EP0193107B1 - Bonded textile fabric and method for its production - Google Patents

Bonded textile fabric and method for its production Download PDF

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Publication number
EP0193107B1
EP0193107B1 EP86102172A EP86102172A EP0193107B1 EP 0193107 B1 EP0193107 B1 EP 0193107B1 EP 86102172 A EP86102172 A EP 86102172A EP 86102172 A EP86102172 A EP 86102172A EP 0193107 B1 EP0193107 B1 EP 0193107B1
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EP
European Patent Office
Prior art keywords
bonded
binder
weight
fibre fleece
dispersion
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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EP86102172A
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German (de)
French (fr)
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EP0193107A2 (en
EP0193107A3 (en
Inventor
Herbert Dr. Dipl.-Chem. Fink
Klaus Dr. Dipl.-Chem. Hübner
Heiner Kniese
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Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
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Publication date
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Classifications

    • 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
    • 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
    • D04H1/425—Cellulose series
    • D04H1/4258—Regenerated cellulose series
    • 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
    • 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
    • D04H3/013—Regenerated cellulose series
    • 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
    • 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
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
    • Y10T442/291—Coated or impregnated polyolefin fiber fabric

Definitions

  • the invention relates to a method for producing bound textile fabrics by applying an acrylic resin dispersion which is free of formaldehyde and formaldehyde-releasing substances.
  • the invention further relates to the textile fabrics produced by the method.
  • Aqueous acyl resin dispersions whose plastic content contained self-crosslinking amide methylol groups have hitherto been used frequently for the production of bound textile fabrics which are notable for high wet strength and for water and wash liquor resistance.
  • binders for textile fabrics which provide sufficient wet strength, water and wash liquor resistance for practical purposes, but do not give off any formaldehyde when heated.
  • EP-A 19 169 describes aqueous dispersions which are suitable as binders for nonwoven fabrics and which contain, as binders, a copolymer of acrylic or methacrylic esters or other monomers and 3 to 10% by weight of units of acrylamidoglycolic acid. It is therefore a binder that does not release formaldehyde when heated. However, since the desired wet strength of the textile fabrics finished with them is not achieved with these binders, small proportions of N-methylolacrylamide are polymerized into the copolymers, thereby increasing the wet strength of the finished fiber structures. however, the risk of formaldehyde release occurs again.
  • EP-A 96 230 describes coating compositions which contain, as self-crosslinking binders, copolymers of acrylic monomers and a crosslinking system composed of methyl acrylamido-glycolic acid methyl ether and hydroxyl, carboxy or amido-functional comonomers. When heated, condensation reactions of the monomer units, the crosslinker system mentioned, occur. It is not known to use such copolymers as binders for textile fabrics.
  • the invention has for its object to produce bonded fabrics with improved wet strength, from whose binder no formaldehyde is released when heated.
  • the bonded fabrics made according to the invention are distinguished from those with conventional formaldehyde-free binders by a significantly increased wet strength. This is important in cases where the bound textile fabric is exposed to mechanical stress during manufacture, further processing or when used in the wet state.
  • a typical application is the production of bonded nonwovens based on synthetic fibers, in particular polyester fibers, which are used for the production of so-called disposable diapers.
  • the bonded non-woven fabrics form the outer cover of the diaper, which envelops a highly absorbent filler. Due to the low water absorption of the synthetic fibers, the outer shell still appears relatively dry when the coated insert has absorbed considerable amounts of liquid. However, it is essential that the outer casing does not tear under mechanical stress and exposes the liquid-saturated insert.
  • the increased wet strength of the textile fabrics bound in the sense of the invention is based on the units of an acrylamidoglycolic acid monomer of the formula as a component of the copolymer contained in the aqueous dispersion.
  • R, R 'and R'' have the meaning given in claim 1.
  • R 'and R'' can be the same alkyl radicals, especially methyl groups.
  • other alkyl radicals with preferably no more than 8 carbon atoms are also suitable, in particular lower alkyl radicals with up to 4 carbon atoms.
  • the acrylic or methacrylic acid alkyl esters forming the main part of the copolymer, or their mixture with styrene, are selected in a manner known per se so that the dynamic freezing temperature T 1max is not more than 60 °, preferably not more than 20 ° C.
  • the copolymer consists of 30 to 60 wt .-% of monomer units that give hard homopolymers, such as methyl, ethyl, propyl, isopropyl methacrylate or styrene, and about 20 to 70% acrylic acid esters of C1 ⁇ 8 alkanols or methacrylic acid esters of C4 ⁇ 8 alkanols.
  • Unsaturated carboxylic acids such as acrylic or methacrylic acid are suitable as further monomer components Amounts of about 1% by weight improve the stability of the dispersion.
  • Crosslinking comonomers such as glycol dimethacrylate, allyl methacrylate, methylene-bis-methacrylamide or butanediol diacrylate, can also improve the strength properties of the binder in small amounts. Too high a proportion of crosslinking agents would interfere with the film formation process and should therefore be avoided.
  • the comonomers which can also be used also include acrylonitrile and methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride and others. Hydroxyesters and amides of acrylic or methacrylic acid are generally not present in the copolymers.
  • the acrylic resin dispersions can be prepared by all common methods of emulsion polymerization. They can contain anionic, cationic or non-ionic emulsifiers or compatible mixtures thereof. They are expediently produced with solids contents of 50 to 70% by weight.
  • the method of the invention is suitable for binding and solidifying textile fabrics of all kinds; these include woven fabrics, knitted fabrics, wadding and in particular non-woven nonwovens.
  • the invention is not restricted to certain types of fibers, but synthetic fibers or fiber mixtures containing synthetic fibers are fundamentally preferred. These mixtures can contain, for example, 70% or more of synthetic fibers.
  • the synthetic fibers considered include fibers made from regenerated cellulose, such as rayon or rayon, and in particular fully synthetic fibers, such as polyester or polypropylene fibers.
  • Preferred textile fabrics are constructed from 70 to 100% by weight of polyester fibers and 0 to 30% by weight of cellulose.
  • the preparation of the dispersion for the consolidation of fiber structures depends on the application process and the requirements placed on the end product.
  • the additives used in these processes like wetting agents. Anti-foaming agents, thermosensitizers. Plasticizers and smoothing agents. Antistatic. Antimicrobials. Dyes, fillers, flame retardants, fragrances, etc. can also be used.
  • the dispersions are diluted with water to a binder content of 10 to 40 percent by weight.
  • the viscosity of the diluted dispersion can range from 10 to 10,000 mPa.s.
  • For the consolidation of wadding for example made of polyester, polyamide or polyacrylonitrile fibers, an approximately 15 to 25% liquor is sprayed on.
  • Compact nonwovens and needle felts can be solidified well by impregnation with 10 to 40% liquors and subsequent squeezing and drying.
  • Light fiber fleeces can also be consolidated by foam impregnation; To do this, foaming agents and foam stabilizers are added to the approximately 10 to 25% dispersion and foamed with air up to a liter weight of 100 to 300 g. The impregnation is expediently carried out on the horizontal foulard.
  • Very light non-woven fabrics can be partially solidified by printing with pastes that contain 20 to 40% binder and are adjusted to a viscosity of 4000 to 8000 mPa.s. Needle felts for high-quality floor and wall coverings are preferably splashed with thickened, possibly foamed liquors. Finally, nonwoven bonding is also possible by brushing.
  • the solidified fiber structures generally contain between 5 and 100%, based on the fiber weight, of binder.
  • the preferred binder content is between 10 and 30% by weight.
  • the fiber structures equipped according to the invention obtain their favorable application properties only by drying at dryer temperatures above 110 ° to about 200 °, preferably in the range between 120 and 160 ° C.
  • a crosslinking agent for example glyoxal, can be added to the dispersion.
  • thermally pre-consolidated polyester fleece with a weight per unit area of approx. 18 g per m2 is impregnated with the plastic dispersion diluted to approx. 25% dry matter, excess dispersion squeezed out with the padding so that a resin coating of approx. 15% is achieved.
  • the damp fleece is dried in the stenter at 140 ° C for 5 minutes.
  • the breaking resistance is determined according to DIN 53 857, Part 2 on dry fleece (F) and on wet fleece (F n ) after 1 hour of water storage in the middle of a tensile testing machine that corresponds to DIN 51 221.
  • a chromatography paper No. 1, Whatman
  • the breaking resistance is determined according to DIN 53 112, sheets 1 and 2.
  • Example 1 illustrates the invention using dispersion A.
  • Example 2 is a comparative test with comparative dispersion B which was not prepared according to the teaching of the invention.
  • Example 3 is a comparison test according to DE-OS 32 02 122.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Nonwoven Fabrics (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Materials For Medical Uses (AREA)

Description

Gebiet der ErfindungField of the Invention

Die Erfindung betrifft ein Verfahren zur Herstellung gebundener textiler Flächengebilde durch Aufbringen einer Acrylharzdispersion, die frei von Formaldehyd und von Formaldehyd abgebenden Substanzen ist. Die Erfindung betrifft weiterhin die nach dem Verfahren hergestellten textilen Flächengebilde.The invention relates to a method for producing bound textile fabrics by applying an acrylic resin dispersion which is free of formaldehyde and formaldehyde-releasing substances. The invention further relates to the textile fabrics produced by the method.

Zur Herstellung gebundener textiler Flächengebilde, die sich durch hohe Naßfestigkeit, sowie durch Wasser- und Waschlaugenbeständigkeit auszeichnen wurden bisher häufig wäßrige Acylharzdispersionen eingesetzt, deren Kunststoffanteil selbstvernetzende Amid-Methylolgruppen enthielten. Beim Trocknen des behandelten Flächengebildes konnten dabei geringe Mengen an Fomaldehyd freigesetzt werden, wogegen gesundheitliche Bedenken bestehen. Es werden daher Bindemittel für textile Flächengebilde gesucht, die eine für praktische Zwecke ausreichende Naßfestigkeit, Wasser- und Waschlaugenbeständigkeit ergeben, aber beim Erhitzen keinen Fomaldehyd abgeben.Aqueous acyl resin dispersions whose plastic content contained self-crosslinking amide methylol groups have hitherto been used frequently for the production of bound textile fabrics which are notable for high wet strength and for water and wash liquor resistance. When drying the treated fabric, small amounts of fomaldehyde could be released, whereas there are health concerns. We are therefore looking for binders for textile fabrics which provide sufficient wet strength, water and wash liquor resistance for practical purposes, but do not give off any formaldehyde when heated.

Stand der TechnikState of the art

Aus der DE-OS 32 02 122 ist es bekannt. zum Verfestigen von Fasergebilden formaldehyd- und acrylnitrilfreie Acrylharzdispersionen aufzubringen, deren Harzkomponente aus Acryl- oder Methacrylestern, einem geringen Anteil an Hydroxyalkylestern von ungesättigten Carbonsäuren und gegebenenfalls geringen Mengen Acryl- oder Methacrylsäure aufgebaut ist. Obwohl damit ausgerüstete textile Flächengebilde eine höhere Naßfestigkeit aufweisen als solche, deren Bindemittel nicht die erwähnte Hydroxyalkylester-Komponente enthält, läßt die Naßfestigkeit noch zu wünschen übrig. In der EP-A 19 169 sind als Bindemittel für Faservliese geeignete wäßrige Dispersionen beschrieben, die als Bindemittel ein Mischpolymerisat aus Acryl- oder Methacrylestern oder anderen Monomeren und 3 - 10 Gew.-% Einheiten der Acrylamidoglykolsäure enthalten. Es handelt sich demnach um Bindemittel, die beim Erhitzen keinen Formaldehyd abspalten. Da jedoch mit diesen Bindemitteln die erwünschte Naßfestigkeit der damit ausgerüsteten textilen Flächengebilde nicht erreicht wird, werden in die Mischpolymerisate kleine Anteile von N-Methylolacrylamid einpolymerisiert, wodurch die Naßfestigkeit der ausgerüsteten Fasergebilde erhöht wird. jedoch die Gefahr der Formaldehydfreisetzung erneut auftritt.It is known from DE-OS 32 02 122. to solidify To apply fibrous structures formaldehyde- and acrylonitrile-free acrylic resin dispersions, the resin component of which is composed of acrylic or methacrylic esters, a small proportion of hydroxyalkyl esters of unsaturated carboxylic acids and optionally small amounts of acrylic or methacrylic acid. Although textile fabrics equipped therewith have a higher wet strength than those whose binder does not contain the mentioned hydroxyalkyl ester component, the wet strength still leaves something to be desired. EP-A 19 169 describes aqueous dispersions which are suitable as binders for nonwoven fabrics and which contain, as binders, a copolymer of acrylic or methacrylic esters or other monomers and 3 to 10% by weight of units of acrylamidoglycolic acid. It is therefore a binder that does not release formaldehyde when heated. However, since the desired wet strength of the textile fabrics finished with them is not achieved with these binders, small proportions of N-methylolacrylamide are polymerized into the copolymers, thereby increasing the wet strength of the finished fiber structures. however, the risk of formaldehyde release occurs again.

In der EP-A 96 230 sind Überzugsmittel beschrieben, die als selbstvernetzende Bindemittel Mischpolymerisate von Acrylmonomeren und ein Vernetzungssystem aus Acrylamido-glykolsäuremethylester-methyläther und hydroxy-, carboxy- oder amidofunktionellen Comonomeren enthalten. Beim Erhitzen treten Kondensationsreaktionen der Monomereinheiten, des genannten Vernetzersystems ein. Es ist nicht bekannt, derartige Mischpolymerisate als Bindemittel für textile Flächengebilde einzusetzen.EP-A 96 230 describes coating compositions which contain, as self-crosslinking binders, copolymers of acrylic monomers and a crosslinking system composed of methyl acrylamido-glycolic acid methyl ether and hydroxyl, carboxy or amido-functional comonomers. When heated, condensation reactions of the monomer units, the crosslinker system mentioned, occur. It is not known to use such copolymers as binders for textile fabrics.

Aufgabe und LösungTask and solution

Der Erfindung liegt die Aufgabe zugrunde, gebundene textile Flächengebilde mit verbesserter Naßfestigkeit herzustellen, aus deren Bindemittel beim Erhitzen kein Formaldehyd freigesetzt wird.The invention has for its object to produce bonded fabrics with improved wet strength, from whose binder no formaldehyde is released when heated.

Die gestellte Aufgabe wird gelöst durch einThe task is solved by a

Verfahren zur Herstellung gebundender textiler Flächengebilde durch Aufbringen eines Bindemittels, enthaltend eine wäßrige Dispersion eines Mischpolymerisats aus

80 - 99 Gew.-%
Acryl- und/oder Methacrylsäurealkylestern mit 1 bis 8 C-Atomen im Alkylrest oder deren Gemisch mit Styrol,
1 - 10 Gew.-%
eines Acrylamidoglykolsäure-Monomeren
0 - 20 Gew.-%
weiteren Comonomeren,
das dadurch gekennzeichnet ist,
daß als Bindemittel eine Dispersion eines Mischpolymerisats eingesetzt wird, dessen Acrylamidoglykolsäure-Einheiten sich von Monomeren der Formel I
Figure imgb0001
ableiten, worin R ein Wasserstoffatom oder eine Methylgruppe, R' ein Alkylrest und R'' ein Wasserstoffatom oder ein Alkylrest sind.Process for the production of bonded textile fabrics by applying a binder containing an aqueous dispersion of a copolymer
80-99% by weight
Acrylic and / or methacrylic acid alkyl esters with 1 to 8 carbon atoms in the alkyl radical or their mixture with styrene,
1 - 10% by weight
of an acrylamidoglycolic acid monomer
0 - 20% by weight
other comonomers,
which is characterized by
that a dispersion of a copolymer whose acrylamidoglycolic acid units are different from monomers of the formula I is used as the binder
Figure imgb0001
derive, wherein R is a hydrogen atom or a methyl group, R 'is an alkyl radical and R''is a hydrogen atom or an alkyl radical.

Anwendungapplication

Die gemäß der Erfindung hergestellten gebundenen textilen Flächengebilde zeichnen sich gegenüber denen mit herkömmlichen formaldehydfreien Bindemitteln durch eine deutlich erhöhte Naßfestigkeit aus. Dies hat Bedeutung in den Fällen, in denen das gebundene textile Flächengebilde bei der Herstellung, der Weiterverarbeitung oder beim Gebrauch im nassen Zustand einer mechanischen Beanspruchung ausgesetzt ist. Ein typischer Anwendungsfall ist die Herstellung von gebundenen Faservliesen auf Basis von Synthesefasern, insbesondere Polyesterfasern, die zur Herstellung von sogenannten Wegwerfwindeln gebraucht werden. Hier bilden die gebundenen Faservliese die äußere Hülle der Windel, welche einen stark saugfähigen Füllstoff umhüllt. Durch die geringe Wasseraufnahme der Synthesefasern wirkt die äußere Hülle auch dann noch verhältnismäßig trocken, wenn die umhüllte Einlage erhebliche Mengen an Flüssigkeit aufgenommen hat. Es ist jedoch von wesentlicher Bedeutung, daß die äußere Hülle unter mechanischer Belastung nicht reißt und die Flüssigkeits-gesättigte Einlage freilegt.The bonded fabrics made according to the invention are distinguished from those with conventional formaldehyde-free binders by a significantly increased wet strength. This is important in cases where the bound textile fabric is exposed to mechanical stress during manufacture, further processing or when used in the wet state. A typical application is the production of bonded nonwovens based on synthetic fibers, in particular polyester fibers, which are used for the production of so-called disposable diapers. Here, the bonded non-woven fabrics form the outer cover of the diaper, which envelops a highly absorbent filler. Due to the low water absorption of the synthetic fibers, the outer shell still appears relatively dry when the coated insert has absorbed considerable amounts of liquid. However, it is essential that the outer casing does not tear under mechanical stress and exposes the liquid-saturated insert.

Ausführung der ErfindungImplementation of the invention

Die erhöhte Naßfestigkeit der im Sinne der Erfindung gebundenen textilen Flächengebilde beruht auf den Einheiten eines Acrylamidoglykolsäure-Monomeren der Formel

Figure imgb0002

als Bestandteil des in der wäßrigen Dispersion enthaltenen Mischpolymerisats. R, R' und R'' haben die im Anspruch 1 angegebene Bedeutung. Vorzugsweise ist R'' eine Alkylgruppe. R' und R'' können gleiche Alkylreste, insbesondere Methylgruppen sein. Es kommen jedoch auch andere Alkylreste mit vorzugsweise nicht mehr als 8 C-Atomen in Betracht, insbesondere niedere Alkylreste mit bis zu 4 C-Atomen.The increased wet strength of the textile fabrics bound in the sense of the invention is based on the units of an acrylamidoglycolic acid monomer of the formula
Figure imgb0002
as a component of the copolymer contained in the aqueous dispersion. R, R 'and R''have the meaning given in claim 1. Preferably R "is an alkyl group. R 'and R''can be the same alkyl radicals, especially methyl groups. However, other alkyl radicals with preferably no more than 8 carbon atoms are also suitable, in particular lower alkyl radicals with up to 4 carbon atoms.

Die den Hauptteil des Mischpolymerisats bildenden Acryl- oder Methacrylsäurealkylester oder deren Gemisch mit Styrol werden in an sich bekannter Weise so gewählt, daß die dynamische Einfriertemperatur T1max nicht über 60°, vorzugsweise nicht über 20°C liegt. In typischen Fällen besteht das Mischpolymerisat zu 30 bis 60 Gew.-% aus Monomereinheiten, die harte Homopolymerisate ergeben, wie Methyl, Äthyl, Propyl, Isopropyl-Methacrylat oder Styrol, und etwa 20 bis 70 % Acrylsäureestern von C₁₋₈-Alkanolen oder Methacrylsäureestern von C₄₋₈-Alkanolen.The acrylic or methacrylic acid alkyl esters forming the main part of the copolymer, or their mixture with styrene, are selected in a manner known per se so that the dynamic freezing temperature T 1max is not more than 60 °, preferably not more than 20 ° C. In typical cases, the copolymer consists of 30 to 60 wt .-% of monomer units that give hard homopolymers, such as methyl, ethyl, propyl, isopropyl methacrylate or styrene, and about 20 to 70% acrylic acid esters of C₁₋₈ alkanols or methacrylic acid esters of C₄₋₈ alkanols.

Als weitere Monomerbestandteile kommen ungesättigte Carbonsäuren wie Acryl- oder Methacrylsäure in Betracht, die in Mengen von etwa 1 Gew.-% die Stabilität der Dispersion verbessern. Auch vernetzende Comonomere, wie Glykoldimethacrylat, Allylmethacrylat, Methylen-bis-methacrylamid oder Butandioldiacrylat können in geringen Mengen die Festigkeitseigenschaften des Bindemittels verbessern. Zu hohe Anteile an Vernetzungsmitteln würden allerdings den Filmbildungsvorgang stören und sind daher zu vermeiden. Weiterhin gehören zu den mitverwendbaren Comonomeren Acryl- und Methacrylnitril, Vinylacetat, Vinylchlorid, Vinylidenchlorid u.a. Hydroxyester und Amide der Acryl- oder Methacrylsäure sind in der Regel in den Mischpolymerisaten nicht enthalten.Unsaturated carboxylic acids such as acrylic or methacrylic acid are suitable as further monomer components Amounts of about 1% by weight improve the stability of the dispersion. Crosslinking comonomers, such as glycol dimethacrylate, allyl methacrylate, methylene-bis-methacrylamide or butanediol diacrylate, can also improve the strength properties of the binder in small amounts. Too high a proportion of crosslinking agents would interfere with the film formation process and should therefore be avoided. The comonomers which can also be used also include acrylonitrile and methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride and others. Hydroxyesters and amides of acrylic or methacrylic acid are generally not present in the copolymers.

Die Acrylharzdispersionen können nach allen gebräuchlichen Verfahren der Emulsionspolymerisation hergestellt werden. Sie können anionische, kationische oder nicht-ionische Emulgiermittel oder verträgliche Gemische davon enthalten. Sie werden zweckmäßig mit Feststoffgehalten von 50 bis 70 Gew.-% hergestellt.The acrylic resin dispersions can be prepared by all common methods of emulsion polymerization. They can contain anionic, cationic or non-ionic emulsifiers or compatible mixtures thereof. They are expediently produced with solids contents of 50 to 70% by weight.

Das Verfahren der Erfindung eignet sich zum Binden und Verfestigen von textilen Flächengebilden aller Art; dazu gehören Gewebe, Gewirke, Watten und insbesondere nicht gewebte Faservliese. Die Erfindung ist nicht auf bestimmte Faserarten beschränkt, jedoch werden Synthesefasern oder synthesefaserhaltige Fasergemische grundsätzlich bevorzugt. Diese Gemische können z.B. 70 % oder mehr an Synthesefasern enthalten. Zu den in Betracht kommenden Synthesefasern zählen einerseits Fasern aus regenerierter Cellulose, wie Rayon oder Zellwolle, und insbesondere vollsynthetische Fasern, wie Polyester- oder Polypropylenfasern. Bevorzugte textile Flächengebilde sind aus 70 bis 100 Gew.-% Polyesterfasern und 0 bis 30 Gew.-% Zellwolle aufgebaut.The method of the invention is suitable for binding and solidifying textile fabrics of all kinds; these include woven fabrics, knitted fabrics, wadding and in particular non-woven nonwovens. The invention is not restricted to certain types of fibers, but synthetic fibers or fiber mixtures containing synthetic fibers are fundamentally preferred. These mixtures can contain, for example, 70% or more of synthetic fibers. The synthetic fibers considered include fibers made from regenerated cellulose, such as rayon or rayon, and in particular fully synthetic fibers, such as polyester or polypropylene fibers. Preferred textile fabrics are constructed from 70 to 100% by weight of polyester fibers and 0 to 30% by weight of cellulose.

Verfestigung von FasergebildenSolidification of fiber structures

Die Konfektionierung der Dispersion zum Verfestigen von Fasergebilden richtet sich nach dem Auftragsverfahren und den Anforderungen, die an das Endprodukt gestellt werden. Die bei diesen Verfahren gebräuchlichen Zusätze. wie Netzmittel. Schaumdämpfungsmittel, Thermosensibilisierungsmittel. Weichmachungs- und Glättmittel. Antistatika. Antimikrobiotika. Farbstoffe, Füllstoffe, Flammschutzmittel, Duftstoffe usw., können mitverwendet werden. Im allgemeinen werden die Dispersionen mit Wasser auf einen Bindemittelgehalt von 10 bis 40 Gewichtsprozent verdünnt. Die Viskosität der verdünnten Dispersion kann im Bereich von 10 bis 10.000 mPa.s liegen. Zum Verfestigen von Watten, beispielsweise aus Polyester-, Polyamid- oder Polyacrylnitrilfasern, wird eine etwa 15 bis 25 %ige Flotte aufgesprüht. Kompakte Faservliese und Nadelfilze lassen sich gut durch Imprägnieren mit 10- bis 40 %igen Flotten und anschließendes Abquetschen und Trocknen verfestigen. Leichte Faservliese können auch durch Schaumimprägnierung verfestigt werden; dazu setzt man der etwa 10- bis 25 %igen Dispersion Schäummittel und Schaumstabilisatoren zu und schäumt mit Luft bis zu einem Litergewicht von 100 bis 300 g auf. Die Imprägnierung wird zweckmäßig am Horizontalfoulard vorgenommen. Sehr leichte Faservliese können durch Bedrucken mit Pasten, die 20 bis 40 % Binder enthalten und auf eine Viskosität von 4000 bis 8000 mPa.s eingestellt sind, partiell verfestigt werden. Nadelfilze für hochwertige Boden- und Wandbeläge werden bevorzugt mit angedickten, gegebenenfalls geschäumten Flotten gepflatscht. Schließlich ist auch die Vliesverfestigung durch Streichen möglich.The preparation of the dispersion for the consolidation of fiber structures depends on the application process and the requirements placed on the end product. The additives used in these processes. like wetting agents. Anti-foaming agents, thermosensitizers. Plasticizers and smoothing agents. Antistatic. Antimicrobials. Dyes, fillers, flame retardants, fragrances, etc. can also be used. In general, the dispersions are diluted with water to a binder content of 10 to 40 percent by weight. The viscosity of the diluted dispersion can range from 10 to 10,000 mPa.s. For the consolidation of wadding, for example made of polyester, polyamide or polyacrylonitrile fibers, an approximately 15 to 25% liquor is sprayed on. Compact nonwovens and needle felts can be solidified well by impregnation with 10 to 40% liquors and subsequent squeezing and drying. Light fiber fleeces can also be consolidated by foam impregnation; To do this, foaming agents and foam stabilizers are added to the approximately 10 to 25% dispersion and foamed with air up to a liter weight of 100 to 300 g. The impregnation is expediently carried out on the horizontal foulard. Very light non-woven fabrics can be partially solidified by printing with pastes that contain 20 to 40% binder and are adjusted to a viscosity of 4000 to 8000 mPa.s. Needle felts for high-quality floor and wall coverings are preferably splashed with thickened, possibly foamed liquors. Finally, nonwoven bonding is also possible by brushing.

Die verfestigten Fasergebilde enthalten im allgemeinen zwischen 5 und 100 %, bezogen auf das Fasergewicht, an Bindemittel. Der bevorzugte Bindergehalt liegt zwischen 10 und 30 Gew-%. Ihre günstigen anwendungstechnischen Eigenschaften erhalten die erfindungsgemäß ausgerüsteten Fasergebilde erst durch die Trocknung bei Trocknertemperaturen über 110° bis zu etwa 200°, vorzugsweise im Bereich zwischen 120 und 160°C.The solidified fiber structures generally contain between 5 and 100%, based on the fiber weight, of binder. The preferred binder content is between 10 and 30% by weight. The fiber structures equipped according to the invention obtain their favorable application properties only by drying at dryer temperatures above 110 ° to about 200 °, preferably in the range between 120 and 160 ° C.

Wird zusätzlich Beständigkeit des verfestigten Fasergebildes gegen organische Lösemittel gefordert, so kann man der Dispersion ein Vernetzungsmittel, beispielsweise Glyoxal, zusetzen.If additional resistance of the solidified fiber structure to organic solvents is required, a crosslinking agent, for example glyoxal, can be added to the dispersion.

BeispieleExamples Herstellung einer erfindungsgemäß einsetzbaren Dispersion APreparation of a dispersion A which can be used according to the invention

In einem mit Rührer, Thermometer und Rückflußkühler ausgerüsteten Reaktionsgefäß werden 40 Gew.-Teile vollentsalztes Wasser auf 80°C erhitzt und mit 0,02 Gew.-Teilen des Natriumsalzes eines sulfatierten Additionsproduktes aus Triisobutylphenol und 7 Mol Ethylenoxid sowie 0,04 Gew.-Teilen Ammoniumperoxodisulfat versetzt. Hierzu dosiert man innerhalb von 4 Stunden eine Emulsion aus 57 Gew.-Teilen n-Butylacrylat, 39,5 Gew.-Teilen Methylmethacrylat. 3-5 Gew.-Teilen Acrylamidomethylglykolat-methylether, 61,5 Gew -Teilen vollentsalztem Wasser, 1,5 Gew.-Teilen des Natriumsalzes eines sulfatierten Additionsproduktes aus Triisobutylphenol und 7 Mol Ethylenoxid sowie 0,25 Gew.-Teilen Ammoniumperoxodisulfat. Zur Nachpolymerisation hält man den Ansatz noch 2 Stunden bei 80°C. Es wird eine stabile, koagulatfreie Dispersion mit einem Feststoffgehalt von ca. 50 % erhalten.In a reaction vessel equipped with a stirrer, thermometer and reflux condenser, 40 parts by weight of fully demineralized water are heated to 80 ° C. and 0.02 part by weight of the sodium salt of a sulfated addition product of triisobutylphenol and 7 moles of ethylene oxide and 0.04 part by weight. Parts of ammonium peroxodisulfate are added. For this purpose, an emulsion of 57 parts by weight of n-butyl acrylate and 39.5 parts by weight of methyl methacrylate is metered in within 4 hours. 3-5 parts by weight of acrylamidomethylglycolate methyl ether, 61.5 parts by weight of fully deionized water, 1.5 parts by weight of the sodium salt of a sulfated addition product of triisobutylphenol and 7 moles of ethylene oxide and 0.25 part by weight of ammonium peroxodisulfate. For postpolymerization, the batch is kept at 80 ° C. for 2 hours. A stable, coagulate-free dispersion with a solids content of approx. 50% is obtained.

Herstellung einer Vergleichsdispersion B ohne Acrylamidoglykolsäure-MonomereinheitenPreparation of a comparison dispersion B without acrylamidoglycolic acid monomer units

In einem mit Rückflußkühler, Rührer und Thermometer ausgerüsteten Polymerisationsgefäß wird eine aus 44 Gew.-Teilen Methylmethacrylat, 56 Gew.-Teilen n-Butylacrylat, 61,5 Gew.-Teilen vollentsalztem Wasser, 1,5 Gew.-Teilen des Natriumsalzes eines sulfatierten Additionsproduktes aus Triisobutylphenol und 7 Mol Ethylenoxid sowie 0,25 Gew.-Teilen Ammoniumperoxodisulfat bestehende Emulsion im Verlauf von 4 Stunden einer auf 80°C erwärmten Lösung von 0,04 Gew.-Teilen Ammoniumperoxodisulfat und 0,02 Gew.-Teilen des oben genannten Emulgators in 40 Gew.-Teilen vollentsalztem Wasser unter Rühren zugegeben. Anschließend wird die Temperatur noch 2 weitere Stunden auf 80°C gehalten. Man erhält eine stabile koagulatfreie Dispersion von ca. 50 % Feststoffgehalt.In a polymerization vessel equipped with a reflux condenser, stirrer and thermometer, one of 44 parts by weight of methyl methacrylate, 56 parts by weight of n-butyl acrylate, 61.5 parts by weight of completely deionized water, 1.5 parts by weight of the sodium salt of a sulfated Addition product consisting of triisobutylphenol and 7 moles of ethylene oxide and 0.25 part by weight of ammonium peroxodisulfate in the course of 4 hours of a solution of 0.04 part by weight of ammonium peroxodisulfate heated to 80 ° C. and 0.02 part by weight of the above-mentioned emulsifier in 40 parts by weight of deionized water were added with stirring. The temperature is then kept at 80 ° C. for a further 2 hours. A stable coagulate-free dispersion of approximately 50% solids content is obtained.

Verfestigung von Fasergebilden und anwendungstechnische PrüfungStrengthening of fiber structures and application testing

Zur Bestimmung des Bruchwiderstandes wird thermisch vorverfestigtes Polyestervlies mit einem Flächengewicht von ca. 18 g pro m² mit der auf ca. 25 % Trockensubstanz verdünnten Kunststoffdispersion imprägniert, überschüssige Dispersion mit dem Foulard so abgequetscht, daß eine Harzauflage von ca. 15 % erreicht wird. Das feuchte Vlies wird im Spannrahmen 5 Minuten bei 140°C getrocknet. Der Bruchwiderstand wird nach DIN 53 857, Teil 2 am trockenen Vlies (F) und am nassen Vlies (Fn) nach einer 1-stündigen Wasserlagerung mitten einer Zugprüfmaschine, die der DIN 51 221 entspricht, bestimmt.
Um die vorteilhafte Anwendbarkeit der erfindungsgemäßen Bindemittel auch auf hydrophilen Fasergebilden zu demonstrieren, wird ein Chromatographiepapier (Nr.1, Whatman) auf die gleiche Weise, wie oben für das Polyestervlies angegeben, imprägniert. Die Harzauflage beträgt ca. 30 %. Der Bruchwiderstand wird nach DIN 53 112, Blatt 1 und 2 bestimmt.To determine the breaking resistance, thermally pre-consolidated polyester fleece with a weight per unit area of approx. 18 g per m² is impregnated with the plastic dispersion diluted to approx. 25% dry matter, excess dispersion squeezed out with the padding so that a resin coating of approx. 15% is achieved. The damp fleece is dried in the stenter at 140 ° C for 5 minutes. The breaking resistance is determined according to DIN 53 857, Part 2 on dry fleece (F) and on wet fleece (F n ) after 1 hour of water storage in the middle of a tensile testing machine that corresponds to DIN 51 221.
In order to demonstrate the advantageous applicability of the binders according to the invention also on hydrophilic fiber structures, a chromatography paper (No. 1, Whatman) is impregnated in the same way as indicated above for the polyester fleece. The resin layer is approx. 30%. The breaking resistance is determined according to DIN 53 112, sheets 1 and 2.

Die Ergebnisse der anwendungstechnischen Prüfung sind in der folgenden Tabelle zusammengestellt. Die Werte stellen Mittelwerte aus 12 Einzelbestimmungen dar.The results of the application test are summarized in the following table. The values represent mean values from 12 individual determinations.

Beispiel 1 erläutert die Erfindung unter Verwendung der Dispersion A.Example 1 illustrates the invention using dispersion A.

Beispiel 2 ist ein Vergleichsversuch mit der Vergleichsdispersion B, die nicht nach der Lehre der Erfindung hergestellt wurde.
Beispiel 3 ist ein Vergleichsversuch gemäß der DE-OS 32 02 122.

Figure imgb0003
Example 2 is a comparative test with comparative dispersion B which was not prepared according to the teaching of the invention.
Example 3 is a comparison test according to DE-OS 32 02 122.
Figure imgb0003

Claims (11)

  1. Process for producing bonded flat textile structures by applying a binder, containing an aqueous dispersion of a copolymer of
       80-99 wt.-% of alkyl acrylates and/or methacrylates having 1 to 8 C atoms in the alkyl moiety or a mixture thereof with styrene,
       1-10 wt.-% of an acrylamidoglycolic acid monomer,
       0-20 wt.-% of other comonomers,
       characterised in that the binder used is a dispersion of a copolymer the acrylamidoglycolic acid units of which are derived from monomers of formula I
    Figure imgb0005
     wherein R is a hydrogen atom or a methyl group, R' is an alkyl group and R'' is a hydrogen atom or an alkyl group.
  2. Process according to claim 1, characterised in that a fibre fleece is used as the flat textile structure.
  3. Process according to claim 2, characterised in that a fibre fleece made up entirely or predominantly of synthetic fibres is used.
  4. Process according to claim 3, characterised in that a fibre fleece is used, the synthetic fibre content of which consists at least partly of polyester fibres.
  5. Process according to one or more of claims 1 to 4, characterised in that, in the acrylamidoglycolic acid units of formula I, R'' is an alkyl group.
  6. Bonded flat textile structure containing as binder a copolymer of
       80-99 wt.-% of alkyl acrylates and/or methacrylates having 1 to 8 C atoms in the alkyl moiety or a mixture thereof with styrene,
       1-10 wt.-% of acrylamidoglycolic acid monomer of formula I,
       0-20 wt.-% of other comonomers.
  7. Bonded fibre fleece according to claim 6, characterised in that, in the acrylamidoglycolic acid units of formula I, R'' is an alkyl group.
  8. Bonded flat textile structure according to claim 6 or 7, characterised in that it is a bonded, non-woven fibre fleece.
  9. Bonded fibre fleece according to claim 8, characterised in that the fibre content consists wholly or predominantly of synthetic fibres.
  10. Bonded fibre fleece according to claim 9, characterised in that the synthetic fibres consist wholly or predominantly of polyester fibres.
  11. Bonded fibre fleece according to claim 9 or 10, characterised in that it contains 10 to 40 wt.-% of the binder.
EP86102172A 1985-02-28 1986-02-19 Bonded textile fabric and method for its production Expired - Lifetime EP0193107B1 (en)

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DE19853507154 DE3507154A1 (en) 1985-02-28 1985-02-28 TIED TEXTILE AREA AND METHOD FOR THE PRODUCTION THEREOF
DE3507154 1985-02-28

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DE3734752A1 (en) * 1987-10-14 1989-05-03 Basf Ag METHOD FOR THE PRODUCTION OF AQUEOUS (METH) ACRYLIC ACID ESTER COPOLYMER DISPERSIONS IN TWO STAGES AND THE USE THEREOF AS IMPREGNANT, COATING AND BINDING AGENT FOR FLAT FIBER FABRICS
US5369204A (en) * 1991-11-01 1994-11-29 Cytec Technology Corp. Low molecular weight acrylamidoglycolate crosslinker and process
US5486210A (en) 1992-01-30 1996-01-23 Reeves Brothers, Inc. Air bag fabric containing graft polymer thereon
US5407728A (en) * 1992-01-30 1995-04-18 Reeves Brothers, Inc. Fabric containing graft polymer thereon
JPH08510796A (en) * 1993-06-02 1996-11-12 ミネソタ マイニング アンド マニュファクチャリング カンパニー Non-woven fabric product and manufacturing method thereof
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CA1135712A (en) * 1979-05-29 1982-11-16 Peter J. Schirmann Activated ester monomers and polymers
DE3202122A1 (en) * 1982-01-23 1983-07-28 Röhm GmbH, 6100 Darmstadt METHOD FOR STRENGTHENING FIBERBUILDINGS BY MEANS OF AQUEOUS PLASTIC DISPERSIONS
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