EP0807704A1 - Recovery of fibres from bonded nonwovens - Google Patents
Recovery of fibres from bonded nonwovens Download PDFInfo
- Publication number
- EP0807704A1 EP0807704A1 EP97107491A EP97107491A EP0807704A1 EP 0807704 A1 EP0807704 A1 EP 0807704A1 EP 97107491 A EP97107491 A EP 97107491A EP 97107491 A EP97107491 A EP 97107491A EP 0807704 A1 EP0807704 A1 EP 0807704A1
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- EP
- European Patent Office
- Prior art keywords
- alkaline earth
- earth metal
- alkali salt
- binder
- nonwoven
- 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.)
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Classifications
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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
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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
- D04H1/42—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 characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/435—Polyesters
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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
- D04H1/64—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
- D04H1/645—Impregnation followed by a solidification process
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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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
- D04H3/011—Polyesters
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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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/12—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with filaments or yarns secured together by chemical or thermo-activatable bonding agents, e.g. adhesives, applied or incorporated in liquid or solid form
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S260/00—Chemistry of carbon compounds
- Y10S260/31—Ionic cross-link
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S260/00—Chemistry of carbon compounds
- Y10S260/43—Promoting degradability of polymers
Definitions
- the invention relates to a method for recovering fibers from nonwoven fabrics.
- Nonwovens can be consolidated by coating or impregnation with a binder.
- non-crosslinked binders were used for the consolidation of nonwovens, which are soluble in water by converting carboxyl groups into carboxylate groups and can thus be separated from the fibers again.
- binders are used which crosslink after application to the nonwoven fabric.
- the binders can be monomers with several ethylenically unsaturated groups or monomers with other reactive groups, e.g. Methylol groups.
- Crosslinking via metal salt groups, e.g. crosslinking via Ca carboxylate groups is e.g. known from EP 442 370. It is also desirable to recover fibers from nonwovens bonded with crosslinked binders.
- the object of the present invention was therefore a process for the recovery of fibers from nonwoven fabrics bonded or solidified with crosslinked binders.
- Nonwovens made from a wide variety of fibers can be used for the method according to the invention.
- synthetic fibers such as viscose, polyester, polyamide, polypropylene, polyacrylonitrile, carbon fibers or fibers of homo- and copolymers of vinyl chloride or tetrafluoroethylene or fibers of natural origin such as cellulose, cellulose, cellulose, cotton or wood fibers or also glass, ceramic or mineral fibers or mixtures thereof.
- the fibers are folded into non-woven fabrics and then solidified with a binding agent, for which purpose the binding agent e.g. is brought onto the fibers by impregnation, spraying, cracking, dipping or printing. This is generally followed by drying to remove the solvent, generally water. In this manner known to those skilled in the art, a bound, i.e. get consolidated nonwoven.
- a binding agent for which purpose the binding agent e.g. is brought onto the fibers by impregnation, spraying, cracking, dipping or printing. This is generally followed by drying to remove the solvent, generally water.
- nonwoven fabrics find e.g. Use as carrier materials for roofing membranes or floor coverings.
- binders polymers are generally used which are built up from ethylenically unsaturated monomers.
- the polymers contain carboxylate groups which are crosslinked via alkaline earth metal ions, i.e. they are cross-linked with metal salts.
- the polymers preferably contain 0.1 to 30 wt.%, Particularly preferably 0.5 to 25 wt.% And very particularly preferably 5 to 20 wt.
- the carboxylate groups are preferably 50 to 100%, particularly preferably 80 to 100%, as a salt with alkaline earth metal cations.
- Preferred alkaline earth metal cations are Ca 2+ and Ba 2+ , Mg 2+ .
- Ca 2+ is particularly preferred.
- the metal salt-crosslinked polymers can be obtained, for example, from polymers with carboxylic acid or carboxylic anhydride groups by adding an alkaline earth metal salt, for example an oxide, hydroxide, carbonate or hydrogen carbonate, for example for the aqueous dispersion or solution of the polymer, as described in EP-A-442 370.
- an alkaline earth metal salt for example an oxide, hydroxide, carbonate or hydrogen carbonate, for example for the aqueous dispersion or solution of the polymer, as described in EP-A-442 370.
- the metal salt-crosslinked polymer is preferably composed of the following monomers A), B) and C):
- Monomers A) are monomers with at least one carboxylic acid or carboxylic anhydride group, which can be converted into the metal salt groups. Particularly noteworthy are acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride.
- the amount of these monomers results from the desired content of carboxylate groups crosslinked with alkaline earth metal cations.
- Main monomers B) selected from C 1 -C 20 -alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 C atoms, vinyl aromatics with up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides are of particular technical importance.
- Examples include (meth) acrylic acid alkyl esters with a C 1 -C 10 alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
- Vinyl esters of carboxylic acids with 1 to 20 C atoms are e.g. Vinyl laurate, stearate, vinyl propionate, vinyl versatic acid and vinyl acetate.
- Suitable vinyl aromatic compounds are vinyl toluene, ⁇ - and p-methylstyrene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
- nitriles are acrylonitrile and methacrylonitrile.
- the vinyl halides are chlorine, fluorine or bromine-substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
- vinyl ethers examples include Vinyl methyl ether or vinyl isobutyl ether. Vinyl ethers of alcohols containing 1 to 4 carbon atoms are preferred.
- Butadiene, isoprene and chloroprene may be mentioned as hydrocarbons with 2 to 8 carbon atoms and two olefinic double bonds.
- monomers C for example monomers containing hydroxyl groups, in particular C 1 -C 10 -hydroxyalkyl (meth) acrylates or (meth) acrylamide, can be used in the polymer.
- Customary polymers generally consist of at least 40, preferably at least 60, particularly preferably at least 80% by weight of the above main monomers B).
- the polymerization can be carried out by conventional polymerization methods, e.g. by substance, emulsion, suspension, dispersion, precipitation and solution polymerization.
- the polymerization processes mentioned are preferably carried out in the absence of oxygen, preferably in a stream of nitrogen.
- the usual equipment is used for all polymerization methods, e.g. Stirred tanks, stirred tank cascades, autoclaves, tubular reactors and kneaders.
- the method of solution, emulsion, precipitation or suspension polymerization is preferably used.
- the methods of solution and, in particular, emulsion polymerization are particularly preferred.
- the polymerization can be carried out in solvents or diluents, e.g.
- the metal-crosslinked polymers are generally applied to the nonwovens in the form of their aqueous solution or dispersion. After drying, the nonwovens are bound, ie solidified.
- the non-woven fabrics then generally contain 1 to 40 parts by weight, preferably 5 to 30 parts by weight, of the metal-crosslinked binder, based on 100 parts by weight of fibers.
- the fibers can be recovered according to the method of the invention by removing the blinding agent from the nonwoven fabric, i.e. is separated from the fibers.
- the nonwoven fabric is treated with an aqueous solution of a salt (hereinafter referred to as "soluble salt"), the anion of which forms a salt which is poorly soluble in water with the alkaline earth metal.
- soluble salt a salt which is poorly soluble in water with the alkaline earth metal.
- the soluble salt can be an inorganic or organic salt.
- it is an alkali metal salt.
- the anion of the soluble salt can e.g. are oxalate or carbonate, which e.g. form a sparingly soluble salt with the calcium cation.
- the anion of the soluble salt can also be an organic anion, for example, which forms a poorly soluble complex with the alkaline earth metal, for example Ca 2+ .
- EDTA is particularly worth mentioning here.
- the soluble salt contained in the aqueous solution preferably has a solubility of at least 10 g / ⁇ l water at 23 ° C.
- the aqueous solution preferably contains the salt in amounts of 0.02 to 15 parts by weight, particularly preferably in amounts of 0.1 to 10 parts by weight, very particularly preferably 0.5 to 2.5 parts by weight , based on 100 parts by weight of water.
- solubility of the sparingly soluble alkaline earth metal salt formed when treating the nonwoven fabric is preferably less than 0.5 g / l of water at 23 ° C.
- the aqueous solution preferably also contains a phase transfer catalyst.
- phase transfer catalysts are, for example, in Chimia 34 (1980) No. 1, pages 12 to 20.
- phase transfer catalysts are, for example, polyalkylene glycols, which is commercially available, for example, under the name Pluriol® or quaternary, organic Ammonium salts, which are commercially available, for example, under the name lutensite.
- Quaternary organic ammonium salts include, in particular, those of the formula I. mentioned, wherein R 1 -R 4 independently of one another are an organic radical, preferably a hydrocarbon radical having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms and X ⁇ is an anion, preferably an inorganic anion, for example Cl - , Br ⁇ stands.
- phase transfer catalysts are those with alkoxy groups, preferably with 2 to 20 alkoxy groups, e.g. Alkylphenol ethoxylates (e.g. Lutensole® AP, emulsifier 825 fatty alcohol ethoxylates (e.g. Lutensol A8) and oxo alcohol ethoxylates (e.g. Lutensol AO7, Lutensol ON80).
- Alkylphenol ethoxylates e.g. Lutensole® AP
- emulsifier 825 fatty alcohol ethoxylates e.g. Lutensol A8
- oxo alcohol ethoxylates e.g. Lutensol AO7, Lutensol ON80
- phase transfer catalysts By alkoxylation of alkylphenols, fatty alcohols or oxoalcohols with alkylene oxides, preferably ethylene oxide, these phase transfer catalysts contain alkoxy groups.
- the content of the phase transfer catalyst in the aqueous solution is preferably 0.01 to 1 part by weight, particularly preferably 0.08 to 0.5 part by weight, based on 100 parts by weight of water.
- bases in particular sodium hydroxide solution, are also added in order to increase the proportion of alkali cations.
- the temperature of the aqueous solution can e.g. 10 to 100 ° C, in particular 15 to 80 ° C and particularly preferably 20 to 50 ° C. Temperatures above 30 ° C., in particular above 40 ° C., are advantageous in order to achieve an even better and, above all, faster detachment of the binder from the nonwoven fabric.
- the nonwoven fabric can be fed to the method according to the invention as a whole or in comminuted form.
- the nonwoven fabric is preferably chopped into parts with an edge length of 1 to 10 cm.
- the nonwoven fabric is preferably added to the aqueous solution.
- the amount of the nonwoven is preferably 1 to 200 g, particularly preferably 5 to 150 g and very particularly preferably 10 to 80 g per liter of solution.
- the treatment time can be shortened by intensive stirring. Generally, the time required is 5 minutes to 1 hour. With vigorous stirring, however, less than 30 minutes, in particular less than 20 minutes, are sufficient to detach at least 80% by weight of the binder from the fiber and to recover the fibers.
- Acronal® DS 2324x is an aqueous dispersion of a metal salt-crosslinked polymer (crosslinking of the carboxylate groups of the polymer with Ca 2+ cations) on an acrylate basis, the drying was carried out at 5 minutes at 200 ° C. in a Mathis laboratory dryer, after which the approximately A-4 sized fleece sheets were cut into pieces of about 1 cm 2 .
- a cold saturated sodium oxalate solution (approx. 3% by weight) and in each case a 10% by weight solution of soda or Na 4 EDTA (Trilon B) in water were prepared.
- the amounts of the phase transfer catalyst indicated in the table and optionally sodium hydroxide solution were added.
- the fleece pieces were stirred for about 24 hours using a laboratory stirrer for 15 minutes at 2000 rpm.
- the fibers were then filtered off through a 60 ⁇ sieve, dried at 130 ° C. for 2 h and weighed back.
- the degree of recycling is 100%. Values above 100% in the table can be explained by the fact that when the fibers were filtered off, very fine fibers were possibly not retained by the sieve and the weight of the fibers after recycling was too low.
Abstract
Description
Gegenstand der Erfindung ist ein Verfahren zur Rückgewinnung von Fasern aus Faservliesen. Faservliese können durch Beschichten bzw. Imprägnieren mit einem Bindemittel verfestigt werden.The invention relates to a method for recovering fibers from nonwoven fabrics. Nonwovens can be consolidated by coating or impregnation with a binder.
Grundsätzlich besteht der Wunsch nach recycelfähigen Faservliesen, bei denen nach Gebrauch die Fasern wieder zurückgewonnen werden können. Dazu muß das Bindemittel von dem verfestigten Faservlies abgelöst werden. Entsprechend wurden gemäß JP 5 384 189 und der unveröffentlichten deutschen Patentanmeldung P 19 535 792.3 (0050/46241) zur Verfestigung von Faservliesen unvernetzte Bindemittel verwendet, welche durch Überführung von Carboxylgruppen in Carboxylatgruppen in Wasser löslich sind und so von den Fasern wieder abgetrennt werden können.Basically, there is a desire for recyclable nonwovens in which the fibers can be recovered after use. For this purpose, the binder must be removed from the consolidated nonwoven. Correspondingly, according to JP 5 384 189 and the unpublished German patent application P 19 535 792.3 (0050/46241), non-crosslinked binders were used for the consolidation of nonwovens, which are soluble in water by converting carboxyl groups into carboxylate groups and can thus be separated from the fibers again.
Um Faservliese mit guten Festigkeiten zu erhalten, werden Bindemittel verwendet, die nach Aufbringen auf das Faservlies vernetzen. Zur Vernetzung können die Bindemittel Monomere mit mehreren ethylenisch ungesättigten Gruppen oder Monomere mit sonstigen reaktiven Gruppen, z.B. Methylolgruppen, enthalten. Eine Vernetzung über Metallsalzgruppen, z.B. eine Vernetzung über Ca-carboxylatgruppen ist z.B. aus EP 442 370 bekannt. Gewünscht ist, auch Fasern aus mit vernetzten Bindemitteln gebundenen Faservliesen zurückzugewinnen.In order to obtain nonwoven fabrics with good strength, binders are used which crosslink after application to the nonwoven fabric. For crosslinking, the binders can be monomers with several ethylenically unsaturated groups or monomers with other reactive groups, e.g. Methylol groups. Crosslinking via metal salt groups, e.g. crosslinking via Ca carboxylate groups is e.g. known from EP 442 370. It is also desirable to recover fibers from nonwovens bonded with crosslinked binders.
Aufgabe der vorliegenden Erfindung war daher ein Verfahren zur Rückgewinnung von Fasern aus mit vernetzten Bindemitteln gebundenen bzw. verfestigten Faservliesen.The object of the present invention was therefore a process for the recovery of fibers from nonwoven fabrics bonded or solidified with crosslinked binders.
Die Aufgabe wurde gelöst durch ein Verfahren zum Ablösen von Bindemitteln von mit diesen Bindemitteln gebunden Faservliesen, dadurch gekennzeichnet, daß
- die Faservliese mit einem Polymerbindemittel mit Carboxylatgruppen gebunden sind, wobei die Carboxylatgruppen über Erdalkalikationen vernetzt sind
- die Faservliese mit einer wäßrigen Lösung eines Alkalisalzes behandelt werden, wobei das Anion des Alkalisalzes mit den Erdalkalikationen ein schwerlösliches Salz oder Komplex bildet und anschließend
- die vom Bindemittel befreiten Fasern abgetrennt werden.
- the nonwoven fabrics are bound with a polymer binder with carboxylate groups, the carboxylate groups being crosslinked via alkaline earth metal cations
- the nonwoven fabrics are treated with an aqueous solution of an alkali salt, the anion of the alkali salt forming a poorly soluble salt or complex with the alkaline earth metal cations and then
- the fibers freed from the binder are separated.
Für das erfindungsgemäße Verfahren können Faservliese aus unterschiedlichsten Fasern Verwendung finden.Nonwovens made from a wide variety of fibers can be used for the method according to the invention.
In Betracht kommen z.B. synthetische Fasern wie Viskose-, Polyester-, Polyamid-, Polypropylen-, Polyacrylnitril-, Carbonfasern oder Fasern von Homo- und Copolymerisaten des Vinylchlorides oder Tetrafluorethylens oder auch Fasern natürlichen Ursprungs wie Zellstoff-, Zellwolle-, Cellulose-, Baumwolle- oder Holzfasern oder auch Glas-, Keramik-, oder Mineralfasern oder Mischungen hiervon.For example, synthetic fibers such as viscose, polyester, polyamide, polypropylene, polyacrylonitrile, carbon fibers or fibers of homo- and copolymers of vinyl chloride or tetrafluoroethylene or fibers of natural origin such as cellulose, cellulose, cellulose, cotton or wood fibers or also glass, ceramic or mineral fibers or mixtures thereof.
Die Fasern werden zu Faservliesen zusammengelegt und dann mit einem Bindemittel verfestigt, wozu das Bindemittel in bekannter Weise z.B. durch Imprägnieren, Besprühen, Aufrackeln, Tauchen oder Bedrucken auf die Fasern gebracht wird. Anschließend erfolgt im allgemeinen eine Trocknung zur Entfernung des Lösemittels, im allgemeinen Wasser. Auf diese, dem Fachmann bekannte Weise wird ein gebundenes, d.h. verfestigtes Faservlies erhalten.The fibers are folded into non-woven fabrics and then solidified with a binding agent, for which purpose the binding agent e.g. is brought onto the fibers by impregnation, spraying, cracking, dipping or printing. This is generally followed by drying to remove the solvent, generally water. In this manner known to those skilled in the art, a bound, i.e. get consolidated nonwoven.
Die so hergestellten Faservliese finden z.B. Anwendung als Trägermaterialien für Dachbahnen bzw. Fußbodenbeläge. Als Bindemittel werden im allgemeinen Polymerisate verwendet, welche sich aus ethylenisch ungesättigten Monomeren aufbauen.The nonwoven fabrics thus produced find e.g. Use as carrier materials for roofing membranes or floor coverings. As binders, polymers are generally used which are built up from ethylenically unsaturated monomers.
Die Polymerisate enthalten Carboxylatgruppen, welche über Erdalkalikationen vernetzt sind, d.h. sie sind metallsalzvernetzt.The polymers contain carboxylate groups which are crosslinked via alkaline earth metal ions, i.e. they are cross-linked with metal salts.
Bevorzugt enthalten die Polymerisate 0,1 bis 30 Gew.-%, besonders bevorzugt 0,5 bis 25 Gew.-% und ganz besonders bevorzugt 5 bis 20 Gew.-% Carboxylatgruppen, bezogen auf das Polymerisatgewicht (Gewicht der Erdalkalikationen nicht mitberechnet).The polymers preferably contain 0.1 to 30 wt.%, Particularly preferably 0.5 to 25 wt.% And very particularly preferably 5 to 20 wt.
Die Carboxylatgruppen liegen bevorzugt zu 50 bis 100, besonders bevorzugt zu 80 bis 100 % als Salz mit Erdalkalikationen vor.The carboxylate groups are preferably 50 to 100%, particularly preferably 80 to 100%, as a salt with alkaline earth metal cations.
Bevorzugte Erdalkalikationen sind Ca2+ und Ba2+, Mg2+. Besonders bevorzugt ist Ca2+.Preferred alkaline earth metal cations are Ca 2+ and Ba 2+ , Mg 2+ . Ca 2+ is particularly preferred.
Die metallsalzvernetzten Polymerisate sind z.B. ausgehend von Polymerisaten mit Carbonsäure- oder Carbonsäureanhydridgruppen erhältlich durch Zugabe eines Erdalkalisalzes, z.B. eines Oxids, Hydroxids, Carbonats oder Hydrogencarbonate z.B. zur wäßrigen Dispersion oder Lösung des Polymerisats, wie es in EP-A-442 370 beschrieben ist.The metal salt-crosslinked polymers can be obtained, for example, from polymers with carboxylic acid or carboxylic anhydride groups by adding an alkaline earth metal salt, for example an oxide, hydroxide, carbonate or hydrogen carbonate, for example for the aqueous dispersion or solution of the polymer, as described in EP-A-442 370.
Das metallsalzvernetzte Polymerisat ist bevorzugt aus folgenden Monomeren A), B) und C) aufgebaut:The metal salt-crosslinked polymer is preferably composed of the following monomers A), B) and C):
Monomere A) sind Monomere mit mindestens einer Carbonsäure- oder Carbonsäureanhydridgruppe, welche in die Metallsalzgruppen überführt werden können. Zu nennen sind insbesondere Acrylsäure, Methacrylsäure, Itaconsäure, Maleinsäure, Maleinsäureanhydrid.Monomers A) are monomers with at least one carboxylic acid or carboxylic anhydride group, which can be converted into the metal salt groups. Particularly noteworthy are acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride.
Die Menge dieser Monomeren ergibt sich durch den gewünschten Gehalt an mit Erdalkalikationen vernetzten Carboxylatgruppen.The amount of these monomers results from the desired content of carboxylate groups crosslinked with alkaline earth metal cations.
Von technischer Bedeutung sind insbesondere sogenannte Hauptmonomere B), ausgewählt aus C1-C20-Alkyl(meth)acrylaten, Vinylestern von bis zu 20 C-Atome enthaltenden Carbonsäuren, Vinylaromaten mit bis zu 20 C-Atomen, ethylenisch ungesättigten Nitrilen, Vinylhalogeniden, Vinylethern von 1 bis 10 C-Atome enthaltenden Alkoholen, aliphatischen Kohlenwasserstoffen mit 2 bis 8 C-Atomen und 1 oder 2 Doppelbindungen oder Mischungen dieser Monomeren.Main monomers B) selected from C 1 -C 20 -alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 C atoms, vinyl aromatics with up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides are of particular technical importance. Vinyl ethers of alcohols containing 1 to 10 carbon atoms, aliphatic hydrocarbons with 2 to 8 carbon atoms and 1 or 2 double bonds or mixtures of these monomers.
Zu nennen sind z.B. (Meth)acrylsäurealkylester mit einem C1-C10-Alkylrest, wie Methylmethacrylat, Methylacrylat, n-Butylacrylat, Ethylacrylat und 2-Ethylhexylacrylat.Examples include (meth) acrylic acid alkyl esters with a C 1 -C 10 alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
Insbesondere sind auch Mischungen der (Meth)acrylsäurealkylester geeignet.Mixtures of the (meth) acrylic acid alkyl esters are also particularly suitable.
Vinylester von Carbonsäuren mit 1 bis 20 C-Atomen sind z.B. Vinyllaurat, -stearat, Vinylpropionat, Versaticsäurevinylester und Vinylacetat.Vinyl esters of carboxylic acids with 1 to 20 C atoms are e.g. Vinyl laurate, stearate, vinyl propionate, vinyl versatic acid and vinyl acetate.
Als vinylaromatische Verbindungen kommen Vinyltoluol, α- und p-Methylstyrol, α-Butylstyrol, 4-n-Butylstyrol, 4-n-Decylstyrol und vorzugsweise Styrol in Betracht. Beispiele für Nitrile sind Acrylnitril und Methacrylnitril.Suitable vinyl aromatic compounds are vinyl toluene, α- and p-methylstyrene, α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene. Examples of nitriles are acrylonitrile and methacrylonitrile.
Die Vinylhalogenide sind mit Chlor, Fluor oder Brom substituierte ethylenisch ungesättigte Verbindungen, bevorzugt Vinylchlorid und Vinylidenchlorid.The vinyl halides are chlorine, fluorine or bromine-substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
Als Vinylether zu nennen sind z.B. Vinylmethylether oder Vinylisobutylether. Bevorzugt wird Vinylether von 1 bis 4 C-Atome enthaltenden Alkoholen.Examples of vinyl ethers include Vinyl methyl ether or vinyl isobutyl ether. Vinyl ethers of alcohols containing 1 to 4 carbon atoms are preferred.
Als Kohlenwasserstoffe mit 2 bis 8 C-Atomen und zwei olefinischen Doppelbindungen seien Butadien, Isopren und Chloropren genannt.Butadiene, isoprene and chloroprene may be mentioned as hydrocarbons with 2 to 8 carbon atoms and two olefinic double bonds.
Neben diesen Hauptmonomeren können weitere Monomere C), z.B. Hydroxylgruppen enthaltende Monomere, insbesondere C1-C10-Hydroxyalkyl(meth)acrylate oder (Meth)acrylamid, im Polymerisat Verwendung finden.In addition to these main monomers, other monomers C), for example monomers containing hydroxyl groups, in particular C 1 -C 10 -hydroxyalkyl (meth) acrylates or (meth) acrylamide, can be used in the polymer.
Übliche Polymerisate bestehen im allgemeinen zu mindestens 40, vorzugsweise zu mindestens 60, besonders bevorzugt zu mindestens 80 Gew.-% aus den obigen Hauptmonomeren B).Customary polymers generally consist of at least 40, preferably at least 60, particularly preferably at least 80% by weight of the above main monomers B).
Die Polymerisation kann nach üblichen Polymerisationsverfahren erfolgen, z.B. durch Substanz-, Emulsions-, Suspensions-, Dispersions-, Fällungs- und Lösungspolymerisation. Bei den genannten Polymerisationsverfahren wird bevorzugt unter Ausschluß von Sauerstoff gearbeitet, vorzugsweise in einem Stickstoffstrom. Für alle Polymerisationsmethoden werden die üblichen Apparaturen verwendet, z.B. Rührkessel, Rührkesselkaskaden, Autoklaven, Rohrreaktoren und Kneter. Bevorzugt wird nach der Methode der Lösungs-, Emulsions-, Fällungs- oder Suspensionspolymerisation gearbeitet. Besonders bevorzugt sind die Methoden der Lösungs- und insbesondere Emulsionspolymerisation. Die Polymerisation kann in Lösungs- oder Verdünnungsmitteln, wie z.B. Toluol, o-Xylol, p-Xylol, Cumol, Chlorbenzol, Ethylbenzol, technischen Mischungen von Alkylaromaten, Cyclohexan, technischen Aliphatenmischungen, Aceton, Cyclohexanon, Tetrahydrofuran, Dioxan, Glykolen und Glykolderivaten, Polyalkylenglykolen und deren Derivate, Diethylether, tert.-Butylmethylether, Essigsäuremethylester, Isopropanol, Ethanol, Wasser oder Mischungen wie z.B. Isopropanol/Wasser-Mischungen ausgeführt werden. Vorzugsweise wird als Lösungs- oder Verdünnungsmittel Wasser gegebenenfalls mit Anteilen bis zu 60 Gew.-% an Alkoholen oder Glykolen verwendet. Besonders bevorzugt wird Wasser eingesetzt.The polymerization can be carried out by conventional polymerization methods, e.g. by substance, emulsion, suspension, dispersion, precipitation and solution polymerization. The polymerization processes mentioned are preferably carried out in the absence of oxygen, preferably in a stream of nitrogen. The usual equipment is used for all polymerization methods, e.g. Stirred tanks, stirred tank cascades, autoclaves, tubular reactors and kneaders. The method of solution, emulsion, precipitation or suspension polymerization is preferably used. The methods of solution and, in particular, emulsion polymerization are particularly preferred. The polymerization can be carried out in solvents or diluents, e.g. Toluene, o-xylene, p-xylene, cumene, chlorobenzene, ethylbenzene, technical mixtures of alkyl aromatics, cyclohexane, technical aliphate mixtures, acetone, cyclohexanone, tetrahydrofuran, dioxane, glycols and glycol derivatives, polyalkylene glycols and their derivatives, diethyl ether, tert-ether, tert-ether Methyl acetate, isopropanol, ethanol, water or mixtures such as Isopropanol / water mixtures can be run. Water is preferably used as the solvent or diluent, if appropriate with proportions of up to 60% by weight of alcohols or glycols. Water is particularly preferably used.
Die metallvernetzten Polymerisate werden im allgemeinen in Form ihrer wäßrigen Lösung oder Dispersion auf die Faservliese aufgebracht. Nach der Trocknung sind die Faservliese gebunden, d.h. verfestigt. Die Faservliese enthalten dann im allgemeinen 1 bis 40 Gew.-Teile, bevorzugt 5 bis 30 Gew.-Teile, der metallvernetzten Bindemittels, bezogen auf 100 Gew.-Teile Fasern.The metal-crosslinked polymers are generally applied to the nonwovens in the form of their aqueous solution or dispersion. After drying, the nonwovens are bound, ie solidified. The non-woven fabrics then generally contain 1 to 40 parts by weight, preferably 5 to 30 parts by weight, of the metal-crosslinked binder, based on 100 parts by weight of fibers.
Nach der späteren Verwendung der gebundenen Faservliese können die Fasern gemäß dem erfindungsgemäßen Verfahren zurückgewonnen werden, indem das Blndemittel aus dem Faservlies, d.h. von den Fasern abgetrennt wird.After the later use of the bonded nonwoven fabrics, the fibers can be recovered according to the method of the invention by removing the blinding agent from the nonwoven fabric, i.e. is separated from the fibers.
Dazu wird das Faservlies mit einer wäßrigen Lösung eines Salzes, (im nachfolgenden "lösliches Salz genannt), dessen Anion mit dem Erdalkalikation ein in Wasser schwerlösliches Salz bildet, behandelt.For this purpose, the nonwoven fabric is treated with an aqueous solution of a salt (hereinafter referred to as "soluble salt"), the anion of which forms a salt which is poorly soluble in water with the alkaline earth metal.
Bei den löslichem Salz kann es sich um ein anorganisches oder organisches Salz handeln.The soluble salt can be an inorganic or organic salt.
Insbesondere handelt es sich um ein Alkalimetallsalz.In particular, it is an alkali metal salt.
Bei dem Anion des löslichen Salzes kann es sich z.B. um Oxalat oder Carbonat handeln, welche z.B. mit dem Calziumkation ein schwerlösliches Salz bilden.The anion of the soluble salt can e.g. are oxalate or carbonate, which e.g. form a sparingly soluble salt with the calcium cation.
Bei dem Anion des löslichen Salzes kann es sich z.B. auch um ein organisches Anion handeln, welches mit den Erdalkalikation, z.B. Ca2+, einem schwerlöslichen Komplex bildet. Als Anion zu nennen ist hier insbesondere EDTA.The anion of the soluble salt can also be an organic anion, for example, which forms a poorly soluble complex with the alkaline earth metal, for example Ca 2+ . EDTA is particularly worth mentioning here.
Das lösliche Salz, das in der wäßrigen Lösung enthalten ist, hat vorzugsweise eine Löslichkeit von mindestens 10 g/·l Wasser bei 23°C.The soluble salt contained in the aqueous solution preferably has a solubility of at least 10 g / · l water at 23 ° C.
Die wäßrige Lösung enthält das Salz vorzugsweise in Mengen von 0,02 bis 15 Gew.-Teile, besonders bevorzugt in Mengen von 0,1 bis 10 Gew.-Teilen, ganz besonders bevorzugt von 0,5 bis 2,5 Gew.-Teilen, bezogen auf 100 Gew.-Teile Wasser.The aqueous solution preferably contains the salt in amounts of 0.02 to 15 parts by weight, particularly preferably in amounts of 0.1 to 10 parts by weight, very particularly preferably 0.5 to 2.5 parts by weight , based on 100 parts by weight of water.
Die Löslichkeit des bei Behandlung des Faservlieses gebildeten, schwerlöslichen Erdalkalisalzes ist dagegen vorzugsweise kleiner als 0,5 g/l Wasser bei 23°C.In contrast, the solubility of the sparingly soluble alkaline earth metal salt formed when treating the nonwoven fabric is preferably less than 0.5 g / l of water at 23 ° C.
Die wäßrige Lösung enthält neben dem löslichen Salz vorzugsweise noch einen Phasentransferkatalysator.In addition to the soluble salt, the aqueous solution preferably also contains a phase transfer catalyst.
Geeignete Phasentransferkatalysatoren sind z.B. in Chimia 34 (1980) Nr. 1, Seite 12 bis 20. Als Phasentransferkatalysatoren genannt seien z.B. Polyalkylenglykole, welcher z.B. unter dem Namen Pluriol® im Handel ist oder quaternäre, organische Ammoniumsalze, welche z.B. unter dem Namen Lutensit im Handel sind.Suitable phase transfer catalysts are, for example, in Chimia 34 (1980) No. 1, pages 12 to 20. Examples of phase transfer catalysts are, for example, polyalkylene glycols, which is commercially available, for example, under the name Pluriol® or quaternary, organic Ammonium salts, which are commercially available, for example, under the name lutensite.
Als quaternäre, organische Ammoniumsalze seien insbesondere solche der Formel I
Besonders bevorzugte Phasentransferkatalysatoren sind solche mit Alkoxygruppen, bevorzugt mit 2 bis 20 Alkoxygruppen, z.B. Alkylphenolethoxylate (z.B. Lutensole® AP, Emulgator 825 Fettalkoholethoxylate (z.B. Lutensol A8) und Oxo-alkoholethoxylate (z.B. Lutensol AO7, Lutensol ON80).Particularly preferred phase transfer catalysts are those with alkoxy groups, preferably with 2 to 20 alkoxy groups, e.g. Alkylphenol ethoxylates (e.g. Lutensole® AP, emulsifier 825 fatty alcohol ethoxylates (e.g. Lutensol A8) and oxo alcohol ethoxylates (e.g. Lutensol AO7, Lutensol ON80).
Durch Alkoxylierung von Alkylphenolen, Fettalkoholen bzw. von Oxoalkoholen mit Alkylenoxiden, vorzugsweise Ethylenoxid enthalten diese Phasentransferkatalysatoren Alkoxygruppen.By alkoxylation of alkylphenols, fatty alcohols or oxoalcohols with alkylene oxides, preferably ethylene oxide, these phase transfer catalysts contain alkoxy groups.
Der Gehalt des Phasentransferkatalysators in der wäßrigen Lösung beträgt vorzugsweise 0,01 bis 1 Gew.-Teil, besonders bevorzugt 0,08 bis 0,5 Gew.-Teile, bezogen auf 100 Gew.-Teile Wasser.The content of the phase transfer catalyst in the aqueous solution is preferably 0.01 to 1 part by weight, particularly preferably 0.08 to 0.5 part by weight, based on 100 parts by weight of water.
Zusätzlich können der wäßrigen Lösung z.B. noch Basen, insbesondere Natronlauge zugesetzt werden, um den Anteil von Alkalikationen zu erhöhen.In addition, e.g. bases, in particular sodium hydroxide solution, are also added in order to increase the proportion of alkali cations.
Die Temperatur der wäßrigen Lösung kann z.B. 10 bis 100°C, insbesondere 15 bis 80°C und besonders bevorzugt 20 bis 50°C betragen. Vorteilhaft sind Temperaturen über 30, insbesondere über 40°C, um eine noch bessere und vor allem schnellere Ablösung des Bindemittels von dem Faservlies zu erreichen.The temperature of the aqueous solution can e.g. 10 to 100 ° C, in particular 15 to 80 ° C and particularly preferably 20 to 50 ° C. Temperatures above 30 ° C., in particular above 40 ° C., are advantageous in order to achieve an even better and, above all, faster detachment of the binder from the nonwoven fabric.
Das Faservlies kann als ganzes oder in zerkleinerter Form den erfindungsgemäßen Verfahren zugeführt werden.The nonwoven fabric can be fed to the method according to the invention as a whole or in comminuted form.
Bevorzugt wird das Faservlies in Teile mit einer Kantenlänge von 1 bis 10 cm zerkleinert.The nonwoven fabric is preferably chopped into parts with an edge length of 1 to 10 cm.
Zur Behandlung mit der wäßrigen Lösung wird das Faservlies vorzugsweise in die wäßrige Lösung gegeben. Die Menge des Faservlieses beträgt dabei vorzugsweise 1 bis 200 g, besonders bevorzugt 5 bis 150 g und ganz besonders bevorzugt 10 bis 80 g pro Liter Lösung. Die Behandlungsdauer kann durch intensives Rühren verkürzt werden. Im allgemeinen liegt die notwendige Dauer bei 5 Minuten bis 1 Stunde. Bei starkem Rühren sind jedoch schon weniger als 30 Minuten, insbesondere weniger als 20 Minuten ausreichend um mindestens 80 Gew.-% des Bindemittels von der Faser zu lösen und die Fasern zurückzugewinnen.For treatment with the aqueous solution, the nonwoven fabric is preferably added to the aqueous solution. The amount of the nonwoven is preferably 1 to 200 g, particularly preferably 5 to 150 g and very particularly preferably 10 to 80 g per liter of solution. The treatment time can be shortened by intensive stirring. Generally, the time required is 5 minutes to 1 hour. With vigorous stirring, however, less than 30 minutes, in particular less than 20 minutes, are sufficient to detach at least 80% by weight of the binder from the fiber and to recover the fibers.
Polyester-Spinnvliese der Fa. Hoechst, Bobingen wurden imprägniert mit Acronal® DS 2324x (Bindemittelauftrag von 20 Gew.-% ±2 (fest/fest). Bei Acronal DS 2324X handelt es sich um eine wäßrige Dispersion eines metallsalzvernetzten Polymerisats (Vernetzung der Carboxylatgruppen des Polymerisats mit Ca2+ Kationen) auf Acrylatbasis. Die Trocknung erfolgte bei 5 Min. bei 200°C im Mathis Labortrockner. Anschließend wurden die in etwa DIN A-4 großen Vliesbögen in Stücke von ca. 1 cm2 geschnitten.Polyester spunbonded fabrics from Hoechst, Bobingen were impregnated with Acronal® DS 2324x (binder application of 20% by weight ± 2 (solid / solid). Acronal DS 2324X is an aqueous dispersion of a metal salt-crosslinked polymer (crosslinking of the carboxylate groups of the polymer with Ca 2+ cations) on an acrylate basis, the drying was carried out at 5 minutes at 200 ° C. in a Mathis laboratory dryer, after which the approximately A-4 sized fleece sheets were cut into pieces of about 1 cm 2 .
Es wurde eine kaltgesättigte Natriumoxalatlösung (ca. 3 Gew.-%) und jeweils eine 10 gew.-%ige Lösung von Soda bzw. Na4 EDTA (Trilon B) in Wasser hergestellt. In je 250 g der erhaltenen Lösung wurden die in der Tabelle angegebenen Mengen des Phasentransferkatalysators und gegebenenfalls noch Natronlauge gegeben.A cold saturated sodium oxalate solution (approx. 3% by weight) and in each case a 10% by weight solution of soda or Na 4 EDTA (Trilon B) in water were prepared. In each 250 g of the solution obtained, the amounts of the phase transfer catalyst indicated in the table and optionally sodium hydroxide solution were added.
Zur Rückgewinnung der bindemittelfreien Fasern aus den Faservliesen wurden Stücke des zerkleinerten Faservlieses (s.o.) in 250 g der Lösung gegeben. Die Temperatur der Lösung und die Menge des Faservlieses ist in der Tabelle angegeben.In order to recover the binder-free fibers from the nonwovens, pieces of the comminuted nonwoven (see above) were placed in 250 g of the solution. The temperature of the solution and the amount of the nonwoven is shown in the table.
Die Vliesstücke wurden nach ca. 24 h Standzeit mittels einem Laborrührer 15 Min mit 2000 U/min aufgerührt.The fleece pieces were stirred for about 24 hours using a laboratory stirrer for 15 minutes at 2000 rpm.
Anschließend wurden die Fasern über ein 60 µ-Sieb abfiltriert, 2 h bei 130°C getrocknet und zurückgewogen.The fibers were then filtered off through a 60 μ sieve, dried at 130 ° C. for 2 h and weighed back.
Der in der Tabelle angegebene Rezykliergrad R berechnet sich gemäß
Im Falle, daß die zurückgewogenen Fasern völlig bindemittelfrei sind, ergibt sich ein Recyclierungsgrad von 100 %. Werte über 100 % in der Tabelle erklären sich dadurch, daß bei Abfiltrierung der Fasern gegebenenfalls sehr feine Fasern vom Sieb nicht zurückgehalten wurden und so das Gewicht der Fasern nach Recyclierung zu gering war.
Claims (7)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19619639A DE19619639A1 (en) | 1996-05-15 | 1996-05-15 | Recovery of fibers from bonded nonwovens |
DE19619639 | 1996-05-15 |
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EP0807704A1 true EP0807704A1 (en) | 1997-11-19 |
EP0807704B1 EP0807704B1 (en) | 2000-11-02 |
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EP97107491A Expired - Lifetime EP0807704B1 (en) | 1996-05-15 | 1997-05-07 | Recovery of fibres from bonded nonwovens |
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US (1) | US6004428A (en) |
EP (1) | EP0807704B1 (en) |
AT (1) | ATE197323T1 (en) |
DE (2) | DE19619639A1 (en) |
ES (1) | ES2152593T3 (en) |
Cited By (10)
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WO1998044181A1 (en) * | 1997-03-31 | 1998-10-08 | Kimberly-Clark Worldwide, Inc. | Dispersible nonwoven fabric and method of making same |
WO1998053006A1 (en) * | 1997-05-23 | 1998-11-26 | Kimberly-Clark Worldwide, Inc. | Ion sensitive binder for fibrous materials |
US6194517B1 (en) | 1997-03-17 | 2001-02-27 | Kimberly-Clark Worldwide, Inc. | Ion sensitive polymeric materials |
US6277768B1 (en) | 1996-12-31 | 2001-08-21 | Kimberly Clark Worldwide | Temperature sensitive polymers and water-dispersible products containing the polymers |
US6423804B1 (en) | 1998-12-31 | 2002-07-23 | Kimberly-Clark Worldwide, Inc. | Ion-sensitive hard water dispersible polymers and applications therefor |
US6695993B2 (en) | 2001-01-25 | 2004-02-24 | Wacker Polymer Systems Gmbh & Co. Kg | Process for forming recyclable articles |
US6814974B2 (en) | 2000-05-04 | 2004-11-09 | Kimberly-Clark Worldwide, Inc. | Ion-sensitive, water-dispersible polymers, a method of making same and items using same |
US6828014B2 (en) | 2001-03-22 | 2004-12-07 | Kimberly-Clark Worldwide, Inc. | Water-dispersible, cationic polymers, a method of making same and items using same |
US6835678B2 (en) | 2000-05-04 | 2004-12-28 | Kimberly-Clark Worldwide, Inc. | Ion sensitive, water-dispersible fabrics, a method of making same and items using same |
US7772138B2 (en) | 2002-05-21 | 2010-08-10 | Kimberly-Clark Worldwide, Inc. | Ion sensitive, water-dispersible polymers, a method of making same and items using same |
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US5976694A (en) | 1997-10-03 | 1999-11-02 | Kimberly-Clark Worldwide, Inc. | Water-sensitive compositions for improved processability |
US6579570B1 (en) | 2000-05-04 | 2003-06-17 | Kimberly-Clark Worldwide, Inc. | Ion-sensitive, water-dispersible polymers, a method of making same and items using same |
US6713414B1 (en) | 2000-05-04 | 2004-03-30 | Kimberly-Clark Worldwide, Inc. | Ion-sensitive, water-dispersible polymers, a method of making same and items using same |
US6599848B1 (en) | 2000-05-04 | 2003-07-29 | Kimberly-Clark Worldwide, Inc. | Ion-sensitive, water-dispersible polymers, a method of making same and items using same |
US6429261B1 (en) | 2000-05-04 | 2002-08-06 | Kimberly-Clark Worldwide, Inc. | Ion-sensitive, water-dispersible polymers, a method of making same and items using same |
US6815502B1 (en) | 2000-05-04 | 2004-11-09 | Kimberly-Clark Worldwide, Inc. | Ion-sensitive, water-dispersable polymers, a method of making same and items using same |
US6683143B1 (en) | 2000-05-04 | 2004-01-27 | Kimberly Clark Worldwide, Inc. | Ion-sensitive, water-dispersible polymers, a method of making same and items using same |
US6653406B1 (en) | 2000-05-04 | 2003-11-25 | Kimberly Clark Worldwide, Inc. | Ion-sensitive, water-dispersible polymers, a method of making same and items using same |
US6548592B1 (en) | 2000-05-04 | 2003-04-15 | Kimberly-Clark Worldwide, Inc. | Ion-sensitive, water-dispersible polymers, a method of making same and items using same |
US7255816B2 (en) * | 2000-11-10 | 2007-08-14 | Kimberly-Clark Worldwide, Inc. | Method of recycling bonded fibrous materials and synthetic fibers and fiber-like materials produced thereof |
US6586529B2 (en) | 2001-02-01 | 2003-07-01 | Kimberly-Clark Worldwide, Inc. | Water-dispersible polymers, a method of making same and items using same |
DE102005037113A1 (en) * | 2005-08-03 | 2007-02-08 | Basf Ag | Use of a thermally curable aqueous composition as a binder for substrates |
DE102009010938A1 (en) * | 2009-02-27 | 2010-09-09 | Celanese Emulsions Gmbh | Mineral wool fiber mats, process for their preparation and use |
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- 1997-05-06 US US08/852,064 patent/US6004428A/en not_active Expired - Fee Related
- 1997-05-07 ES ES97107491T patent/ES2152593T3/en not_active Expired - Lifetime
- 1997-05-07 AT AT97107491T patent/ATE197323T1/en not_active IP Right Cessation
- 1997-05-07 EP EP97107491A patent/EP0807704B1/en not_active Expired - Lifetime
- 1997-05-07 DE DE59702552T patent/DE59702552D1/en not_active Expired - Fee Related
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GB2006233A (en) * | 1977-10-20 | 1979-05-02 | Wacker Chemie Gmbh | Aqueous vinyl acetate copolymer dispersions for use as binders for non-woven materials |
EP0442370A2 (en) * | 1990-02-16 | 1991-08-21 | BASF Aktiengesellschaft | Use of aqueous polymer dispersions |
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Cited By (14)
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US6277768B1 (en) | 1996-12-31 | 2001-08-21 | Kimberly Clark Worldwide | Temperature sensitive polymers and water-dispersible products containing the polymers |
US6451429B2 (en) | 1996-12-31 | 2002-09-17 | Kimberly-Clark Worldwide, Inc. | Temperature sensitive polymers and water-dispersible products containing the polymers |
US6194517B1 (en) | 1997-03-17 | 2001-02-27 | Kimberly-Clark Worldwide, Inc. | Ion sensitive polymeric materials |
US5935880A (en) * | 1997-03-31 | 1999-08-10 | Wang; Kenneth Y. | Dispersible nonwoven fabric and method of making same |
WO1998044181A1 (en) * | 1997-03-31 | 1998-10-08 | Kimberly-Clark Worldwide, Inc. | Dispersible nonwoven fabric and method of making same |
US6291372B1 (en) | 1997-05-23 | 2001-09-18 | Kimberly Clark Worldwide, Inc. | Ion sensitive binder for fibrous materials |
US6043317A (en) * | 1997-05-23 | 2000-03-28 | Kimberly-Clark Worldwide, Inc. | Ion sensitive binder for fibrous materials |
WO1998053006A1 (en) * | 1997-05-23 | 1998-11-26 | Kimberly-Clark Worldwide, Inc. | Ion sensitive binder for fibrous materials |
US6423804B1 (en) | 1998-12-31 | 2002-07-23 | Kimberly-Clark Worldwide, Inc. | Ion-sensitive hard water dispersible polymers and applications therefor |
US6814974B2 (en) | 2000-05-04 | 2004-11-09 | Kimberly-Clark Worldwide, Inc. | Ion-sensitive, water-dispersible polymers, a method of making same and items using same |
US6835678B2 (en) | 2000-05-04 | 2004-12-28 | Kimberly-Clark Worldwide, Inc. | Ion sensitive, water-dispersible fabrics, a method of making same and items using same |
US6695993B2 (en) | 2001-01-25 | 2004-02-24 | Wacker Polymer Systems Gmbh & Co. Kg | Process for forming recyclable articles |
US6828014B2 (en) | 2001-03-22 | 2004-12-07 | Kimberly-Clark Worldwide, Inc. | Water-dispersible, cationic polymers, a method of making same and items using same |
US7772138B2 (en) | 2002-05-21 | 2010-08-10 | Kimberly-Clark Worldwide, Inc. | Ion sensitive, water-dispersible polymers, a method of making same and items using same |
Also Published As
Publication number | Publication date |
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US6004428A (en) | 1999-12-21 |
EP0807704B1 (en) | 2000-11-02 |
ES2152593T3 (en) | 2001-02-01 |
DE59702552D1 (en) | 2000-12-07 |
DE19619639A1 (en) | 1997-11-20 |
ATE197323T1 (en) | 2000-11-15 |
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