EP0084810B1 - Verfahren zum Verfestigen von Fasergebilden mittels wässriger Kunststoffdispersionen - Google Patents

Verfahren zum Verfestigen von Fasergebilden mittels wässriger Kunststoffdispersionen Download PDF

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Publication number
EP0084810B1
EP0084810B1 EP83100224A EP83100224A EP0084810B1 EP 0084810 B1 EP0084810 B1 EP 0084810B1 EP 83100224 A EP83100224 A EP 83100224A EP 83100224 A EP83100224 A EP 83100224A EP 0084810 B1 EP0084810 B1 EP 0084810B1
Authority
EP
European Patent Office
Prior art keywords
acrylic
weight
methacrylic acid
optionally
fibre structure
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.)
Expired
Application number
EP83100224A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0084810A2 (de
EP0084810A3 (en
Inventor
Herbert Paul Dr. Dipl.-Chem. Fink
Heiner Kniese
Norbert Dr. Dipl.-Chem Sütterlin
Klaus Müller
Willi Tilch
Werner Dr. Dipl.-Chem. Siol
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP0084810A2 publication Critical patent/EP0084810A2/de
Publication of EP0084810A3 publication Critical patent/EP0084810A3/de
Application granted granted Critical
Publication of EP0084810B1 publication Critical patent/EP0084810B1/de
Expired legal-status Critical Current

Links

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
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • 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
    • Y10T442/2344—Coating or impregnation is anti-slip or friction-increasing other than specified as an abrasive
    • 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

Definitions

  • the invention relates to the solidification of fiber structures by applying aqueous acrylic resin dispersions which are free of formaldehyde and acrylonitrile and formaldehyde-releasing substances.
  • the invention further relates to the fiber structures solidified with these dispersions.
  • Aqueous acrylic resin dispersions whose plastic content contained self-crosslinking amide methylol groups and optionally nitrile groups have hitherto been used to solidify fiber structures which are notable for wet strength, water and wash liquor resistance and low water absorption. When the treated fiber material was dried, small amounts of formaldehyde or acrylonitrile could be released, whereas health concerns have recently arisen. We are therefore looking for ways to solidify fiber structures with acrylic resin dispersions that do not give off acrylonitrile or formaldehyde when heated, but that achieve comparable performance properties as the previously used dispersions.
  • Solidified fiber structures are described in EP-A-12 032 and 12 033, for the production of which formaldehyde-free and acrylonitrile-free acrylic resin dispersions have been used.
  • the fiber structure is practice mainly composed of hydrophilic fibers, especially cellulosic fibers, an acrylic resin dispersion is used, the plastic fraction mainly consisting of C 4 - C s alkyl esters of acrylic or methacrylic acid, from methyl methacrylate or styrene and from 0.5 - 10% is built up from an unsaturated dicarboxylic acid or a mixture thereof with an unsaturated monocarboxylic acid.
  • amides or hydroxyalkyl esters of acrylic or methacrylic acid can be present in proportions of up to 10% by weight in the structure of the plastics component, but these comonomers are not believed to have any influence on the performance properties of the dispersion.
  • very similar dispersions are proposed, in whose structure unsaturated monocarboxylic acids can also be involved as a component containing carboxyl groups.
  • the minimum content of unsaturated carboxylic acids is 1% by weight, but 2-4% by weight is preferred.
  • the wash resistance of the fiber structures finished with these dispersions is unsatisfactory. This may be due to the content of acid groups, but these groups are essential in order to achieve a satisfactory wet adhesion or wet strength in the absence of crosslinking comonomers, such as n-methylolacrylamide.
  • fiber structures made from hydrophilic or hydrophobic fibers or from mixtures of such fibers can be solidified. Preference is given to the consolidation of fiber structures composed predominantly of hydrophobic fibers.
  • the most important types of fibers include polyester, polyamide and polypropylene. Polyester fibers are preferred.
  • the hydrophilic fibers include, above all, native or regenerated cellulosic fibers such as cotton, rayon and rayon.
  • An interesting field of application of the invention is the consolidation of mineral fiber structures.
  • nonwovens occupy the most important position.
  • the solidification according to the invention gives you the strength required for the application.
  • the focus is on improving the sliding resistance or knot strength.
  • the fiber structures solidified according to the invention are notable for a particularly low loss of strength in the wet state compared to the dry state.
  • the level of dry strength values can be adjusted in a known manner by controlling the film hardness according to the requirements. The aim of maintaining this level of strength largely in the wet state is achieved by the invention in a satisfactory manner.
  • the acrylic resins In order for them to be sufficiently wash-resistant even without crosslinking, the acrylic resins must be relatively hydrophobic. For this reason, they contain as component A at least 40% by weight of units of alkyl esters of acrylic or / and methacrylic acid with at least 4 carbon atoms in the alkyl radical. Alkyl radicals with 4 to 8 carbon atoms are preferred. The n-butyl esters are particularly preferred. The proportion of this hydrophobic ester component is preferably 500 to 80% by weight of the acrylic resin.
  • the acrylic resin can be soft and self-adhesive to hard and non-tacky. These properties are determined in a manner known per se by coordinating the quantitative ratio between hardening and softening monomer components. Since the hydrophobizing higher alkyl esters of component A are at the same time mostly plasticizing, alkyl esters of acrylic and / or methacrylic acid with at most 3 C atoms in the alkyl radical and / or styrene can be involved in the formation of the acrylic resins in order to set a greater hardness than component B. The hardness of the acrylic resin can also be increased by increasing the proportion of methacrylic acid esters in component A at the expense of the proportion of acrylic acid esters.
  • acrylic resin contains carboxyl groups. Because of the improved stability of the aqueous dispersion, however, it may be advantageous if acrylic or methacrylic acid is involved in the amount of at least 0.1% by weight of acrylic resin as component C. If the proportion of acrylic or methacrylic acid is increased above 1%, the resistance to washing of the solidified fiber structures decreases considerably. The proportion of these acids should therefore be less than 1%, preferably not more than 0.5% by weight.
  • Hydroxyalkyl esters of ⁇ , ⁇ -unsaturated polymerizable mono- or dicarboxylic acids form an essential component (D) of the emulsion polymer.
  • the hydroxyalkyl esters are preferably derived from acrylic or methacrylic acid, in particular from the former. As a rule, they contain a hydroxyl group which is bonded to an alkyl radical with 2-4 C atoms. Hydroxyethyl acrylate and methacrylate, 2-hydroxypropyl acrylate and methacrylate and 4-hydroxybutyl acrylate and methacrylate are preferred.
  • the acrylic resin preferably contains 4 or more% by weight of units of these hydroxyalkyl esters. Shares above 10% by weight generally no longer have any advantages, so that this limit is preferably not exceeded.
  • monoethylenically unsaturated comonomers other than components A to D can optionally be involved in the construction of the acrylic resin.
  • Polyunsaturated, crosslinking monomers should not be involved.
  • Such monomers, such as. B. ethylene glycol dimethacrylate, are occasionally contained in the hydroxyalkyl esters to be used as component D as an impurity.
  • the content of such polyunsaturated monomers should not exceed 0.1% by weight of the acrylic resin.
  • Acrylonitrile and methacrylonitrile are also preferably not involved in the build-up of the acrylic resins because residues of these monomers remain in the aqueous phase and could be released when the finished fiber structure dries.
  • Examples of comonomers which can be involved in the construction of the acrylic resins as component E are vinyl esters, in particular vinyl acetate, vinyl chloride, vinylidene chloride, N-vinylpyrrolidone, and butadiene, ethylene or propylene. Their proportion is usually less than 20% by weight. If amides of acrylic or methacrylic acid are involved in the structure of the polymer, their proportion in the polymer should be less than 4% by weight.
  • 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 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 such as wetting agents, foam suppressants, thermal sensitizers, plasticizers and smoothing agents, antistatic agents, antimicrobiotics, dyes, fillers, flame retardants, fragrances, etc., can also be used.
  • the dispersions are diluted with water to a binder content of 10 to 40% by weight.
  • the viscosity of the diluted dispersion can range from 10 to 10,000 mPa.s.
  • An approximately 15 to 25% liquor is sprayed on to consolidate wadding, for example made of polyester, polyamide or polyacrylonitrile fibers.
  • Compact nonwovens and needle felts can be easily consolidated 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.
  • Polyester fabric freed of any existing conditions (sizing, finishing agents), impregnated with the approx. 50% plastic dispersion, squeezed off excess dispersion by means of a pad to a liquor absorption of 80-100%.
  • the fabric strip is dried in a forced-air drying cabinet at 80 ° C. for 5 minutes, after cooling the resin layer is determined.
  • the 18 X 18 cm specimen is then washed in 125 ml of a solution containing 3 g of Marseille soap and 2 g of calcined soda per liter for 10 minutes at 40 ° C. in a laboratory washing machine (Linitest ® device). After rinsing in hot and then in cold water, drying is carried out at 90 ° C. for 30 minutes, and the resin coating is determined again after cooling.
  • the binder cooking wash loss (BKV) is given in the table in part C as a percentage of the resin coating.
  • thermally pre-consolidated polyester fleece with a weight per unit area of approx. 18 g per m 2 is impregnated with the plastic dispersion diluted to approx. 25% dry substance, 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 a 1-hour water storage using a tensile testing machine that corresponds to DIN 51 221. The results are shown in the table in part C.
  • Examples 9 to 12 are comparative experiments with dispersions which are not based on the teaching of the invention.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Nonwoven Fabrics (AREA)
  • Reinforced Plastic Materials (AREA)
EP83100224A 1982-01-23 1983-01-13 Verfahren zum Verfestigen von Fasergebilden mittels wässriger Kunststoffdispersionen Expired EP0084810B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19823202122 DE3202122A1 (de) 1982-01-23 1982-01-23 Verfahen zum verfestigen von fasergebilden mittels waessriger kunststoffdispersionen
DE3202122 1982-01-23

Publications (3)

Publication Number Publication Date
EP0084810A2 EP0084810A2 (de) 1983-08-03
EP0084810A3 EP0084810A3 (en) 1987-04-08
EP0084810B1 true EP0084810B1 (de) 1989-03-29

Family

ID=6153762

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83100224A Expired EP0084810B1 (de) 1982-01-23 1983-01-13 Verfahren zum Verfestigen von Fasergebilden mittels wässriger Kunststoffdispersionen

Country Status (5)

Country Link
US (1) US4476182A (fi)
EP (1) EP0084810B1 (fi)
JP (1) JPS58126374A (fi)
DE (2) DE3202122A1 (fi)
FI (1) FI71775C (fi)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4563289A (en) * 1984-04-10 1986-01-07 Polysar Limited Impregnation of non-woven webs
DE3507154A1 (de) * 1985-02-28 1986-08-28 Röhm GmbH, 6100 Darmstadt Gebundenes textiles flaechengebilde und verfahren zu seiner herstellung
DE3541187C2 (de) * 1985-11-21 1994-10-06 Kaemmerer Gmbh Verfahren zur Herstellung einer mit Kunstharzen imprägnierten Papierbahn sowie deren Verwendung
US4908176A (en) * 1986-03-20 1990-03-13 Mitsubishi Yuka Badische Co., Ltd. Process for producing moldable non-woven fabrics
IT1217321B (it) * 1987-06-30 1990-03-22 Fisi Fibre Sint Spa Procedimento perfezionato per la realizzazione di una imbottitura con caratteristiche di isolamento termico migliorate,particolarmente studiata per abbigliamento
US5030507A (en) * 1990-01-12 1991-07-09 National Starch And Chemical Investment Holding Corporation Formaldehyde-free nonwoven binder composition
JPH0413833U (fi) * 1990-05-23 1992-02-04
KR950700443A (ko) * 1992-01-30 1995-01-16 어거스 투스 아이. 듀폴 혼성중합물이 포함된 천(fabric containing graft polymer thereon)
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
US6645255B2 (en) 2001-04-04 2003-11-11 Healthtex Apparel Corp. Polymer-grafted stretchable cotton
US6638319B2 (en) 2001-04-04 2003-10-28 Healthtex Apparel Corp. Polymer for printed cotton
US6645256B2 (en) 2001-04-04 2003-11-11 Healthtex Apparel Corp. Polymer grafted cotton
CA2716523A1 (en) * 2008-02-29 2009-09-03 Dow Global Technologies Inc. Carpet backing compositions
DK3176187T4 (da) 2015-12-02 2022-10-03 Organik Kimya Sanayi Ve Tic A S Hærdbar polymersammensætning
US20190375867A1 (en) * 2018-06-06 2019-12-12 Organik Kimya Sanayi Ve Tic. A.S. Formaldehyde-free thermally curable polymers

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1965740C3 (de) * 1969-12-31 1979-11-22 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von pulverisierbaren Acryl-Harzen
JPS5143119B2 (fi) * 1973-03-29 1976-11-19
JPS5131880B2 (fi) * 1973-07-18 1976-09-09
JPS5310796A (en) * 1976-07-16 1978-01-31 Mitsubishi Gas Chemical Co Bundling and coupling agent for glass fiber
DE2749386A1 (de) * 1977-11-04 1979-05-10 Roehm Gmbh Dispersionen hydrophiler acrylharze
DE2833601A1 (de) * 1978-07-31 1980-02-28 Roehm Gmbh Kunststoffpulver fuer beschichtungsmittel zur herstellung glaenzender, nicht- blockender, elastischer ueberzuege
CA1144294A (en) * 1978-12-04 1983-04-05 Walter G. De Witt, Iii Bonded nonwoven fabrics suitable for diaper coverstock
CA1132856A (en) * 1978-12-04 1982-10-05 Jerome F. Levy Non-woven fabrics

Also Published As

Publication number Publication date
DE3379511D1 (en) 1989-05-03
FI71775C (fi) 1987-02-09
JPS58126374A (ja) 1983-07-27
JPH0372743B2 (fi) 1991-11-19
FI71775B (fi) 1986-10-31
US4476182A (en) 1984-10-09
EP0084810A2 (de) 1983-08-03
DE3202122A1 (de) 1983-07-28
FI824482L (fi) 1983-07-24
FI824482A0 (fi) 1982-12-28
EP0084810A3 (en) 1987-04-08

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