EP0527411B1 - Liant aqueux pour matériau textile - Google Patents

Liant aqueux pour matériau textile Download PDF

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Publication number
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
Authority
EP
European Patent Office
Prior art keywords
binding agent
polymer
methacrylamide
aqueous
amount
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 - Lifetime
Application number
EP92113160A
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German (de)
English (en)
Other versions
EP0527411A1 (fr
Inventor
Herbert Dr. Fink
Thomas Dr. Süfke
Heiner Kniese
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
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Roehm GmbH Darmstadt
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Publication of EP0527411A1 publication Critical patent/EP0527411A1/fr
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Publication of EP0527411B1 publication Critical patent/EP0527411B1/fr
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Classifications

    • 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
    • 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)
  • Adhesives Or Adhesive Processes (AREA)
  • Nonwoven Fabrics (AREA)

Claims (10)

  1. Liant aqueux pour produits textiles en nappes, contenant
    A) une dispersion aqueuse d'un produit de polymérisation en émulsion, filmogène et auto-réticulant, et
    B) un polymère qui est dissous dans la phase aqueuse du liant et qui est constitué, pour 10 à 100% en poids, d'acrylamide et/ou de méthacrylamide,
    le rapport pondéral de A à B étant compris entre 95 : 5 et 70 : 30 et le liant ne contenant pas de résine aminoplaste,
    caractérisé en ce que le produit de polymérisation en émulsion A contient 1 à 15% en poids de motifs de N-méthylolacrylamide et/ou de N-methylolméthacrylamide.
  2. Liant aqueux selon la revendication 1, caractérise en ce que le polymère B dissous est constitué, pour 10% en poids au maximum, par du N-méthylolacrylamide et/ou du N-méthylolméthacrylamide.
  3. Liant aqueux selon la revendication 2, caractérisé en ce que le polymère B dissous est constitué pour 10 à 100% en poids par de l'acrylamide et/ou du méthacrylamide, pour 0 à 90% en poids par des monomères hydrosolubles à insaturation éthylénique, susceptibles de polymérisation radicalaire, et pour 30% en poids au maximum par des monomères non hydrosolubles à insaturation éthylénique, susceptibles de polymérisation radicalaire.
  4. Liant aqueux selon la revendication 3, caractérisé en ce que le polymère B dissous est constitué pour 50 à 95% en poids par de l'acrylamide et/ou du méthacrylamide, pour 5 à 50% en poids par des monomères hydrosolubles à insaturation éthylénique, susceptibles de polymérisation radicalaire, et pour 20% en poids au maximum par des monomères non hydrosolubles à insaturation éthylénique, susceptibles de polymérisation radicalaire.
  5. Liant aqueux selon l'une quelconque des revendications 1 a 4, caractérisé en ce que le polymère B dissous contient des motifs d'un ester hydroxyalkylique de l'acide acrylique et/ou méthacrylique.
  6. Liant aqueux selon l'une quelconque des revendications 1 à 5, caractérise en ce que le produit de polymérisation en émulsion A est constitué, pour 60 à 97% en poids, par des esters alkyliques de l'acide acrylique et/ou méthacrylique contenant 1 à 8 atomes de carbone dans le reste alkyle.
  7. Liant aqueux selon l'une quelconque des revendications 1 a 6, caractérisé en ce que le produit de polymérisation en émulsion A est constitué, pour 3 à 10% en poids, par des motifs de N-méthylolacrylamide et/ou de N-méthylolméthacrylamide et, pour 10% en poids au maximum, par des motifs d'acrylamide et/ou de méthacrylamide.
  8. Liant aqueux selon l'une quelconque des revendications 1 à 7, caractérise en ce qu'il a une teneur ne dépassant pas 5% en poids en formaldéhyde réactif sous forme libre et latente liée, par rapport au liant résineux pur.
  9. Utilisation du liant aqueux selon l'une quelconque des revendications 1 à 8 pour le fixage de produits textiles en nappes.
  10. Utilisation du liant aqueux selon la revendication 9, caractérisée en ce qu'un non-tissé de fibres de polyester est traité en tant que produit textile en nappe.
EP92113160A 1991-08-14 1992-08-01 Liant aqueux pour matériau textile Expired - Lifetime EP0527411B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE9110054U DE9110054U1 (de) 1991-08-14 1991-08-14 Wäßriges Bindemittel für textile Flächengebilde
DE9110054U 1991-08-14

Publications (2)

Publication Number Publication Date
EP0527411A1 EP0527411A1 (fr) 1993-02-17
EP0527411B1 true EP0527411B1 (fr) 1995-02-22

Family

ID=6870258

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92113160A Expired - Lifetime EP0527411B1 (fr) 1991-08-14 1992-08-01 Liant aqueux pour matériau textile

Country Status (3)

Country Link
EP (1) EP0527411B1 (fr)
AT (1) ATE118836T1 (fr)
DE (2) DE9110054U1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020042128A1 (fr) * 2018-08-31 2020-03-05 宿迁市神龙家纺有限公司 Adhésif d'impression aux pigments respectueux de l'environnement et son procédé de préparation

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19814873A1 (de) 1998-04-02 1999-10-07 Basf Ag Verfahren zur Verminderung des C¶1¶-C¶2¶-Aldehyd-Gehalts aus Verbindungen mit CH¶2¶-CHR-0- oder -CH¶2¶-CH(OH)-Gruppen
DE102006006200B4 (de) 2006-02-09 2008-01-10 Röhm Gmbh Wässrige N-Methylol-methacrylamid-Methacrylamid-Mischung

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1181171A (fr) * 1956-08-13 1959-06-12 Rohm & Haas Produit fibreux non-tissé et sa fabrication
DE1073432B (de) * 1956-11-30 1960-01-21 Farbenfabriken Bayer Aktiengesellschaft, Leverkusen-Bayerwerk Verfahren zum Beflocken bzw. Beschichten von Textilien
DE1619056C3 (de) * 1967-10-19 1974-01-31 Farbwerke Hoechst Ag, Vormals Meister Lucius & Bruening, 6000 Frankfurt Bindemittel und Verfahren zur Verfestigung von Faservliesen
US4107120A (en) * 1976-06-17 1978-08-15 Rohm And Haas Company Heteropolymer acrylic latices and textiles treated therewith
DE2920377A1 (de) * 1979-05-19 1980-12-04 Basf Ag Binde-, impraegnier- und ueberzugsmittel auf basis einer waessrigen dispersion eines amidgruppenhaltigen copolymerisats
DE3902067A1 (de) * 1989-01-25 1990-07-26 Roehm Gmbh Filmbildende, selbstvernetzende waessrige kunststoffdispersion

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020042128A1 (fr) * 2018-08-31 2020-03-05 宿迁市神龙家纺有限公司 Adhésif d'impression aux pigments respectueux de l'environnement et son procédé de préparation

Also Published As

Publication number Publication date
DE9110054U1 (de) 1991-10-10
ATE118836T1 (de) 1995-03-15
EP0527411A1 (fr) 1993-02-17
DE59201449D1 (de) 1995-03-30

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