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
  • 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
• • 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
  • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
• • 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
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
• • 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
• • 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
  • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
  • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
• • 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
  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
  • D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
• • 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
  • Y10T442/2549—Coating or impregnation is chemically inert or of stated nonreactance
  • Y10T442/2566—Organic solvent resistant [e.g., dry cleaning fluid, etc.]

Definitions

• the invention relates to self-crosslinking vinyl ester dispersions which contain, as crosslinking component, silanolalkoxy- and / or silanoloxy-functional comonomers, optionally in combination with ethylenically unsaturated N-methylolamide and / or N-methyloletheramide comonomers.
• Self-crosslinking vinyl ester dispersions in the production of nonwovens - the so-called non-wovens - is known.
• Self-crosslinking polymeric binders increase the wet and dry strength under mechanical stress and improve the cleaning resistance to water and solvents.
• the crosslinkers used in practice are predominantly monomers containing N-methylol groups; such as N-methylol derivatives of unsaturated organic acid amides (N-methylol-acrylamide) or their ethers (N- (iso-butoxy-methyl) -acrylamide). When these compounds are used as crosslinking agents, free methylol groups are present in the dispersion or they become by hydrolysis of the derivatives formed in the aqueous medium.
• N-methylol compounds split off formaldehyde in an aqueous medium, although the equilibrium is strongly on the side of the undecomposed N-methylol group.
• Aqueous dispersions themselves Crosslinking copolymers containing N-methylol groups therefore always contain formaldehyde, even if only in small amounts. Due to the toxicological concerns about formaldehyde that have been discussed for a long time and the requirement that only formaldehyde-free plastic dispersion systems may be used for nonwovens in the sanitary and hygiene sector, there is a need to reduce the formaldehyde content in self-crosslinking polymer dispersions or formaldehyde-free self-crosslinking polymer dispersions deliver.
• EP-B1 80 635 A route analogous to DE-A1 33 28 456 with the disadvantages just mentioned is followed in EP-B1 80 635.
• urea is added to the dispersion as a formaldehyde scavenger.
• Formaldehyde-free acrylic ester dispersions are claimed in EP-A2 193 107.
• Derivatives of acrylamidoglycolic acid are copolymerized with (meth) acrylic acid ester as crosslinker components.
• the nonwovens consolidated with these dispersions are characterized by high wet strength and high water and wash liquor resistance; However, the resistance to organic solvents is unsatisfactory here too - additional crosslinking agents have to be introduced into the dispersion.
• EP-A2 184 153 describes formaldehyde-free binders for nonwovens based on copolymers which contain unsaturated dicarboxylic acids and (meth) acrylamide as crosslinkable comonomers.
• the nonwovens consolidated with them have inadequate mechanical strength values and poor solvent resistance because of the lack of self-crosslinkability speed.
• the object has been achieved in that the crosslinking monomers with N-methylolamide or N-methylol ether amide groups have been partially or completely substituted by monomers containing silanolalkoxy groups or silanoloxy groups.
• the amounts by weight are based on the total weight of the copolymer, the individual proportions add up to 100% by weight.
• a) z.
• B vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl 2-ethylhexanoate, vinyl versatate, vinyl laurate, preferably vinyl acetate.
• a) is preferably used at 70 to 98% by weight, for soft binder systems preferably at 40 to 80% by weight.
• Component b) used in amounts of 1-6% by weight preferably contains methyl as the alkyl radical, preferably methoxy, ethoxy, methoxyethylene, ethoxyethylene, methoxypropylene glycol ether, ethoxypropylene glycol ether radicals as the alkoxy radical.
• methyl as the alkyl radical
• vinyl trimethoxysilane and vinyl triethoxysilane are used.
• B) is preferably polymerized in amounts of 1-4% by weight.
• Component c) ethylene is preferably used in soft binder systems at 5 to 35% by weight.
• d) is polymerized in at 0 to 7.5% by weight.
• Component e) preferably comprises monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and ethylenically unsaturated dicarboxylic acids and their half esters, such as maleic acid, fumaric acid, itaconic acid.
• the preferred content of e) in the polymer is 0 to 5% by weight.
• Acrylamide, N-methylolacrylamide and N- (iso-butoxymethyl) acrylamide are preferred as component f); f) is preferably used in amounts of 0.5 to 2.5% by weight.
• formaldehyde-free polymer dispersions contain no component f).
• Di- and trifunctional unsaturated compounds such as allyl methacrylate, divinyl adipate and triallyl cyanurate are preferably used as component g).
• the dispersions containing the copolymers according to the invention are coagulate-free and have a low degree of pre-crosslinking and, accordingly, high storage stability.
• a very high degree of self-crosslinking is obtained, which even exceeds that of copolymers containing N-methylolamide, so that extremely low levels of crosslinking and correspondingly good values with regard to mechanical strength and solvent content are obtained at contents which are much lower than with N-methylolamide-containing comonomers maintains stability.
• Another advantage is the significantly milder crosslinking temperature of vinylsilanes compared to the usual self-crosslinking comonomers, which brings about a significant reduction in the thermal load during crosslinking and drying of the nonwovens.
• N-methylolamide comonomers are replaced by vinylsilanes, the polymerization can be carried out under much more economical conditions because of the more advantageous copolymerization parameters in non-woven binders based on vinyl acetate.
• the vinyl ester copolymer dispersions claimed according to the invention can be prepared by the customary methods of Emulsion polymerization can be produced.
• the monomers can be initially introduced into the aqueous dispersant at the start of the polymerization; however, they can also be metered in partially or completely in the course of the polymerization.
• the dispersants used can be any of the emulsifiers and protective colloids commonly used in emulsion polymerization. Mixtures of protective colloids and emulsifiers, but also protective colloid and emulsifier can each be used alone. Anionic, cationic and nonionic can be used as emulsifiers.
• the polymerization can be carried out in a temperature range from 0 to 100 ° C. using water-soluble radical-forming catalysts which are customary in emulsion polymerization, if appropriate together with a reducing agent.
• the solids content of the dispersions is 45 to 60% by weight.
• nonwovens with good mechanical properties and solvent resistance can be produced.
• the conventional polymer compositions with, for example, N-methylolacrylamide units they not only have the advantage of being free of formaldehyde, but due to the milder crosslinking conditions via silanol condensation - the crosslinking takes place even at low temperatures around 50 ° C - more gentle drying conditions can be achieved
• Nonwoven bonding can be selected, which reduces the yellowing of the nonwovens, which is undesirable in practice, due to the high thermal load for crosslinking and drying which has been customary up to now.
• the binding agents can be applied to the nonwovens in a conventional manner by impregnation, foam impregnation, Spraying, splashing or printing. After squeezing the binder, the impregnated fleece is dried at 100 - 150 ° C. The binder content on the dried and tempered fleece is usually 20-40% by weight.
• Nonwovens made of cellulose and polyester are consolidated with the dispersions containing the copolymers described below.
• the amount of binder applied is 30% by weight, based on the total weight of fiber and binder.
• the maximum tensile forces (N) are determined in dry and wet condition in water and perchlorethylene.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Dispersion Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Nonwoven Fabrics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (3)

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Cited By (7)

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• 1987
  • 1987-08-14 DE DE19873727181 patent/DE3727181A1/de not_active Withdrawn
• 1988
  • 1988-08-09 AT AT88112928T patent/ATE76667T1/de not_active IP Right Cessation
  • 1988-08-09 EP EP88112928A patent/EP0306716B1/fr not_active Expired - Lifetime
  • 1988-08-09 DE DE8888112928T patent/DE3871465D1/de not_active Expired - Lifetime
  • 1988-08-11 JP JP63199071A patent/JPS6468576A/ja active Pending
• 1989
  • 1989-10-18 US US07/423,002 patent/US4959249A/en not_active Expired - Fee Related

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