EP1343539A2 - Nano-sized materials in hygiene products - Google Patents

Nano-sized materials in hygiene products

Info

Publication number
EP1343539A2
EP1343539A2 EP20010994777 EP01994777A EP1343539A2 EP 1343539 A2 EP1343539 A2 EP 1343539A2 EP 20010994777 EP20010994777 EP 20010994777 EP 01994777 A EP01994777 A EP 01994777A EP 1343539 A2 EP1343539 A2 EP 1343539A2
Authority
EP
Grant status
Application
Patent type
Prior art keywords
acid
surface
particles
particle
acids
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP20010994777
Other languages
German (de)
French (fr)
Inventor
Melita Heller
Claudia Hundeiker
Christian Kropf
Raymond Mathis
Christine Wild
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cognis IP Management GmbH
Original Assignee
Henkel AG and Co KGaA
Cognis Deutschland GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES; PREPARATION OF CARBON BLACK; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04Compounds of zinc
    • C09C1/043Zinc oxide
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, E.G. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/15Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/84Accessories, not otherwise provided for, for absorbent pads
    • A61F13/8405Additives, e.g. for odour, disinfectant or pH control
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/02Cosmetics or similar toilet preparations characterised by special physical form
    • A61K8/0208Tissues; Wipes; Patches
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/19Cosmetics or similar toilet preparations characterised by the composition containing inorganic ingredients
    • A61K8/27Zinc; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION, OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/18Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION, OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/46Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, E.G. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/15Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/51Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers
    • A61F13/511Topsheet, i.e. the permeable cover or layer facing the skin
    • A61F13/51113Topsheet, i.e. the permeable cover or layer facing the skin comprising an additive, e.g. lotion or odour control
    • A61F2013/51117Topsheet, i.e. the permeable cover or layer facing the skin comprising an additive, e.g. lotion or odour control the lotion having skin care properties
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41Particular ingredients further characterized by their size
    • A61K2800/413Nanosized, i.e. having sizes below 100 nm
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/74Biological properties of particular ingredients
    • A61K2800/75Anti-irritant
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION, OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION, OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/106Halogens or compounds thereof, e.g. iodine, chlorite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION, OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/112Phosphorus-containing compounds, e.g. phosphates, phosphonates
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION, OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/114Nitric oxide, i.e. NO
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION, OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404Biocides, antimicrobial agents, antiseptic agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION, OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/41Anti-inflammatory agents, e.g. NSAIDs
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION, OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/62Encapsulated active agents, e.g. emulsified droplets
    • A61L2300/624Nanocapsules
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention relates to the use of body-compatible substances for the production of hygiene products. The substances are present in the form of nanoparticles which have been chemically or physically modified on the surface thereof. The body-compatible substances are selected from oxides, oxidhydrates, hydroxides, halogenides, phosphates, sulfides, nitrides and carbides of AI, SI, of alkaline and alkaline-earth metals in addition to subgroup elements including mixed salts of said groups such as hydroxides/halogenides, halogenides/phosphates or hydroxides/halogenides/ phosphates. The chemical or physical modification of the particle surface is carried out with the aid of organic compounds such as; (a) carboxyl acids (mono, di and polycarboxylic acids) or derivatives thereof; (b) amino acids, particularly naturally occurring amino acids; (c) hydroxy-carboxyl acids and sugar acids such as glucaric acid, gluconic acid, glucuronic acid; (d) polyglycolic acids and with (e) ethercarboxylic acids of general formula R-(O-CH2-CH2)n-O-CH2-COOH.

Description

Nanoscale materials in hygiene products

The present invention relates to the field of hygiene products, in particular the field of diapers for babies and adults (incontinence products), panty liners and tampons. In particular, the present invention relates to the use of nanoscale particles in such hygiene products.

Hygiene products of the type described above are used for absorbing urine, feces, blood, and perspiration, has been eliminated by the body. Because of the waste products occurs in the situation of wear to an alkaline medium. This in turn may activate enzymes that attack the skin and capable of causing as diaper rash irritation and / or inflammation of the skin. Since the excretions also provide a moist to wet environment, the complaints referred to may occur more quickly, not least because of the friction of the hygiene product on the skin. On the other hand, it can also lead to unpleasant odors during extended wearing time because certain constituents of the waste products are decomposed.

Baby diapers that on the side facing the skin surface (non-woven) are already known a skin care lotion containing (Procter & Gamble). Also known (WO99 / 59538) are topical compositions ZnO high surface area (30 to 100m 2 / g) and contain a mean particle size of 0.1 to 200 microns (in diameter). These compositions are particularly recommended for the absorption of body fluid, such as sweat, sebum (tallow), urine, and water. The effect (eg in the treatment of acne or diaper eczema) of the ZnO is attributed to its good antibacterial (antiseptic) effect.

The known products have various quite significant disadvantages: First of adverse significance is the fact that traditional absorbent materials do not affect the pH. Follow the above mentioned basic medium through which the skin is irritated. Another disadvantage is that the comparatively large particles or agglomerates are responsible on the skin for a bad feeling. Other drawbacks also go back to the too large particle size. That is, first, a large particle needs and secondly a poor stability in the application systems due to sedimentation of the relatively large particles. Finally and thirdly, a further disadvantage of the known products is that an increased risk of skin irritation caused by abrasion is due to large particles / agglomerates.

Some of these disadvantages can already be avoided in the present state of the art. These are all the above mentioned disadvantages associated with the non-small enough in particle size in the context, since the EP-A 0,791,681 describes ZnO particles of a by--average particle size of not more than 100 nm, the (for coating substrates such as synthetic, natural and inorganic fibers) are suitable. The substrates provided with the ZnO particles act on the one hand and on the other antibacterial suppressing odors.

The task which the inventors have found to solve compared to the prior art, is to provide hygiene products in the above sense willing to absorb moisture next to the property or absorb, on the one hand and antibacterial (antiseptic) and anti-inflammatory and / or on the other hand should have a neutralizing effect on the basic milieu and the odors. The aim is for the same time a comfortable fit. This will be done through appropriate nanoscale inorganic particles, which due to their small size, sedimentation work into the application systems and application are already showing a low concentration high efficiency and not interfere with the skin feel when worn.

For this purpose, the inventors of the present invention, numerous body tested compatible substances to the desired properties and found that various oxides, oxide hydrates, hydroxides, halides, phosphates, sulfides, nitrides, carbides of AI, Si, of the alkali and alkaline earth metals as well as of subgroup elements including mixed salts of these groups, such as hydroxides / halides or halides / phosphates or

Hydroxide / halides / phosphates, but the task to solve able numerous phyllosilicates are, if they are modified on their upper Smiling's and in the form of nanoparticles in as little as possible or not agglomerated form. The skilled artisan is immediately clear, of course, whether a particular substance (also) has the ability to neutralize the alkaline environment, for therefore it must at least be weakly acidic. Even if the substance on an alkaline environment has no neutralizing effect per se, acid groups on the surface, which account for the modification of the substance, but lower the pH value and thus reduce the risk of skin irritation and inflammation can.

Thus, an object of the present invention relates to the use of biocompatible materials for the manufacture of hygiene products, wherein the substances in the form of chemically or physically modified at its surface nanoparticles are present. According to preferred embodiments, it is in the hygiene product is a diaper for babies or for adults, a panty liner or a tampon. According to another preferred embodiment, the chemical or physical modification of the particle surface with organic compounds, especially with (a) carboxylic acids (mono-, di- and polycarboxylic acids) or derivatives thereof such as anhydrides, halides and esters (including lactones) is carried out; more particularly with stearic acid, palmitic acid, lauric acid, capric acid, caprylic acid, caproic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, ricinoleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, citric acid, malic acid, lactic acid, tartaric acid; with (b) amino acids, particularly with the naturally occurring amino acids (Gly, Ala, Val, Leu, lle, Phe, Tyr, Trp, Pro, Hy-Pro, Ser, Asp, Glu, Asn, Gin, Arg, Lys, Thr , His, Cys, Met); with (c) hydroxycarboxylic acids and sugar acids such as glucaric acid, gluconic acid, glucuronic acid; with (d) polyglycolic acids having the general formula HOOC-CH 2 -O- (CH 2 -CH 2 -O) n -CH 2 -COOH, wherein n is an integer from 1 to 100, but preferably 1, 2, 3, 4 is 5, 6, 7, 8, 9, 10, 11 or 12; with (e) ether carboxylic acids of the general formula R- (O-CH 2 -CH 2) n -O-CH 2 - COOH, where n is an integer from 1 to 100, but preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, and wherein R is an alkyl, alkenyl or alkynyl radical, but preferably R = CQ, C 8 -, Cι 0 -, Cι 2 -, C -ι 4 -, Cι 6 -, Cι 8 alkyl, -alkenyl or - alkynyl; with (f) alkyl halides; or with (g) silanes of the type (OR) - n SiR 'n, where R is an alkyl radical, preferably R = methyl, ethyl, propyl, i-propyl, butyl, t-butyl, and R' is an organic, in particular an aliphatic, radical having functional groups such as -OH, -COOH, ester, amine, or epoxy, preferably wherein R '= C 6 -, C 8 -, Cι 0 -, Cι 2 -, Cι -, Cι 6 -, Cι 8 alkyl, alkenyl or alkynyl, aminopropyl, N-aminoethyl-3-aminopropyl, n- or i-propyl-N, N, N, - dimethyloctadecylammonium chloride, n- or i-propyl-N, N, N- trimethyl ammonium chloride, n- or i-propylsuccinic.

Another object of the present invention relates to a process for producing hygiene products, wherein the substances in the form of chemically or physically modified at its surface nanoparticles are applied to the surface of the hygiene product.

Another object of the present invention finally relates to a hygiene product with a body compatible substance, wherein the substance is chemically or physically modified at its surface.

The average primary particle size of the nanoparticles (diameter) according to the present invention is in the range 1-100 nm, preferably in the range 10-100 nm and 15-95 nm, and 20 - 80 nm Particularly preferred values ​​(ranges) for the. average primary particle size 25 - 70 nm, 30 - 50 nm, 60 - 80 nm and 40 -. 85 nm, the specific surface of the particles is at least 10 m 2 / g, preferred are values of at least 30 m 2 / g, 50 m 2 / g or 80 m 2 / g or at least 125 m 2 / g, values of at least 150 m 2 / g, 180 m 2 / g, 200 m 2 / g or even at least 250 up to 300 m 2 / g, preferably are.

Accordingly, the present invention hygiene products or parts thereof, relates to (associated with contacting the skin, in particular non-woven materials), which contain nanoscale particles (nanoparticles) and the one part, moisture-keits- due to these particles and odor absorbing, on the other hand the pH neutralizing, antibacterial (antiseptic) and / or anti-inflammatory effect. These so-called nanoparticles are preferably oxide materials and layered silicates (particularly suitable for the absorption of moisture and odors), in particular bentonite, hectorite, montmorillonite, zeolites (eg, sodium, potassium, magnesium, calcium aluminosilicates); ZnO (particularly suitable, useful as antibacterial and / or anti-inflammatory agent but also for the absorption of odors), MgO (particularly suitable for the absorption of odors), AlOOH (boehmite), Al 2 O 3, ZrO 2, TiO 2 (all particularly suitable for the absorption of odors and for pH neutralization), and mixtures of these substances. the above-mentioned phyllosilicates, AlOOH (Disperal® Sol particular boehmites from P type Condea), MgO and ZnO and their mixtures are preferred. Particularly preferred, especially as a moisture and odor absorbing substances are synthetic hectorite (Optigel types eg from Sudchemie) and silicates of the empirical formula Na + 0th [(Si 8 Mg 5. 5 Lio. 3) 2 O o (OH) 4] 0.7 "(eg Laponite from Laporte.) The layered silicates have suitable liquid absorbing properties and are therefore not only for the top fabric, but can also be used between the uppermost and the underlying tissue, without further.

Basically have "ultra-small" particles (nanoparticles) properties which differ fundamentally from those of larger particles. You do not scatter light in certain circumstances, as they are much smaller than the wavelength of light. so you can give transparent formulations if they are dispersed to the primary particle size. They have a very large specific surface area (10 - 300 m 2 / g) and therefore also a high reactivity.

To fully develop their inventive properties, the nanoparticles must be smaller than 100 nm. Particle sizes between 2 and 60 nm are preferably aimed at. Another important criterion for the quality of the nanoparticles according to the invention is a narrow primary particle size distribution so that the particles are monodisperse as possible. In other words, this means that the particle or particle agglomeration should be controlled to avoid excessive agglomeration.

To use the potential of the nanoparticles according to the invention optimally, we need manufacturing processes that make it possible to prepare large amounts of nanocrystalline materials with controlled particle size and narrow particle size distribution. The expenditure on equipment must thereby be manageable, so that costs can be kept low. Such methods are known in the prior art, to be below but briefly described to illustrate the present invention better.

First, the nanoscale particles have to be produced that must be treated subsequently, to control the particle agglomeration. Therefore, to follow each such first production method, and thereafter treatment or modification methods are described which inhibit the agglomeration. The nanoparticles are so inventively used in chemically or physically modified on its surface shape for hygiene products.

Essentially, the production method of nanoparticles (metals, oxides, nitrides, etc.) can be based on inorganic materials divided into syntheses via liquid phase (which includes the sol / gel process, the precipitation reaction and the microemulsion) and Gasphasenver-drive.

liquid phase

In the sol / gel process hydrolyzable molecular starting compounds (eg TiCl 4, Ti (OEt) 4, Zr (OPr) 4, Si (OEt) 4, wherein OPr n-propoxy or isopropoxy group) controlled with water (optionally with brought adding a catalyst) to the reaction (as an overview for TiO 2 described in EP-B 0774443, page 2, [0004] to [0011] and the references cited therein). The hydrolysis condense in the connection to the oxide nanoparticles. These particles have an extremely large and reactive surface, so that located on the surface of the particles OH groups react with one another (condensation) and thus initiate the agglomeration. This agglomeration can be prevented by present during the sol / gel process, protective colloids or surfactants: The polar groups occupy the particle surface and provide both steric and for electrostatic repulsion of the particles.

Another method for preventing aggregates is the surface modification of the material with carboxylic acids and alkoxysilanes. In this method, the reactivity of the particles for their (partial) is utilized deactivation: The free OH groups are either esterified (carboxylic acids) or silanized. In both cases, results in the formation of covalent bonds between the particle surfaces and the surface-active substance. Length and functionality of the organic radical essentially determine the dispersibility of the material in various media.

In the precipitation reaction dissolved ions (often by shifting the pH value) is precipitated by addition of a suitable precipitating reagent (for TiO 2 described in EP-B 0774443, pages 3 to 6, [0019] to [0065]). By thermal treatment, crystalline powder can be obtained which normally but contain agglomerates. In general, to some extent, the mean particle size, particle size distribution, degree of crystallinity, under certain circumstances even the crystal structure and the degree of dispersion, be influenced by the reaction kinetics.

If, surfactants such as polycarboxylic acids, polyalcohols, surfactants or to the precipitation process, these show the surfaces of the growing bacteria and so prevent uncontrolled further growth of the particles. The surface coverage also supports the later redispersibility of the isolated powders. This variant of the precipitation reaction is preferred for this reason for the production of nanoscale powders and is particularly suitable for the production of metal (mixed) oxides, phosphates, and sulfides.

In microemulsions (ME) one uses the aqueous phase of w / o-emulsions as reaction chambers for the representation of nanoscale materials. All reactions which serve in aqueous media to represent nanoscale materials, that can be carried out in principle in microemulsions. This is especially true for precipitation reactions and the sol / gel process. The growth of the particles is limited by the size of the reaction space of the nm-sized droplets. A number of review articles provide an overview of ME as reaction media for showing nanoscale materials [eg Chhabra et al., Surfactants, Surfactants, Deterg. 34, 156-168 (1997); Eastoe et al., Curr. Opin. Colloid Interface Sci. 1, 800-805 (1996); .. Schwuger et al, Chem Rev. 95, 849-864 (1995); Lopez-Quintela et al., J. Colloid Interface Sci. 158, 446-451 (1993)].

Further treatment or modification methods, including

Surface modifiers, all of which are suitable for use in the invention are described in W096 / 34829, WO97 / 38058, WO98 / 51747, EP-B 0636111 and DE-A 43 36 694th

gas phase

In the past 10 years numerous gas-phase processes have been newly or further developed so that processes are available sufficient (eg Kruis et al., J. Aerosol. Sci. 29, 511 (1998)). These processes in the gas phase lead because of the high pressure (with simultaneously high production rate) to excessive agglomeration of the nanoparticles already in the manufacturing process, ie, the reactive particles are deposited by sintering processes to form larger agglomerates, so that it is according to the invention required to provide a method for the control of agglomeration, that is, a method for modifying the nanoparticles to connect. To stand by the quality of the nanoparticles, which means, among other things, to their average particle distribution judge, different methods are available, of which the most important are to be briefly explained below.

The method of transmission electron microscopy (TEM) requires not only a complicated apparatus also a lot of tact by the operator and is therefore unsuitable as a standard laboratory method. The X-ray diffraction utilizes the evaluation of the width of X-ray diffraction reflections advantage and gives indications of the size of the existing material in the primary particles. The line width resulting from the instrumental width (up-Iösung), the broadening due to smaller particle sizes and the broadening due to microstrain. Assuming that the widening of the reflections is mainly caused by small, spherical particles are obtained by application of the Scherrer equation, the volume average size of the crystallites examined.

To determine the size of colloidal particles further dynamic light scattering offers itself, which has now matured to the standard method (Powder and Bulk Engineering, February. 1995, 37-45). The advantage of this method lies in the easy and quick handling. The disadvantage, however, that the viscosity of the dispersion and refractive index of the particle must be known.

The methods of the BET isotherm and OH-group density can be used as routine methods for further characterization of the material.

By receiving the BET isotherm is obtained, the specific surface of the material. In the case of slightly agglomerated powder should thus vary the measured BET surface area of ​​the computed for isolated particles only insignificantly. Larger differences thus give a direct indication of larger and more dense agglomerates / aggregates (sintering), although the primary particles by XRD can be very small. Determining the density of hydroxyl groups on the surfaces of the powder is an important indication of the reactivity and the functionalization: A low density means that the material has been exposed during the synthesis of very high temperatures and is at least partially "Dead-burned". A high hydroxyl group density facilitates the functionalization and stabilization of the particles and is therefore preferred.

To determine the density of OH groups, the powder is reacted with thionyl chloride (exchange OH - »Cl), and then quantitatively hydrolyzed (release of chloride ions). The titration of chloride ions gives a value for the hydroxyl group with knowledge of the specific surface area.

The use of chemically or physically modified at its surface ZnO nanoparticles for the inventive hygiene products, for example, in contrast to conventional (unmodified) ZnO with an average particle size in the micrometer range (known from WO99 / ​​59538 for example) clearly preferable for various reasons. First, the nanoscale material is easier to formulate (without unnecessarily severe sedimentation of the particles occurs), since the modification reduces the hydrophilic property of the ZnO particles and thus the formulation facilitated with (hydrophobic) creams (if incorporation into a hydrophobic matrix necessary is).

Furthermore, the effectiveness of ZnO in consequence of its increased specific surface higher in ZnO inserted with the same quantity (but has nothing to do with the modification). Finally, the small primary particle size also leads to improved sensory (tactility) on the skin: it is felt no granular feeling as the conventional ZnO particles. In addition, the abrasive property of the particles can be smaller at a lower particle size, and thus the stress (mechanical damage) of the skin is reduced with decreasing particle size. It should be apparent to those skilled in saying that the benefits referred to do not apply to nanoscale, restrict on its surface modified ZnO but for all inventively relevant materials, provided they have a chemically or physically modified surface and have a primary particle size in the nanometer range , particularly when the particle size below 100 nm, below 90 nm, below 80 nm, below 70 nm, below 60 nm and preferably less than 50 nm, more preferably still less than 40 nm, for example at from 5 to 15 nm. Preferred materials (body compatible substances) are in this sense oxide materials and layered silicates, in particular bentonites, hectorites, montmorillonites, zeolites such as sodium, potassium, magnesium or calcium aluminosilicates; MgO; AlOOH (boehmite); Al 2 O 3; ZrO 2; TiO 2 and mixtures of these substances.

The invention relevant properties of ZnO are firstly its antibacterial (antiseptic) effect, for other skin soothing (anti-inflammatory) effect and additionally the odor absorption. These properties depend on the surface of the ZnO particles is not a coating in the sense result of the modification that the nanoscale particles are completely covered, but that Zn ions by the modified surface to the environment will be issued. Concrete modification means the coating of the particle surface with organic compounds which interact via chemical bonds or physical forces with the surface of the particles.

Surface modifiers which can be used according to the invention, for example, are all as such in the publications WO96 / 34829 (page 8, line 20 to page 9, line 7), WO97 / 38058 (page 5, line 28 to page 6, line 17 ), WO98 / 51747 (page 5, paragraph 2 to page 8, paragraph 1), EP-B 0636111 (column 3, line 38 to column 4, line 56) and DE-A 43 36 694 ( compounds mentioned column 6, lines 1/63). For modifying preferred compounds are especially (a) carboxylic acids (mono-, di- and polycarboxylic acids) or derivatives thereof such as anhydrides, halides and esters (including lactones); in particular stearic acid, palmitic acid, lauric acid, capric acid, caprylic acid, caproic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, ricinoleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, citric acid, malic acid, lactic acid, tartaric acid;

(B) amino acids, in particular (the naturally occurring amino acids Gly, Ala, Val, Leu, lle, Phe, Tyr, Trp, Pro, Hy-Pro, Ser, Asp, Glu, Asn, Gin, Arg, Lys, Thr, His , Cys, Met);

(C) hydroxycarboxylic acids and sugar acids such as glucaric acid, gluconic acid, glucuronic acid;

(d) polyglycolic acids having the general formula HOOC-CH 2 -O- (CH 2 -CH 2 -O) n -CH 2 - COOH, where n is preferably 1, 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11 or 12;

(e) ether carboxylic acids of the general formula R- (O-CH 2 -CH 2) n -O-CH 2 -COOH, wherein n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 and R is C 6 -, C 8 -, C 10 -, C 12 -, C 14 -, C 6 -, Cι 8 alkyl, alkenyl or alkynyl;

(F) alkyl halides;

(g) silanes of the type (OR) 4 -nSiR'n wherein R is methyl, ethyl, propyl, i-propyl, butyl, t-butyl, wherein R 'is an organic, in particular an aliphatic, radical having functional groups such as - OH, -COOH, ester, amine, or epoxy, preferably wherein R '= C 6 -, C 8 -, Cι 0 -, Cι 2 -, Cι -, C 16 -, Cι 8 alkyl, -alkenyl or - alkynyl , aminopropyl, N-aminoethyl-3-aminopropyl, n- or i-propyl-N, N, N, - dimethyloctadecylammonium chloride, n- or i-propyl-N, N, N- trimethylammonium chloride, n- or i-propylsuccinic.

Other modifiers are surfactants such as fatty alcohol (FA) derivatives and alkyl polyglucosides (APGs), polymers such as polyethylene glycols, polypropylene glycols, polyvinyl alcohols, polyvinyl pyrrolidone, Polyvinylbutyrole or polyaspartic acid, or protective colloids (for example, gelatin, starch, dextrin, dextran, pectin, casein, gum arabic) and derivatives thereof, or mixtures of these.

The modification is as described in the above mentioned references, depending on the solubility of the substance used for the modification in water, alcohol (ethanol, n-propanol, i-propanol, propylene glycol), ethers (tetrahydrofuran, diethyl ether) or an aprotic solvent ( LM) such as hexane, cyclohexane, heptane, i-octane, toluene performed. To be modified powder is dispersed in the LM and possibly liberated by boiling in a water separator of water residues. Subsequently, the modifying reagent is added and heated to a temperature between RT and the boiling point of LM (at atmospheric pressure) under reflux. In this case, the water formed is separated, if necessary, a water separator. Subsequently, the powder is separated for example by filtration or centrifugation of the suspension, washed and optionally dried (drying oven, freeze-drying).

Another particularly preferred material for the inventive hygiene products is one which is particularly suitable due to acidic surfaces (that is, materials having an isoelectric point of less than 7) for neutralization. These include in particular boehmite (AlOOH), Al 2 O 3, ZrO 2 and TiO 2. In the chemically or physically modified at its surface particles, preferred are those which produce acidic groups on the surface: tri-, dicarboxylic acids or alkoxysilanes of the general formula (OR ') - n SiR n where at least one (1) R is a group having an acidic group (for example carboxylic acid residue) is. In contrast to conventional materials with a rather average particle size in the micrometer range, the use of the nanoscale particles from the reasons already mentioned above the present invention is clearly preferable: (i) the nanoscale material is easier to formulate (without unnecessarily strong sedimentation the particle comes); (Ii) it has an improved efficacy in sequence enlarged specific surface area inserted with the same amount of particles; (Iii) the small particle size leads to improved sensory (tactility) on the skin: it is felt no granular feeling as in the conventional size particles.

The application of the chemically or physically modified at its surface nanoparticles on the hygiene product is produced by methods which are known from the prior art, and can for example by watering (foulard), roller application or spraying of the hygiene product with a solution / suspension done of the nanoparticle-containing lubricant and subsequent drying.

The nanoparticles can be suspended in both anhydrous and in aqueous systems. Both the anhydrous and the aqueous systems may be composed in order to give the hygiene products is a necessary for the different application areas hydrophilic or hydrophobic behavior of the one part of hydrophobic, but on the other hand also of hydrophilic components. Is intended to absorb the nonwoven fluid, it is rendered hydrophilic; should it reject the other hand, liquid, it must be hydrophobic. Thus, the central portion of a topsheet (uppermost web of a diaper) is hydrophilic to absorb the liquid and to forward them to the lower layers. The outer portion of the topsheet is hydrophobic on the other hand, to prevent leakage. For both areas, but an anti-bacterial and anti-inflammatory equipment is desired.

The nanoparticle content of such (above) lubricant is present in the range of 0.1 to 50.%, More preferably in the range of 0.5 to 30 wt manner.%, Particularly preferably in the range of 1 to 10 wt.% ,

Another way to apply the nanoparticles to the hygiene product, consists in the incorporation of the nanoparticles in a (skin-care and hydrophobic) Lotion, preferably, which is applied to the non-woven material / fabric layer based on wax. The application of the waxes can be carried out during the manufacture of non-woven or in the preparation of the ready-hygiene product (z. B. Windel).

This embodiment is particularly suitable for ZnO particles as antibacterial and anti-inflammatory substance. The content of the nanoparticles, in particular of the nanoscale ZnO, in the lotion is less than that of the lubricant, since the application amount of the lotion is higher and is in the range of 0.1 to 10 wt.%, More preferably in the range of 0.1 to 8 wt.%, the modified nanoparticles optionally have acidic groups on the surface that react with those contained in the urine bases under neutralization. Particularly advantageously, the nanoparticles are due to the fact that they have a large surface area in conjunction with a high density of active (eg acid) groups on the surface. Correspondingly low, the amount of nanoparticles used may be. On one hand, an environment is created through the neutralization of the waste products in the hygiene product, which is unfavorable for the growth of bacteria, so that the risk of irritation and inflammation of the skin is reduced. On the other hand, the nanoparticles absorb the odor-causing or responsible for the odor substances. To avoid annoying odors is thus reduced. Finally, the nanoparticles, due to their small particle size of below 100 nm and its surface texture capable of swelling and therefore absorb humidity, thereby ensuring a dry hygiene product and a dry feel to the skin.

Examples

Example 1: modification of nanoscale ZnO with stearic acid

60 g of nano-ZnO were dispersed in 250 ml of n-octane and the water freed from adhering water (ca. 1 ml). Thereafter, 10.7 g of stearic acid (98%) were added and the mixture refluxed for 5 h. In this case, an additional 0.5 ml of water were deposited. The then obtained chemically or physically modified on the surface nanoscale ZnO powder was separated by centrifugation, washed with n-octane and first in air, then about 8 hours at 50 ° C in a circulating air drying cabinet.

Example 2: modification of nanoscale ZnO with ether carboxylic acid

Since the ether carboxylic acid R- (O-CH 2 -CH 2) 2.5 -O-CH 2 -COOH (R = C i24) its preparation process contains water, 2.7 g of Akypo RLM were initially 25 (92% ig , trade name of the Fa. Kao) dissolved in 200 ml of n-hexane and boiled on a water separator until the water was completely removed (it is in the above formula to the description of the average degree of polymerization of EO groups). 92 g of nano-ZnO were dispersed in this solution and 4 h at reflux cooked. Resulting water (2.8 mL) was deposited as before. Subsequently, the modified powder was separated by filtration, washed with n-hexane and 4-5 h at 50 ° C in a circulating air drying cabinet.

Example 3: Studies on human three-dimensional skin model

There was a PIT (phase inversion temperature) cream prepared with conventional or with nanoscale ZnO ZnO, which was Coated form with stearic acid. These creams were on three-dimensional human skin model (Fa. Matek Corp., MA Ashland, USA) with respect. Their influence examined on the vitality or on the release of inflammatory mediators (interleukin-1α, prostaglandin E2) back.

Four skin models demineralized water (aqua demin.) Was applied. All other skin models were incubated with 80μl of a 0.16% Na-lauryl sulfate (SDS) solution for one hour, incubated (37 ° C, 5% C0 2, 90% rel. Humidity). Subsequently, the skin models were washed with phosphate buffer and then PIT cream 1 (with conventional ZnO) and PIT cream 2 (of coated with stearic nano-ZnO) applied. In each case, carried out quadruple provisions. As a control, each have four skin models cortisone cream (SDS / aqua demin.) And four skin models aqua demin. (Aqua demin. Aqua demin.) Was applied.

After 24 hours of incubation (37 ° C, 5% CO 2, 90% rel. Humidity) were washed again the skin models with phosphate buffer. Following the skin using the MTT assay (Methylthiazoltetrazolium) was tested for its vitality to and in the medium of the release of inflammatory mediators interleukin-1 α and prostaglandin E2 determined. Table 1: PIT zinc oxide - creams for tests on human skin models

The determination of inflammatory mediators was carried out by ELISA assay (Enzyme Linked Immuno Sorbent Assay).

Result:

The treatment of the skin models with Na lauryl sulfate solution and subsequently with aqua demin. (SDS / aqua demin.) Resulted in a reduction of vitality of the skin models as well as to an increased release of interleukin-1α and prostaglandin E2. For the treatment of the skin models with cortisone cream after incubation with sodium lauryl sulfate solution, the release of prostaglandin E2 was significantly, the only marginally reduced from interleukin-1α. Treatment with PIT cream 1 and with PIT cream 2 resulted in a slight decrease in vitality. A reduction of the inflammatory mediator interleukin-1α was only achieved after treatment with PIT cream 2 which contained the nanoscale, coated with stearic acid ZnO, not with PIT cream 1. The trend decreased Cream 2 also the release of prostaglandin E2 compared to cream 1.

Table 2: Vitality of the skin models

Vitality (MTT assay)

Table 3: Distribution of the inflammatory mediator interleukin-1

Table 4: Distribution of inflammatory mediator prostaglandin E2

prostaglandin E2

Claims

claims
1. The use of biocompatible materials for the manufacture of hygiene products, wherein the substances in the form of chemically or physically modified at its surface nanoparticles are present.
2. Use according to claim 1, wherein the hygiene products selected from diapers for babies and adults, panty liners and tampons.
3. Use according to claim 1 or 2, wherein the substances moisture and / or absorb or absorb odors and / or (antiseptic) and anti-inflammatory and / or neutralize the pH and thus urine, feces, blood and sweat, anti-bacterial the can the body has excreted record.
4. Use according to one of the preceding claims, wherein the body acceptable substances are selected from oxides, hydrated oxides, hydroxides, halides, Phos-triphosphates, sulfides, nitrides and carbides of Al, Si, of the alkali and alkaline earth metals and of transition group elements including mixed salts of these groups such as hydroxides / halides, halides / phosphates or hydroxides / halides / phosphates.
5. Use according to one of the preceding claims, wherein the body be compatible substances in the form of chemically or physically modified at its surface nanoparticles, the average primary particle size (diameter) in the range 1-100 nm, preferably in the range 10-100 nm or 15 to 95 nm and 20 - 80 nm, more preferably in the range 25 to 70 nm, 30 - 50 nm, 60-80 nm and 40-85 nm.
6. Use according to one of the preceding claims, wherein the body acceptable substances in the form of chemically or physically modified at its surface nanoparticles have a specific surface area of at least 10 m 2 / g, or preferably at least 30, 50 or 80 m 2 / g . at least 125 m 2 / g, more preferably of at least 150 m 2 / g, 180 m 2 / g, 200 m 2 / g or even at least 250 up to 300 m 2 / g.
7. Use according to one of the preceding claims, wherein the body compatible substance ZnO as an antibacterial (antiseptic) and / or anti-inflammatory agent, and odor absorbent, MgO for the absorption of moisture and odors, AlOOH, Al 2 O 3, Zr0 2 or TiO 2 is for the absorption of odors and for the pH neutralization.
8. Use according to one of the preceding claims, wherein the chemical or physical modification of the particle surface with organic compounds, especially with (a) carboxylic acids (mono-, di- and polycarboxylic acids) or derivatives thereof such as anhydrides, halides and esters (including the lactones); more particularly with stearic acid, palmitic acid, lauric acid, capric acid, caprylic acid, caproic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, ricinoleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, citric acid, malic acid, lactic acid, tartaric acid; with (b) amino acids, particularly with the naturally occurring amino acids (Gly, Ala, Val, Leu, lle, Phe, Tyr, Trp, Pro, hybrid Pro, Ser, Asp, Glu, Asn, Gin, Arg, Lys, Thr , His, Cys, Met); with (c) hydroxycarboxylic acids and sugar acids such as glucaric acid, gluconic acid, glucuronic acid; with (d) polyglycolic acids having the general formula HOOC-CH 2 - O- (CH 2 -CH 2 -O) n -CH 2 -COOH, wherein n is 1, 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11 or 12; with (e) ether carboxylic acids of the general formula R- (0-CH 2 -CH 2) n -O-CH 2 -COOH, wherein n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; wherein R = C 6 -, C 8 -, C 10 -, C i2 -, C i4 -, C 16 -, Cι 8 alkyl, alkenyl or alkynyl; with (f) alkyl halides; or with (g) silanes of the type (OR) - n SiR 'n, where R = methyl, ethyl, propyl, i-propyl, butyl, t-butyl and R' is an organic, in particular an aliphatic, radical having functional groups such as -OH, - COOH, ester, amine, or epoxy, preferably wherein R 1 = C 6 -, Cs, C10, C1 2 -, Cu, Cιe-, cis alkyl, alkenyl or alkynyl, aminopropyl, N-aminoethyl-3-aminopropyl, n- or i-propyl-N, N, N, -dimethyloctadecylammoniumchlorid, n- or i-propyl-N, N, N-trimethyl ammonium chloride, nor i-
Propylbemsteinsäureanhydrid, takes place.
9. hygiene product with a body compatible substance, as defined in any one of the preceding claims.
10. The hygiene product of claim 9, wherein the hygiene products is a diaper for babies or for adults, a panty liner or a tampon.
11.A method for producing a hygiene product which is as defined in claim 9 or 10, characterized in that on the surface chemically or physically-modified nanoparticles as defined in any one of claims 1 to 8, on the surface of the hygiene -Produkts is applied.
12. The method of claim 11, characterized in that the application of the chemically or physically modified on the surface of the nanoparticles to the hygiene product by impregnation (foulard), roller application or spraying of the hygiene product of the containing with a solution / suspension of the nanoparticles finishing agent and then drying.
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