EP0527411B1 - Aqueous binder for textile material - Google Patents
Aqueous binder for textile material Download PDFInfo
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- EP0527411B1 EP0527411B1 EP92113160A EP92113160A EP0527411B1 EP 0527411 B1 EP0527411 B1 EP 0527411B1 EP 92113160 A EP92113160 A EP 92113160A EP 92113160 A EP92113160 A EP 92113160A EP 0527411 B1 EP0527411 B1 EP 0527411B1
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- Prior art keywords
- binding agent
- polymer
- methacrylamide
- aqueous
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
- D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
Definitions
- the invention relates to an aqueous binder for textile fabrics based on a self-crosslinking emulsion polymer dispersed in an aqueous phase and containing units of N-methylol-acrylamide or methacrylamide and a polymer containing amide groups dissolved in the aqueous phase.
- N-methylol groups in the self-crosslinking dispersions for solidifying textile fabrics form covalent crosslinking bridges to the hydroxyl or amide groups of the binder or the fibers of the textile fabric.
- binders are in some cases added to polymers which are soluble in the aqueous phase, such as water-soluble aminoplast resins.
- the storage and shear stability of an aqueous dispersion of an acrylic or butadiene polymer for various technical purposes, for example for textile finishing, is improved by the addition of a water-soluble polymeric material.
- a water-soluble polymeric material For example, partially or fully hydrolyzed polyvinyl acetate, starch, etherified cellulose, polyethylene glycol, polyvinyl pyrrolidone, alkali polyacrylate or polyacrylamide can be used as the water-soluble polymeric material.
- polyvinyl alcohol and a water-soluble aminoplast resin were added as water-soluble polymers.
- DE-A 25 27 804 describes a binder for solidifying a cellulose fabric which, in addition to a predominant amount of a water-soluble aminoplast resin, contains smaller amounts of an emulsion polymer containing N-methylol methacrylamide and a solution polymer made from acrylic and methacrylamide and ethyl acrylate.
- a total bound formaldehyde content of 29% by weight can be calculated, more than 99% of which is in the aminoplast resin.
- Such binders release considerable amounts of formaldehyde when they are condensed in the heat.
- the invention has for its object to provide an aqueous binder for textile fabrics that gives high strength values when finishing non-cellulosic fiber products even at high temperatures.
- This property is of technical importance, for example, when impregnating solid fiber webs with molten bitumen, which can have a temperature of 180 ° C.
- the binder should not contain more than 5% by weight of free and latently bound formaldehyde and release as little formaldehyde as possible during processing. For this reason, a solution to the problem by adding formaldehyde-rich aminoplast resins was out of the question.
- Binder strength could be increased by adding aminoplast resins, but only at the cost of a drastic increase in formaldehyde emissions.
- the task in the narrower sense was therefore to achieve a high level of high-temperature binder strength for self-crosslinking plastic dispersions without using expensive reactive monomers or aminoplast resins to solve this task, or accepting an increase in formaldehyde emissions.
- an emulsion polymer A which contains 1 to 15% by weight of units of the N-methylol acrylamide or / and methacrylamide. Surprisingly, it is precisely this combination of polymers A and B that gives textile finishes with high strength properties with significantly reduced formaldehyde release.
- the amide-containing polymer B now has the surprising ability, on the one hand, to condense with the emulsion polymer A similarly to an aminoplast resin and, on the other hand, to bind formaldehyde released during processing. Although this ability should be correspondingly inherent in the water-soluble polymer which is formed during the emulsion polymerization, its action is limited by the relatively small amount. In any case, the effect of the additionally used polymer B is shown in an advantageous manner when finishing textile fabrics.
- the binders according to the invention are distinguished by the fact that they impart increased strength to a textile fabric equipped therewith. Despite the The latent bound formaldehyde content in the binder according to the invention shows only a low formaldehyde emission when solidifying textile products.
- a commercially available self-crosslinking polyacrylate dispersion A1 is composed of 3% by weight of N-methylol methacrylamide and 5% by weight of methacrylamide. When used alone, it releases 300 ppm of formaldehyde within 5 minutes when heated to 160 ° C .; the amount released in this test is referred to as "cleavable formaldehyde”.
- the weight ratio A2: B1 is 9: 1.
- the following table contains the measured values of the breaking resistance (Fmax) and the breaking elongation value for a series of polyester fiber nonwovens impregnated with 33% by weight of binder resin and condensed at 180 o C under acid catalysis with a basis weight of 125 g / m2 (Lutradur® H1015) (DFmax), each for 20 o C and 180 o C.
- the breaking resistance and elongation at break values that can be determined on finished textiles are associated with the crosslinking density of the plastic used.
- the N-methylolamide groups contained in the emulsion polymer react either with one another with elimination of formaldehyde or with additionally incorporated primary amide groups to form N, N'-methylene-bis-amide bridges.
- the prevailing view is that the number of crosslink bridges in the condensation of the self-crosslinking emulsion polymer remains below the theoretical value that would result from the complete conversion of all reactive groups. This leaves behind N-methylolamide groups, which can split off formaldehyde with gradual decomposition.
- the polymer B dissolved in the aqueous phase of the binder preferably reacts with the N-methylol groups of the emulsion polymer. This can be explained from the closer position of the amide groups. The conversion of the N-methylolamide groups appears to be more complete than in the absence of polymer B. Even if only a part of the amide groups of polymer B reacts with N-methylol groups, each such reaction step leads to an effective cross-linking bridge between polymers A and B. In addition, remaining amide groups can act as formaldehyde scavengers and thus even generate additional cross-linking bridges. As a result of a high crosslinking density, high strength properties are achieved with a low content of formaldehyde that can be split off.
- Any self-crosslinking plastic dispersion with crosslinkable N-methylolamide groups suitable for textile finishing can be used as the aqueous dispersion A.
- the emulsion polymer A is 3 to 10% by weight of units of N-methylol-acrylamide and / or -methacrylamide and bis built up to 10 wt .-% of units of acrylic and / or methacrylamide.
- the binders according to the invention can be constructed in such a way that the film formed from the binder during drying and condensation is hard, brittle and dry or soft and sticky or has a nature lying between these extremes.
- these properties depend on the dynamic freezing temperature (T-lambda-max according to DIN 53 445) of the film, which is preferably in the range from 10 to 80 ° C., in particular 20 to 60 ° C. This size is largely determined in a manner known per se by the structure of the emulsion polymer.
- the emulsion polymer A is preferably 60 to 97% by weight of alkyl esters of acrylic and / or methacrylic acid with 1 to 8 carbon atoms built up in the alkyl radical.
- alkyl esters of acrylic acid are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and 2-ethylhexyl acrylate.
- Preferred alkyl esters of methacrylic acid are methyl, ethyl, propyl, isopropyl, n-butyl and isobutyl methacrylate.
- alkyl methacrylates can be replaced by styrene or polymerizable derivatives of styrene, such as vinyltoluene or alpha-methylstyrene.
- styrene or polymerizable derivatives of styrene such as vinyltoluene or alpha-methylstyrene.
- the softness and extensibility of the polymer are promoted by alkyl esters of acrylic acid, hardness and brittleness by lower alkyl esters of methacrylic acid or by styrenes.
- Typical polyacrylate dispersions for the purposes of the invention therefore preferably contain units of these two groups of monomers in a weight ratio of about 70:30 to 20:80.
- Suitable self-crosslinking dispersions can be prepared by known emulsion polymerization processes with a solids content of between 30 and 65% by weight, but are generally made up to 15 to 45% by weight with water or with the aqueous solution of polymer B to prepare an impregnation liquor. diluted. As a rule, they are stabilized by anionic and / or nonionic emulsifiers.
- the additionally used polymer B can be made up solely of acrylamide or methacrylamide or a mixture thereof. It is preferably free of formaldehyde-donating monomer units, such as N-methylolacrylamide and methacrylamide; at least the proportion of such monomer units should not exceed 10% by weight (based on B).
- the proportion of acrylic and / or methacrylamide is not less than 10% by weight and preferably at least 50% by weight.
- other ethylenically unsaturated, radically polymerizable monomers can be involved in their construction.
- Comonomers which are themselves water-soluble or at least form water-soluble homopolymers, such as lower hydroxyalkyl esters of acrylic and / or methacrylic acid, can form a proportion of up to 90% by weight of polymer B, while the proportion of non-water-soluble or sparingly water-soluble comonomers is always limited must ensure that polymer B as a whole is sufficiently soluble in the aqueous phase of the binder. It rarely exceeds 30% by weight.
- Preferred polymers B are 50 to 95% by weight of acrylic and / or methacrylamide, 5 to 50% by weight of water-soluble or water-soluble homopolymers, ethylenically unsaturated, free-radically polymerizable monomers and at most 20% by weight built up from water-insoluble ethylenically unsaturated, radically polymerizable monomers. Monomers containing latent bound formaldehyde are not contained in the preferred polymers B.
- the copolymer B can be prepared in a simple manner by dissolving the corresponding monomers in a concentration of, for example, 10 to 40% by weight in water and after adding a water-soluble free radical initiator, such as alkali metal or ammonium peroxodisulfate, at temperatures of 60 up to 90 o C triggers the polymerization.
- a water-soluble free radical initiator such as alkali metal or ammonium peroxodisulfate
- the molecular weight is preferably in the range from 1,000 to 200,000 (weight average) and can optionally be added during the polymerization by adding a Set chain transfer agents such as thioglycolic acid to a value in this range.
- the aqueous polymer solution is preferably mixed directly with the plastic dispersion A without isolating the polymer B. However, it is also possible to prepare or isolate polymer B in pure form and to dissolve it as a powder in the aqueous phase of the dispersion.
- the proportion of polymer B is preferably 5 to 15% by weight, based on the emulsion polymer A.
- the binder can have a viscosity in the range of 20 to 10,000 mPas. It can be combined with other additives, such as bactericides, fungicides, defoamers, acidic curing catalysts, thermosensitizers, buffer substances, surfactants, plasticizers, film-forming aids, flame retardants and the like. can be assembled according to the requirements of the application.
- additives such as bactericides, fungicides, defoamers, acidic curing catalysts, thermosensitizers, buffer substances, surfactants, plasticizers, film-forming aids, flame retardants and the like.
- the binders of the invention are capable of film formation at temperatures between 0 and 100 o C.
- conventional film formation aids such as volatile solvents or low-volatility plasticizers for the emulsion polymer
- the binder like conventional film-forming, self-crosslinking aqueous plastic dispersions, can be used to finish textile fabrics.
- textile Fabrics knitted fabrics and nonwovens made from natural or synthetic fibers, in particular from cotton, rayon, viscose, cellulose acetate, polyester, polyamide, polyacrylonitrile, polypropylene or from mixtures of such fibers or from glass fibers are to be understood as flat structures. They can have a basis weight of 50 to 500 g / qm.
- Non-woven fabrics made of polyester fibers are preferred.
- the binder is applied to the textile fabric, for example by dipping, spraying, slapping, knife coating or printing in an amount of, for example, 5 to 100% by weight, calculated as a dry product and based on the fiber weight.
- acidic catalysts such as p-toluenesulfonic acid, citric acid, phosphoric acid or ammonium phosphate
- dyes or pigments adjusted to the viscosity required by the application with water or thickeners and, if appropriate, foamed.
- the impregnation obtained is crosslinked at from 100 to 180 ° C. within 180 to 30 seconds. In this way, consolidated textile fabrics with excellent resistance to solvents and plasticizers are obtained.
- Condensation makes the binder insoluble and infusible. It therefore gives the textile fabric equipped with it increased mechanical strength, in particular tensile strength.
- the remarkably high strength at elevated temperature is of particular importance when impregnating nonwoven webs, preferably made of polyester fibers, with melted bitumen for the production of roofing webs.
- the bitumen has in the Impregnation at a temperature of 150 to 200 degrees C. At this temperature, the nonwoven web must neither tear nor stretch strongly during transport through the impregnation bath, even at high speeds.
- polymer B1 To prepare polymer B1, 590 parts of water at 85 ° C. are mixed with a solution of 2.5 parts of ammonium peroxodisulfate in 8 parts of water. A solution of 144 parts of acrylamide, 25 parts of methacrylamide and 25 parts of 2-hydroxyethyl methacrylate in 144 parts of water is metered in over the course of 2 hours and the polymerization is continued for 2 hours. An approximately 25% strength aqueous solution with a viscosity of 420 mPas is obtained.
- Aqueous binders are composed of the percentage proportions (solids) of dispersions A and polymer solutions B given in Table 3 and diluted with water to a solids content of 25% by weight.
- the pH value specified in each case is adjusted, if necessary, with p-toluenesulfonic acid.
- Thermally pre-consolidated spunbonded webs of polyester fibers having a basis weight of 125 g / m2 (Lutradur ® H1015, BASF) are so impregnated with the aqueous binders and squeezed that the binder support, after drying and condensing at 180 o C (10 min) 33-35 wt .-%.
- the breaking resistance of the impregnated nonwovens is determined in the strip tensile test according to DIN 53 857, part 2 using a tensile testing machine according to DIN 53 112 on strips 5 cm wide.
- Table 3 shows the breaking resistance Fmax in N / 5 cm and the elongation at break in% of the length of the test strip.
- a sample of the aqueous binder is weighed onto quartz sand and heated to 160 ° C. for 5 minutes.
- the formaldehyde released is collected and determined photometrically according to the acetylacetone method (official collection of examination procedures of the BGA, ⁇ 35 LMBG B 82.02-1, June 1985) and related in parts per million parts (ppm) to the amount of binder used.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Nonwoven Fabrics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
Die Erfindung betrifft ein wäßriges Bindemittel für textile Flächengebilde auf Basis eines in einer wäßrigen Phase dispergierten selbstvernetzenden Emulsionspolymerisats mit einem Gehalt an Einheiten des N-Methylol-acrylamids bzw. methacrylamids und eines in der wäßrigen Phase gelösten amidgruppenhaltigen Polymerisats.The invention relates to an aqueous binder for textile fabrics based on a self-crosslinking emulsion polymer dispersed in an aqueous phase and containing units of N-methylol-acrylamide or methacrylamide and a polymer containing amide groups dissolved in the aqueous phase.
Nach Untersuchungen von A. Zosel, W. Heckmann, G. Ley und W. Mächtle (Makromol.Chem., Macromol.Symp.35/36, 1990, S.423-446) wird bei der Emulsionspolymerisation von einer Mischung von Monomeren unterschiedlicher Hydrophilie in Wasser ein Teil der stärker wasserlöslichen Monomeren zu einem in der wäßrigen Phase gelösten Polymerisat polymerisiert. Bei der Herstellung selbstvernetzender Dispersionen unter Mitverwendung von N-Methylolacrylamid oder -methacrylamid, gegebenenfalls zusammen mit freiem Acrylamid oder Methacrylamid, entstehen demnach gelöste Polymerisate dieser Monomere. Ihre Menge dürfte stets unter 5 Gew.-%, bezogen auf das dispergierte Emulsionspolymerisat, liegen.According to studies by A. Zosel, W. Heckmann, G. Ley and W. Mächtle (Makromol.Chem., Macromol.Symp.35 / 36, 1990, pp.423-446), a mixture of monomers is different in emulsion polymerization Hydrophilicity in water polymerized part of the more water-soluble monomers to a polymer dissolved in the aqueous phase. When self-crosslinking dispersions are produced using N-methylolacrylamide or -methacrylamide, optionally together with free acrylamide or methacrylamide, polymers of these monomers are formed. Their amount should always be less than 5% by weight, based on the dispersed emulsion polymer.
Die N-Methylol-Gruppen in den selbstvernetzenden Dispersionen zum Verfestigen von textilen Flächengebilden bilden kovalente Vernetzungsbrücken zu den Hydroxyl- oder Amidgruppen des Bindemittels oder der Fasern des textilen Flächengebildes aus. Um eine stärkere Vernetzung zu erreichen, werden derartigen Bindemitteln in manchen Fällen in der wäßrigen Phase lösliche Polymerisate, wie wasserlösliche Aminoplastharze, zugesetzt.The N-methylol groups in the self-crosslinking dispersions for solidifying textile fabrics form covalent crosslinking bridges to the hydroxyl or amide groups of the binder or the fibers of the textile fabric. In order to achieve greater crosslinking, such binders are in some cases added to polymers which are soluble in the aqueous phase, such as water-soluble aminoplast resins.
Gemäß der DE-A 25 23 051 wird die Lagerungs- und Scherstabilität einer wäßrigen Dispersion eines Acryl-oder Butadien-Polymerisats für verschiedene technische Zwecke, beispielsweise zur Textilausrüstung, durch den Zusatz eines wasserlöslichen polymeren Materials verbessert. Als wasserlösliches polymeres Material kann beispielsweise teilweise oder völlig hydrolysiertes Polyvinylacetat, Stärke, verätherte Cellulose, Polyethylenglykol, Polyvinylpyrrolidon, Alkali-polyacrylat oder Polyacrylamid verwendet werden. Zur Stabilisierung einer selbstvernetzenden Acrylpolymerdispersion wurden Polyvinylalkohol und ein wasserlösliches Aminoplastharz als wasserlösliche Polymere zugesetzt.According to DE-A 25 23 051, the storage and shear stability of an aqueous dispersion of an acrylic or butadiene polymer for various technical purposes, for example for textile finishing, is improved by the addition of a water-soluble polymeric material. For example, partially or fully hydrolyzed polyvinyl acetate, starch, etherified cellulose, polyethylene glycol, polyvinyl pyrrolidone, alkali polyacrylate or polyacrylamide can be used as the water-soluble polymeric material. To stabilize a self-crosslinking acrylic polymer dispersion, polyvinyl alcohol and a water-soluble aminoplast resin were added as water-soluble polymers.
In der DE-A 25 27 804 wird ein Bindemittel zur Verfestigung eines Zellwollgewebes beschrieben, das neben einer überwiegenden Menge eines wasserlöslichen Aminoplastharzes kleinere Mengen eines Emulsionspolymerisats mit einem Gehalt an N-Methylolmethacrylamid sowie eines Lösungspolymerisats aus Acryl- und Methacrylamid und Ethylacrylat enthält. Für die festen Harzkomponenten läßt sich ein Gesamtgehalt an gebundenem Formaldehyd von 29 Gew.-% errechnen, der sich zu mehr als 99 % in dem Aminoplastharz befindet. Beim Kondensieren in der Wärme setzen derartige Bindemittel erhebliche Mengen an Formaldehyd frei.DE-A 25 27 804 describes a binder for solidifying a cellulose fabric which, in addition to a predominant amount of a water-soluble aminoplast resin, contains smaller amounts of an emulsion polymer containing N-methylol methacrylamide and a solution polymer made from acrylic and methacrylamide and ethyl acrylate. For the solid resin components, a total bound formaldehyde content of 29% by weight can be calculated, more than 99% of which is in the aminoplast resin. Such binders release considerable amounts of formaldehyde when they are condensed in the heat.
Aus der EP-A 326 298 sind formaldehydfreie Textilbinder für Cellulosefaservliese bekannt, die aus einem filmbildenden, schnell härtenden Emulsionspolymerisat mit einem Gehalt an nicht Formaldehyd abspaltenden reaktiven Monomereinheiten und aus einem Amidgruppen enthaltenden wasserlöslichen Polymerisat zusammengesetzt sind. Als reaktive Monomereinheiten des Emulsionspolymerisats werden Acrylamidoglykolat-methylether (MAGME) und Isobutoxymethylacrylamid genannt, während N-Methylolacrylamid wegen seiner Fähigkeit zur Abspaltung von latent gebundenem Formaldehyd als ungeeignet bezeichnet wird. Anscheinend bewirkt das stark hydrophile Lösungspolymerisat eine Verfestigung des Faservlieses, die auf Wasserstoffbrücken zwischen hydrophilen Gruppen der Cellulose und des Polymerisats beruht. Ein Nachteil dieser Bindemittel ist der verhältnismäßig hohe Preis der verwendeten reaktiven Monomeren, der für manche Anwendungsfälle, wie zur Verfestigung von Dachbahnvliesen, nicht tragbar ist. Die Binderfestigkeit bei hohen Temperaturen ist nicht befriedigend.From EP-A 326 298 formaldehyde-free textile binders for cellulose fiber nonwovens are known, which are composed of a film-forming, fast-curing emulsion polymer containing non-formaldehyde-releasing reactive monomer units and a water-soluble polymer containing amide groups. As reactive Monomer units of the emulsion polymer are called acrylamidoglycolate methyl ether (MAGME) and isobutoxymethylacrylamide, while N-methylolacrylamide is said to be unsuitable because of its ability to split off latently bound formaldehyde. Apparently, the highly hydrophilic solution polymer causes a consolidation of the fiber fleece, which is based on hydrogen bonds between hydrophilic groups of the cellulose and the polymer. A disadvantage of these binders is the relatively high price of the reactive monomers used, which is unsustainable for some applications, such as for strengthening roofing membrane nonwovens. The binder strength at high temperatures is unsatisfactory.
Der Erfindung liegt die Aufgabe zugrunde, ein wäßriges Bindemittel für textile Flächengebilde zur Verfügung zu stellen, das bei der Ausrüstung von nicht-cellulosischen Faserprodukten auch bei hohen Temperaturen hohe Festigkeitswerte ergibt. Diese Eigenschaft hat z.B. bei der Imprägnierung von verfestigten Faserbahnen mit geschmolzenem Bitumen, das eine Temperatur von 180oC haben kann, technische Bedeutung. Gleichzeitig soll das Bindemittel nicht mehr als 5 Gew.-% an freiem und latent gebundenem Formaldehyd enthalten und bei der Verarbeitung möglichst wenig Formaldehyd abgeben. Aus diesem Grunde kam eine Lösung der Aufgabe durch Zusatz von formaldehydreichen Aminoplastharzen nicht in Betracht.The invention has for its object to provide an aqueous binder for textile fabrics that gives high strength values when finishing non-cellulosic fiber products even at high temperatures. This property is of technical importance, for example, when impregnating solid fiber webs with molten bitumen, which can have a temperature of 180 ° C. At the same time, the binder should not contain more than 5% by weight of free and latently bound formaldehyde and release as little formaldehyde as possible during processing. For this reason, a solution to the problem by adding formaldehyde-rich aminoplast resins was out of the question.
Die erwünschten Festigkeitswerte lassen sich mit üblichen selbstvernetzenden Kunststoffdispersionen allein nicht erreichen, da sich ihr Gehalt an vernetzungsfähigen N-Methylolamidgruppen ohne Gefährung der kolloidchemischen Stabilität nicht beliebig erhöhen läßt. Zwar ließe sich die Binderfestigkeit durch den Zusatz von Aminoplastharzen steigern, jedoch nur um den Preis einer drastischen Zunahme der Formaldehydemission.The desired strength values cannot be achieved with conventional self-crosslinking plastic dispersions alone achieve because their content of crosslinkable N-methylolamide groups can not be increased arbitrarily without ensuring colloid chemical stability. Binder strength could be increased by adding aminoplast resins, but only at the cost of a drastic increase in formaldehyde emissions.
Die Aufgabe bestand deshalb im engeren Sinne darin, ein hohes Niveau der Hochtemperatur-Binderfestigkeit von selbstvernetzenden Kunststoffdispersionen zu erreichen, ohne zur Lösung dieser Aufgabe teure Reaktivmonomere oder Aminoplastharze einzusetzen oder eine Steigerung der Formaldehydemission in Kauf zu nehmen.The task in the narrower sense was therefore to achieve a high level of high-temperature binder strength for self-crosslinking plastic dispersions without using expensive reactive monomers or aminoplast resins to solve this task, or accepting an increase in formaldehyde emissions.
Es wurde gefunden, daß dieses Ziel durch die Kombination einer wäßrigen Binderdispersion, die latent gebundenen Formaldehyd enthält, mit einem zusätzlich in der wäßrigen Phase gelösten, Amidgruppen enthaltenden Polymer erreicht werden kann. Gegenstand der Erfindung ist ein wäßriges Bindemittel für textile Flächengebilde enthaltend
- A) eine wäßrige Dispersion eines filmbildenden, selbstvernetzenden Emulsionspolymerisats und
- B) ein in der wäßrigen Phase des Bindemittels gelöstes Polymer, das zu 10 bis 100 Gew.-% aus Acryl- und/oder Methacrylamid aufgebaut ist,
- A) an aqueous dispersion of a film-forming, self-crosslinking emulsion polymer and
- B) a polymer which is dissolved in the aqueous phase of the binder and which is composed of 10 to 100% by weight of acrylic and / or methacrylamide,
Erfindungsgemäß wird zusammen mit dem gelösten Polymer B ein Emulsionspolymerisat A eingesetzt, das 1 bis 15 Gew.-% an Einheiten des N-Methylol-acrylamids oder/und -methacrylamids enthält. Überraschenderweise ergibt gerade diese Kombination von Polymeren A und B Textilausrüstungen mit hohen Festigkeitseigenschaften bei deutlich verminderter Formaldehydfreisetzung.According to the invention, together with the dissolved polymer B, an emulsion polymer A is used which contains 1 to 15% by weight of units of the N-methylol acrylamide or / and methacrylamide. Surprisingly, it is precisely this combination of polymers A and B that gives textile finishes with high strength properties with significantly reduced formaldehyde release.
Würden solche Dispersionen allein oder in Kombination mit Aminoplastharzen angewendet, so gäben sie bei der Ausrüstung von Textilien merkliche Mengen an Formaldehyd an die Atmosphäre ab. Das träfe manchmal sogar für die ausgerüsteten Textilien selbst zu. Das amidhaltige Polymer B hat nun die überraschende Fähigkeit, einerseits mit dem Emulsionspolymerisat A ähnlich wie ein Aminoplastharz zu kondensieren und andererseits bei der Verarbeitung freiwerdenden Formaldehyd zu binden. Diese Fähigkeit sollte zwar dem wasserlöslichen Polymer, das während der Emulsionspolymerisation entsteht, in entsprechender Weise zu eigen sein, jedoch ist seine Wirkung durch die verhältnismäßig geringe Menge beschränkt. Jedenfalls zeigt sich die Wirkung des zusätzlich verwendeten Polymers B bei der Ausrüstung textiler Flächengebilde in vorteilhafter Weise.If such dispersions were used alone or in combination with aminoplast resins, they would emit noticeable amounts of formaldehyde into the atmosphere when finishing textiles. Sometimes this even applies to the finished textiles themselves. The amide-containing polymer B now has the surprising ability, on the one hand, to condense with the emulsion polymer A similarly to an aminoplast resin and, on the other hand, to bind formaldehyde released during processing. Although this ability should be correspondingly inherent in the water-soluble polymer which is formed during the emulsion polymerization, its action is limited by the relatively small amount. In any case, the effect of the additionally used polymer B is shown in an advantageous manner when finishing textile fabrics.
Im Vergleich zu herkömmlichen selbstvernetzenden Dispersionen zeichnen sich die erfindungsgemäßen Bindemittel dadurch aus, daß sie einem damit ausgerüsteten textilen Flächengebilde eine erhöhte Festigkeit verleihen. Trotz des Gehalts an latent gebundenem Formaldehyd in dem erfindungsgemäßen Bindemittel ist nur eine geringe Formaldehydemission bei der Verfestigung von textilen Flächenprodukten festzustellen.Compared to conventional self-crosslinking dispersions, the binders according to the invention are distinguished by the fact that they impart increased strength to a textile fabric equipped therewith. Despite the The latent bound formaldehyde content in the binder according to the invention shows only a low formaldehyde emission when solidifying textile products.
Die vorteilhafte Eigenschaftskombination von hoher Binderfestigkeit, namentlich in der Wärme, und geringer Formaldehydemission, die durch den Zusatz des wasserlöslichen Acryl- und/oder Methacrylamid-Polymers erreicht wird, geht aus den nachfolgend beschriebenen Vergleichsversuchen hervor. Eine handelsübliche selbstvernetzende Polyacrylatdispersion A1 ist - neben Methylmethacrylat und Butylacrylat (im Gewichtsverhältnis 60 : 40) als Hauptkomponenten - zu 3 Gew.-% aus N-Methylolmethacrylamid und zu 5 Gew.-% aus Methacrylamid aufgebaut. Sie gibt bei alleiniger Verwendung beim Erhitzen auf 160oC innerhalb 5 Minuten 300 ppm Formaldehyd ab; die bei dieser Prüfung freigesetzte Menge wird als "abspaltbarer Formaldehyd" bezeichnet. Wenn die Gehalte an N-Methylolmethacrylamid auf 4 Gew.-% und an Methacrylamid auf 6 Gew.-% erhöht werden, steigt der abspaltbare Formaldehyd auf 1130 ppm. Trotz des gesteigerten Gehalts an vernetzungsfähigen Gruppen sind die mit dieser Polyacrylatdispersion A2 erreichbaren Festigkeitswerte nur mäßig erhöht, wie aus der nachfolgenden Tabelle 1 hervorgeht. Die Tabelle zeigt auch den drastischen Anstieg der Formaldehydemission, wenn zur Verbesserung der Binderfestigkeit 10 % (bezogen auf ges. Bindergewicht) eines wasserlöslichen Aminoplastharzes B2 (Cassurit MT ® ) zugesetzt werden.The advantageous combination of properties of high binder strength, especially in the heat, and low formaldehyde emission, which is achieved by adding the water-soluble acrylic and / or methacrylamide polymer, is evident from the comparative experiments described below. In addition to methyl methacrylate and butyl acrylate (in a weight ratio of 60:40) as main components, a commercially available self-crosslinking polyacrylate dispersion A1 is composed of 3% by weight of N-methylol methacrylamide and 5% by weight of methacrylamide. When used alone, it releases 300 ppm of formaldehyde within 5 minutes when heated to 160 ° C .; the amount released in this test is referred to as "cleavable formaldehyde". If the contents of N-methylol methacrylamide are increased to 4% by weight and of methacrylamide to 6% by weight, the formaldehyde which can be split off increases to 1130 ppm. Despite the increased content of crosslinkable groups, the strength values achievable with this polyacrylate dispersion A2 are only moderately increased, as can be seen from Table 1 below. The table also shows the drastic increase in formaldehyde emissions when 10% (based on total binder weight) of a water-soluble aminoplast resin B2 (Cassurit MT ®) is added to improve the binder strength.
Eine deutliche Verbesserung der Festigkeitswerte, namentlich bei hohen Temperaturen, wird erfindungsgemäß durch die Kombination der Polyacrylatdispersion A2 mit einem Lösungpolymerisat B1 aus 60 Gew.-% Acrylamid, 30 Gew.-% Methacrylamid und 10 Gew.-% Hydroxyethyl-methacrylat erreicht. Das Gewichtsverhältnis A2 : B1 ist 9 : 1.A significant improvement in the strength values, especially at high temperatures, is achieved according to the invention by combining the polyacrylate dispersion A2 with a solution polymer B1 composed of 60% by weight of acrylamide, 30% by weight of methacrylamide and 10% by weight of hydroxyethyl methacrylate. The weight ratio A2: B1 is 9: 1.
Die nachfolgende Tabelle enthält für eine Reihe von mit 33 Gew.-% Binderharz imprägnierten und bei 180oC unter saurer Katalyse kondensierten Polyesterfaservliesen mit einem Flächengewicht von 125 g/qm (Lutradur® H1015) die gemessenen Werte des Bruchwiderstandes (Fmax) und des Bruchdehnungswertes (DFmax), jeweils für 20oC und 180oC.
Die an ausgerüsteten Textilien feststellbaren Bruchwiderstände und Bruchdehnungswerte werden mit der Vernetzungsdichte des verwendeten Kunststoffes in Verbindung gebracht. Die in dem Emulsionspolymerisat enthaltenen N-Methylolamidgruppen reagieren entweder untereinander unter Abspaltung von Formaldehyd oder mit zusätzlich eingebauten primären Amidgruppen zu N,N'-Methylen-bis-amid-Brücken. Nach herrschender Auffassung bleibt die Zahl der Vernetzungsbrücken bei der Kondensation des selbstvernetzenden Emulsionspolymerisats allein unter dem theoretischen Wert, der sich aus der vollständigen Umsetzung aller reaktiven Gruppen ergeben würde. Dadurch bleiben N-Methylolamidgruppen zurück, die unter allmählicher Zersetzung Formaldehyd abspalten können.The breaking resistance and elongation at break values that can be determined on finished textiles are associated with the crosslinking density of the plastic used. The N-methylolamide groups contained in the emulsion polymer react either with one another with elimination of formaldehyde or with additionally incorporated primary amide groups to form N, N'-methylene-bis-amide bridges. To The prevailing view is that the number of crosslink bridges in the condensation of the self-crosslinking emulsion polymer remains below the theoretical value that would result from the complete conversion of all reactive groups. This leaves behind N-methylolamide groups, which can split off formaldehyde with gradual decomposition.
Ohne die Erfindung auf eine bestimmte Theorie festlegen zu wollen, wird vermutet, daß sich das in der wäßrigen Phase des Bindemittels gelöste Polymer B bevorzugt mit den N-Methylolgruppen des Emulsionspolymerisats umsetzt. Dies ist schon aus der dichteren Stellung der Amidgruppen erklärlich. Die Umsetzung der N-Methylolamidgruppen scheint vollständiger als in Abwesenheit des Polymeren B abzulaufen. Auch wenn nur ein Teil der Amidgruppen des Polymeren B mit N-Methylolgruppen reagiert, so führt dennoch jeder solche Umsetzungsschritt zu einer wirksamen Vernetzungsbrücke zwischen den Polymeren A und B. Übrig bleibende Amidgruppen können darüberhinaus als Formaldehydfänger wirken und dadurch sogar zusätzliche Vernetzungsbrücken erzeugen. Infolge einer hohen Vernetzungsdichte werden hohe Festigkeitseigenschaften bei einem niedrigen Gehalt an abspaltbarem Formaldehyd erreicht.Without wishing to fix the invention to a specific theory, it is assumed that the polymer B dissolved in the aqueous phase of the binder preferably reacts with the N-methylol groups of the emulsion polymer. This can be explained from the closer position of the amide groups. The conversion of the N-methylolamide groups appears to be more complete than in the absence of polymer B. Even if only a part of the amide groups of polymer B reacts with N-methylol groups, each such reaction step leads to an effective cross-linking bridge between polymers A and B. In addition, remaining amide groups can act as formaldehyde scavengers and thus even generate additional cross-linking bridges. As a result of a high crosslinking density, high strength properties are achieved with a low content of formaldehyde that can be split off.
Als wäßrige Dispersion A kann jede für die Textilausrüstung geeignete selbstvernetzende Kunststoffdispersion mit vernetzungsfähigen N-Methylolamidgruppen verwendet werden.Any self-crosslinking plastic dispersion with crosslinkable N-methylolamide groups suitable for textile finishing can be used as the aqueous dispersion A.
Ihr Gehalt an Formaldehyd in freier und latent gebundener Form, bezogen auf reines Binderharz, soll möglichst nicht mehr als 5 Gew.-% betragen; das ist bei der Mehrzahl der für die Textilausrüstung hergestellten Kunststoffdispersionen der Fall. Wenn auch im Interesse einer hohen Vernetzungsdichte ihr Gehalt an N-Methylolacrylamid und - methacrylamid-Einheiten verhältnismäßig hoch liegen sollte und bis zu 15 Gew.-% betragen kann, ergeben auch Kunststoffdispersionen mit einem Gehalt von wenigstens 1 Gew.-% an N-Methylolacrylamid und -methacrylamid-Einheiten in Verbindung mit der Komponente B höhere Binderfestigkeiten als Bindemittel ohne die Komponente B. In der Regel ist das Emulsionspolymerisat A zu 3 bis 10 Gew.-% aus Einheiten des N-Methylol-acrylamids und/oder -methacrylamids und bis zu 10 Gew.-% aus Einheiten des Acryl- und/oder Methacrylamids aufgebaut.Their formaldehyde content in free and latently bound form, based on pure binder resin, should preferably not be more than 5% by weight; this is the case with the majority of plastic dispersions manufactured for textile finishing. If, in the interest of a high crosslinking density, their content of N-methylolacrylamide and - methacrylamide units should be relatively high and can be up to 15% by weight, plastic dispersions with a content of at least 1% by weight of N-methylolacrylamide also result and -methacrylamide units in connection with component B have higher binder strengths than binders without component B. As a rule, the emulsion polymer A is 3 to 10% by weight of units of N-methylol-acrylamide and / or -methacrylamide and bis built up to 10 wt .-% of units of acrylic and / or methacrylamide.
Je nach den erwünschten Eigenschaften der ausgerüsteten textilen Flächengebilde können die erfindungsgemäßen Bindemittel so aufgebaut sein, daß der aus dem Bindemittel beim Trocknen und Kondensieren entstehende Film hart, spröde und trocken oder weich und klebrig ist oder eine zwischen diesen Extremen liegende Beschaffenheit hat. Bekanntlich hängen diese Eigenschaften von der dynamischen Einfriertemperatur (T-lambda-max nach DIN 53 445) des Films ab, die vorzugsweise im Bereich von 10 bis 80oC, insbesondere 20 bis 60oC liegt. Diese Größe wird in an sich bekannter Weise weitgehend durch den Aufbau des Emulsionspolymerisats bestimmt.Depending on the desired properties of the finished textile fabrics, the binders according to the invention can be constructed in such a way that the film formed from the binder during drying and condensation is hard, brittle and dry or soft and sticky or has a nature lying between these extremes. As is known, these properties depend on the dynamic freezing temperature (T-lambda-max according to DIN 53 445) of the film, which is preferably in the range from 10 to 80 ° C., in particular 20 to 60 ° C. This size is largely determined in a manner known per se by the structure of the emulsion polymer.
Bevorzugt ist das Emulsionspolymerisat A zu 60 bis 97 Gew.-% aus Alkylestern der Acryl- und/oder Methacrylsäure mit 1 bis 8 Kohlenstoffatomen im Alkylrest aufgebaut. Bevorzugte Alkylester der Acrylsäure sind Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl- und 2-Ethyl-hexyl-acrylat. Bevorzugte Alkylester der Methacrylsäure sind Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl- und Isobutylmethacrylat. Die Alkylmethacrylate können ganz oder zum Teil durch Styrol oder polymerisierbare Derivate des Styrols, wie Vinyltoluol oder alpha-Methylstyrol, ersetzt sein. Bekanntlich werden Weichheit und Dehnbarkeit des Polymerisats durch Alkylester der Acrylsäure, Härte und Sprödigkeit durch niedere Alkylester der Methacrylsäure oder durch Styrole gefördert. Typische Polyacrylatdispersionen für die Zwecke der Erfindung enthalten daher vorzugsweise Einheiten dieser beiden Gruppen von Monomeren im Gewichtsverhältnis von etwa 70 : 30 bis 20 : 80.The emulsion polymer A is preferably 60 to 97% by weight of alkyl esters of acrylic and / or methacrylic acid with 1 to 8 carbon atoms built up in the alkyl radical. Preferred alkyl esters of acrylic acid are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and 2-ethylhexyl acrylate. Preferred alkyl esters of methacrylic acid are methyl, ethyl, propyl, isopropyl, n-butyl and isobutyl methacrylate. All or part of the alkyl methacrylates can be replaced by styrene or polymerizable derivatives of styrene, such as vinyltoluene or alpha-methylstyrene. As is known, the softness and extensibility of the polymer are promoted by alkyl esters of acrylic acid, hardness and brittleness by lower alkyl esters of methacrylic acid or by styrenes. Typical polyacrylate dispersions for the purposes of the invention therefore preferably contain units of these two groups of monomers in a weight ratio of about 70:30 to 20:80.
Geeignete selbstvernetzende Dispersionen lassen sich nach bekannten Verfahren der Emulsionspolymerisation mit einem Feststoffgehalt zwischen 30 und 65 Gew.-% herstellen, werden aber zur Herstellung einer Imprägnierflotte im allgemeinen mit Wasser bzw. mit der wäßrigen Lösung des Polymeren B auf 15 bis 45 Gew.-% verdünnt. In der Regel sind sie durch anionische oder/und nichtionische Emulgatoren stabilisiert.Suitable self-crosslinking dispersions can be prepared by known emulsion polymerization processes with a solids content of between 30 and 65% by weight, but are generally made up to 15 to 45% by weight with water or with the aqueous solution of polymer B to prepare an impregnation liquor. diluted. As a rule, they are stabilized by anionic and / or nonionic emulsifiers.
Das zusätzlich verwendete Polymer B kann allein aus Acrylamid oder Methacrylamid oder deren Mischung aufgebaut sein. Vorzugsweise ist es frei von Formaldehyd abgebenden Monomereinheiten, wie N-Methylolacrylamid und - methacrylamid; zumindest sollte der Anteil derartiger Monomereinheiten 10 Gew.-% (bez. auf B) nicht überschreiten.The additionally used polymer B can be made up solely of acrylamide or methacrylamide or a mixture thereof. It is preferably free of formaldehyde-donating monomer units, such as N-methylolacrylamide and methacrylamide; at least the proportion of such monomer units should not exceed 10% by weight (based on B).
Um gute Wasserlöslichkeit zu gewährleisten, beträgt der Anteil des Acryl- und/oder Methacrylamids nicht weniger als 10 Gew.-% und vorzugsweise mindestens 50 Gew.-%. Daneben können andere ethylenisch ungesättigte, radikalisch polymerisierbare Monomere an ihrem Aufbau beteiligt sein. Comonomere, die selbst wasserlöslich sind oder wenigstens wasserlösliche Homopolymerisate bilden, wie niedere Hydroxyalkylester der Acryl- und/oder Methacrylsäure, können einen Anteil bis zu 90 Gew.-% des Polymeren B bilden, während der Anteil nicht oder schwer wasserlöslicher Comonomerer stets so begrenzt sein muß, daß das Polymer B als ganzes in der wäßrigen Phase des Bindemittels ausreichend löslich ist. Er übersteigt selten 30 Gew.-%. Bevorzugte Polymere B sind zu 50 bis 95 Gew.-% aus Acryl- und/oder Methacrylamid, zu 5 bis 50 Gew.-% aus wasserlöslichen bzw. wasserlösliche Homopolymerisate bildenden, äthylenisch ungesättigten, radikalisch polymerisierbaren Monomeren und zu höchstens 20 Gew.-% aus nicht wasserlöslichen äthylenisch ungesättigten, radikalisch polymerisierbaren Monomeren aufgebaut. Latent gebundenen Formaldehyd enthaltende Monomere sind in den bevorzugten Polymeren B nicht enthalten.In order to ensure good solubility in water, the proportion of acrylic and / or methacrylamide is not less than 10% by weight and preferably at least 50% by weight. In addition, other ethylenically unsaturated, radically polymerizable monomers can be involved in their construction. Comonomers which are themselves water-soluble or at least form water-soluble homopolymers, such as lower hydroxyalkyl esters of acrylic and / or methacrylic acid, can form a proportion of up to 90% by weight of polymer B, while the proportion of non-water-soluble or sparingly water-soluble comonomers is always limited must ensure that polymer B as a whole is sufficiently soluble in the aqueous phase of the binder. It rarely exceeds 30% by weight. Preferred polymers B are 50 to 95% by weight of acrylic and / or methacrylamide, 5 to 50% by weight of water-soluble or water-soluble homopolymers, ethylenically unsaturated, free-radically polymerizable monomers and at most 20% by weight built up from water-insoluble ethylenically unsaturated, radically polymerizable monomers. Monomers containing latent bound formaldehyde are not contained in the preferred polymers B.
Das Copolymer B kann auf einfache Weise hergestellt werden, indem man die entprechenden Monomeren in einer Konzentration von beispielsweise 10 bis 40 Gew.-% in Wasser löst und nach Zusatz eines wasserlöslichen radikalbildenden Initiators, wie Alkali- oder Ammonium-peroxodisulfat, bei Temperaturen von 60 bis 90oC die Polymerisation auslöst. Das Molekulargewicht liegt vorzugsweise im Bereich von 1.000 bis 200.000 (Gewichtsmittelwert) und läßt sich während der Polymerisation gegebenenfalls durch Zusatz eines Kettenübertragungsmittels wie Thioglykolsäure auf einen Wert in diesem Bereich einstellen.The copolymer B can be prepared in a simple manner by dissolving the corresponding monomers in a concentration of, for example, 10 to 40% by weight in water and after adding a water-soluble free radical initiator, such as alkali metal or ammonium peroxodisulfate, at temperatures of 60 up to 90 o C triggers the polymerization. The molecular weight is preferably in the range from 1,000 to 200,000 (weight average) and can optionally be added during the polymerization by adding a Set chain transfer agents such as thioglycolic acid to a value in this range.
Die wäßrige Polymerisatlösung wird vorzugsweise ohne Isolierung des Polymeren B unmittelbar mit der Kunststoffdispersion A vermischt. Es ist jedoch auch möglich, das Polymer B in reiner Form herzustellen oder zu isolieren und als Pulver in der wäßrigen Phase der Dispersion zu lösen. Vorzugsweise beträgt der Anteil des Polymers B 5 bis 15 Gew.-%, bezogen auf das Emulsionspolymerisat A.The aqueous polymer solution is preferably mixed directly with the plastic dispersion A without isolating the polymer B. However, it is also possible to prepare or isolate polymer B in pure form and to dissolve it as a powder in the aqueous phase of the dispersion. The proportion of polymer B is preferably 5 to 15% by weight, based on the emulsion polymer A.
Das Bindemittel kann eine Viskosität im Bereich von 20 bis 10.000 mPa s haben. Es kann mit weiteren Zusätzen, wie Bakteriziden, Fungiziden, Entschäumern, sauren Härtungskatalysatoren, Thermosensibilisierungsmitteln, Puffersubstanzen, Tensiden, Weichmachern, Filmbildungshilfsmitteln, Flammschutzmitteln u.ä. je nach den Erfordernissen des Anwendungsfalles konfektioniert werden.The binder can have a viscosity in the range of 20 to 10,000 mPas. It can be combined with other additives, such as bactericides, fungicides, defoamers, acidic curing catalysts, thermosensitizers, buffer substances, surfactants, plasticizers, film-forming aids, flame retardants and the like. can be assembled according to the requirements of the application.
Die erfindungsgemäßen Bindemittel sind zur Filmbildung bei Temperaturen zwischen 0 und 100oC befähigt. Um die Filmbildung zu erleichtern, können dem Bindemittel übliche Filmbildungshilfsmittel, wie flüchtige Lösemittel oder schwer flüchtige Weichmacher für das Emulsionspolymerisat, zugesetzt werden. Das Bindemittel kann ebenso wie herkömmliche filmbildende, selbstvernetzende wäßrige Kunststoffdispersionen zum Ausrüsten von textilen Flächengebilden eingesetzt werden. Unter textilen Flächengebilden sind Gewebe, Gewirke und Faservliese aus natürlichen oder synthetischen Fasern, insbesondere aus Baumwolle, Zellwolle, Viskose, Celluloseacetat, Polyester, Polyamid, Polyacrylnitril, Polypropylen oder aus Gemischen solcher Fasern oder aus Glasfasern zu verstehen. Sie können ein Flächengewicht von 50 bis 500 g/qm haben. Faservliese aus Polyesterfasern sind bevorzugt. Das Bindemittel wird beispielsweise durch Tauchen, Sprühen, Pflatschen, Rakeln oder Drucken in einer Menge von beispielsweise 5 bis 100 Gew.-%, berechnet als Trockenprodukt und bezogen auf das Fasergewicht, auf das textilen Flächengebilde aufgebracht. Es kann dazu mit sauren Katalysatoren, wie p-Toluolsulfonsäure, Citronensäure, Phosphorsäure oder Ammoniumphosphat, mit Farbstoffen oder Pigmenten versetzt, mit Wasser oder Verdickungsmitteln auf die anwendungstechnisch erforderliche Viskosität eingestellt und gegebenenfalls geschäumt werden. Nach dem Trocknen wird die erhaltene Imprägnierung bei Temperaturen von 100 bis 180oC innerhalb von 180 bis 30 sec vernetzt. Man erhält auf diese Weise verfestigte textile Flächengebilde mit einer hervorragenden Beständigkeit gegen Lösemittel und gegen Weichmacher.The binders of the invention are capable of film formation at temperatures between 0 and 100 o C. In order to facilitate film formation, conventional film formation aids, such as volatile solvents or low-volatility plasticizers for the emulsion polymer, can be added to the binder. The binder, like conventional film-forming, self-crosslinking aqueous plastic dispersions, can be used to finish textile fabrics. Under textile Fabrics, knitted fabrics and nonwovens made from natural or synthetic fibers, in particular from cotton, rayon, viscose, cellulose acetate, polyester, polyamide, polyacrylonitrile, polypropylene or from mixtures of such fibers or from glass fibers are to be understood as flat structures. They can have a basis weight of 50 to 500 g / qm. Non-woven fabrics made of polyester fibers are preferred. The binder is applied to the textile fabric, for example by dipping, spraying, slapping, knife coating or printing in an amount of, for example, 5 to 100% by weight, calculated as a dry product and based on the fiber weight. To this end, acidic catalysts, such as p-toluenesulfonic acid, citric acid, phosphoric acid or ammonium phosphate, can be admixed with dyes or pigments, adjusted to the viscosity required by the application with water or thickeners and, if appropriate, foamed. After drying, the impregnation obtained is crosslinked at from 100 to 180 ° C. within 180 to 30 seconds. In this way, consolidated textile fabrics with excellent resistance to solvents and plasticizers are obtained.
Durch die Kondensation wird das Bindemittel unlöslich und unschmelzbar. Es verleiht daher dem damit ausgerüsteten textilen Flächengebilde erhöhte mechanische Festigkeit, insbesondere Zugfestigkeit. Die bemerkenswert hohe Festigkeit bei erhöhter Temperatur ist von besonderer Bedeutung bei der Imprägnierung von Faservliesbahnen, vorzugsweise aus Polyesterfasern, mit geschmolzenem Bitumen zur Herstellung von Dachbahnen. Das Bitumen hat bei der Imprägnierung eine Temperatur von 150 bis 200 Grad C. Bei dieser Temperatur darf die Vliesbahn beim Transport durch das Imprägnierbad auch bei hoher Geschwindigkeit weder reißen noch stark gedehnt werden.Condensation makes the binder insoluble and infusible. It therefore gives the textile fabric equipped with it increased mechanical strength, in particular tensile strength. The remarkably high strength at elevated temperature is of particular importance when impregnating nonwoven webs, preferably made of polyester fibers, with melted bitumen for the production of roofing webs. The bitumen has in the Impregnation at a temperature of 150 to 200 degrees C. At this temperature, the nonwoven web must neither tear nor stretch strongly during transport through the impregnation bath, even at high speeds.
In einem 1-Liter- Rundkolben mit Rührwerk, Rückflußkühler und Zulaufgefäß werden 120 Teile Wasser und 0,02 Teile Na-Laurylsulfat vorgelegt, auf 80oC erhitzt und mit 0,1 Teil Ammoniumperoxodisulfat versetzt. Bei dieser Temperatur wird innerhalb von 4 Stunden eine Emulsion aus
250,0 Teilen Wasser
12,0 Teilen einer 10%igen wäßr.Lösung von Nalaurylsulfat,
10,0 Teilen einer 10%igen wäßr.Lösung von Ammoniumperoxodisulfat,
400,0 Teilen einer Monomermischung gemäß Tabelle 2 zugesetzt. Man erhält etwa 50-%ige wäßrige Dispersionen.
250.0 parts water
12.0 parts of a 10% aqueous solution of nalauryl sulfate,
10.0 parts of a 10% aqueous solution of ammonium peroxodisulfate,
400.0 parts of a monomer mixture according to Table 2 were added. About 50% aqueous dispersions are obtained.
Beteutung der Kurzbezeichnungen:
- MMA
- - Methylmethacrylat
- EA
- - Ethylacrylat
- BA
- - n-Butylacrylat
- MMAM
- - N-Methylol-methacrylamid
- MAM
- - Methacrylamid
- MAA
- - Methacrylsäure
- MAGME
- - Methylacrylamidoglykolat-methylether
- MMA
- - methyl methacrylate
- EA
- - ethyl acrylate
- BA
- n-butyl acrylate
- MMAM
- - N-methylol methacrylamide
- MAM
- - methacrylamide
- MAA
- - methacrylic acid
- MAGME
- - Methyl acrylamidoglycolate methyl ether
Zur Herstellung des Polymers B1 werden 590 Teile Wasser von 85oC mit einer Lösung von 2,5 Teilen Ammoniumperoxodisulfat in 8 Teilen Wasser versetzt. Innerhalb von 2 Stunden wird eine Lösung von 144 Teilen Acrylamid, 25 Teilen Methacrylamid und 25 Teilen 2-Hydroxyethylmethacrylat in 144 Teilen Wasser zudosiert und 2 Stunden nachpolymerisiert. Es wird eine etwa 25-%ige wäßrige Lösung mit einer Viskosität von 420 mPa s erhalten.To prepare polymer B1, 590 parts of water at 85 ° C. are mixed with a solution of 2.5 parts of ammonium peroxodisulfate in 8 parts of water. A solution of 144 parts of acrylamide, 25 parts of methacrylamide and 25 parts of 2-hydroxyethyl methacrylate in 144 parts of water is metered in over the course of 2 hours and the polymerization is continued for 2 hours. An approximately 25% strength aqueous solution with a viscosity of 420 mPas is obtained.
Zur Herstellung des Polymers B3 wird ebenso verfahren, jedoch eine Monomerenmischung aus 185 Teilen Methacrylamid, 45 Teilen Acrylamid sowie 12 Teile Thioglykolsäure als Regler zugesetzt. Die Polymerisatlösung hat bei einem Feststoffgehalt von etwa 26 Gew.-% eine Viskosität von 350 mPa s.
- B1:
- Zusammensetzung 60 Gew.-% Acrylamid
30 Gew.-% Methacrylamid
10 Gew.-% Hydroxyethyl-methacrylat - B3:
- Zusammensetzung 80 Gew.-% Methacrylamid
20 Gew.-% Acrylamid - B2:
- Für Vergleichszwecke wird als lösliches Polymer B2 ein handelsübliches Melamin-Formaldehyd-Kondensationsharz in Form einer 75-%igen wäßrigen Lösung (Handelsbezeichnung Cassurit MT ®, Cassella AG) verwendet.
- B1:
- Composition 60% by weight acrylamide
30% by weight methacrylamide
10% by weight of hydroxyethyl methacrylate - B3:
- Composition 80% by weight methacrylamide
20% by weight acrylamide - B2:
- For comparison purposes, a commercially available melamine-formaldehyde condensation resin in the form of a 75% strength aqueous solution (trade name Cassurit MT®, Cassella AG) is used as soluble polymer B2.
Die Mengenangaben beziehen sich auf Feststoff.The quantities given relate to solids.
Wäßrige Bindemittel werden aus den in Tabelle 3 angegebenen prozentualen Mengenverhältnissen (Feststoff) der Dispersionen A und der Polymerlösungen B zusammengesetzt und mit Wasser auf einen Feststoffgehalt von 25 Gew.-% verdünnt. Der jeweils angegebene pH-Wert wird - soweit erforderlich - mit p-Toluolsulfonsäure eingestellt. Thermisch vorverfestigte Spinnvliese aus Polyesterfasern mit einem Flächengewicht von 125 g/m² (Lutradur ® H1015, BASF) werden mit den wäßrigen Bindemitteln so imprägniert und abgequetscht, daß die Binderauflage nach dem Trocknen und Kondensieren bei 180oC (10 min) 33 - 35 Gew.-% beträgt.Aqueous binders are composed of the percentage proportions (solids) of dispersions A and polymer solutions B given in Table 3 and diluted with water to a solids content of 25% by weight. The pH value specified in each case is adjusted, if necessary, with p-toluenesulfonic acid. Thermally pre-consolidated spunbonded webs of polyester fibers having a basis weight of 125 g / m² (Lutradur ® H1015, BASF) are so impregnated with the aqueous binders and squeezed that the binder support, after drying and condensing at 180 o C (10 min) 33-35 wt .-%.
Der Bruchwiderstand der imprägnierten Vliesstoffe wird im Streifenzugversuch nach DIN 53 857, Teil 2 mittels einer Zugprüfmaschine gemäß DIN 53 112 an 5 cm breiten Streifen bestimmt. In Tabelle 3 werden der Bruchwiderstand Fmax in N/5 cm und die Bruchdehnung in % der Prüfstreifenlänge angegeben.The breaking resistance of the impregnated nonwovens is determined in the strip tensile test according to DIN 53 857, part 2 using a tensile testing machine according to DIN 53 112 on strips 5 cm wide. Table 3 shows the breaking resistance Fmax in N / 5 cm and the elongation at break in% of the length of the test strip.
Eine Probe des wäßrigen Bindemittels wird auf Quarzsand eingewogen und 5 Minuten auf 160oC erhitzt. Der freigesetzte Formaldehyd wird aufgefangen und photometrisch nach der Acetylaceton-Methode (Amtliche Sammlung von Untersuchungsverfahren des BGA, § 35 LMBG B 82.02-1, Juni 1985) bestimmt und in Teilen pro Million Teile (ppm) auf die eingesetzte Menge des Bindemittels bezogen.
Claims (10)
- An aqueous binding agent for textile surfaces, containing(A) an aqueous dispersion of a film-forming, self-cross-linking emulsion polymer and(B) a polymer which is dissolved in the aqueous phase of the binding agent and synthesised, in an amount of 10 to 100 wt.%, from acryl- and/or methacrylamide,in which the weight ratio of A to B is 95 : 5 to 70 : 30 and the binding agent does not contain any amino plastic resins, characterised in that the emulsion polymer A contains 1 to 15 wt.% of units of N-methylol-acrylamide or/and -methacrylamide.
- An aqueous binding agent according to claim 1, characterised in that the dissolved Polymer B is synthesised, in a maximum amount of 10 wt.%, from N-methylolacryl- and/or methacrylamide.
- An aqueous binding agent according to claim 2, characterised in that the dissolved Polymer B is synthesised, in an amount of 10 to 100 wt.%, from acryl- and/or methacrylamide and, in an amount from 0 to 90 wt.%, from water-soluble, ethylenically unsaturated radically polymerisable monomers, and, in a maximum amount of 30 wt.%, from water-insoluble, ethylenically unsaturated, radically polymerisable monomers.
- An aqueous binding agent according to claim 3, characterised in that the dissolved Polymer B is synthesised, in an amount of 50 to 95 wt.%, from acryl- and/or methacrylamide and, in an amount of 5 to 50 wt.%, from water-soluble, ethylenically unsaturated, radically polymerisable monomers and, in a maximum amount of 20 wt.%, from water-insoluble, ethylenically unsaturated, radically polymerisable monomers.
- An aqueous binding agent according to one or more of claims 1 or 4, characterised in that the dissolved Polymer B contains units of a hydroxyalkyl ester of acrylic and/or methacrylic acid.
- An aqueous binding agent according to one or more of claims 1 to 5, characterised in that the emulsion Polymer A is synthesised, in an amount of 60 to 97 wt.%, from alkyl esters of acrylic and/or methacrylic acid having 1 to 8 carbon atoms in the alkyl group.
- An aqueous binding agent according to one or more of claims 1 to 6, characterised in that the emulsion Polymer A is synthesised, in an amount of 3 to 10 wt.%, from units of N-methylol-acrylamide and/or -methacrylamide and, in an amount of up to 10 wt.%, from units of acryl- and/or methacrylamide.
- An aqueous binding agent according to one or more of claims 1 to 7, characterised in that it has a content of not more than 5 wt.% of reactive formaldehyde in free and latently bound form, based on pure binder resin.
- Use of the aqueous binding agent according to one or more of claims 1 to 8 for strengthening textile surfaces.
- Use of the aqueous binding agent according to claim 9, characterised in that a fleece made of polyester fibres is used as a textile surface.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE9110054U DE9110054U1 (en) | 1991-08-14 | 1991-08-14 | Aqueous binder for textile fabrics |
DE9110054U | 1991-08-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0527411A1 EP0527411A1 (en) | 1993-02-17 |
EP0527411B1 true EP0527411B1 (en) | 1995-02-22 |
Family
ID=6870258
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92113160A Expired - Lifetime EP0527411B1 (en) | 1991-08-14 | 1992-08-01 | Aqueous binder for textile material |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0527411B1 (en) |
AT (1) | ATE118836T1 (en) |
DE (2) | DE9110054U1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020042128A1 (en) * | 2018-08-31 | 2020-03-05 | 宿迁市神龙家纺有限公司 | Environment-friendly pigment printing adhesive and preparation method therefor |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19814873A1 (en) | 1998-04-02 | 1999-10-07 | Basf Ag | A method for reducing the C¶1¶-C¶2¶-aldehyde content of compounds with CH¶2¶-CHR-0 or -CH¶2¶-CH (OH) groups |
DE102006006200B4 (en) * | 2006-02-09 | 2008-01-10 | Röhm Gmbh | Aqueous N-methylol-methacrylamide-methacrylamide mixture |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1181171A (en) * | 1956-08-13 | 1959-06-12 | Rohm & Haas | Nonwoven fibrous product and its manufacture |
DE1073432B (en) * | 1956-11-30 | 1960-01-21 | Farbenfabriken Bayer Aktiengesellschaft, Leverkusen-Bayerwerk | Process for flocking or coating textiles |
DE1619056C3 (en) * | 1967-10-19 | 1974-01-31 | Farbwerke Hoechst Ag, Vormals Meister Lucius & Bruening, 6000 Frankfurt | Binders and methods for consolidating nonwovens |
US4107120A (en) * | 1976-06-17 | 1978-08-15 | Rohm And Haas Company | Heteropolymer acrylic latices and textiles treated therewith |
DE2920377A1 (en) * | 1979-05-19 | 1980-12-04 | Basf Ag | BINDING, IMPREGNATING AND COATING AGENTS BASED ON AN AQUEOUS DISPERSION OF A COPOLYMERS CONTAINING AMID GROUPS |
DE3902067A1 (en) * | 1989-01-25 | 1990-07-26 | Roehm Gmbh | FILM-FORMING, SELF-NETWORKING AQUEOUS PLASTIC DISPERSION |
-
1991
- 1991-08-14 DE DE9110054U patent/DE9110054U1/en not_active Expired - Lifetime
-
1992
- 1992-08-01 DE DE59201449T patent/DE59201449D1/en not_active Expired - Fee Related
- 1992-08-01 EP EP92113160A patent/EP0527411B1/en not_active Expired - Lifetime
- 1992-08-01 AT AT92113160T patent/ATE118836T1/en not_active IP Right Cessation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020042128A1 (en) * | 2018-08-31 | 2020-03-05 | 宿迁市神龙家纺有限公司 | Environment-friendly pigment printing adhesive and preparation method therefor |
Also Published As
Publication number | Publication date |
---|---|
ATE118836T1 (en) | 1995-03-15 |
DE59201449D1 (en) | 1995-03-30 |
EP0527411A1 (en) | 1993-02-17 |
DE9110054U1 (en) | 1991-10-10 |
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