bias field is generated by a permanent magnetic film placed in association with a magnetoelastic film.

  According to the invention, the described absorbent structure comprises at least one sensing means comprising a magnetoelastic film. Suitable magnetoelastic films may be films having non-zero magnetostriction and high magnetoelastic coupling, such as iron-nickel alloys, rare earth metals, ferrites, many different alloys and mixtures thereof, as described above. . Film is intended to mean a film having a thickness of about 0.01 to 1000 μm, such as 0.01 to 200 μm, 5 to 100 μm, or 0.01 to 100 μm. Also, the thickness of the film may be much smaller than the width and length of the film.

  A magnetoelastic material could be used as a sensor for changes in environmental properties as long as the magnetoacoustic resonance frequency changes when the environmental properties change. Changes in environmental properties include changes in substances that are further described as chemical analytes such as water, liquids, urine, moisture or moisture, or proteins, hormones, microorganisms such as pathogenic and non-pathogenic as described below Achieved by binding of biological or chemical analytes such as bacteria, viruses, fungi, and parasites such as protozoan; glucose or bacterial toxins, nutritional markers, DNA, RNA, mammalian cells such as blood cells such as lymphocytes Is done.

  According to the invention, the magnetic field is applied to the magnetoelastic film in the absorbing structure. The magnitude of the pulsed magnetic field must be large enough to magnetize a material, such as a magnetoelastic film, to achieve a sufficiently large change in material dimensions. The particular magnetic field must therefore be optimized for each selected magnetostrictive material.

  A further example is where a pulsed magnetic field or a pulsed sinusoidal magnetic field is applied to the magnetoelastic film in the absorbing structure according to the invention. At that time, the characteristic resonance frequency between magnetic pulses, ie the magnetoacoustic effect, could be detected.

  Various examples include the case where the pulse frequency is about 10 to 1000 Hz.

  Still further examples include the case where the pulse frequency is about 50-700 Hz.

  The duty cycle of the pulse may be about 1-90%. Further examples include the case where the duty cycle is 10-50%.

  In a special example, the magnetic field is a pulsed sinusoidal field. Such a sine wave may be about 50-60 kHz.

  In one example of using METGLAS® from Honeywell as the magnetoelastic material, the magnetic field magnitude of the pulse field may be about 0.05 to 0.1 mT.

  Yet a further example may include a magnetic bias field of about 0.5-1 mT when using METGLAS® from Honeywell.

  Further examples are the case where the excitation frequency is liquid, moisture or moisture, such as urine, or absorption of at least one biological analyte and / or at least one chemical analyte, or surface coating of a magnetoelastic film such as a METGLAS® film. For desorption, this includes the case where the frequency shift and Q value change (where Q = F / (ΔF)) is swept across the resonance frequency (is swept cross).

  In a further example, a thin ribbon of magnetoelastic material is used. For example, the magnetoacoustic resonance frequency for a thin ribbon of magnetoelastic material is inversely proportional to the length of the ribbon. Thus, various resonance frequencies can be achieved in one sensing means.

  In order to detect changes in the resonance frequency, here the magnetoacoustic effect, the sensor must be designed to measure the correct mass change. The sensor may then be coated with a polymer or other material that interacts with moisture, eg, moisture, liquid, or moisture, which produces a detectable change in magnetoacoustic vibration.

  One way to do this is to coat the magnetoelastic film with a mass changing material or a material whose properties can be changed in such a way as to affect the mass of the sensing means. This may be achieved in various ways, for example by weight gain by combining liquids or by weight loss by dissolving, for example as shown in FIG. 4d. This method, as well as suitable materials for accomplishing this, are described in detail in the paragraphs “absorbing structures with sensing means for sensing wetness” or “absorbing structures with sensing means for sensing biological or chemical analytes” below. Has been described.

Various sensor examples Various sensor examples are possible.

  One example includes a sensor that can be packaged or encapsulated that is not exposed to mechanical pressure that may affect, for example, the resonant frequency. In such an example, the sensor is found in the detected bodily waste or exudate, wet, at least one bioanalyte and / or at least one chemical analyte is passed through the package by a hole, groove or hole in the package material. It may be packaged in such a way that it can penetrate into the magnetoelastic sensor. Suitable encapsulations include, for example, tag-shaped encapsulations such as commercially available tags from Sensomatic, or similar products. Thus, the encapsulation is designed or selected by those skilled in the art to fit the specific example in each case.

  In a particular example, the mechanical pressure may correspond to the amount of analyte to be detected, eg, wet, moisture or moisture, at least one biological analyte and / or at least one chemical analyte. Such an example may include the case where the package around the sensor is designed with a magnetoelastic sensor to allow liquid to permeate the area where the absorbent material, eg SAP, is present. There may then be a mechanical pressure on the sensor corresponding to the amount of liquid such as urine, at least one biological analyte that prevents or reduces vibration and / or at least one chemical analyte. Such an example is shown in FIG. 4b.

  In another example, a permanent magnet is included in the sensing means as shown in FIG. 4c. Thus, when the absorbent material swells due to the absorption of liquids such as urine, moisture or moisture, the absorbent material will push the permanent magnet closer to or away from the magnetoelastic sensor, which will change the magnetic field. Such changes in the DC magnetic field on the sensor affect magnetoacoustic vibration and are correlated with the amount of liquid such as urine, moisture or moisture absorbed.

  Further examples including coatings are described in detail below in the paragraph “Absorbing structure with sensing means for sensing wetness”.

  FIG. 2 shows how detection from the magnetoacoustic effect is performed by using one excitation coil to magnetize the magnetic material and one pickup coil to detect the reaction from the material.

  In FIG. 3, the same thing as FIG. 2 is shown, but the experimental setup for detecting the magnetoacoustic effect is shown. In the figure, the external coil is an excitation coil. The internal coil is a pickup coil positioned around the METGLAS® film. The central coil is used to block the magnetic field from the excitation coil by this experimental setup. The positions of the excitation coil and the pickup coil are further described in the following “Handheld Unit” paragraph.

  In various examples according to the invention, the absorbing structure includes at least one sensing means. Due to the different sizes and shapes of such products, the number of sensing means may vary according to different examples. Specific examples may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 30, 40, 50 sensing means.

  The actual position of the sensor may vary depending on various absorption patterns of body fluids, body excretion or body exudates such as urine, feces, blood, menstrual blood, fluid material from wounds, rinses and saliva. Also, different types of absorbent structures and absorbent articles produce different types of absorbent patterns due to the different preferred thicknesses of the absorbent articles and the different examples of different wettability properties, which place the sensors on the absorbent structures and absorbent articles Sometimes it must be taken into account.

  Various examples of the invention shown in the drawings and specification illustrate the invention showing a sensor placed on an absorbent product. It will be understood that the present invention is not limited to the illustrated or described examples with respect to the actual number of sensing means and how at least one sensing means is located.

Handheld unit Handheld an excitation coil for applying a magnetic field (which may be a pulsed magnetic field or a pulsed sinusoidal field) and a pickup coil that collects the generated signal (ie magnetoacoustic effect) It may be provided in the unit. In one example, the handheld unit includes both an excitation coil and a pickup coil.

  In a further example, the same coil may be used as both an excitation coil and a pickup coil, i.e. for both excitation and detection.

  In FIG. 5, a schematic of a handheld unit that may be used to excite the magnetoelastic film, detect the reaction from the film, and provide the result to the user is provided. It includes a signal generator that generates and sends a signal to the excitation coil and a detection circuit that receives and detects the signal from the pickup coil. The presentation unit presents the results to the user in an appropriate way. The signal generator is connected to the detection circuit so that the detection circuit “knows” when the signal is sent to the excitation coil. Furthermore, the handheld unit must be designed to minimize the magnetic coupling between the excitation coil and the pickup coil. The position of the pickup coil relative to the excitation coil is optimized for maximum signal from the film and minimum signal due to the magnetic field from the excitation coil. The pick-up coil may be oriented at 90 ° with respect to the excitation coil and may be placed on the excitation coil. There may be signal noise in the pip-up coil due to changes in the magnetic field of the excitation coil, but this is handled by appropriate signal processing.

  In a further example, the excitation coil and the pickup coil may be separated in different units.

Absorbent structure with sensing means for sensing wetness The absorbent structure comprises in a particular example a magnetoelastic film coated with a wet sensitive material. The coating may be applied directly on the magnetoelastic film or may indirectly have other layers between the magnetoelastic film and the polymer.

  In a particular example, the moisture sensitive material may absorb moisture such as urine, in which case the mass of the sensing means may be changed, which will increase or decrease the total weight of the sensor. This mass change increases or decreases the resonance frequency, ie the magnetoacoustic effect, and is therefore measurable and is further related to the amount of urine-like moisture absorbed by the sensing means.

  In FIGS. 4a-f, various examples of sensing means are shown. FIG. 4a shows the mechanical vibration from the Metglas film, which can vary differently in various examples depending on how wetting is detected. Various examples are described in further detail below.

  With respect to FIG. 5, the change in mass will be picked up by the pickup coil as a change in magnetoacoustic frequency due to the change in mass of the magnetoelastic film, and the signal will be detected by a detection circuit that detects the signal from the pickup coil.

  A further example is shown in FIG. This example includes the case where the package around the sensor is designed to allow liquid to penetrate into the area where the absorbent material, e.g. SAP, is present with the magnetoelastic sensor as shown in Fig. 4b. The SAP will exert a mechanical pressure on the sensor when it absorbs liquid, moisture or moisture. The pressure will be related to the amount of liquid or moisture, for example, which dampens the vibration completely or partially. Thus, a decrease in the magnetoacoustic effect will be detected when the vibration is attenuated.

  Yet another example is shown in FIG. In this example, an absorbent material such as SAP pushes the permanent magnet close to or away from the magnetoelastic sensor when wet or when wet. This will change the magnetic field. Such a change in the DC magnetic field on the sensor affects the magnetoacoustic vibration. Thus, an increase or decrease in magnetoacoustic effect can be detected in the example shown in FIG. 4c or a similar example that detects such a change in vibration.

  In FIG. 4d a further example is shown. The magnetoelastic film of FIG. 4d is coated with a material that dissolves when exposed to a moist liquid, for example, a low molecular weight compound such as NaCl, as shown. This can also cause mass changes and thus increase the magnetoacoustic resonance frequency.

  In FIG. 4e an example of a sensing means including a bias field coil is shown. Such an example may include two electrodes made of, for example, Cu or Al.

  In FIG. 4f, an example of sensing means is shown. The magnetoelastic film of FIG. 4f is coated with a moisture sensitive material that swells when exposed to moisture liquid as shown. This can cause a mass change and thus increase the magnetoacoustic resonance frequency. Wet sensitive materials are based on polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide and copolymers thereof, polyurethane, polyamide, starch and derivatives thereof, cellulose and derivatives thereof, polysaccharides, proteins, polyacrylonitrile, acrylate based polymers, and mixtures thereof. Selected from the group consisting of linear and hydrophilic polymers or chemically / physically crosslinked swellable polymer gels.

  In yet another example, sensors including different lengths of magnetoelastic film (which would give different resonance frequencies) may be placed at various locations in the product. This would allow a readout looking for the exact location or part of the wet product.

Absorbing structure with sensing means for sensing biological or chemical analytes The absorbing structure may comprise a magnetoelastic film in a further example, which is directly coated with at least one detection molecule on the sensing means or indirectly Covered, i.e. with other layers, such as a suitable binding layer in between, adapted to detect body excrement, body exudates or target biological or chemical analytes in the skin of the user / wearer The

  The term “biological analyte” is used herein to refer to biologically derived materials, such as enzymes; antibodies, membrane receptor proteins; DNA, RNA; proteins, peptides, organelles, natural or synthetic cell membranes; It is intended to mean a living, non-viable bacterium, plant or animal cell; or piece of plant or mammalian tissue or other biologically derived molecule. Further examples are given below.

  The absorption structure according to the invention may in further examples comprise at least one sensing means for sensing biological or chemical analytes, which analytes are enzymes, antibodies, nucleic acids such as DNA or RNA, proteins such as soluble proteins or membranes. A protein; a peptide such as an oligopeptide or polypeptide; a cell membrane or capsid, such as a bacterial or mammalian cell membrane, or a virus capsid, lipid, carbohydrate, lectin, and mixtures thereof.

  Further examples are that at least one sensing means is a pathogenic bacterium, a non-pathogenic bacterium, such as a colony bacterium, a virus, a parasite, a bacterial toxin, a fungus, an enzyme, a protein, a peptide, a mammalian blood cell, such as a human white or red blood cell, When targeting a biological or chemical analyte selected from the group consisting of hormones, mammals including humans, blood components such as blood sugar; urine and its components such as glucose, ketones, urobilinogen, and bilirubin; and mixtures thereof It is.

  Still further examples are pathogenic or non-pathogenic bacteria such as Escherichia coli, Salmonella typhi, Salmonella paratyphi, Salmonella salmonella salmonella salmonella ), Salmonella heidelberg, Staphylococcus aureus, Shigella sonnei, Shigella flexneri, Shigella flexneri igella boydii), Shigella Daisen terrier d (Shigella dysenteriae), Byiburio cholera (Vibrio cholerae), Mycobacterium Chubakuroshisu (Mycobacterium tuberculosis), Erushina enterocolitica (Yersina enterocolitica), Aeromonas hydrophila (Aeromonas hydrophia), Purimonasu Shigeroidesu (Plemonas shigelloides, Campylobacter jejuni, Campylobacter coli, Bacteroides fragilis, Black Torijia septicum (Clostridia septicum), Clostridia perfringens (Clostridia perfringens), Clostridia botulinum (Clostridea botulinum), Clostridia Jifishire (Clostridia difficile), and the case is selected from the group consisting of mixtures thereof.

  Another example is where the sensing means includes sensing chemical compounds or analytes such as health markers or nutritional markers. The health marker or nutrition marker reflects the nutritional status of the wearer.

  Nutritional markers include, for example, metabolic efficiency, nutritional deficiencies, nutrient absorption or malabsorption, food and beverage absorption, food allergies (eg against peanuts), food intolerance (eg lactose or gluten intolerance), colony bacterial ecology (bifidobacteria and lactose) Beneficial bacteria such as Bacillus), and markers for total energy balance.

  Health markers include heavy metals (eg, lead, mercury, etc.), radioactive substances (eg, cesium, strontium, uranium, etc.), fats, enzymes, endogenous secretions, protein substances (eg, white spheres), mucus, and microorganisms as described above Chemical analytes such as those that may be associated with various health problems such as disease infection, diarrhea, gastrointestinal disease, or addiction. Heavy metals are a serious health risk, especially in some developing countries and in developed countries where they are not wealthy or old. For example, lead and mercury poisoning can occur with ingestion of these heavy metals from environmental sources (eg, from lead paint, chaotic heavy industry, etc.) and can be fatal. More generally, low-level poisoning with these and other heavy metals particularly delays children's intellectual and / or physical development, which occurs over a long period of time and can have a lasting effect on the individual.

  Other examples of nutrition markers are calcium, vitamins (eg thiamine, riboflavin, nicotinic acid, biotin, folic acid, pantothenic acid, ascorbic acid, vitamin E etc.), electrolytes (eg sodium, potassium, chlorine, bicarbonate etc.), Contains fats, fatty acids (long and short chains), soaps (eg calcium palmitate), amino acids, enzymes (eg lactose, amylase, lipase, trypsin, etc.) bile acids and their salts, steroids and carbohydrates. For example, calcium malabsorption is important in that it can lead to long-term bone material deficiency.

  Examples 8-11 are for example cationic polymers such as polyethyleneimine (eg PEI from Sigma-Aldrich), colloidal suspensions such as polybead polystyrene (PS) microspheres (eg from Scientific Polymer Products), or polystyrene. METGLAS® as a biosensor such as a biosensing device using a detection molecule that is totally or partially physiologically absorbed using a hydrophobic polymer such as (for example from Scientific Polymer Products) Demonstrate the use of The experiment shows the use of coated METGLAS® for the detection of bacteria and blood cells such as lymphocytes.

  Suitable for binding or coating directly or indirectly on a sensing means, i.e. a magnetoelastic surface, e.g. Metglas, i.e. a metallic glass, an amorphous metal, and thus a magnetoelastic surface sensing bioanalytes or chemical analytes. Such detection molecules may include any biological recognition element, and may further include carbohydrates, antibodies or portions thereof, synthetic antibodies or portions thereof, enzymes, lectins, DNA (deoxyribonucleic acid), RNA (ribonucleic acid), cells, and / or Explained by cell membranes or other molecules that have the ability to bind to a defined biological or chemical analyte.

  It will be apparent to those skilled in the art that suitable means of applying the detection molecule by physical adsorption onto the Metglas surface is suitable for other applications. For example, the detection molecule may be chemically coupled directly or indirectly to the surface using any one of a variety of common cross-linking molecules (including but not limited to glutaraldehyde, N-hydroxysuccinimide, carbodiimide). May be desirable.

  It may be desirable to use a technique for making a self-assembled monolayer (SAM) on the detection surface as a means of coating the detection molecules, especially for high precision applications. SAMs can be made by a number of different techniques familiar to those skilled in the art. One preferred method of making a SAM is to first deposit a monolayer of an element such as gold, copper, silver, lead, platinum, or carbon on the sensing surface of a Metglas film. Gold is the most preferred element for use in coating films.

  By immersing the coated Metglas film in a solution of organic molecules containing thiol, dithiol, nitrile, carboxylic acid, amine or silane functional groups, the SAM layer will spontaneously form on the coated surface. Long-chain alkanes or aromatic molecules with thiol functional groups are particularly preferred for forming stable, tightly packed monolayers on the gold surface. SAMs can also be formed directly on the Metglas surface without first being coated with a monolayer of gold or other elements. Alkane phosphates and phosphonates have been shown to form SAMs on transition metal oxide surfaces and would therefore be suitable for forming SAMs on iron, cobalt or niobium based Metglas. Other methods known in the art can also be used to form the SAM.

  Once the SAM has been formed, the detection molecules can be easily bound to the monolayer by a number of known means. The detection molecule can be physically absorbed on the monolayer. The detection molecule can also be covalently attached to the monolayer molecule using a second functional group located on the individual molecule (including but not limited to succinimide, amino, carboxyl, aldehyde groups). Finally, the detection molecule can be immobilized by the use of a monolayer and a detection molecule that are labeled together with the appropriate half of the receptor-ligand pair, and the streptavidin-biotin system is used in positioning the detection molecule on the sensor. Particularly preferred for use.

  If so desired, the non-binding surface of the sensor can be blocked to prevent non-specific binding of analyte molecules to the surface. Such blocking can be accomplished in a number of ways, including but not limited to: adsorption of globular proteins such as albumin or casein on the surface, or covalent attachment of the blocking polymer to unbound sites on the SAM. Medium or short chain PEG molecules are preferred blocking agents.

Absorbent articles The absorbent structure according to the present invention may be included in various types of absorbent articles. Various examples include the case where the structure forms part of a disposable absorbent article, said article being a diaper, pant diaper, incontinence clothing, sanitary napkin, wipe, towel, tissue, bed protector, wound dressing, or the present invention. A similar article comprising an absorbent structure, a body fluid permeable top sheet, and a body fluid impermeable bottom sheet.

  Absorbent articles are further described below without limiting the invention.

Diapers FIG. 6a-c shows the absorbent structure according to the invention, the front part, the rear part, the crotch part between the front part and the rear part, and the diaper comprising at least one sensing means 20 in various parts of the diaper. Various examples are shown.

  Further, the absorbent structure is spaced from the user / wearer, and the front and rear end portions, the middle middle portion, and the inner upper sheet layer located on the side intended to face the user / wearer. There may be an outer top sheet layer located on the opposite side that is intended to face the front.

  In various examples, the diaper may be a diaper including about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 sensing means 20 in which the absorbent structure according to the present invention.

  In one example, one sensing means 20 is included. The position of such sensing means 20 may be according to FIG. 6a. The position may vary in other examples of diapers, for example depending on various diapers, eg, wetting profile and wetting point.

  The wetting point is the area of the diaper surface where bodily fluids or bodily excretion first contact. As will be appreciated, it is not generally possible to establish a specific point or area in this regard, but it is generally accepted to carry body fluids or body excrement to the diaper within that predetermined limited area. . In general, this region is slightly displaced toward the front of the diaper portion in the case of both male and female wearers. Since there is only a slight dispersion of the liquid in the first absorbent layer, ie the acquisition layer, it is sufficient for this layer to cover only the area of the diaper where wetting is most likely. Therefore, such aspects are analyzed and considered when placing the sensing means on an absorbent structure such as a diaper according to the present invention.

  In a further example, several sensors 20 that may have different resonance frequencies are placed in the absorbing structure. That position may be the front and side after the diaper, as seen in FIG. 6b. This may, for example, allow measurement of the elapsed time of wetting of the entire diaper. The position of the sensor on the side may also indicate a leak in the crotch part of the diaper, for example liquid or feces.

  The location of the sensor 20 in FIGS. 6a and 6b is only considered as an example, and further examples for the particular application and analysis to be performed are apparent. For example, if urine is to be measured, several sensors 20 may be placed in front of the diaper as shown in FIG. 6c, thus indicating a urination event.

  The diaper shown in FIGS. 6a-c is a liquid permeable top sheet 1, such as a nonwoven or perforated plastic film, a liquid impervious top sheet 2, such as a plastic film or a hydrophobic nonwoven material, and two layers 1, It consists of the absorber 3 enclosed between two.

  The diaper is intended to enclose the lower part of the wearer's torso like absorbent underpants. The diaper has a rear part 4 positioned behind the wearer when the diaper is worn, a front part 5 located in front of the wearer when the diaper is worn, and a front part 5 and a rear part 4 of the diaper. And is provided with a narrow crotch portion 6 located in the crotch region between the wearer's thighs when the diaper is worn. Fixing tabs 7 on the side edges 9, 10 of the longitudinally extending rear part 4 near the rear waist edge 11 of the diaper so as to allow the diaper to be secured in the desired pant-like form. , 8 is given. When the diaper is used, the secured tabs 7, 8 are secured to the outer surface of the front portion 5 of the diaper near the front waist edge 12, thereby holding the diaper together around the wearer's waist. .

  The diaper shown in FIG. 6 also includes pre-tensioned elastic means 13, 14 that extend over the diaper in a V-shaped pattern, with the vertex of V positioned on the front waist edge 12 of the diaper. The elastic means 13, 14 may be made of a suitable material such as an elastic foam, an elastic band or a coated elastic yarn. For convenience, the elastic means 13, 14 are shown in a stretched state. However, as soon as the tension is removed, the elastic means will contract, thereby forming an elastic leg opening on the diaper.

  The absorption structure 3 consists of different layers. Closest to the liquid permeable top sheet 1 is a thin cellulose fluff pulp layer 15 having a high critical bulk, a large pore volume and a low liquid dispersion capacity. The critical bulk means a volume that does not collapse or expand when the cellulose body is wet. High critical bulk cellulose fluff pulp will retain an open structure with a large pore volume even when wet.

  When viewed in the direction of the liquid impervious top sheet 2, then a first absorbent layer 16 consisting of cellulose fluff pulp having a large pore volume, high wet resilience and low liquid dispersion capacity, and a low pore volume, low wet resilience and high A second absorbent layer 7 made of cellulose fluff pulp having liquid dispersing ability follows. Both absorbent layers also include a superabsorbent material.

  The cellulose fluff pulp layer 15 closest to the liquid permeable upper sheet layer 17 has a T shape, and the T cross member is located in the front part of the diaper. On the other hand, the first absorbent layer 16 has an elliptical shape and is generally located in the crotch portion 6 of the diaper around a so-called wet point.

  The first receiving layer, i.e. the acquisition layer, in the diaper according to the invention functions as a receiving area for the released body fluid or body waste. CTMP fluff, CF fluff, fillings or foams are suitable for use in the first absorbent layer. SAP may also be added to this layer in various proportions.

  The first absorbent layer 16 may comprise 2 to 30%, for example 2 to 15%, of superabsorbent material, calculated on the total dry weight of the layer in the region where the superabsorbent material is mixed. The superabsorbent material may be evenly distributed within at least one region in the layer, and any remaining in the layer even when drained by the second absorbent layer 17, which may be a wicking layer. Intended to bind to liquids.

  As described above, the superabsorbent material in the first absorbent layer preferably has a high gel strength in order to maintain an open fiber structure even when wet.

  The second absorbent layer 17 also contains a superabsorbent material, which may be in the form of one or more layers such as flakes, fibers, granules, powders and the like. The layer extends throughout the absorbent layer 17 or is limited to at least one region thereof. This region may be slightly larger than the absorbent layer 16 and may be essentially limited to the crotch portion of the diaper, similar to the layer.

  The percentage of superabsorbent material contained in the second absorbent layer 17 will preferably be 2-60%, preferably 19-50%, calculated as part of the total dry weight of the layer.

  The superabsorbent material in the second absorbent layer 17 preferably has a high gel strength so as not to block or prevent the dispersion of the liquid. That is, it has the ability to swell without being substantially affected by the pressure normally generated. The property of these superabsorbent materials is that they have a high degree of cross-linking, which makes them difficult to compress compared to gels with a low degree of cross-linking.

The fluff pulp in the second absorbent layer 17 may comprise substantially fluff pulp or other absorbent material having a high liquid dispersion capacity. A chemically produced fluff pulp of cellulosic material generally satisfies this. The final fiber may have 140-190 [mu] g / m, low stiffness and low wet stability, and a critical bulk below 8 cm < ³ > / g at 2.5 kPa.

  The second layer 17 may comprise a selected fluff pulp such as CTMP pulp or chemical pulp.

  Therefore, the released body fluid or body excretion is first absorbed by the first absorbent layer 16, which functions as a buffer or reservoir, and this layer is continuously drained as the second absorbent layer 17, Absorb and disperse.

  It will be understood that the diapers shown and described are only intended to illustrate the invention and should not be considered to limit the scope of the invention. For example, the shape of the diaper and its configuration at other points may be changed. Similarly, the first absorbent layer 16 may completely cover the second absorbent layer. Further, the thin cellulose fluff pulp layer 15 located closest to the liquid permeable upper sheet layer 1 may be omitted.

  The diapers used herein are used in particular in connection with incontinence, in particular adult incontinence, and the present invention is not limited to this particular use or the particular size or type of diaper contemplated thereby, and will be understood by those skilled in the art. It should be noted that any obvious diaper can be used.

  In a further example, the diaper product including the sensing means 20 for detecting wetness is a disposable diaper.

Pant-type diaper According to the present invention, a pant-type diaper including the absorbent structure according to the present invention is disclosed. Such pant diapers include a front portion, a rear portion, and a crotch portion between the front portion and the rear portion.

  In addition, it may include at least two side closure portions that join each side edge portion of the front and rear portions together so that the diaper provides one waist opening and two leg openings. The absorbent structure has front and rear end portions, and an intermediate central portion, an inner upper sheet layer positioned on the side intended to face the user / wearer, and a surface away from the user / wearer You may have an outer top sheet layer located on the opposite side that is intended to do.

  The pant-type diaper according to the invention is in particular a diaper pant, in which the absorbent structure according to the invention comprises 1,2,3,4,5,6,7,8,9,10 sensing means.

  In FIG. 7a, one sensing means 35 is included in the pant diaper.

  FIG. 7c shows a further example with four sensing means 35 according to the invention. The sensor may be placed in a pant-type diaper such as the above diaper, or any other configuration that suits the user's wetness detection purpose.

  FIG. 7b is a perspective view of a simplified example of a pant diaper assembled or ready for wearing. Figures 7a and c show the same diaper in an unassembled state but with a different number of sensing means in the absorbent structure. The pants-type diaper has a waist opening 9 between each edge 6, 7 of the front and rear parts and two leg openings 10, 11 surrounded by each side edge 8 of the crotch part. Each side edge 4 of the front part is joined to each corresponding side edge 5 of the rear part, so that the pants are on each side of the diaper two side closure parts 12, extending from the waist opening 9 to each leg opening 10, 11. Will give thirteen. The side closure may be obtained with the aid of heat sealing, ultrasonic welding, gluing or sewing techniques or other suitable conventional techniques.

  In FIGS. 7a and c, the pant diaper is a front part 1 intended to be located in front of the wearer, a rear part 2 intended to be located behind the wearer, and a front part 1 and a rear part. 2 and includes a crotch portion 3 intended to be located between the thighs of the wearer. No exact limit can be drawn between each part, and the size relationship can be changed. As a result, the pant diaper of FIGS. 6 and 7 is only a schematic example. Each of the front and rear parts has two side edges 4, 5 and one end edge 6, 7. The crotch portion 3 has two side edges 8.

  As seen in FIG. 7b, when the pant diaper is assembled or ready for wearing, the diaper has a waist opening 9 between each edge of the front and rear parts, and each side edge of the crotch part. 8 has two leg openings 10, 11 surrounded by 8. Each side edge 4 of the front part is joined to each corresponding side edge 5 of the rear part, so that the pant diaper has two side closure parts extending from the waist opening 9 to the leg openings 10, 11 on each side of the diaper. Will give 12,13.

  7a and 7b, the pant-type diaper includes an elongated absorbent structure 14 according to the present invention, which extends in the longitudinal direction of the diaper and is enclosed between an inner upper sheet layer and an outer upper sheet layer 16 (outer upper sheet layer). Is located on the observer side of FIGS. 7a and 7b). The inner upper sheet layer is located on the side of the absorbent structure 14 facing the wearer in use and is liquid impervious and comprises, for example, a nonwoven material. The fiber may comprise, for example, polyethylene, polypropylene, polyester or mixtures thereof. They may consist of viscose fibers. It is also conceivable that the inner upper sheet layer comprises a perforated plastic sheet such as a polyethylene film. The outer upper sheet layer, or lower sheet 16, is liquid impermeable or at least hydrophobic, and includes a sheet of non-woven material or polyethylene, for example coated or laminated with polyolefin to be liquid impermeable or at least hydrophobic. But you can.

  The absorbent material in the absorbent structure 14 according to the present invention may be essentially the same as for the diaper article.

  Another example includes cellulose fluff. The absorbent material may include other absorbent materials such as polymeric hydrocolloid materials, eg superabsorbents. The absorbent structure may include non-absorbent materials such as thermoplastic molten fibers intended to strengthen the absorbent structure. Although the absorbent structure of FIGS. 7a-c has only a single layer, it is understood that the absorbent structure may include more than one layer in other embodiments according to the invention.

  The absorbent structure is not limited to the shape shown in FIGS. 7a-c, and other shapes such as an hourglass shape or a T shape are contemplated.

  Since several variations are possible within the scope of the invention, the various examples should not be considered limited to the illustrated examples. Further possible pant-type diapers used are described in WO 93/17648, which is hereby incorporated by reference.

  Further examples include the case where the pant diaper is disposable.

Tampon-like Structure The present invention further includes an absorbent article such as a tampon-like structure. Such an absorbent article includes an absorbent structure according to the present invention. The tampon-like structure may be suitable for absorption of blood, such as menstrual blood, or as a tampon-like structure that absorbs wound fluid. A similar tampon-like structure may also be suitable, for example, for absorption of saliva in the oral cavity.

  In one example, the structure, when calculated as part of the total weight of the structure in the dry state, contains 5 to 100% cellulose fibers predominantly from Chemi thermomechanical pulp (CTMP) fibers, and 0 to 15% superabsorbent material. To do. In a further example, the tampon-like structure comprises an absorbent structure according to the invention comprising 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 sensing means.

FIG. 8 shows an illustrative example of an absorbent article suitable for the absorption of blood such as a tampon or similar product comprising an absorbent structure according to the present invention comprising a single sensing means 39. The tampon includes an absorbent material that is rolled into a cylindrical form 38. In connection with rolling the absorbent material into a cylindrical shape, the string 31 is placed in the middle of the cylindrical body 38 in a conventional manner and the cylindrical body 38 is compressed to the desired thickness and shape in a conventional manner. Prior to being compacted and shaped, the absorbent material will preferably have a density range of 0.4 to 0.9 g / cm ³ and a weight per unit area of 200 to 600 g / m ² .

In a further example, an absorbent article suitable for blood absorption comprises an airlaid web absorbent structure of cellulose fibers used as an absorbent material. The fiber is compressed into a dry formed sheet having a first density of about 0.2-1.0 g / cm ³ , and the compressed sheet is mechanically softened by a non-cutting method and is lower than the original first density A second reduced density results. The sheet may be peeled to form a plurality of partially separated thin fiber layers. Such a thin fiber layer exhibits a density of about 0.2-1.0 g / cm ³ . The structure of such an example shows a density reduction of 75% or less after softening and a weight per unit area of 30-2000 g / m ² .

  Absorbent articles suitable for the absorption of blood, such as tampon or similar products, comprise an absorbent structure according to the present invention. Thus, various numbers of sensing means are included as described above. In FIG. 7, one sensing means is included in the absorption structure. A sensor with a tampon-like structure needs to be placed inside the absorbing structure.

Sanitary napkin An example of the present invention is a sanitary napkin. The napkin includes an absorbent structure in a conventional manner, which may include a perforated plastic film or similar material and is enclosed between a body fluid permeable top sheet and a body fluid impermeable bottom sheet lying near the wearer when in use. Is done. For example, a thin body fluid permeable layer of nonwoven material may be placed between the absorbent structure and the top sheet. The upper sheet and the lower sheet have portions protruding beyond the absorbent structure, and both sheets are joined to each other at these protruding portions. The lower sheet is made of a suitable plastic material such as polyethylene. However, it will be understood that other known materials may be used for the upper and lower sheets within the scope of the present invention.

The absorbent structure may comprise a single layer or several layers. A single layer may consist of a dry-formed material according to the present invention, which contains 0-10% superabsorbent material. The preferred density range for the absorbent structure is 0.6-0.9 g / cm ³ and the preferred weight per unit area is 200-300 g / m ² . When the absorbent structure consists of a chemithermomechanical pulp (CTMP) material or other material having a yellow or brown color, a white chemical pulp cover layer may be applied over the absorbent structure.

Sensing and Absorbing System The present invention also includes a sensing and absorbing system, which optionally includes an absorbing structure according to the present invention that is part of an absorbent article, such as those described above, and an excitation coil that generates a magnetic field to magnetize the magnetoelastic film and A handheld unit including a pickup coil for detecting the magnetoacoustic resonance frequency is included as desired.

  In a further example, the sensing and absorption system is disposable.

  Further examples include a signal generator, a detection circuit and a presentation unit, as seen in FIG.

  In one example, the sensing and absorption unit includes a handheld unit that includes the excitation coil and the pickup coil.

  In the sense absorption unit, the magnetic pulses from the excitation coil must be high enough to sufficiently magnetize the magnetoelastic film so that the pickup coil can detect the magnetoacoustic signal. This will of course depend on the distance between the handheld unit and the magnetoelastic film, to some extent on the relative orientation between the handheld unit and the magnetoelastic film and therefore must be optimized for the particular combination used. I must.

  In one example, METGLAS® film is used as a magnetoelastic film. In this example, the 0.06 mT field amplitude in the film is high enough to detect the magnetoacoustic signal. A 1 kHz magnetic pulse with a 20% duty cycle is used, but other frequencies and duty cycles may be used. A magnetic field in the range of 0.05 mT to 0.1 mT will create sufficient magnetism in the magnetoelastic film. The exact value depends on the material selected in the magnetoelastic film and must therefore be optimized for each example. The exact values of pulse frequency, duty cycle and magnetic field amplitude in the film must also be optimized when the magnetoelastic film material and sensor system application is selected. Also, the distance of the handheld unit must be considered here and the magnetoelastic film needs to be defined when optimizing other parameters of different examples. The minimum distance is the outer surface of the absorbent article. The detection may be designed to achieve a maximum coverage of about xm, where x is selected by the caregiver / caretaker user by appropriate design of the excitation coil and pickup.

  In one example, detection achieves a maximum coverage of about xm (where x is about 0-10 m, eg, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 m). May be designed to do.

  In a further example, the detection may be designed to achieve a maximum coverage of about xm, where x is about 0-5 m.

  In a still further example, the detection is about xm (where x is about 0-1 m, eg, 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, It may be designed to achieve a maximum coverage range (0.8, 0.9, 1 m).

Method for manufacturing an absorbent structure The present invention includes an absorbent structure according to the present invention or an absorbent such as a diaper, a pant diaper, an incontinence garment, a sanitary napkin, a wipe, a towel, a tissue, a bed protector, a wound dressing, or the like. Also included is a method of manufacturing an article, which includes the following steps:
a) providing a liquid-impermeable bottom sheet;
b) providing at least one wet sensor and / or at least one bioanalyte sensor and / or at least one chemical analyte sensor;
c) spraying hot melt adhesive on all or part of the lower sheet;
d) mounting at least one absorbent structure on the lower sheet;
e) providing a nonwoven on the absorbent structure of c) on the opposite side of the lower sheet;
f) Stamp the absorbent product from the nonwoven fabric-absorbent structure-lower sheet structure of e) above.

  The sensor in b) may first be attached to the liquid impervious lower sheet and then applied simultaneously with the lower sheet.

  In another example, the sensor is attached to the lower sheet after the hot melt adhesive has been sprayed into the lower sheet.

  The sensor may be mounted on other parts of the absorbent structure, on a different absorbent structure of the absorbent product, inside or in between.

Method for detecting wet, bioanalytes or chemical analytes According to the invention for detecting bioanalytes such as bacteria or blood cells, or chemical analytes such as metals or moist in the absorption structure according to the invention A method is provided. The absorbent structure may be incorporated into absorbent articles such as diapers, pant diapers, incontinence clothing, sanitary napkins, wipes, towels, tissues, bed protectors, wound dressings, or the like. The method includes the following steps:
a) providing an absorbent structure according to the invention, or an absorbent article according to the invention,
b) applying a magnetic field;
c) exciting the magnetoelastic film of at least one sensing means in the absorbing structure;
d) Turn off the magnetic field,
e) record the magnetoacoustic resonance frequency;
f) repeat steps b) -e) if desired, and g) detect changes in magnetoacoustic resonance frequency to detect wet, at least one bioanalyte and / or at least one chemical analyte in the absorbing structure. .

  The method according to the invention comprises in a further example a magnetic field, which is a pulsed magnetic field.

  Further examples include the case where the magnetoelastic film excited in c) above is excited by an excitation coil.

  A further example is when the record of e) above is detected by a pickup coil.

  Still further examples are where the excitation frequency determines frequency shift and Q value change (Q = F / (ΔF)) by adsorption of liquid, moisture or moisture, eg urine adsorption, or desorption of a surface coating of a magnetoelastic film such as a Metglas film. To be swept across the resonance frequency.

  FIG. 2 shows a schematic view of the sensing means used in the method. FIG. 3 shows a photograph of the experimental setup.

  In another example of the method, an excitation coil and optionally a pick-up coil are in the handheld unit, which absorbs when exciting the magnetoelastic film in c) above and optionally recording the magnetoacoustic resonance frequency in e) above. It is 0.1 to 2 m from the structure.

  A handheld unit used in accordance with the present invention is also disclosed for use in the method according to the present invention. A schematic diagram is given in FIG.

  In a further example, the sensing and absorption system of the paragraph “Sense and Absorption System” may be used in the method.

General In Experiments 1-7, the METGLAS® film and capsules used were Ultra Strip III Narrow from Sensomatic.

  The capsules also contained permanent magnets in all experiments except for Experiments 6 and 7.

  In Experiment 8-11, the METGLAS® film used was an Ultra Strip III Narrow from Sensomatic.

In Experiment 8-11, before the coating process, METGLAS® film was etched with 1M NHO ₃ , washed with deionized water and acetone and dried. In Experiments 8-11, the measurements were made in the dry state, i.e. after being immersed and dried.

Preparation of Metglas films In all experiments, the capsules were open cut on the short side and the METGLAS® film was pulled out of the capsules. The METGLAS® film was then coated in various ways according to the various experimental conditions described in each case below. The coated METGLAS® film was then reinserted into the capsule. The upper side of the capsule was split open to allow liquid to penetrate the capsule and reach the coating on the METGLAS® film.

  The capsules were then packaged with a surfactant-treated polypropylene nonwoven material. The resulting means (denoted AA) was integrated into the diaper according to the following description.

Diapers In all experiments, diapers consisted of:
1. A liquid-impermeable envelope sheet based on polyethylene (ME 1148 from Trioplanes International),
2. Cellulose CP fluff pulp (Supersoft Plus from International Paper containing 48 g / m ² of superabsorbent polymer (SAP) Drytech S230R from Dow Chemicals),
3. Cellulose CTMP fluff pulp (SF 70HD VSM from Metsae Serla containing 73 g / m ² of SAP Drytech S230R from Dow Chemicals),
4). Surfactant treated non-woven fabric based on polypropylene (Holmestra Spunbond HO18B7W from Fiberweb Sweden),
5. Hot melt adhesive (0700108 from National Starch).

Experimental Configuration In Experiments 1-7, the configuration included an eight-shaped detector coil of 25 turns and a 25 cm diameter excitation coil and two 25 turns square coils having a side length of 3 cm. The excitation coil was vertically aligned and the detection coil was horizontally aligned along the central axis of the excitation coil as shown in FIG. Referring to FIG. 11, the diaper was placed in such a way that the integrated sensor was positioned over the detection coil.

  A magnetic field is generated when an amplitude-modulated sinusoidal current is applied to the excitation coil. The amplitude modulation is a square wave shape that turns the sine wave signal on and off at a frequency near 100 Hz and a duty cycle of 10-50 percent. The peak-to-peak value of the applied current is about 0.1 A and the frequency is 10 kHz to 100 kHz. The magnetic field causes magnetoacoustic vibrations in the Metglas film. The vibration induces a voltage in the detection coil. The amplitude and frequency of the detection coil voltage are measured with a spectrum analyzer.

  In Experiments 6 and 7, no permanent magnet was present in the capsule. Therefore, the experimental design in these experiments was changed to include an extra circular vial coil of 25 turns and a diameter of 25 cm to generate a magnetic bias field, the bias coil being given a current of 2.2 A, and thus about 200 mT. Generated a magnetic field. This bias field replaces the bias magnet used in other experiments, ie, a permanent magnet. The bias coil is placed at the same position as the excitation coil.

  In Experiment 8-11, the means under test was placed 8 mm above the figure 8 coil as shown in FIG. The 8-shaped coil was constructed by connecting two 25-turn square coils having a side length of 3 cm. An 8-shaped coil was used for both excitation and detection. The 8-shaped coil was connected to a magnetoelastic resonance detection system containing a signal generator, a detection circuit and a data acquisition unit. The acquired data was sent to a desktop computer where the data was analyzed. The configuration also included a 100 turn (each coil) Helmholtz coil with a diameter of 19.5 cm. Helmholtz coils were used to generate a uniform magnetic bias field around the means under test.

  A current of 0.9 A was passed through a Helmholtz coil that produced a magnetic field of about 0.4 mT. In order to excite the means under test, a magnetic field was generated by passing a sinusoidal current through an 8-shaped coil. The amplitude of the current was about 30 mA, and the frequency was 50 kHz to 60 kHz. The excitation signal was cut after 5 ms. The vibration of the means under test induced a voltage in the detected 8-shaped coil. The amplitude and frequency of the induced voltage was analyzed using Matlab® software (The MathWorks, Inc.) on a desktop computer. An outline of the experimental setup can be seen in FIG.

Experiment 1 Wet sensor coated with hydrophilic linear polymer Objective The purpose of this experiment is to analyze the wetness of diapers using a wet sensor coated with a hydrophilic linear polymer.

Materials and Methods METGLAS® films were coated with a 1% (w / w) polyvinylpyrrolidone (PVP) solution.

  PVP with a molecular weight of 360 kDa was supplied by Scientific Polymer Products. The Metglas film was dried at 70 ° C. and a PVP coating was formed on the Metglas film. The PVP film was thin and weighed a total of 0.017 g.

  The sensor was included in the absorbent structure by attaching AA means to a liquid impervious lower sheet 27 cm from the center front of the liquid impervious surrounding sheet.

  The absorbent structure was coated with two cellulose fluff pulp materials in the following order: CP followed by CTMP.

  Finally, a surfactant treated nonwoven was placed on top.

Results A total volume of 100 ml synthetic urine was added in three aliquots at different time points: 20 ml at 60 seconds, 20 ml at 560 seconds and 60 ml at 1050 seconds.

  The wetting point was located 36 cm below the central front of the liquid impervious lower sheet.

The frequency was shifted from 5.93 × 10 ⁴ Hz to 5.75 × 10 ⁴ Hz as shown in FIG.

Conclusion Changes in frequency indicate that the sensor absorbs synthetic urine. The sensor changes its resonant frequency due to the density shift of the coated Metglas film when absorbing synthetic urine.

Experiment 2 Wet sensor coated with hydrophilic cross-linked polymer Objective The purpose of this experiment is to analyze the wetness of diapers using a wet sensor coated with hydrophilic cross-linked polymer.

Materials and Methods Metglas films were coated with a gel based on slightly cross-linked polyvinyl alcohol (PVOH). The gel was formed by mixing 1 part of a 5% (w / w) PVOH solution with 1.5 parts of 4% (w / w) disodium tetraborate decahydrate. The gel is formed after 5 minutes of mixing. The gel was then rolled onto a Metglas film and dried in an indoor climate for at least 12 hours. The dried film weighed a total of 0.0011 g.

  PVOH has a molecular weight of 125 kDa (supplied by Scientific Polymer Products) and disodium tetraborate decahydrate (analytical level) was supplied by Merck.

  The product was made by attaching AA means to a liquid impervious lower sheet 27 cm from the center front of the liquid impervious surrounding sheet. The absorbent structure was coated with two cellulose fluff pulp materials in the following order: CP followed by CTMP. Finally, the surfactant treated nonwoven was placed on top.

Results A total volume of 250 ml of synthetic urine was added in five aliquots: 20 ml in 120 seconds, 20 ml in 600 seconds, 60 ml in 1200 seconds, 50 ml in 3050 seconds, 100 ml in 4000 seconds.

The wetting point was located 36 cm below the central front of the liquid impervious lower sheet. The frequency was shifted from 5.83 × 10 ⁴ Hz to 5.69 × 10 ⁴ Hz.

Conclusion Changes in frequency indicate that the sensor absorbs synthetic urine. The sensor changes its resonant frequency due to the density shift of the coated Metglas film when absorbing synthetic urine.

Experiment 3 Wet Sensor Coated with Low Molecular Weight Compounds Purpose The purpose of this experiment is to analyze the wetness of diapers using a wet sensor coated with low molecular weight compounds.

Materials and Methods Metglas films were coated with 12% (w / w) sodium chloride (NaCl) solution.

  NaCl (analytical level) was supplied by Aldrich. The Metglas film was dried at 70 ° C. and NaCl crystals were formed on the Metglas film. The NaCl crystals weighed 0.003 g.

  The product was made by attaching AA means to a liquid impervious lower sheet 27 cm from the center front of the liquid impervious surrounding sheet.

  The absorbent structure was coated with two cellulose fluff pulp materials in the following order: CP followed by CTMP. Finally, a surfactant treated nonwoven was placed on top.

Results A total volume of 100 ml synthetic urine was added in three aliquots: 20 ml at 80 seconds, 20 ml at 305 seconds, and finally 60 ml at 804 seconds.

The wetting point was located 36 cm below the central front of the liquid impervious lower sheet. The frequency was shifted from 5.71 × 10 ⁴ Hz to 5.63 × 10 ⁴ Hz.

Conclusion Changes in frequency indicate that the sensor absorbs synthetic urine. The sensor changes its resonant frequency due to the density shift of the coated Metglas film when the salt is hydrolyzed on the Metglas film and thereby absorbs synthetic urine.

Experiment 4 Sensors at different cross-sectional positions in the absorbent structure Objective The purpose of this experiment is to analyze the wetness of the diaper using a coated wet sensor located at different cross-sections in the absorbent structure. The sensor position in this experiment should be compared to the sensor position in Experiment 1.

Materials and Methods Metglas films were coated with a 1% (w / w) polyvinylpyrrolidone (PVP) solution.

  PVP was supplied by Scientific Polymer Products and had a molecular weight of 360 kDa. The Metglas film was dried at 70 ° C. and a PVP coating was formed on the Metglas film. The PVP film was thin and weighed a total of 0.017 g.

  The product was made by placing CP fluff pulp on a liquid impervious bottom sheet. AA means was attached to this absorbent structure 27 cm from the central front of the liquid-impermeable lower sheet. Compare this position with that of Experiment 1.

  The CTMP absorption structure was placed on top. Finally, a surfactant treated nonwoven was placed on top.

Results A total volume of 100 ml synthetic urine was added in three aliquots: 20 ml at 80 seconds, 20 ml at 675 seconds and 60 ml at 1075 seconds.

The wetting point was located 36 cm below the central front of the liquid impervious lower sheet. The frequency was shifted from 5.81 × 10 ⁴ Hz to 5.74 × 10 ⁴ Hz.

Conclusion The change in frequency in this experiment should be compared to the change in frequency in experiment 1. Two different positions give different changes in frequency.

  Also, because of the different positions, the frequency change starts at different time points, ie 150 seconds in Experiment 1 and approximately 85 seconds in Experiment 4.

  Thus, wet sensors in the absorbent structure at different locations may be used to monitor the moisture in the product or the dispersion of liquids such as urine.

Experiment 5 Two sensors placed at different positions in the absorbing structure Objective The purpose of this experiment is to analyze the frequency shift when using two sensors placed at different positions in the absorbing structure.

Materials and Methods Two Metglas films were coated with a 1% (w / w) polyvinylpyrrolidone (PVP) solution.

  PVP had a molecular weight of 360 kDa (supplied by Scientific Polymer Products).

  The Metglas film was dried at 70 ° C. and a PVP coating was formed on the Metglas film. The PVP film was thin and weighed a total of 0.017 g. One of the Metglas films was cut 3 mm shorter than the other.

  The product was made by attaching AA means to a liquid impervious bottom sheet of 27 cm and 60 cm, respectively, from the center front.

  The absorbent structure was coated with two cellulose fluff pulp materials in the following order: CT followed by CTMP. Finally, the surfactant treated nonwoven was placed on top.

Results A total volume of 460 ml of synthetic urine was added in seven aliquots: 20 ml in 140 seconds, 20 ml in 640 seconds, 60 ml in 1100 seconds, 60 ml in 2050 seconds, 100 ml in 2700 seconds, 100 ml in 3300 seconds, and finally in 4600 seconds. 100 ml.

The wetting point was located 36 cm below the center front of the liquid impermeable sheet. The frequency is first shifted from 6.36 × 10 ⁴ Hz to 6.26 × 10 ⁴ Hz for a sensor located 27 cm from the center and then 5.74 for a sensor located 60 cm from the center front. It shifted × from ¹⁰ 4 Hz to 5.64 × ¹⁰ 4 Hz.

Conclusion This experiment shows a simple and clear way to detect the frequency shift exhibited by two sensors placed at two different positions in one absorbing structure. The different positions of the two sensors lead to kinetic differences in frequency changes. Such differences may be used to calculate a quantitative change in the amount of liquid dispersed in the absorbent structure when the wet profile of the particular absorbent structure is known.

Experiment 6 Sensor without Metglas film encapsulation Objective The purpose of this experiment is to analyze the frequency shift when using a sensor without Metglas film encapsulation.

Materials and Methods Metglas films were coated with a gel based on partially crosslinked polyvinyl alcohol PVOH. The gel was formed by mixing 1 part of a 5% (w / w) PVOH solution with 1.5 parts of 4% (w / w) disodium tetraborate decahydrate. A gel was formed after 5 minutes of mixing. The gel was rolled onto Metglas film and dried at room temperature for at least 12 hours. The dried film weighed a total of 0.0039 g.

  PVOH was purchased from Scientific Polymer Products, had a molecular weight of 125 kDa, and disodium tetraborate decahydrate (analytical level) was supplied by Merck.

  The product was made by placing CP fluff pulp on a liquid impervious bottom sheet. The coated Metglas film was placed without capsules on an absorbent structure 41 cm from the central front of the liquid-impermeable bottom sheet.

  The CTMP absorption structure was placed on top. Finally, the surfactant treated nonwoven was placed on top.

Results A total volume of 170 ml synthetic urine was added in 5 aliquots: 20 ml at 190 seconds, 20 ml at 570 seconds, 20 ml at 1300 seconds, 40 ml at 1980 seconds, and finally 50 ml at 3350 seconds. The wetting point was located 36 cm below the central front of the liquid impervious lower sheet. The frequency was shifted from 5.76 × 10 ⁴ Hz to 5.66 × 10 ⁴ Hz.

Conclusion The change in frequency indicates that the wet sensor works even without encapsulation.

Experiment 7 Sensor without permanent magnet Objective The purpose of this experiment is to analyze the frequency shift when using a sensor without a permanent magnet. The frequency was shifted from 6.00 × 10 ⁴ Hz to 5.95 × 10 ⁴ Hz.

Materials and Methods Metglas films were coated with a 1% (w / w) polyvinylpyrrolidone (PVP) solution.

  PVP was supplied by Scientific Polymer Products and had a molecular weight of 360 kDa. The Metglas film was dried at 70 ° C. and a PVP coating was formed on the Metglas film. The PVP film was thin and weighed a total of 0.017 g.

  Means AA were changed when compared to the summary description for the other experiments. The permanent magnet was removed from the capsule, thereby forming a means termed “AA”.

  The product was made by attaching "AA" means to a liquid impervious sheet 27 cm from the center front of the liquid impervious surrounding sheet.

  The absorbent structure was coated with two cellulose fluff pulp materials in the following order: CP followed by CTMP. Finally, the surfactant-treated nonwoven was placed on top.

Results A total volume of 200 ml of synthetic urine was added in four aliquots: 20 ml in 70 seconds, 20 ml in 450 seconds, 60 ml in 1100 seconds, and finally 100 ml in 2000 seconds.

The wetting point was located 36 cm below the central front of the liquid impervious lower sheet. The frequency was shifted from 6.00 × 10 ⁴ Hz to 5.95 × 10 ⁴ Hz.

Experiment 8 Biosensor for detection of Staphylococcus aureus using Metglas coated with cationic polymer Purpose The purpose of this experiment was to detect Metglas coated with cationic polymer and primary antibody. To detect the pathogen Staphylococcus aureus in the target solution using a based biosensor.

Materials and Methods Polyethyleneimine, PEI, high molecular weight water-free polymer and 50% glutaraldehyde sol in water were purchased from Sigma-Aldrich. Mouse monoclonal antibody against Staphylococcus aureus peptidoglycan was purchased from Abcam Limited. CCUG 10788 Staphylococcus aureus was purchased from the University of Gotenburg, Department of Clinical Bacteriology.

  The Metglas film was coated with PEI by dip coating with a 0.5% (w / w) PEI / methanol solution. Metglas was removed from the coating solution and air dried to allow solvent evaporation. Chemical crosslinking was performed by exposing the thin polymer layer to vapor of 5% (v / v) glutaraldehyde / phosphate buffered salt solution (pH 7.0) for 2 hours at room temperature. Metglas was removed from the glutaraldehyde environment and placed in a heating oven at 100 ° C. for 4 minutes.

  Finally, the monoclonal antibody (mAb) was immobilized on the coated surface of the sensor. 200 μl mAb solution (1.4 mg / ml) was added onto the polymer layer and incubated for 1 hour at room temperature. After the incubation step, the mAb solution was removed. The surface was washed with PBS, pH 7.2 and air dried.

  Staphylococcus aureus was grown overnight in TSB medium at 37 ° C. The bacterial suspension was centrifuged, the supernatant was discarded, and the bacteria were resuspended with 0.9% NaCl.

Measurement Procedure The frequency for the dry biosensor was first measured and then the biosensor was immersed in 3 ml bacterial suspension at room temperature for 58 minutes. The sensor was removed from the suspension, air dried, and a new frequency was measured.

Results As can be seen in FIG. 20, measurement 1 gave a frequency of 58680 Hz and measurement 2 gave a frequency of 58480 Hz. Δf is 200 Hz.

Conclusion The frequency shift indicates the binding of the target species to the biosensor. The change in frequency indicates the response of the sensor to additional surface mass loading.

Experiment 9 Biosensor for detection of Staphylococcus aureus using Metglas coated with colloidal suspension Objective The purpose of this experiment was based on Metglas coated with polystyrene beads and primary antibody The detection of the pathogenic staphylococcus aureus in the target solution using a biosensor.

Materials and Methods Polybead polystyrene (PS) microspheres (2.65% solids-latex, θ1μ) were purchased from Scientific Polymer Products. Mouse monoclonal antibody against Staphylococcus aureus peptidoglycan was purchased from Abcam Limited. CCUG 10778 Staphylococcus aureus was purchased from the University of Gothenburg, Department of Clinical Bacteriology. Metglas films were coated with PS microspheres by dip coating in 2.5% Ps-latex colloidal suspension. Metglas was immersed in 2 ml coating solution for 30 minutes at room temperature. Metglas was removed from the coating suspension and placed in a heating oven at 50 ° C. for 15 minutes. Finally, the monoclonal Ab was immobilized on the coated surface of the sensor.

  Coated Metglas was immersed in 400 μl Ab solution (1.4 mg / ml) and incubated for 1 hour at room temperature. After the incubation step, the Ab solution was removed and the sensor was air dried at room temperature.

  Staphylococcus aureus was grown overnight in TSB medium at 37 ° C. The bacterial suspension was centrifuged, the supernatant was discarded, and the bacteria were resuspended with 0.9% NaCl.

Measurement Procedure First, the frequency for a dry biosensor was measured, then the biosensor was immersed in 3 ml bacterial suspension for 45 minutes at room temperature. The sensor was removed from the suspension, air dried, and a new frequency was measured.

Results As can be seen in FIG. 21, measurement 1 gave 58140 Hz and measurement 2 gave 57980 Hz. Δf is 160 Hz.

Conclusion Changes in frequency indicate the sensor's response to additional surface mass loading. The frequency shift indicates the binding of the target species to the biosensor.

Experiment 10 Biosensor for detection of Staphylococcus aureus using Metglas coated with a hydrophobic polymer Objective The purpose of this experiment is based on Metglas coated with a hydrophobic polymer and a primary antibody Is to detect the pathogenic staphylococcus aureus in the target solution using a biosensor.

Materials and Methods Polystyrene having a molecular weight of 45 kDa was purchased from Scientific Polymer Products. Mouse monoclonal antibody against Staphylococcus aureus peptidoglycan was purchased from Abcam Limited. CCUG 10778 Staphylococcus aureus was purchased from the University of Gothenburg, Department of Clinical Bacteriology.

  The Metglas film was coated with polystyrene (PS) by dip coating in a 1% (w / w) PS / toluene solution. Metglas was removed from the coating solution and air dried to allow solvent evaporation. Metglas was placed in a heating oven at 100 ° C. for 4 minutes.

  Finally, the monoclonal Ab was immobilized on the coated surface of the sensor. A 200 μl stock solution of mAb (1.4 mg / ml) was added onto the polymer layer and incubated for 1 hour at room temperature. After the incubation step, the Ab solution was removed and the surface was washed with PBS, pH 7.2 and air dried.

  Staphylococcus aureus was grown overnight in TSB medium at 37 ° C. The bacterial suspension was centrifuged, the supernatant was discarded, and the bacteria were resuspended with 0.9% NaCl.

Measurement Procedure First, the frequency for a dry biosensor was measured, and then the biosensor was immersed in 3 ml bacterial suspension at room temperature for 58 minutes. The sensor was removed from the suspension, air dried, and a new frequency was measured.

Results As can be seen in FIG. 22, measurement 1 gave 57899 Hz and measurement 2 gave 58060 Hz. Δf is −60 Hz.

Conclusion The results show the opposite reaction after immersion of the biosensor in the target solution. Upon excitation of the sensor, more flexible binding can result in a complex orientation away from the sensor surface. This phenomenon can produce different vibration directions. That is, the vibration of the Ab-Ag complex is not synchronized with the vibration of the sensor, which may explain the reverse reaction of the sensor.

  The reverse reaction can also be obtained if the sensor surface becomes stiffer due to the binding of the target molecule.

Experiment 11 Biosensor for detection of lymphocytes using Metglas coated with a cationic polymer Objective The purpose of this experiment was to use a Metglas-based biosensor coated with a cationic polymer and a first antibody. And detecting lymphocytes present in the target solution.

Materials and Methods Polyethyleneimine, PEI, high molecular weight water-free polymer and 50% glutaraldehyde sol in water were purchased from Sigma-Aldrich. Mouse anti-sheep B and activated T cells were purchased from Serotec. Sheep blood was purchased from Statens Veterinermedinska Anstalt. Ficoll 400, sodium diatrizoate and cell culture saline (BSS) were purchased from Sigma-Aldrich.

  The Metglas film was coated with PEI by dip coating in a 0.5% (w / w) PEI / methanol solution. Metglas was removed from the coating solution and air dried to allow solvent evaporation. Chemical crosslinking was performed by dip coating in 2.5% (v / v) glutaraldehyde / phosphate buffered salt solution, PBS (pH 7.0) for 30 minutes at room temperature. Metglas was removed from the glutaraldehyde environment and placed in a heating oven at 100 ° C. for 4 minutes.

  Finally, the monoclonal antibody (mAb) was immobilized on the coated surface of the sensor. A 200 μl stock solution of mAb (received from Serotac) was added onto the polymer layer and incubated for 1 hour at room temperature. After the incubation step, the mAb solution was removed. The surface was washed with PBS, pH 7.2 and air dried.

  Isolation of lymphocytes from raw sheep blood was performed by a gradient gradient technique. The separation medium containing Ficoll and sodium diatrizoate has a concentration of 1.077 g / ml at room temperature. BSS (25 ml) was added to a centrifuge tube (50 ml) containing raw sheep blood (25 ml). After mixing by tube inversion, a 25 ml blood sample was carefully layered on a 15 ml separation medium and centrifugation was performed at room temperature. The lymphocyte layer was carefully collected, washed with sterile PBS (2x), and resuspended in PBS (2.5 ml).

Measurement Procedure First, the frequency for a dry biosensor was measured, and then the biosensor was immersed in 2.5 ml lymphocyte suspension for 30 minutes at room temperature. The sensor was removed from the suspension, air dried, and a new frequency was measured.

Results As can be seen in FIG. 23, measurement 1 gave 58665 Hz and measurement 2 gave 58428 Hz. Δf is 237 Hz.

Conclusion The frequency shift indicates the binding of the target species to the biosensor. The change in frequency indicates the response of the sensor to additional surface mass loading.

1 shows an absorbent structure 11 according to the present invention suitable for an absorbent article such as a diaper. 1 shows an absorbent structure 11 according to the present invention suitable for an absorbent article such as a diaper. A magnetoelastic film, an excitation coil, and a pickup coil are shown. An experimental configuration for detecting the magnetoacoustic effect is shown. 5 shows five different examples for sensors that use magnetic METGLAS® film to detect wetness, at least one bioanalyte and / or at least one chemical analyte. FIG. 2 shows a diagram of a handheld unit that may be used to excite a magnetoelastic film, detect a reaction from the film, and provide a result to a user. 1 shows a diaper comprising an absorbent structure according to the invention, a front part, a rear part, a crotch part between the front part and the rear part. FIG. 6A is a diaper having one sensing means 20 in the absorbent structure. 1 shows a diaper comprising an absorbent structure according to the invention, a front part, a rear part, a crotch part between the front part and the rear part. FIG. 6B is a diaper having five sensing means 20 placed on various parts of the absorbent structure. 1 shows a diaper comprising an absorbent structure according to the invention, a front part, a rear part, a crotch part between the front part and the rear part. FIG. 6C is a diaper having four sensing means 20 in the front part of the absorbent structure. FIG. 6 is a perspective view of a simplified example of an unassembled pant diaper having a single sensing means 35 placed in an absorbent structure. FIG. 6 is a perspective view of a simplified example of a pant-type diaper in an assembled state or ready to be worn. Although the same as FIG. 7A is shown, four sensing means 35 are placed on the absorbing structure. A cut-away view of the tampon structure is shown to show the sensing means 39 placed in the tampon absorption structure. Fig. 2 shows a wipe having a plurality of individual sheets. Fig. 4 shows an absorption sensing unit. An experimental configuration in an experiment having a circular excitation coil and an 8-shaped pickup coil is shown. A diaper placed in an experimental setup. FIG. 5 shows a frequency shift from 5.93 × 10 ⁴ Hz to 5.75 × 10 ⁴ Hz when synthetic urine is detected by a wet sensor coated with polyvinylpyrrolidone (PVP). FIG. 5 shows a frequency shift from 5.83 × 10 ⁴ Hz to 5.69 × 10 ⁴ Hz when synthetic urine is detected by a wet sensor coated with cross-linked polyvinyl alcohol (PVOH). FIG. 6 shows a frequency shift from 5.71 × 10 ⁴ Hz to 5.63 × 10 ⁴ Hz when synthetic urine is detected by a wet sensor coated with sodium chloride (NaCl). Figure 5 shows a frequency shift from 5.81 x 10 ⁴ Hz to 5.74 x 10 ⁴ Hz when the AA means is attached to an absorbent structure 27 cm from the central front of the liquid-impermeable bottom sheet. Figure 3 shows the frequency shift from two different sensors placed at various positions on the absorbing structure. FIG. 5 shows a frequency shift from 5.76 × 10 ⁴ Hz to 5.66 × 10 ⁴ Hz when using the sensor without Metglas film containment. Shows a 6.00 frequency shift from × ¹⁰ 4 Hz to 5.95 × ¹⁰ 4 Hz when using the sensor without permanent magnets. Figure 5 shows a frequency shift from 58680 Hz to 58480 Hz when using Metglas coated with a cationic polymer. Figure 5 shows a frequency shift from 58140 Hz to 57980 Hz when using Metglas coated with a colloidal suspension. Figure 5 shows a frequency shift from 57899 Hz to 58060 Hz when using Metglas coated with a hydrophobic polymer. Figure 5 shows a frequency shift from 58665 Hz to 58428 Hz when using Metglas coated with a cationic polymer. A close-up of the central part of the experimental setup showing the configuration of the U-shaped excitation / detection coil 2 of the devices 1 and 8 under test is shown. The whole image of the experimental configuration of Experiment 7-11 is shown.

Claims (21)

  An absorbent structure comprising at least one absorbent layer and at least one sensing means comprising a magnetoelastic film.   The absorbent structure according to claim 1, wherein at least one absorbent layer comprises 0 to 100% superabsorbent material.   The absorbent structure according to claim 1, wherein the at least one absorbent layer forms at least one acquisition layer and at least one storage layer.   3. Absorption according to any one of the preceding claims, wherein at least one absorbent layer comprises at least one dry layer, the layer optionally comprising a plurality of individual sheets and bonding means for joining the individual sheets. Construction.   The absorption structure according to claim 1, wherein the magnetoelastic film vibrates at a magnetoacoustic resonance frequency after the magnetoelastic film is excited by a magnetic field and when the magnetic field is cut off.   The absorption structure according to claim 1, wherein at least one sensing means is 1 to 20 sensing means.   The magnetoelastic film is a thin film, and the film is selected from the group consisting of magnetostrictive materials such as magnetoelastic materials, soft magnetoelastic materials, amorphous magnetoelastic materials, and mixtures thereof. Absorption structure in any one.   The magnetoelastic film is based on polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide and copolymers thereof, polyurethane, polyamide, starch and derivatives thereof, cellulose and derivatives thereof, polysaccharides, proteins, polyacrylonitrile, acrylate-based polymers, and mixtures thereof. 8. Absorbent structure according to any of claims 1 to 7, coated with a wet sensitive polymer selected from the group consisting of linear and hydrophilic polymers or chemical / physically cross-linked swellable polymer gels.   Absorbent structure according to any of claims 1 to 7, wherein the magnetoelastic film is directly or indirectly coated with at least one detection molecule adapted to detect at least one target organism and / or chemical analyte. .   A diaper, a pant-type diaper, an incontinence garment, a sanitary napkin, a wipe, a towel, comprising the absorbent structure according to any one of claims 1 to 9, a body fluid permeable sheet, and an essentially body fluid impermeable lower sheet. Absorbent articles such as tissue, bed protectors, wound dressings, or similar products.   A diaper and a pants-type diaper including the absorbent structure according to claim 1, a front part, a rear part, a crotch part between the front part and the rear part.   The diaper according to claim 11, wherein the absorption structure according to any one of claims 1 to 9 includes 1 to 10 sensing means.   An absorbent article, such as a tampon-like product, comprising the absorbent structure according to claim 1.   14. Absorption according to claim 13, wherein the absorbent structure comprises 5-100% cellulose fibers composed primarily of chemithermomechanical pulp fibers and 0-95% superabsorbent material when calculated by the total weight of the dry structure. Goods.   The absorption structure according to any one of claims 1 to 9, which is a part of the absorbent article according to any one of claims 10 to 14, and an excitation coil that generates a magnetic field to magnetize the magnetoelastic film. And a sensing and absorption system including a handheld unit including a pickup coil for detecting the magnetoacoustic resonance frequency, if desired.   The sensing and absorbing system of claim 15, wherein the handheld unit includes an excitation coil and a pickup coil. The absorbent structure according to any one of claims 1 to 9, the absorbent article according to any one of claims 10 to 14, or the system according to any one of claims 15 to 16, and / or at least one of A method for detecting a biological and / or chemical analyte comprising the following steps:
a) preparing an absorbent structure according to any of claims 1-9, an absorbent article according to any of claims 10-14, or a system according to any of claims 15-16;
b) applying a magnetic field;
c) exciting the magnetoelastic film of at least one sensing means in the absorbing structure;
d) turn off the magnetic field;
e) record the magnetoacoustic resonance frequency;
f) repeat steps b) to e) if desired; and g) change in magnetoacoustic resonance frequency to detect wet / moisture / humidity and / or at least one biological and / or chemical analyte in the absorbing structure. Detect
Including methods.   The method of claim 17, wherein the magnetic field is a pulsed magnetic field.   The method according to claim 17, wherein the magnetoelastic film excited in c) is excited by an excitation coil.   20. A method according to any one of claims 17 to 19, wherein the recording at e) is detected by a pickup coil.   An excitation coil and optionally a pick-up coil in the handheld unit, when the handheld unit excites the magnetoelastic film in c) and optionally records the magnetoacoustic resonance frequency in e) 0-5 m from the absorbing structure. The method according to any one of claims 17 to 20.

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