EP3575466B1 - Matériau composite fibreux pouvant être dissout dans l'eau - Google Patents

Matériau composite fibreux pouvant être dissout dans l'eau Download PDF

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Publication number
EP3575466B1
EP3575466B1 EP18174929.2A EP18174929A EP3575466B1 EP 3575466 B1 EP3575466 B1 EP 3575466B1 EP 18174929 A EP18174929 A EP 18174929A EP 3575466 B1 EP3575466 B1 EP 3575466B1
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EP
European Patent Office
Prior art keywords
composite material
binder
fibre composite
fiber composite
fiber
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EP18174929.2A
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German (de)
English (en)
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EP3575466A1 (fr
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Intervisa Beteiligung und Verwaltung GmbH
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Intervisa Beteiligung und Verwaltung GmbH
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Priority to ES18174929T priority Critical patent/ES2924110T3/es
Application filed by Intervisa Beteiligung und Verwaltung GmbH filed Critical Intervisa Beteiligung und Verwaltung GmbH
Priority to PL18174929.2T priority patent/PL3575466T3/pl
Priority to EP18174929.2A priority patent/EP3575466B1/fr
Priority to HUE18174929A priority patent/HUE060920T2/hu
Priority to JP2020566705A priority patent/JP2021525320A/ja
Priority to PCT/EP2019/063447 priority patent/WO2019228920A1/fr
Priority to US17/059,339 priority patent/US20210230806A1/en
Publication of EP3575466A1 publication Critical patent/EP3575466A1/fr
Application granted granted Critical
Publication of EP3575466B1 publication Critical patent/EP3575466B1/fr
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • D21H17/26—Ethers thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/002—Tissue paper; Absorbent paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/002—Tissue paper; Absorbent paper
    • D21H27/004—Tissue paper; Absorbent paper characterised by specific parameters
    • D21H27/005—Tissue paper; Absorbent paper characterised by specific parameters relating to physical or mechanical properties, e.g. tensile strength, stretch, softness

Definitions

  • the invention relates to a water-disintegratable fiber composite material, comprising a number of fiber elements and at least one binder, which is formed from a water-soluble polysaccharide or comprises such.
  • Corresponding fiber composite materials which can be broken down in water or fiber products made from them are known in principle. Corresponding fiber composite materials are required to disintegrate quickly and completely or to decompose quickly and completely when they come into contact with water. Corresponding fiber composite materials should therefore disintegrate or decompose as quickly and as completely as possible when they come into contact with water.
  • the structural properties of corresponding fiber composite materials can sometimes be improved, i. H. in particular their mechanical properties. This applies in particular to fiber composite materials, the specific area of application or use of which at least temporarily includes a certain mechanical stress on the fiber composite materials.
  • WO 2013/081911 A1 discloses a water-disintegrable fiber composite material with a binder whose viscosity is below 500 mPas.
  • EP 1 630 288 A1 discloses a water-disintegratable fibrous composite material.
  • the object of the invention is to provide a, in particular with regard to its structural properties, ie. H. in particular its mechanical properties to indicate improved water-disintegrable fiber composite material.
  • fiber composite material described herein, which is referred to below as “fiber composite material” for short, has special properties which are in particular special disintegration properties in water and special structural properties, d. H. in particular mechanical properties.
  • the fiber composite material has a comparatively low wet strength, ie a comparatively low mechanical strength on contact with water.
  • the low wet strength enables rapid and complete disintegration or rapid and complete decomposition of the fiber composite material into individual fiber elements on contact with water.
  • the fiber composite material decomposes or decomposes very quickly due to its low wet strength or its high ability to disintegrate or decompose, so that after disposal of the fiber composite material, e.g. B. in drains, toilets, etc., blockages in a sewage system are avoided or the fiber composite material in the sewage treatment plant does not have to be separated separately before the actual cleaning of the waste water.
  • the fiber composite material thus enables (largely) complete disintegration upon contact with water, ie in particular after it has been placed in water.
  • the fiber composite material further disintegrates or degrades within less than 1 hour, preferably within less than 15 minutes, after being placed in water preferably within less than 1 minute, more preferably within less than 30 seconds, more preferably within less than 10 seconds.
  • individual fiber elements are present after the decomposition, which are no longer connected to one another and - in particular due to a comparatively short fiber length - can also no longer be connected to one another in dispersion, so that e.g. B. deposits, clumping or blockages in / of sewage systems can be avoided.
  • the fiber length is typically so short that tangling of fiber elements in a (turbulent) flow field, e.g. B. a sewage system is not possible.
  • the low wet strength and the generally good biodegradation and availability of the fiber composite material lead to rapid and complete decomposition up to complete metabolization of the fiber composite material even if it is (accidentally) released into nature and the environment.
  • wet strength is understood to mean the strength of the fiber composite material when it comes into contact with water or in the presence of an excess of water.
  • the wet strength can e.g. B. according to a wet tensile test DIN EN ISO 12625, Part 5 (Issue date: 2005-09) "Determination of the width-related wet breaking strength " be determined.
  • the fiber composite material preferably has a wet strength, determined by means of a wet tensile test according to DIN EN ISO 12625 at 20° C. and a relative humidity of 65%, of at most 2 N, preferably at most 1 N, more preferably at most 0.5 N.
  • the fiber composite material has a wet strength of at most 2N, preferably at most 1N, more preferably at most 0.5N.
  • exceptions above and below are conceivable.
  • the fiber composite material typically also has a comparatively high moisture strength, i. H. a comparatively high mechanical strength when wet.
  • the fiber composite material thus has a comparatively high mechanical strength even in the wet state under short-term mechanical stress, for example due to friction on a substrate.
  • moisture strength is understood to mean the strength of the fiber composite material, in particular in water or in the presence of an aqueous liquid containing at least one organic component.
  • the at least one organic component can, for. B. from the group: aliphatic alcohols, aliphatic ethers, aliphatic esters, monosaccharides, oligosaccharides and mixtures or combinations thereof.
  • the wet strength can e.g. B. be determined by a strip tensile test according to DIN EN ISO 13934-1 (issue date: 1999-04).
  • the fiber composite material preferably has a moisture resistance, determined by means of a strip tensile test in accordance with DIN EN ISO 13934-1 at 20° C. and a relative humidity of 65%, of more than 3 N, in particular in a range between 3 N and 250 N, preferably in a range between 4N and 150N, more preferably in a range between 4.5N and 120N, more preferably in a range between 5N and 80N, more preferably in a range between 6N and 55N.
  • a moisture resistance determined by means of a strip tensile test in accordance with DIN EN ISO 13934-1 at 20° C. and a relative humidity of 65%, of more than 3 N, in particular in a range between 3 N and 250 N, preferably in a range between 4N and 150N, more preferably in a range between 4.5N and 120N, more preferably in a range between 5N and 80N, more preferably in a range between 6N and 55N.
  • the wet strength of the fiber composite material is defined by the composition of the constituents or components that make up the fiber composite material, or can be determined by specifically varying the composition of the Fiber composite material-forming ingredients or components specifically define. In particular, it is possible to tailor the wet strength of the fiber composite material to a specific application or use of the fiber composite material by specifically varying the composition of the constituents or components forming the fiber composite material. The same applies to the moisture resistance of the fiber composite material.
  • the fiber composite material comprises a number or a large number of fiber elements and at least one binder as essential parts or components. Concrete embodiments of the fiber elements or the binder and any other constituents or components of the fiber composite material are explained in more detail below.
  • the fiber elements can be wetted in water or in an aqueous solution.
  • the fiber elements can be swellable on contact with water.
  • the fiber elements can therefore have a certain absorption capacity for water, which leads to swelling (increase in volume) of the fiber elements when they come into contact with water.
  • the fiber elements can form a basic matrix of the fiber composite material or be understood as such.
  • the fiber elements can be formed from natural, ie animal or vegetable, or synthetic, inorganic and/or organic fibers or fiber materials.
  • the fiber elements are preferably formed from natural organic fibers or fiber materials. Chemically and/or geometrically and/or physically identical or chemically and/or geometrically and/or physically different fiber elements can be used. Consequently, there can also be mixtures of different fiber elements, ie fiber elements that differ in at least one chemical, geometric or physical property.
  • inorganic fiber elements are basalt, glass, silicic acid, mineral and carbon fibers.
  • organic fiber elements are hemp or cellulose fibers.
  • Examples of synthetic organic fiber elements are polyester, polyamide, polyimide, polyamideimide, polyethylene, polypropylene, polyvinyl chloride fibers.
  • Mainly natural fiber elements are preferred, i. H. in particular cellulose fibers.
  • cellulose fibers for example, rayon, cotton, wool, acetate or tencel fibers can be used.
  • the fiber elements comprise 40 to about 98% by weight, more preferably 60 to 95% by weight, cellulose fibers, based in each case on the total weight of the dry fiber composite material.
  • the cellulose fibers used can be obtained by chemical pulping of plant fibers or by using recycled fibers. Both wood fibers, fibers from palm or annual plants, such as hay, straw, bagasse, kenaf or bamboo, and mixtures or combinations thereof can be used.
  • any wood pulp i. H. both softwood pulp and hardwood pulp, can be used.
  • the fiber elements preferably have a length of at least 0.1 mm, preferably in a range between 0.1 mm and 10 mm, more preferably in a range between 0.2 and 6 mm, more preferably in a range between 1 mm and 4 mm , more preferably in a range between 1.1 and 3 mm.
  • the fiber composite material preferably has no fiber elements that have a fiber length of more than 6 mm. After dissolving the fiber composite material in water, a mechanical connection, i. H. e.g. B. knotting, looping, felting and/or knotting, of one or more fiber elements with the formation of fiber element aggregates, which fiber element aggregates can lead to blockages, is prevented.
  • the fiber elements therefore typically have a fiber length below a concentration- and fiber material-dependent tangle limit. Regardless of their geometry, the fiber elements are preferably water-soluble and/or dispersible.
  • the fiber elements can have a specific fiber geometry, ie in particular a specific fiber length, which makes it difficult to connect the fiber elements to one another after the fiber composite material has disintegrated or prevented.
  • the fiber elements are typically chosen to be so short, in particular they typically have a fiber length of less than 6 mm, that neither in the dry, moist or wet state nor in the state in which the fiber composite material has decomposed or decomposed in water, e.g . B. formed by tangles, loops or plaiting, can form mechanical connection with each other.
  • the fiber elements thus typically have a fiber length below an optionally fiber element-specific tangle limit, above which a z. B.
  • the tangle limit which can also be referred to as the tangle limit fiber length, is a concentration- and fiber-material-dependent fiber length that leads to the formation of mechanically stable fiber-fiber agglomerates or fiber-fiber bonds in the flow field.
  • the structural cohesion or the resulting structural or mechanical properties, i. H. in particular the strength of the fiber composite material in the dry, damp or wet state is typically produced solely by the binder or its setting process. Consequently, typically the binder alone is used to achieve a typically chemical or physico-chemical fixation, d. H. in particular to form or ensure the formation of hydrogen bonds, fiber element-fiber element bridges or binder films, formed, sufficiently stable connection of the fiber elements or between the fiber elements.
  • the fiber elements are, at least in sections, in particular completely, surrounded by the binding agent or embedded in it or fixed to one another at contact points and fiber element-fiber element crossing points (gusset area).
  • the binder is formed from a water-soluble polysaccharide, in particular one containing acid groups, ie having at least one acid group, or comprises at least one such polysaccharide.
  • the Water solubility of the polysaccharide means in particular that at least 1 g, in particular at least 2 g, preferably at least 5 g, is soluble in 100 g of distilled water at a temperature of 25° C. and a pressure of 1 atm.
  • the Z. B. as an aqueous solution and / or as a foam applied binder typically has a certain absorption capacity for water, which is retained even after the binder has set and leads to swelling (volume increase) and / or dissolution of the binder on renewed contact with water.
  • the binder is used to connect the fiber elements, e.g. B. adhesively or cohesively with each other.
  • the binder can adhere to the fiber elements after application to the fiber elements and subsequent drying, as a result of which the fiber elements are connected to one another adhesively or cohesively.
  • the binder can be connected to the fiber elements via hydrogen bonds.
  • the binder has a viscosity of more than 500 mPas measured in an aqueous solution containing 2% by weight of binder or in water at 20.degree.
  • the binder has a viscosity of (much) more than 500 mPas measured on an aqueous solution containing 2% by weight of binder or in water at 20.degree.
  • the measurement of the viscosity of the binder takes place (e) z. B. by means of a rotational viscometer z. B. of the type Haake Viscotester VT 550 with a cylinder system, measuring cup MV at a speed of 2.55 s -1 .
  • the binder has a viscosity defined in claim 1--again measured on an aqueous solution containing 2% by weight of binder or in water at 20.degree. Specific conceivable viscosity ranges are - again measured on an aqueous solution containing 2% by weight of binder or in water at 20° C. - e.g. B. ranges between 550 mPas and 600 mPas, between 520 and 660 mPas, between 600 and 700 mPas.
  • the binder can thus z. B. a viscosity of more than 550 mPas, preferably more than 600 mPas, more preferably more than 700 mPas, measured on an aqueous solution containing 2% by weight of binder at 20° C.
  • the binder can have a viscosity of more than 510 mPas, in particular more than 520 mPas, preferably more than 530 mPas, more preferably more than 540 mPas, more preferably more than 550 mPas, more preferably more than 560 mPas, more preferably more than 570 mPas, more preferably more than 580 mPas, more preferably more than 590 mPas, more preferably more than 600 mPas, more preferably more than 610 mPas, more preferably more than 620 mPas, more preferably more than 630 mPas, more preferably more than 640 mPas , more preferably more than 650 mPas, more preferably more than 660 mPas, more preferably more than 670 mPas, more preferably more than 680 mPas, more preferably more than 690 mPa
  • the binder therefore has a comparatively high viscosity.
  • the comparatively high viscosity of the binder is typically associated with a comparatively high molar mass of the binder or of the binder molecules.
  • the binder therefore typically has a comparatively high molar mass.
  • the molar mass of the binder can, for. B. in a range between more than 50,000 g/mol and 400,000 g/mol, in particular in a range between 100,000 g/mol and 350,000 g/mol, preferably in a range between 150,000 g/mol and 300,000 g/mol.
  • the binder can e.g. B. a molecular weight of more than 75,000 g/mol, in particular more than 100,000 g/mol, in particular more than 125,000 g/mol, in particular more than 150,000 g/mol, in particular more than 175,000 g/mol, in particular more than 200,000 g/mol, in particular more than 225,000 g/mol mol, in particular more than 250,000 g/mol, in particular more than 275,000 g/mol, in particular more than 300,000 g/mol, in particular more than 325,000 g/mol, in particular more than 350,000 g/mol, in particular more than 375,000 g/mol, in particular have more than 400,000 g/mol.
  • the comparatively high viscosity of the binder surprisingly leads to special structural properties, i. H. in particular to special mechanical properties of the fiber composite material.
  • the composition of the fiber composite material described here is based on the finding that surprisingly precisely higher viscosities of the binder lead to significantly improved structural and mechanical properties of the fiber composite material.
  • the special structural or mechanical properties of the fiber composite material result in particular in a comparatively high tear strength (dry) or in a comparatively high tear value (dry).
  • the fiber composite material is improved in terms of its structural or mechanical properties, in particular due to the comparatively high viscosity of the binder.
  • the fiber composite material is therefore particularly suitable for areas of application or use that at least temporarily involve a certain mechanical stress on the fiber composite materials.
  • the binder can have a proportion by weight of 0.5-50% by weight, based on the dry weight or total dry weight of the fiber composite material.
  • the weight The proportion of binder based on the dry weight or total dry weight of the fiber composite material is in a range between 1 and 20% by weight, in particular in a range between 2 and 17% by weight, preferably in a range between 3 and 15% by weight.
  • the fiber composite material can, for. B. a tear value (dry) of at least 30 N, preferably at least 35 N, more preferably at least 40 N, more preferably at least 45 N, more preferably at least 50 N, more preferably at least 55 N, in particular at least 60 N, more preferably at least 65 N, more preferably at least 70 N, more preferably at least 75 N, more preferably at least 80 N, more preferably at least 90 N, more preferably at least 100 N.
  • the tear values can be in a range between 45 and 60 N in particular.
  • the tear values are each measured in the dry state in the longitudinal direction.
  • the tear values (dry) can e.g. B. be determined according to DIN EN ISO 1924-2.
  • the binder is a water-soluble polysaccharide or the binder comprises at least one such.
  • the water-soluble polysaccharide typically has at least one residue containing acid groups or carboxyl groups.
  • the water-soluble polysaccharide can e.g. B.
  • carboxymethyl cellulose CMC
  • carboxymethyl starch CMS
  • carboxyethyl cellulose CEC
  • carboxypropyl cellulose carboxymethyl methyl cellulose
  • CMMC carboxymethyl ethyl cellulose
  • CMHEC carboxymethyl hydroxypropyl cellulose
  • carboxyethyl hydroxymethyl cellulose carboxyethyl hydroxyethyl cellulose and mixtures or combinations thereof.
  • the binder can also be made from water-soluble starch, i. H. in particular from other water-soluble types or types of starch than those mentioned above.
  • a suitable commercially available binder is e.g. B. the sodium carboxymethyl cellulose Rheolon ® 500G, the z. B. from the company Ugur Seluloz Kimya (Aydin, TR).
  • Other suitable commercially available binders are, for example, the carboxymethyl cellulose varieties Calexis ® and Finnfix ® , each z. B. from the company CP Kelco Germany GmbH (Grossenbrode, DE) are available.
  • the fiber composite material can also contain at least one dampening agent, i. H. in particular an organic dampening solution, contain or comprise.
  • the fountain solution can be selected in particular from the group: aliphatic alcohols, aliphatic ethers, aliphatic esters or mixtures of at least one aliphatic alcohol and/or at least one aliphatic ether and/or at least one aliphatic ester.
  • ethanol, propanol, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 1,2,3-propanetriol and mixtures or combinations are suitable.
  • the dampening solution can therefore contain at least one volatile organic component, i. H.
  • e.g. B. ethanol e.g. ethanol
  • low-volatile organic component in particular a monomeric, oligomeric or polymeric diol or polyol compound, d. H. e.g. As propylene glycol included.
  • the dampening solution can make up a proportion by weight of 1 to 90% by weight, in particular below 50% by weight, preferably below 35% by weight, more preferably below 20% by weight, particularly preferably below 10% by weight on the weight or total weight of the fiber composite material.
  • the proportion of dampening solution is in a range between 30 and 70% by weight, in particular in a range between 35 and 65% % by weight, preferably in a range between 40 and 60% by weight.
  • the fountain solution or the fiber composite material can, especially if it contains alcoholic components such.
  • the fiber composite material is therefore particularly suitable for use as disinfection or cleaning paper.
  • the dampening solution or the fiber composite material can also have bactericidal and/or bacteriostatic or fungicidal and/or fungiostatic properties, in particular if it comprises alcoholic components. Bactericidal and/or bacteriostatic or fungicidal and/or fungiostatic properties can be useful for certain areas of application of the fiber composite material.
  • the fiber composite material can additionally contain or comprise an organic amphoteric component.
  • the organic amphoteric component is typically water soluble.
  • the amphoteric organic component which, as follows, is in particular an amphoteric amine or amine salt, can serve both as an acceptor and as a donor of protons, i. H. react as both a Bronsted acid and a Bronsted base.
  • the amphoteric organic component can serve in particular to form a (structure-forming) polysalt and/or a polymeric aggregate which is insoluble or non-dispersible together with the fountain solution, if present.
  • the organic amphoteric component can be, in particular, an amphoteric amine or amine salt.
  • the organic amphoteric component is not a surfactant, ie in particular not an amphoteric surfactant.
  • the organic amphoteric component is therefore not a surfactant, ie in particular not a surfactant based on an amine or amine salt.
  • quaternary or long chain, high molecular weight amphoteric amines are not as amphoteric as organic Component suitable because these act as a plasticizer and / or with a permanent cationic charge dispersing or structure-destroying and impair or prevent the moisture resistance of the fiber composite material.
  • a corresponding amine suitable for use as an amphoteric organic component for the fiber composite material can be a preferably water-soluble aminocarboxylic acid, preferably alpha-aminocarboxylic acid, which is preferably selected from the group: alanine, arginine, asparagine, aspartic acid, citrulline, cysteine, S-methylcysteine, Cystine, creatine, homocysteine, homoserine, norleucine, 2-aminobutanoic acid, 2-amino-3-mercapto-3-methylbutanoic acid, 3-aminobutanoic acid, 2-amino-3,3-dimethylbutanoic acid, 4-aminobutanoic acid, 2-amino- 2-methylpropanoic acid, 2-amino-3-cyclohexylpropanoic acid, 3-aminopropanoic acid, 2,3-diaminopropanoic acid, 3-aminohexanoic acid, gamma
  • short-chain peptides ie eg dipeptides, tripeptides, up to oligomeric peptides or oligopeptides with up to eight amino acid building blocks, which consist of one or different amino acids, can serve as amphoteric organic components and can therefore be used.
  • the organic amphoteric component if present, preferably has at least one protonatable and/or protonated amino group and further at least one deprotonatable and/or deprotonated acid group, more preferably carboxyl group.
  • the protonatable and/or protonated amino group is preferably selected from the group: primary amino group, secondary amino group, and combinations thereof.
  • an amphoteric amine is an amino carboxylic acid and/or a salt and/or a complex thereof, more preferably an alpha-amino acid and/or a salt and/or a complex thereof.
  • a salt of an amphoteric amine is in particular a salt of a polyvalent metal cation, expediently with a uniform spherical charge distribution on the surface, ie preferably Ca 2+ and/or Zn 2+ .
  • a complex of an amphoteric amine is in particular a complex of a polyvalent metal cation, preferably Ca 2+ and/or Zn 2+ . More preferably, an amphoteric amine has a first, preferably protonatable and/or protonated, amino group and a first acid group, preferably carboxyl group, and optionally also a second, preferably protonatable and/or protonated, amino group and/or a second acid group, preferably carboxyl group .
  • An amphoteric amine preferably has no permanently positively charged nitrogen atoms, more preferably no quaternary ammonium group, for example a tetraalkylammonium group.
  • the fiber composite material can accordingly, in particular polyvalent, metal cations or, in particular polyvalent, metal cation salts for complex formation with other components of the fiber composite material, in particular with the binder and/or with an or the amphoteric organic component, if present.
  • Corresponding metal cations or metal cation salts can in particular be water structure-forming and/or hygroscopic and/or osmotically active or effective. Examples of such salts can be organic salts based on low molecular weight organic acids or amino acids with polyvalent metal cations, e.g. B. calcium, magnesium, zinc ions, and / or inorganic metal cation salts, z. B.
  • the proportion by weight of corresponding metal cations or metal cation salts is in particular between 0.01 and 20% by weight, preferably between 0.1 and 10% by weight, more preferably between 0.2 and 8% by weight, particularly preferably between 0 , 3 and 5% by weight.
  • Suitable polyvalent metal cations are preferably selected from the group consisting of polyvalent, ie in particular bivalent or trivalent, ions of transition metals, polyvalent ions of metals of main groups 3 and 4 of the Periodic Table of the Elements, ions of alkaline earth metals, ions of transition metals and mixtures or combinations thereof, is selected. Furthermore, or accordingly, suitable polyvalent metal cations from the group consisting of Al 3+ , Mg 2+ , Co 2+ , Fe 2+ , Fe 3+ , Ca 2+ , Mn 2+ , Ni 2+ , Zn 2+ , and mixtures or combinations thereof, particularly preferably Ca 2+ , Zn 2+ and mixtures or combinations thereof.
  • Suitable metal cations can, for example, be in the form of water-soluble salts and/or complexes of the corresponding metal cations, preferably as bicarbonate, chloride, acetate, lactate, tartrate, fumarate, as carboxylate and/or complex of one of the abovementioned aminocarboxylic acids or a mixture thereof, preferably as chloride , carboxylate and/or complex of one of the above amino carboxylic acids or a mixture thereof, the corresponding metal cations, in the preferably aqueous solution, preferably lotion.
  • Suitable amphoteric amines are preferably selected from the group consisting of amino carboxylic acids, which may be unsubstituted or substituted, salts thereof, complexes thereof and mixtures or combinations thereof.
  • Suitable aminocarboxylic acids which can be unsubstituted or substituted, are organic compounds which preferably have at least one carboxyl group and at least one amino group.
  • suitable amphoteric amines are not surfactants; H. especially no amphoteric surfactants.
  • Suitable aminocarboxylic acids are preferably from the group consisting of alanine, arginine, asparagine, aspartic acid, citrulline, cysteine, S-methylcysteine, cystine, creatine, homocysteine, homoserine, norleucine, 2-aminobutanoic acid, 2-amino-3-mercapto-3- methyl-butanoic acid, 3-aminobutanoic acid, 2-amino-3,3-dimethylbutanoic acid, 4-aminobutanoic acid, 2-amino-2-methylpropanoic acid, 2-amino-3-cyclohexylpropanoic acid, 3-aminopropanoic acid, 2,3-diaminopropanoic acid, 3- Aminohexanoic acid, gamma-carboxyglutamic acid (3-aminopropane-1,1,3-tricarboxylic acid), glutamine, glutamic acid, glycine, his
  • the one amphoteric amine is selected from the group consisting of the above peptides consisting of one or different of the amino acids listed immediately above.
  • Metal cations preferably polyvalent metal cations, can form salts and/or complexes with one of the abovementioned aminocarboxylic acids. More preferably, the aforementioned amphoteric amines, preferably the aforementioned aminocarboxylic acids, can be used as salts and/or complexes of polyvalent metal cations, preferably Ca 2+ and/or Zn 2+ .
  • a corresponding amphoteric amine preferably the at least one aminocarboxylic acid, which can be unsubstituted or substituted, and/or a salt thereof and/or a complex thereof with a radical containing acid groups, preferably a radical containing carboxyl groups, of the binder or
  • the polysaccharide forms a polysalt after application to the fibrous elements.
  • the control of the wet strength of the fiber composite material, d. H. the decomposability of the fiber composite material in water can be improved.
  • the mentioned formation of salts or complexes or polysalts from organic amphoteric components, i. H. in particular aminocarboxylic acids, and metal cations can also have a positive influence on the moisture resistance of the fiber composite material.
  • a corresponding amphoteric amine which is preferably selected from the group of aforesaid aminocarboxylic acids, which may be unsubstituted or substituted, salts thereof, complexes thereof and mixtures or combinations thereof, has a proportion by weight in one Range between 0.1% and 30% by weight, preferably in a range between 0.5% and 20% by weight, more preferably in a range between 0.7% and 17% by weight % by weight, more preferably in a range between 2% by weight and 15% by weight, more preferably in a range between 3.3% by weight and 13% by weight, in each case based on the weight or total weight of the dry fiber composite material.
  • the fiber composite material contains or comprises at least one amphoteric organic component
  • the fiber composite material is particularly suitable for use as disinfection or cleaning paper.
  • the fiber composite material can therefore be designed in particular as disinfection or cleaning paper.
  • the special wet strength is to be regarded as an indicator effect for the (current) disinfection or cleaning effect of the fiber composite material, as the disinfection or cleaning effect of the fiber composite material is reduced if the fiber composite material disintegrates.
  • the disintegration of the fiber composite material is therefore typically accompanied by a decrease in the disinfecting or cleaning effect of the fiber composite material.
  • the fiber composite material is suitable e.g. B. also for use as water-disintegratable sanitary paper, in particular as moisture-resistant cosmetic paper that disintegrates in water, or toilet paper that disintegrates in water; the fiber composite material can thus be designed as water-breakable hygienic paper, in particular as water-breakable cleaning paper or as water-breakable toilet paper.
  • the fiber composite material in addition to the fiber elements and the binder also contain water, ie a proportion of water.
  • the water content results from the proportions of the fiber elements, the binder and any other (optional) components, such as e.g. B. the fountain solution and the organic amphoteric component of the fiber composite material.
  • the water content typically represents the rest, so that the respective components of the fiber composite material complement each other to 100%.
  • the fiber composite material can be formed in one or more layers.
  • the invention also relates to a method for producing a water-disintegrable fiber composite material, in particular a fiber composite material as described herein according to claim 13.
  • the fiber elements can be provided or present in the form of a fleece.
  • the fiber elements to be provided or provided can, e.g. B. by carding, wet-laying, air-laying, spunbonding or meltblowing into a fibrous web and are provided as a fibrous element web.
  • the web of fiber elements can be formed by the air-laying process, also referred to as the airlaid process, in which the fiber elements are closely mixed.
  • the airlaid fibrous elements can then be compressed or densified.
  • step (a1) and/or during steps (a2) and/or (a3) the binder and the organic amphoteric component, if present, are applied sequentially, together or simultaneously as an aqueous solution and/or as a foam and subsequently at a temperature greater than 100°C, preferably greater than 120°C, preferably greater than 150°C. Then the dampening solution, if available, can be applied.
  • the binder, the organic amphoteric component, if present, and the fountain solution, if present are applied in or after step (a3).
  • the binder, the optional organic amphoteric component and the optional dampening solution are preferably each applied independently of one another by padding, foam application and/or spraying.
  • the binder, the optional organic amphoteric component and the optional dampening solution can be applied separately to the same side or to different sides of the fiber elements or the fiber composite material.
  • the application of the binder, the optional organic amphoteric component and the optional dampening solution can take place simultaneously or not simultaneously (sequentially), with the order of application being variable.
  • the compaction or compression that takes place in step (a3) can be carried out by various methods that are simultaneous or staggered in time, ie a pre-compression and post-compression or compression divided, such as, for example, B. calendering, rolling, embossing done.
  • the thickness and/or density of the fiber composite material can be adjusted by compacting or compressing the fiber composite material.
  • step (a4) following step (a3) can be a, e.g. B. by embossing the fiber composite material taking place, connect formation of a three-dimensional structuring or surface structuring of the fiber composite material. In this way, depressions and/or elevations can be formed in a targeted manner in the fiber composite material.
  • the figure shows a basic representation of a single-layer or multi-layer fiber composite material 1 that is capable of breaking down in water, according to an exemplary embodiment.
  • the fiber composite material 1 shows on the one hand a comparatively high moisture strength, ie a comparatively high mechanical strength in the moist state, and on the other hand a comparatively low wet strength, ie a comparatively low mechanical strength on contact with water.
  • the comparatively low wet strength enables the fiber composite material 1 to decompose quickly and completely into individual fiber elements 2 when it comes into contact with water.
  • the fiber composite material 1 thus has a sufficiently high mechanical moisture resistance in the event of short-term mechanical stress, for example due to friction on a substrate.
  • the fiber composite material 1 shows sufficiently low wet strength or high decomposability so that blockages in a waste water system are avoided after the fiber composite material 1 has been disposed of.
  • the fiber composite material 1 is therefore particularly suitable for use as disinfecting or cleaning paper that disintegrates in water.
  • a use as sanitary paper disintegratable in water, cosmetic paper disintegrable in water or as toilet paper disintegratable in water is also conceivable.
  • the fiber composite material 1 comprises a number of fiber elements 2, i. H. e.g. B. cellulose fibers, and the fiber elements 2 surrounding binder 3, which is formed from a water-soluble polysaccharide or includes such.
  • the water-soluble polysaccharide can be e.g. Example, be carboxymethyl cellulose (CMC).
  • the binder 3 has a viscosity above 500 mPas measured on an aqueous solution containing 2% by weight of binder or in water at 20.degree.
  • the measurement of the viscosity of the binder 3 takes place (e) z. B. by means of a rotational viscometer z. B. of the type Haake Viscotester VT 550 with a cylinder system, measuring cup MV at a speed of 2.55 s -1 .
  • the high viscosity of the binder 3 results in special structural properties, i. H. in particular special mechanical properties of the fiber composite material 1, which result in particular in a high tear value (dry).
  • the following table shows examples of possible compositions of the fiber composite material 1, ie in particular different binders #1 -4, and associated tear values (dry), each averaged from six measured values: binder Viscosity [mPas] Tear value (dry) [N] #1 880-1150 48 #2 550 - 600 51 #3 600-700 38 #4 520 - 660 69
  • Binder #1 is Rheolon® 1000 G carboxymethyl cellulose
  • Binder #2 is Calexis® carboxymethyl cellulose
  • Binder #3 is Rheolon® 500 G carboxymethyl cellulose
  • Binder #4 is a carboxymethyl cellulose of the Finnfix ® variety
  • the viscosity of binder 3 was measured using a Haake Viscotester VT 550 rotational viscometer with a cylinder system, measuring cup MV at a speed of 2.55 s ⁇ 1 .
  • the tear values were measured in each case on dry specimens with a width of 50 mm and a length of 100 mm in the longitudinal direction.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paper (AREA)
  • Sanitary Thin Papers (AREA)
  • Nonwoven Fabrics (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)

Claims (13)

  1. Matériau composite renforcé par des fibres (1) pouvant se décomposer dans l'eau, comprenant :
    - un nombre d'éléments fibreux (2),
    - au moins un liant (3), lequel est formé à partir d'un polysaccharide hydrosoluble ou comprend un élément de ce type, caractérisé en ce que l'au moins un liant (3) présente une viscosité entre 501 mPas et 750 mPas, laquelle est mesurée au moyen d'un viscosimètre rotatif du type Haake Viscotester VT 550 avec un système de cylindre, un gobelet gradué MV à une vitesse de rotation de 2,55 s-1 sur une solution aqueuse contenant 2 % en poids de liant à 20 °C, et une masse molaire supérieure à 50 000 g/mol.
  2. Matériau composite renforcé par des fibres selon la revendication 1, caractérisé en ce que l'au moins un liant (3) présente une fraction proportionnelle au poids de 0,5 - 50 % en poids par rapport au poids sec du matériau composite renforcé par des fibres (1).
  3. Matériau composite renforcé par des fibres selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il présente une valeur de résistance au déchirement d'au moins 30 N, de manière préférée d'au moins 35 N, de manière davantage préférée d'au moins 40 N, de manière davantage préférée d'au moins 45 N, de manière davantage préférée d'au moins 50 N, de manière davantage préférée d'au moins 55 N, en particulier d'au moins 60 N, de manière davantage préférée d'au moins 65 N, de manière davantage préférée d'au moins 70 N, de manière davantage préférée d'au moins 75 N, de manière davantage préférée d'au moins 80 N, de manière davantage préférée d'au moins 90 N, de manière davantage préférée d'au moins 100 N.
  4. Matériau composite renforcé par des fibres selon l'une quelconque des revendications précédentes, caractérisé en ce que l'au moins un liant (3) est ou comprend de la carboxyméthylcellulose (CMC).
  5. Matériau composite renforcé par des fibres selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il comprend au moins un agent de mouillage, en particulier un agent de mouillage organique, de manière préférée issu du groupe : alcools aliphatiques, éthers aliphatiques, esters aliphatiques ou mélanges d'au moins un alcool aliphatique et/ou d'au moins un éther aliphatique et/ou d'au moins un ester aliphatique.
  6. Matériau composite renforcé par des fibres selon la revendication 5, caractérisé en ce que l'au moins un agent de mouillage présente une fraction proportionnelle au poids de 1 à 90 % en poids, en particulier inférieure à 50 % en poids, de manière préférée inférieure à 35 % en poids, de manière davantage préférée inférieure à 20 % en poids, de manière particulièrement préférée inférieure à 10 % en poids, par rapport au poids total du matériau composite renforcé par des fibres (1).
  7. Matériau composite renforcé par des fibres selon l'une quelconque des revendications 4 à 6, caractérisé en ce que l'au moins un agent de mouillage présente des propriétés bactéricides et/ou bactériostatiques ou fongicides et/ou fongistatiques.
  8. Matériau composite renforcé par des fibres selon l'une quelconque des revendications 5 à 7, caractérisé en ce que l'au moins un agent de mouillage contient de l'éthanol et/ou au moins un composé diol ou polyol monomère, oligomère ou polymère.
  9. Matériau composite renforcé par des fibres selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il comprend en supplément au moins un composant amphotère organique.
  10. Matériau composite renforcé par des fibres selon la revendication 9 et selon l'une quelconque des revendications 5 à 8, caractérisé en ce que l'au moins un composant organique amphotère sert en combinaison avec l'au moins un liant (3) à réaliser un polysel et/ou un agrégat polymère, lequel n'est pas soluble ou n'est pas dispersible conjointement avec un ou l'agent de mouillage.
  11. Matériau composite à base de fibres selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il comprend des cations métalliques ou des sels de cations métalliques pour la formation complexe avec d'autres constituants du matériau composite à base de fibres (1), en particulier avec le liant (3) et/ou avec un ou le composant organique amphotère.
  12. Matériau composite à base de fibres selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il est un papier de désinfection ou de nettoyage.
  13. Procédé de fabrication d'un matériau composite à base de fibres (1) pouvant se décomposer dans l'eau, en particulier d'un matériau composite à base de fibres selon l'une quelconque des revendications précédentes, comprenant les étapes :
    - de fourniture d'un nombre d'éléments fibreux (2), en particulier sous la forme d'une bande d'éléments fibreux contenant les éléments fibreux,
    - d'application d'au moins un liant (3) sur les éléments fibreux (2), en particulier sur la bande d'éléments fibreux, lequel est formé à partir d'un polysaccharide contenant des groupes acides ou en comprend un de ce type, dans lequel
    l'au moins un liant (3) présente une viscosité entre 501 mPas et 750 mPas, laquelle est mesurée au moyen d'un viscosimètre rotatif du type Haake Viscotester VT 550 avec un système de cylindre, gobelet gradué MV à une vitesse de rotation de 2,55 s-1 sur une solution aqueuse contenant 2 % en poids de liant à 20 °C, et une masse molaire supérieure à 50 000 g/mol.
EP18174929.2A 2018-05-29 2018-05-29 Matériau composite fibreux pouvant être dissout dans l'eau Active EP3575466B1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
PL18174929.2T PL3575466T3 (pl) 2018-05-29 2018-05-29 Włóknisty materiał kompozytowy rozpadający się w wodzie
EP18174929.2A EP3575466B1 (fr) 2018-05-29 2018-05-29 Matériau composite fibreux pouvant être dissout dans l'eau
HUE18174929A HUE060920T2 (hu) 2018-05-29 2018-05-29 Vízben oldható szálas kompozit anyag
ES18174929T ES2924110T3 (es) 2018-05-29 2018-05-29 Material compuesto de fibra desintegrable en agua
JP2020566705A JP2021525320A (ja) 2018-05-29 2019-05-24 水分解性繊維複合材
PCT/EP2019/063447 WO2019228920A1 (fr) 2018-05-29 2019-05-24 Matériau composite renforcé par des fibres susceptible de se désagréger dans l'eau
US17/059,339 US20210230806A1 (en) 2018-05-29 2019-05-24 Water-disintegratable fiber composite material

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EP3575466B1 true EP3575466B1 (fr) 2022-05-11

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Citations (1)

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EP1630288A1 (fr) * 2004-08-20 2006-03-01 Kao Corporation Article pour le nettoyage désintegrable et à haut gonflant ainsi qu' un procédé pour la fabrication d'un papier désintegrable

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JP2584508B2 (ja) * 1989-02-28 1997-02-26 花王株式会社 清掃用品用水解紙
US5281306A (en) * 1988-11-30 1994-01-25 Kao Corporation Water-disintegrable cleaning sheet
DE68913161T2 (de) * 1988-11-30 1994-07-07 Kao Corp Im Wasser abbaubares Reinigungsblatt.
JP3237495B2 (ja) * 1995-12-18 2001-12-10 東洋インキ製造株式会社 水崩壊性シート
JPH1096187A (ja) * 1996-09-24 1998-04-14 Dai Ichi Kogyo Seiyaku Co Ltd 水解紙用カルボキシメチルセルロース塩およびそれを用いた水解紙
JP3296989B2 (ja) * 1997-03-31 2002-07-02 ユニ・チャーム株式会社 水解性シート及びその製造方法
SG83698A1 (en) * 1998-01-16 2001-10-16 Uni Charm Corp Method of manufacturing a water disintegratable non-woven fabric and the water disintegratable non-woven fabric
JP2001279596A (ja) * 2000-03-29 2001-10-10 Wakoudou Kk 水解紙及びその製造方法
JP2004316024A (ja) * 2003-04-16 2004-11-11 Kao Corp 水解性清掃物品
JP4219323B2 (ja) * 2004-08-20 2009-02-04 花王株式会社 水解紙の製造方法
CN100560011C (zh) * 2004-08-20 2009-11-18 花王株式会社 膨松水解性清扫物品以及水解纸的制造方法
WO2013081911A1 (fr) * 2011-11-30 2013-06-06 Dow Global Technologies Llc Feuille fibreuse non tissée désintégrable dans l'eau
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EP1630288A1 (fr) * 2004-08-20 2006-03-01 Kao Corporation Article pour le nettoyage désintegrable et à haut gonflant ainsi qu' un procédé pour la fabrication d'un papier désintegrable

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US20210230806A1 (en) 2021-07-29
EP3575466A1 (fr) 2019-12-04
HUE060920T2 (hu) 2023-04-28
PL3575466T3 (pl) 2022-12-27
ES2924110T3 (es) 2022-10-04
WO2019228920A1 (fr) 2019-12-05

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