EP0264869B1 - Etoffe non tissée avec un interpolymère d'acrylate comme liant, et procédé pour la fabriquer - Google Patents

Etoffe non tissée avec un interpolymère d'acrylate comme liant, et procédé pour la fabriquer Download PDF

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Publication number
EP0264869B1
EP0264869B1 EP87115223A EP87115223A EP0264869B1 EP 0264869 B1 EP0264869 B1 EP 0264869B1 EP 87115223 A EP87115223 A EP 87115223A EP 87115223 A EP87115223 A EP 87115223A EP 0264869 B1 EP0264869 B1 EP 0264869B1
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Prior art keywords
polymer
acrylate
itaconic acid
weight parts
reactor
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German (de)
English (en)
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EP0264869A3 (en
EP0264869A2 (fr
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Vic Stanislawczyk
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Goodrich Corp
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BF Goodrich Corp
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/042—Acrylic polymers
    • 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

Definitions

  • the present invention concerns nonwoven fabrics, i.e., those fabrics composed of loosely assembled fibers either bound chemically, thermally, or through fiber entanglements, forming an interlocking web of fibers to make a fabric.
  • the present invention concerns loosely assembled fibers saturated, coated, sprayed, or otherwise treated with an acrylate interpolymer, which gives a unique balance of physical properties including, but not limited to, a "soft hand", high resilience, low temperature flexibility and good dry, wet, and solvent properties.
  • Non-woven fabrics have distinct features and advantages over woven fabrics and can be prepared using anyone of a variety of processes.
  • chemically bonded nonwoven fabrics can be formed by impregnating, printing, or otherwise coating a loosely assembled web of fibers with a binder such as an acrylate interpolymer.
  • Thermally bonded nonwovens can be bound by choosing fibers that will fuse onto other fibers in the web when the web is subjected to heat and/or pressure and/or sonic energy.
  • Nonwovens produced by entangling the fibers can have strength and integrity without any thermal or chemical bonding. Entangling techniques include hydraulic methods, needle punching methods, and arrangement of spun filaments.
  • thermally bonded or entangled nonwovens will have strength and integrity but will lack resiliency.
  • Chemically bonded nonwovens will have a degree of resilience dependent upon the resilience of the binder and the strength of interaction between the fibers.
  • Nonwoven textile fibers are typically less than 1 millimeter to 10 millimeters in length.
  • Nonwoven textile fibers are generally from about 10 millimeters to 75 millimeters in length.
  • a continuous filament fiber can be employed. They may be composed of synthetic fibers such as polyester, rayon, dacron, nylon, etc., or natural fibers such as cotton, wool, or the like.
  • the nonwoven fabric can be manufactured by conventional techniques such as spinning, carding, garnetting, air laying, wet laying, or other known process.
  • a clothing interliner is an example of a chemically bonded nonwoven application where the balance of soft hand, durability, resilience, and strength properties is highly desirable.
  • Thermally bonded nonwovens although possessing strength and durability due to the fusion of fibers in a web, will generally lack resiliency.
  • the present invention relative to thermally bonded nonwovens can impart resiliency while maintaining or improving the "hand" characteristics of the finished material.
  • untreated, entangled materials will have strength and durability but lack resiliency.
  • the present invention relative to entangled nonwovens can provided a balance of resiliency and soft "hand".
  • resiliency is less important, while strength, tear resistance and fold endurance are generally more important. Strongly interacting fibers, such as cellulose, limit resiliency.
  • the present invention relative to such chemically bonded nonwovens demonstrates a balance of properties not found in the prior art.
  • EP-A-0 021 693 discloses a process for maleing a non-woven fabric which comprises bringing together fibers and a binder composition comprising a polymer polymerized from a monomer mixture, said composition being substantially free of crosslinking compounds.
  • WO 86/01519 discloses an aqueous emulsion of a thermally self-crosslinkable copolymer having a molecular weight in the range of 50 000 to 10 000 000, a second order transition temperature in the range of -50 °C to 30 °C and useful in treating textiles comprising 0.5 to 3 % by weight of itaconic acid, 2 to 12 % by weight of glycidyl methacryl acrylate , 1 to 7 % by weight of N-methylol acryl amide or N-methylol methacryl amide, 35 to 96.5 % by weight of ethyl acrylate, and at least one compatible monoethylenically unsaturated monomer.
  • the present invention relates to the combination of a unique acrylic latex binder and fibers thus forming a nonwoven fabric.
  • the latex of the present invention may be applied to fibers as a coating, binder or impregnant, or otherwise deposited on the fibers.
  • the present invention also relates to a process of making this combination of the unique latex and fibers.
  • the present invention pertains to a non-woven fibrous material comprising fibers bonding together with a binder consisting essentially of predominantly acrylate-containing polymer chains including repeated units derived from itaconic acid and up to 98.9 weight parts of an acrylate represented by the structure wherein
  • the polymers in these latexes have a unique and improved balance of properties.
  • the novel polymers are low Tg, soft acrylic polymers that have a good balance of tensile strength and elongation and excellent hysteresis characteristics. They are rubbery, tough, and highly resilient, and exhibit tensile strength and elongation properties common in some "harder" acrylic polymers.
  • the glass transition temperature (Tg) of the novel polymers is from -20°C. to -60°C.
  • novel latexes can be prepared by polymerizing the monomers and other ingredients using a premix of the monomers which is metered into a reactor containing initiator.
  • a preferred process is to prepare a premix in the usual manner but devoid of all or a substantial part of the itaconic acid, and add the itaconic acid initially to the reactor before metering the premix into the reactor.
  • the latex of the present invention When using the acrylic latex of the present invention with a web of fibers, a unique nonwoven is produced.
  • the latex can impart durable resilience, while maintaining or improving the hand.
  • the latex In loosely assembled fibers bonded with the latex of the present invention, the latex can impart a unique balance of properties such as good wet, dry, and solvent strength properties, flexibility, softness, and resiliency.
  • the raw polymer of the latex having a tensile strength of at least 2.07 MPa (300 psi), an elongation of at least 350% and a percent hysteresis loss of less than 20%.
  • the present invention relates to process of making a non-woven fabric which comprises associating within a web, a mass of fibers, bringing into contact with the fibers a binder comprising an aqueous emulsion of a binder consisting essentially of predominantly acrylate-containing polymer chains including repeating units derived from itaconic acid and up to 98.9 weight parts of an acrylate represented by the structure wherein
  • novel latexes disclosed herein can be used in conjunction with fibers to yield nonwoven articles that have unique properties.
  • the novel polymers exhibit a unique and improved balance of properties. They have excellent low temperature flexibility and yet exhibit a good balance of tensile strength and elongation and excellent hysteresis characteristics. More specifically, the novel polymers have an improved balance of high resilience, rubberyness, toughness, low surface tack considering their softness, heat and light stability, dry and wet and solvent strength, and low temperature flexibility. Certain properties of the novel polymers are comparable to those of some much harder acrylate polymers. For example, the novel polymers exhibit abrasion resistance comparable to harder acrylate polymers.
  • the novel polymers exhibit rubbery behavior when compared to the more plastic behavior observed with harder acrylate polymers.
  • low Tg, soft acrylic polymers basically exhibited a poor balance of tensile strength and elongation properties and inadequate hysteresis characteristics.
  • the polymers of this invention exhibit a much improved balance of properties in this regard.
  • the novel polymers of this invention are low Tg, soft acrylic polymers that have a good balance of tensile strength and elongation and excellent hysteresis characteristics as shown by a low percent hysteresis loss.
  • novel latexes disclosed herein are prepared by polymerizing itaconic acid containing 4 to 10 carbon atoms, with the above-mentioned copolymerizable acrylate monomer in the presence of an initiator and a surfactant.
  • a crosslinking monomer can be interpolymerized with the itaconic acid and the copolymerizable monomer(s). The total amount of all of the monomers charged to the reactor, whether batchwise, incrementally, and/or metered in, equals 100 parts by weight.
  • the amount of the itaconic acid employed is from 1 part to 20 parts by weight, and more preferably from 2 parts to 8 parts by weight.
  • the use of itaconic acid in amounts above 8 parts by weight necessitates suitable adjustments in polymerization ingredients due to a destabilizing effect of the acid and some retardation of the polymerization.
  • the resulting latex had a high residual monomer content which caused some difficulty in forming an even or level film.
  • 20 weight parts of itaconic acid was charged initially into the reactor, a latex was formed but the residual monomer level was quite high.
  • the polymerization conditions and ingredients can be readily adjusted to obtain latexes with acceptable amounts of residual monomers. This can be done by increasing the amounts of surfactant and/or initiator used, by increasing the temperature of polymerization, by metering in part of the unsaturated dicarboxylic acid, by stripping the latex, or combinations of the above. Excellent results have been obtained using 3 to 6 parts by weight of itaconic acid.
  • novel polymers of this invention are interpolymers of (a) itaconic acid with (b) the above-described copolymerizable acrylate monomer and (c) optionally, a crosslinking monomer(s).
  • a polymer may be an interpolymer as simple in structure as a copolymer of 95% by weight n-butyl acrylate and 5% by weight itaconic acid.
  • the novel polymers are more likely to contain interpolymerized units of more than two monomers.
  • the copolymerizable acrylate monomer used in this invention can be any unsaturated monomer capable of interpolymerizing with itaconic acid.
  • the amount of copolymerizable monomer employed is such that the weight parts of itaconic acid, and the crosslinking monomer(s), if used, together with the weight parts of the copolymerizable monomer used total up to one hundred (100) weight parts.
  • a novel copolymer of the invention containing 4 parts by weight of itaconic acid and 2 parts by weight of a crosslinking monomer would then contain 94 parts by weight of a copolymerizable monomer.
  • the weight parts of monomer charged substantially equals the weight percent of the interpolymerized monomer in the final polymer. If this is not the case, the use of conventional analytical techniques readily establishes the weight percent of any interpolymerized monomer in the polymer.
  • the total amount of copolymerizable monomer charged into the reactor is at least 70 parts by weight, and more typically at least 90 parts by weight of the total weight of all monomers.
  • Examples of the copolymerizable monomers are alkyl, alkoxyalkyl, alkylthioalkyl, and cyanoalkyl acrylates and methacrylates containing 1 to 20 carbon atoms in the alkyl group; diacrylates and dimethacrylates such as ethyleneglycol dimethacrylate and diethylene glycol diacrylate; monolefins containing 2 to 10 carbon atoms such as ethylene, propylene, isobutylene, 1-hexene and 1-octene; vinyl and allyl acetates containing 4 to 20 carbon atoms such as vinyl acetate, vinyl propionate and allyl acetate; vinyl ketones containing 4 to 20 carbon atoms such as methyl vinyl ketone; vinyl and allyl ethers containing 4 to 20 carbon atoms such as vinyl methyl ether, vinyl ethyl ether, vinyl-n-butyl ether, allyl methyl ether; vinyl aromatics containing 8 to 20 carbon
  • the two conditions on the selection of the copolymerizable monomer are (1) that the glass transition temperature (Tg) of the polymer made is from -20°C. to -60°C., and more preferably from -25°C., to -50°C. and (2) that the copolymerizable monomer contains a major portion of an acrylate monomer.
  • Tg glass transition temperature
  • the acrylate monomer employed is an alkyl, alkoxyalkyl, alkylthioalkyl, or cyanoalkyl acrylate of the formula wherein R1 is hydrogen or methyl, and R2 is an alkyl radical containing 1 to 20 carbon atoms, an alkoxyalkyl or alkylthioalkyl radical containing a total of 2 to 12 carbon atoms, or a cyanoalkyl radical containing 2 to 12 carbon atoms.
  • the alkyl structure can contain primary, secondary, or tertiary carbon configurations.
  • acrylates are methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methyl pentyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate; methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxypropyl acrylate, methylthioethyl acrylate, hexylthioethylacrylate; and ⁇ and ⁇ -cyanoethyl acrylate, ⁇ , ⁇ and
  • the copolymerizable monomer used contains at least forty percent (40%) by weight of acrylates of the above formula acrylate wherein R1 is hydrogen and R2 is an alkyl radical containing 4 to 10 carbon atoms or an alkoxyalkyl radical containing 2 to 8 carbon atoms.
  • R1 is hydrogen
  • R2 is an alkyl radical containing 4 to 10 carbon atoms or an alkoxyalkyl radical containing 2 to 8 carbon atoms.
  • examples of the most preferred acrylates are n-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and methoxyethyl acrylate, ethoxyethyl acrylate. Both an alkyl acrylate and an alkoxyalkyl acrylate can be used.
  • the acrylate monomer(s) employed is the most preferred acrylate monomer(s) and such monomer(s) comprises about seventy-five percent (75%) to one hundred percent (100%) of the copolymerizable monomer.
  • the two criteria on the selection of the copolymerizable monomer such that the novel polymer has a low Tg and contains a major portion of interpolymerized acrylate monomer(s) are somewhat complementary in that the use of a high level of the preferred acrylate monomer(s) as the copolymerizable monomer readily yields a novel polymer having the required Tg value. It is understood that the novel polymers of this invention can have more than one Tg value within the prescribed Tg range.
  • the Tg of a polymer can be easily determined using differential thermal analysis. Further, the Tg of a polymer is predictable from the interpolymerized monomers using known formulas and readily obtainable data following the procedure and teachings given in many publications.
  • One such publication is the book Mechanical Properties of Polymers by L. E. Nielsen, Reinhold Publishing Corp. (1962) Library of Congress catalog card no. 62-18939.
  • Chapter 2 is devoted to transitions in polymers, and the tables given on pages 16 to 24 list out the Tg values of many polymers, including acrylate polymers, based on the monomers employed.
  • the Tg of the novel polymers can be determined through knowledge of the types and amounts of copolymerizable monomers employed.
  • the "hard" copolymerizable monomers i.e. those which would yield a homopolymer Tg value of +80°C. or above, would typically be used in amounts of from 0 percent to 25 percent by weight of the total weight of the copolymerizable monomers.
  • hard monomers examples include the vinyl aromatics such as styrene, ⁇ -methyl styrene, vinyl toluene; vinyl nitriles such as acrylonitrile and methacrylonitrile; and monomers containing a halogen group such as vinyl chloride, vinylidene chloride, vinyl benzyl chloride. Further, certain of the copolymerizable monomers have an activity which, if the monomers were present in large amounts, could overshadow the features of the polymers of this invention.
  • copolymerizable monomers such as the vinyl amides, the diacrylates and dimethacrylates, the unsaturated sulfonate monomers, and the unsaturated monocarboxylic acids would typically be used in amounts of from 0 percent to 5 percent by weight of the total weight of the copolymerizable monomers.
  • novel polymers benefit from the presence of a crosslinking monomer in the polymer or the addition of a crosslinking agent to the novel polymer.
  • crosslinking monomers used herein can be any monomer or oligomer polymerizable with the unsaturated dicarboxylic acid and copolymerizable monomer which exhibits crosslinking or which can be converted into a crosslinking site.
  • An example of a crosslinking monomer which can be interpolymerized with the itaconic acid and copolymerizable monomer, and then converted to yield a crosslinking site is acrylamide, which, when treated with formaldehyde, forms a methylol group.
  • the more preferred crosslinking monomers are monoethylenically unsaturated monomers containing N-methylol groups such as N-methylol acrylamide, or N-methylol derivatives of allyl carbamate which may contain one or two N-methylol groups.
  • N-methylol groups may be left unreacted or they may be etherized, as with C1 to C4 carbon alcohols. The alcohol is released on curing to regenerate the N-methylol group for cure.
  • Alcohol etherifying agents are illustrated by methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, 2-ethoxyethanol, and 2-butoxy ethanol.
  • the preferred crosslinking monomers are selected from N-alkylol acrylamides that contain from 4 to 18, preferably 4 to 12 carbon atoms in the alkyl group, and lower alkyl acrylamidoglycolate lower alkyl ethers containing from 7 to 20 carbon atoms.
  • Specific examples of the particularly preferred crosslinking monomers include N-methylol acrylamide, N-methylol methacrylamide, N-butoxymethyl acrylamide, iso-butoxymethyl acrylamide and methyl acrylamidoglycolate methyl ether.
  • N-methylol acrylamide as the crosslinking monomer.
  • the crosslinking monomer is used in the range from 0.1 to 10 parts by weight, and more preferably from 0.5 to 5 parts by weight based on 100 parts by weight total of all monomers.
  • the novel polymer can still be crosslinked by the post-polymerization addition of a crosslinking agent to the latex or the polymer.
  • crosslinking agents are urea-formaldehyde resins, melamine-formaldehyde resins and partially methylolated melamine-formaldehyde resins and glyoxal resins. These crosslinking agents can be used in levels of from 0.1 part to 20 parts, and more preferably from 0.5 part to 2 parts, by weight, based on 100 parts by weight of polymer.
  • novel polymers are prepared as latexes.
  • novel polymers have great utility used in the form of a latex, the latexes themselves are unique and novel.
  • the aqueous medium in which the novel polymers are prepared may be free of traditional emulsifiers, or it may contain traditional emulsifiers.
  • traditional emulsifiers are used to prepare the unique latexes of this invention, the standard types of anionic and nonionic emulsifiers can be employed.
  • Useful emulsifiers include alkali metal or ammonium salts of the sulfates of alcohols having from 8 to 18 carbon atoms such as sodium lauryl sulfate, ethanolamine lauryl sulfate, and ethylamine lauryl sulfate; alkali metal and ammonium salts of sulfonated petroleum and paraffin oils; sodium salts of sulfonic acids such as dodecane-1-sulfonic acid and octadiene-1-sulfonic acid; aralkyl sulfonates such as sodium isopropyl benzene sulfonate, sodium dodecyl benzene sulfonate and sodium isobutyl naphthalene sulfonate; alkali metal and ammonium salts of sulfonated dicarboxylic acid esters such as sodium dioctyl sulfosuccinate and disodium-N
  • Nonionic emulsifiers such as octyl- or nonylphenyl polyethoxyethanol may also be used.
  • Latexes of the invention having excellent stability are obtained using the alkali metal and ammonium salts of aromatic sulfonic acids, aralkyl sulfonates, long chain alkyl sulfonates and poly(oxyalkylene) sulfonates as emulsifiers.
  • the emulsifier or a mixture thereof may be added entirely at the outset of the polymerization or it may be added incrementally or metered throughout the run. Typically, some of the emulsifier is added to the reactor at the outset of the polymerization and the remainder is charged incrementally or proportionately to the reactor as the monomers are proportioned.
  • the polymerization of the monomers may be conducted at temperatures from 0°C up to 100°C in the presence of a compound capable of initiating the polymerizations.
  • Initiating compounds and mixtures thereof are chosen, often in conjunction with oxidation-reduction catalysts, in an amount and type which results in a suitable initiation rate at a chosen polymerization temperature profile.
  • Commonly used initiators include the free radical initiators like the various peroxygen compounds such as persulfates, benzoyl peroxide, t-butyl diperphtahlate, pelargonyl peroxide and 1-hydroxycyclohexyl hydroperoxide; azo compounds such as azodiisobutyronitrile and dimethylazodiisobutyrate.
  • Particularly useful initiators are the water-soluble peroxygen compounds such as hydrogen peroxide and sodium, potassium and ammonium persulfates used by themselves or in activated systems.
  • Typical oxidation-reduction systems include alkali metal persulfates in combination with a reducing substance such as polyhydroxyphenols, oxidizable sulfur compounds such as sodium sulfite or sodium bisulfite, reducing sugars, dimethylamino propionitrile, diazomercapto compounds, water-soluble ferricyanide compounds, or the like.
  • Heavy metal ions may also be used to activate persulfate catalyzed polymerizations.
  • the amount of surfactant used is from 0.01 to 10 parts by weight, and the amount of initiator is used from 0.01 to 1.5 parts by weight, both based on 100 weight parts of the total amount of monomers.
  • Polymer latexes of the invention having excellent stability are obtained using an alkali metal and ammonium persulfate as the initiator.
  • the initiator may be charged completely into the reactor at the outset of the polymerization, or incremental addition or metering of the initiator throughout the polymerization may also be employed. Addition of the initiator throughout the polymerization is often advantageous in providing a suitable rate throughout the polymerization.
  • a premix is prepared by mixing the monomers, optionally with water, a surfactant or a mixture thereof, buffering agents, modifiers and the like. If water is used, the aqueous premix is agitated to form an emulsion. Separately added to a reactor are more water, the initiator, and optional ingredients. The premix is then metered into the reactor and the monomers are polymerized.
  • part of the premix can be added to the reactor, the initiator is then added and polymerization of the initial monomers in the reactor thereto is allowed to form seed polymer particles. Thereafter, the remainder of the premix or another premix is metered into the reactor and the polymerization reaction is concluded in the usual way.
  • the premix can be fed to the reactor incrementally rather than continuously.
  • all of the monomers and other ingredients can be added directly to the reactor and polymerization conducted in a known manner. This last variation is typically called a batch process. Monomers can also be added to the reactor in separate streams other than in the premix.
  • 2 to 8 weight parts of itaconic acid is polymerized in water with 90 to 98 weight parts of an alkyl acrylate monomer such as n-butyl acrylate and 0.5 to 5 weight parts of a crosslinking monomer such as N-methylol acrylamide, in the presence of 0.1 to 5 weight part of a suitable surfactant such as sodium lauryl sulfate and 0.01 to 1.5 weight parts of a suitable initiator such as sodium persulfate.
  • a suitable surfactant such as sodium lauryl sulfate
  • a suitable initiator such as sodium persulfate.
  • the itaconic acid can be added all initially into the reactor before metering of the premix is commenced, or part or all of the said acid can be metered into the reactor during polymerization.
  • the itaconic acid is all initially added to the reactor, and the premix containing the copolymerizable monomer(s) and crosslinking monomer(s) is metered into the reactor.
  • the best balance of polymer physical properties was obtained when all of the itaconic acid was added initially to the reactor.
  • polymers having an improved balance of properties are also obtained when some or all of itaconic acid is added to the premix.
  • a premix is typically prepared containing one or more monomers, optionally surfactant, water and ingredients such as buffering agents, chain modifiers, and the like.
  • the premix is vigorously agitated to form an emulsion at ambient temperature.
  • the reactor is also prepared for polymerization by addition of water, initiator, monomer (if added to the reactor), optionally buffering agents, and other ingredients.
  • the reactor and its contents can be preheated.
  • the premix is metered to the reactor over a period of 0.5 to 10 or more hours, preferably 1 to 4 hours.
  • a cold water or other type of cooling jacket around the reactor can be used to control the polymerization temperature, preferably at 30°C. to 90°C.
  • the latex obtained is typically treated or processed to reduce residual monomers and the pH is adjusted to whatever value is desired.
  • the latex is then often filtered through a cheesecloth or filter sock and stored.
  • the stored latex has a total solids content of from 10 to 68%, and more typically from 40% to 60%.
  • the itaconic acid is all added initially to the reactor, unlike prior art processes in which all of the monocarboxylic acid is typically added to the premix.
  • Addition of large amounts of the itaconic acid to the reactor initially requires adjustments in the polymerization recipe in order to obtain a latex with optimum properties. For example, placing all of the itaconic acid into the reactor without making any other changes in the polymerization recipe or process can result in a larger particle size latex.
  • the dicarboxylic acid reduces the efficiency of the initiator in the reactor and/or causes destabilization of forming particles in the reactor, which, in turn, can affect the particle size of the latex polymer.
  • novel latexes disclosed herein have typical colloidal properties. They are anionically stabilized, have a pH of from 1 to 6 as prepared, have a particle size in the range of 100 to 500mm (1000 to 5000 angstroms), and exhibit good mechanical stability when their pH is raised above neutral.
  • the novel polymers prepared herein have very tight hysteresis curves.
  • the tighter a hysteresis curve the more resilient the polymer.
  • the tighter the hysteresis curve the less heat will be generated on stretching or working of the polymer.
  • the percent hysteresis loss of polymers were determined from the polymer's hysteresis curve using the following procedure. Dumbell samples of the raw polymer having 178 to 254 »m (7 to 10 mils) thickness were prepared from the latex using a draw bar. The cast films were air-dried then heated at 149°C (300°F). for 5 minutes. By raw polymer is it meant that no compounding ingredients such as fillers, pigments, plasticizers and the like were added, and no curative ingredients were added. The samples were placed in an Instron tensile testing machine and elongated to 200% elongation at a speed of 50.8cm/min (20 inches/minute).
  • the sample was then retracted at 50.8cm/min (20 inches/minute) to its original position (making one cycle), and then elongated and retracted again until five cycles were completed.
  • the tensile/elongation (i.e. hysteresis) curves for each cycle were recorded.
  • the percent hysteresis loss measurements were performed in each case on the recorded data for the second cycle.
  • the area of the figure described by the initial stretch of the polymer to 200% elongation represents the amount of work energy needed to produce the elongation (E A ).
  • the area of the figure described when the polymer is retracted in the cycle represents the work energy exerted by the polymer in returning to its original position (E B ).
  • a perfectly resilient polymer which exhibits no heat or other energy losses would have a hysteresis curve wherein E A would equal E B , i.e. the two curves would lie on top of each other.
  • the deviation from this ideal condition is a measure of the polymer's hysteresis loss.
  • a gummy polymer would have a very high percent hysteresis loss.
  • the percent hysteresis loss of the polymers was determined by the following formula:
  • the polymers of this invention exhibit a percent hysteresis loss of less than 20% as calculated from their hysteresis curves.
  • the polymers prepared from the most preferred unsaturated dicarboxylic acids, copolymerizable monomers, and crosslinking monomers and prepared by the preferred process exhibit a percent hysteresis loss of below 15 percent.
  • the novel polymers have other properties which make them unique. They are soft, yet rubbery and tough. Their ultimate raw polymer tensile strength is at least 2.07 MPa (300 psi) and ultimate percent elongation is at least 350%, as measured on raw polymer films cast with a draw bar, air-dried and heated for 5 minutes at 149°C (300°F). A way of observing the good balance of tensile strength and elongation exhibited by the polymers of this invention is to calculate their "TxE Product", which is simply the figure obtained by multiplying the polymer's ultimate tensile strength by its percent elongation at break. The figure is reported to the nearest 1000.
  • the TxE Product a measure of the overall strength of the polymer.
  • the TxE Product of the novel polymers is at least 140,000, and more preferably at least 200,000.
  • the TxE Product for the novel polymers made from the most preferred monomers using the most preferred process is at least 250,000.
  • the latex was prepared by polymerizing a monomer mix of 93 to 97 parts by weight parts of the copolymerizable monomer, 2 to 4.5 weight parts of itaconic acid, and 1 to 3 weight parts of the crosslinking monomer. In comparative experiments where no acid was used, the amount of copolymerizable monomer was increased accordingly.
  • the premix was prepared in a separate tank by mixing demineralized water, sodium lauryl sulfate as the surfactant, the crosslinking monomer, and the copolymerizable monomer. All or part of the acid was placed in the premix or the reactor, as indicated.
  • the reactor initially contained demineralized water, sodium lauryl sulfate, and sodium persulfate.
  • the premix was metered into the reactor over a period of about 1.5 to about 2.5 hours, during which time the temperature in the reactor was controlled at 70°C. to 80°C.
  • a second initiator system was added to the reactor.
  • the second initiator system consisted of sodium persulfate, sodium lauryl sulfate, and ammonium carbonate in demineralized water.
  • the second initiator was metered into the reactor over a period of 3.5 hours. At times, an initiator booster was merely slugged into the reactor rather than metered in.
  • the latex in the reactor was allowed to stand for about 1.5 hours at 75°C. and was then cooled to 40°C. At this point, the latex was stripped, cooled to 30°C., its pH was adjusted with ammonia to about 4.5 pH, and it was filtered through cheesecloth and stored.
  • Variation A the reaction temperature was 80°C.
  • the premix metering time was 2 hours
  • an initiator booster containing 0.05 weight part of sodium persulfate was added after 2 hours
  • the amount of sodium lauryl sulfate used was 0.05 weight part in the reactor and 0.95 weight part in the premix.
  • Variation B was like Variation A except that the reaction temperature was 75°C.
  • the reaction temperature was 70°C.
  • 0.35 weight part of sodium persulfate initiator was in the reactor
  • a second initiator of 0.15 part of sodium persulfate and 0.05 part of sodium lauryl sulfate was metered in over 3.5 hours
  • the amount of sodium lauryl sulfate in the reactor was 0.4 weight part and in the premix was 0.6 weight part.
  • the raw polymer films were prepared in the following manner. First, the latex was neutralized by adjusting the pH of the latex to between 7 and 8 with ammonia. Thickener was added to the latex, as necessary, to raise its viscosity to about 500 mPa ⁇ s (cps) so that a level film could be obtained. A latex film was deposited on a polyethylene backing using a draw bar so as to yield a dry film of 178 to 254 »m (7 to 10 mils) thickness, and the latex film was dried at room temperature for about 24 hours. The polymer film was then peeled from the backing, dusted with tale if necessary for easier handling, and heated for 5 minutes at 300°F (149°C). The test specimens were prepared and tested using the following procedure.
  • a dumbell shaped test specimen was prepared from the polymer film and placed in an Instron tensile tester at a 2.54cm (1") jaw spacing. The jaws were separated at a speed of 50.8cm/min (20 inches/minute). Elongation was measured using a 1.27cm (0.5 inch) benchmark. Each data point given in the examples represents an average of three separate measurements.
  • This example demonstrates the preparation of a novel latex of the invention, the preparation of a novel polymer of the invention from the latex, and shows a comparison of the properties of the novel polymer with those of polymers containing no acid, acrylic acid, or methacrylic acid in the polymer.
  • Only the polymer prepared from the latex containing polymerized itaconic acid is representative of the invention.
  • the other samples were prepared and are presented for comparison purposes only. All of the latexes were prepared with 2 parts by weight of N-methylol acrylamide as the crosslinking monomer, and using the process described above as Variation B.
  • the acid, if used, was placed all in the premix and the premix was metered into the reactor. All reaction conditions and procedures were identical in these tests except for the particular acid used, if any. Ultimate tensile strength and percent elongation tests were performed on film samples of the raw polymers, which samples were prepared as described above. The results are given in Table A below:
  • the novel polymer of the invention made using itaconic acid (IA) has a superior balance of tensile strength and elongation and percent hysteresis loss.
  • the polymer containing polymerized itaconic acid (IA) had a tensile strength of 4.78 MPa (693 psi) an ultimate elongation of 380%, and a TxE Product of 263000, whereas the corresponding results for acrylic acid (AA) were 2.41 MPa (350 psi), 390%, and 120000, and for methacrylic acid (MAA) were 2.27 MPa (330 psi), and 390%, and 129000 respectively.
  • the tensile strength was only 1.43 MPa (207 psi)
  • elongation was 260%
  • TxE Product was only 53800.
  • the data shows that the polymer of the invention has a good balance of tensile strength and elongation and low hysteresis loss.
  • the properties of a novel polymer of the invention were compared to properties of some commercial polymers.
  • the novel polymer used herein is similar to the polymer prepared in Example 1 above except that, in this case, all of the itaconic acid was placed initially into the reactor (no itaconic acid was in the premix).
  • the commercial polymers are Hycar® 2671 (Acrylic A), Hycar® 2673 (Acrylic B), and an acrylic polymer known as Rhoplex TR934 sold by Rohm and Haas (Acrylic C).
  • novel polymer of the invention gives a unique balance of good tensile strength and elongation and low hysteresis loss.
  • the balance of tensile and elongation properties and hysteresis loss of the novel polymer were actually better than most of those properties of the "harder" acrylic polymers, yet the Tg of the novel polymer was considerably lower than such polymers.
  • This example shows the preparation and testing of polymers of the invention wherein the latexes were prepared using Variation A and all of the unsaturated dicarboxylic acid was placed in the premix.
  • the following monomers were charged on the following weight basis: 4.5 parts of the stated acid, 1.0 part N-methylol acrylamide, and 94.5 parts n-butyl acrylate.
  • the tensile strength, elongation, TxE Product, and hysteresis loss for the polymer made with acrylic acid (AA) in the premix was 2.13 MPa (310 psi), 493%, 153000, and 23.1% respectively.
  • itaconic acid (IA) was used all in the premix, thereby making a polymer of this invention, the tensile strength, elongation, TxE Product, and hysteresis loss was 3.76 MPa (546 psi), 553%, 317000, and 19.6% respectively.
  • the latex prepared in this Example 3 had a pH of about 1.9.
  • the use of all of the unsaturated dicarboxylic acid initially in the reactor has the effect of reducing initiation efficiency of the polymerization and/or destabilizing the forming particles, which can result in a latex which has a larger particle size than when the acid is placed in the premix.
  • the reduction in initiation efficiency can be overcome by increasing the amount of the surfactant or initiator, or both. This was demonstrated by conducting an experiment in which the level of the surfactant used in the reactor was increased from 0.05 weight part to 0.5 weight part, with all other conditions remaining the same. By increasing the amount of surfactant, the preparation of the novel latex was more nearly optimized.
  • the data obtained on the film of the novel polymer prepared in this manner shows that the tensile strength of the polymer increased to 5.33 MPa (773 psi), the elongation dropped to 647%, the TxE Product increased to 500000, and the percent hysteresis loss dropped to 14.9%. This indicates a different balance of properties than obtained using the lesser amount of surfactant. This balance of properties may be preferred in some uses.
  • the suitability of using unsaturated dicarboxylic acid other than itaconic acid is demonstrated in this Example for comparison.
  • the polymers were prepared using 2 parts by weight of N-methylol acrylamide as the crosslinking monomer, and using the process procedure Variation B where all 4.0 weight parts of the defined acid was placed initially into the reactor.
  • the unsaturated dicarboxylic acids employed were itaconic acid (IA), fumaric acid (FA), maleic acid (MA), and citraconic acid (CA).
  • IA itaconic acid
  • FA fumaric acid
  • MA maleic acid
  • CA citraconic acid
  • This example demonstrates the use of other copolymerizable monomers in the preparation of the novel latexes and polymers of this invention.
  • the procedures used were the same as those used in Example 6 wherein the itaconic acid was placed all initially into the reactor. A portion of the n-butyl acrylate in the premix was replaced with one or more of the indicated higher Tg yielding copolymerizable monomers in the amounts shown.
  • the tensile strength of the polymer was 5.77 MPa (838 psi) and elongation was 670%.
  • the polymer tensile strength was 4.67 MPa (678 psi) and elongation was 630%.
  • polymer tensile strength was 6.50 MPa (943 psi) and elongation was 560%.
  • the TxE Products were very high and the percent hysteresis loss was within the stated range.
  • a very low Tg polymer was prepared using the same procedure as given above using 94 weight parts of 2-ethyl hexyl acrylate (2-EHA) as the sole copolymerizable monomer.
  • the polymer was weak, having a tensile strength of 2.27 MPa (230 psi), an elongation of 980%, and a Tg of -65.5°C.
  • This polymer did not meet the necessary criteria of the novel polymers of this invention.
  • This Example shows that a choice of copolymerizable monomer(s) which takes the Tg of the polymer outside of the stated Tg range, results in a polymer that does not have the unique balance of properties described herein.
  • the first column of data in Table G shows data from a latex polymerization wherein N-methylol acrylamide (NMA) was used as the crosslinking monomer.
  • NMA N-methylol acrylamide
  • NMMA N-methylol methacrylamide
  • MAGME methyl acrylamidoglycolate methyl ether
  • a series of latexes were prepared in which the amount of itaconic acid (IA) and the amount of N-methylol acrylamide (NMA) were varied.
  • the copolymerizable monomer used was n-butyl acrylate at 93 to 97 parts by weight.
  • the itaconic acid was placed all initially in the reactor.
  • the initiator used was sodium persulfate.
  • Process procedure C was employed. The results of the tests on the polymers are given in Table H below.
  • the MIT fold test was conducted in this example by saturating 127 »m (5 mil) flat paper with 40% add-on. Forty percent add-on means 40 weight parts of dry polymer has been added to each 100 weight parts of fibers.
  • the saturated paper was dried on a photoprint drier at approximately 100°C (212°F) and then cured at 149°C (300°F) for 3 minutes.
  • the cured paper was cut into 15 millimeter widths in the machine direction and mounted in a MIT tester with a load of 1 kilogram applied to the ends of the strip of paper.
  • the paper was then flexed by the MIT tester at a 180° angle to first one side and then the other side.
  • the number of folds necessary to break the paper was measured to indicate the fold endurance of the latex and paper.
  • Latex A included 86 weight parts of N-butyl acrylate, 6 weight parts acrylonitrile, 4 weight parts itaconic acid, 2 weight parts ethyl acrylate and 2 weight parts N-methylol acrylamide.
  • Latex B included 92 weight parts n-butyl acrylate, 4 weight parts itaconic acid, 2 weight parts ethyl acrylate and 2 weight parts N-methylol acrylamide.
  • Latex of the present invention having a low Tg performs better than the indicated commercially available soft latexes employed in paper applications.
  • Latex B performed better than the above noted commercially available latexes.
  • Latex A was far superior to any of the above noted commercially available latexes. In fact, the number of folds achieved when using Latex A is more than double the best of the above latexes.
  • a Handle-O-Meter test was conducted on 31.1 g (1.1 ounce) per square yard chemically bound saturated polyester nonwoven fabric to measure softness.
  • a latex was applied to an unbound carded polyester fiber web at about 30% add-on.
  • the fabric was dried on a photoprint dryer at approximately 100°C (212°F) and then cured for 3 minutes at 149°C (300°F).
  • Two 7.62cm x 7.62cm (3" x 3") squares were cut from the nonwoven fabric and tested using the Thwing-Albert Digital Handle-O-Meter, which measures the force necessary to advance a sample through a measured open slit width.
  • the polyester nonwoven fabric was tested in the machine direction, cross-direction, then flipped over and again tested in the machine direction and the cross direction. All testing was conducted at 50% relative humidity and 22°C (72°F). The results of this experiment are set forth in Table J. The lower numbers indicate a softer hand. The averages of 8 readings are also shown. Table J Handle-O-Meter Latex Type M.D. C.D. F.M.D. F.C.D. Avg.
  • Jaw separation was 5.08cm (2") and jaw speed was 2.54cm (1") per minute.
  • the tensile strength indicated is the peak or maximum value in pounds.
  • the elongation indicated is the elongation at peak tensile strength.
  • the tensile energy absorption is the TEA at the peak tensile strength.
  • the latex of the present invention having all weight parts of itaconic acid in the reactor produced the highest wet, dry, and solvent strengths.
  • the last five experiments indicate that all the latexes of the present invention using a dicarboxylic acid are an improvement over the commercially available acrylic latexes having the same Tg, and similar composition except with respect to the acid used.
  • Example 12 The same dry, wet, and solvent strength tests as in Example 12 were conducted on chemically bonded polyester nonwoven fabric having 30% add-on.
  • Table L The results for the polyester nonwoven fabric are set forth in Table L.
  • the first five tests indicate again that the latex made with the itaconic acid in the reactor gives the best dry strength while the latex with the itaconic acid in the premix gives the best wet strengths and again the latex made with itaconic acid in the reactor gives the best solvent strengths.
  • Each of the examples of the present invention perform better than the commercially available acrylate latex (Hycar® 26171) having the same Tg.
  • the balance of properties it is shown that the latexes made with the itaconic acid produce the best balance of properties.
  • the last five latexes sampled again indicate that the best dry properties are obtained with all the itaconic acid being in the reactor while the best wet properties are obtained with all the itaconic acid in the premix.
  • the solvent strength data in the last five examples indicates that the best solvent strengths were obtained with the itaconic acid in the reactor.
  • the balance of properties is best achieved when all weight parts of itaconic acid are introduced in the reactor.
  • This example demonstrates the tear strength of a 40% add-on saturated 127 »m (5 mil) flat paper.
  • 6.35cm (2-1/2") square samples of 1-ply paper were tested on the Thwing-Albert Elmendorf tear tester. The paper was dried and cured under the same conditions set forth in Example 7.
  • Latexes A and B are set forth in Example 10.
  • Latex C comprises 82 weight parts 2 ethylhexyl acrylate, 10 weight parts n-butyl acrylate, 2 weight parts ethyl acrylate, 4 weight parts itaconic acid and 2 weight parts N-methylol acrylamide (Tg of -60°C).
  • the three Hycar latexes were selected because they are recommended for use in paper saturations.
  • the nitrile latex was developed specifically to give good tear strength.
  • the Elmendorf tear of the present invention (Latexes A, B, and C) are about as good or better than the commercially available acrylic latexes.
  • the nitrile latex product has excellent tear strength, it has several shortcomings such as poor wet strength and poor resistance to oxidation.
  • the latexes of the present invention do not have these draw backs.
  • This example demonstrates the delamination resistance or internal bond of 40% add-on saturated 5 mil flat paper (the same paper used in Example 10).
  • a sheet of 20 cm long saturated paper (20 cm long in machine direction) was sandwiched between 2 sheets of heat sensitive tape.
  • the sandwich was heated and pressurized at 153°C-155.5°C (308°F-312°F). with a hand iron. Samples were cut into 1.5 cm by 20 cm. After ironing, the samples are positioned in a delamination press for 30 seconds at 135°C (275°F) and 186.2 kPa (27 psig).
  • the samples were then tested on the Thwing-Albert Intellect II. Jaw separation was one inch and jaw speed was 25 cm/min. The test conditions were at 50% relative humidity and 22.2°C (72°F). The results are set forth below in Table N.
  • the delamination resistance of the three samples of the present invention are very comparable to the Hycar latexes designed for paper use.
  • This example demonstrates the durability to dry cleaning and washing of a nonwoven fabric treated with the latex of the present invention.
  • All the samples were saturated with different levels of latex add-on and dried at approximately 100°C (212°F) on a photoprint dryer and cured for 3 minutes at 149°C (300°F) in an air circulating oven.
  • the washability test was a modified AATCC #61-1980-II-A test using a Launder-O-Meter for 1 cycle (1 cycle represents approximately 5 machine washings).
  • the entangled nonwoven fabric chosen was Dupont's Sontara® 8103 fabric. The results are reported in Table O. Table O % Latex Add-On Comments Control - 0% All samples OK - no fabric damage, treated samples were still resilient indicating minimal or no loss of polymer. All samples, including control sample, had a slightly softer hand after testing. 4% 10% 18%
  • the dry cleaning test was a modified AATCC #86-1761 test on a Launder-O-Meter for one 30 minute cycle. The results of this test is set forth in Table P. Table P % Latex Add-On Comments Control - 0% All samples OK - no fabric damage, treated samples were still resilient. All samples including control had a slightly softer hand. 3.9% 9.0% 17%
  • This example shows that a significant level of resiliency can be imparted to an entangled synthetic fiber nonwoven fabric using the latex of this invention.
  • This example demonstrates the resistance to heat aging which can cause latex treated nonwoven fabrics to discolor. Yellowing or other discoloration is not desirable in many end use applications of nonwoven fabrics.

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Claims (14)

  1. Matériau fibreux non tissé, constitué de fibres liées les unes aux autres par un liant composé essentiellement de chaînes polymères contenant en majorité des groupes acrylates comprenant des motifs répétitifs dérivés de l'acide itaconique, et jusqu'à 98,9 parties en poids d'un acrylate représenté par la structure
    Figure imgb0024
     dans laquelle
       R₁ est un hydrogène ou le radical méthyle,
       R₂ est un radical alkyle en C₁-C₂₀, alcoxyalkyle en C₂-C₇, alcoxythioalkyle en C₂-C₇, un radical cyanoalkyle ayant de 2 à 12 atomes de carbone ou un de leurs mélanges ;
       l'acide itaconique est présent dans l'intervalle de 1 à 20 parties en poids ; au moins 40 parties en poids de l'acrylate se trouvant dans le polymère sont présents sous forme d'un acrylate d'alkyle ; le polymère, sous forme d'une émulsion aqueuse, étant appliqué comme il convient dans l'étoffe à une température de transition vitreuse (Tg) comprise dans l'intervalle de -20 à -60°C, caractérisé en ce que le polymère est présent sous forme d'unpolymère réticulé, et que la réticulation est effectuée par un monomère de réticulation présent en une quantité comprise dans l'intervalle de 0,1 à 20 parties en poids.
  2. Matériau fibreux non tissé selon la revendication 1, dans lequel le monomère de réticulation est choisi parmi l'ensemble comprenant le N-méthylolacrylamide et le carbamate de bis-(N-méthylol)allyle, le N-méthylolacrylamide éthérifié par un alcanol en C₁-C₄ et le carbamate de bis-(N-méthylol)allyle éthérifié avec un alcanol en C₁-C₄.
  3. Matériau fibreux non tissé selon la revendication 1, dans lequel les chaînes polymères comprennent des motifs répétitifs d'un monomère copolymérisé choisi parmi l'ensemble comprenant les acrylates d'alkyle, les monomères diacrylates et diméthacrylates ; les monooléfines en C₂-C₁₀, les acétates de vinyle et d'allyle en C₂-C₁₀, les vinylcétones en C₄-C₂₀, les oxydes d'allyle en C₄-C₂₀, les vinylaromatiques en C₈-C₂₀, les vinylnitriles en C₃-C₆, les vinylamides en C₄-C₂₀, les diènes et divinyles en C₄-C₂₀ ; les monomères en C₂-C₂₀ contenant un halogène ; les monomères sulfonates insaturés ; les esters d'acides carboxyliques insaturés et les amides insaturés en C₄-C₂₀ ; et les acides monocarboxyliques insaturés en C₃-C₅.
  4. Matériau fibreux non tissé selon la revendication 1 ou 3, dans lequel le monomère copolymérisé est l'acrylate de n-butyle, et l'acide itaconique est présent en une quantité comprise dans l'intervalle de 2 à 8 parties en poids.
  5. Etoffe non tissée selon la revendication 1 ou 2, dans laquelle monomère de réticulation est le N-méthylolacrylamide, présent en une quantité comprise dans l'intervalle de 0,5 à 10 parties en poids.
  6. Matériau fibreux non tissé selon la revendication 1, dans lequel le matériau est une étoffe non tissée revêtue d'un film non autoporteur d'un polymère.
  7. Etoffe non tissée selon la revendication 1, dans laquelle le polymère a une Tg de -25 à -50°C.
  8. Procédé pour fabriquer une étoffe non tissée, qui consiste à associer, dans un tissu, une masse de fibres, à mettre en contact avec les fibres un liant comprenant une émulsion aqueuse d'un liant constitué essentiellement de chaînes polymeres contenant en majorité des groupes acrylates, comprenant des motifs répétitifs dérivés de l'acide itaconique, et jusqu'à 98,9 parties en poids d'un acrylate représenté par la structure
    Figure imgb0025
     dans laquelle
       R₁ est un hydrogène ou le radical méthyle,
       R₂ est un radical alkyle en C₁-C₂₀, alcoxyalkyle en C₂-C₇, alcoxythioalkyle en C₂-C₇, un radical cyanoalkyle ayant de 2 à 12 atomes de carbone ou un de leurs mélanges;
       l'acide itaconique est présent dans l'intervalle de 1 à 20 parties en poids ; au moins 40 parties en poids de l'acrylate se trouvant dans le polymère sont présents sous forme d'un acrylate d'alkyle ; le polymère, sous forme d'une émulsion aqueuse, étant appliqué comme il convient dans l'étoffe à une température de transition vitreuse (Tg) comprise dans l'intervalle de -20 à -60°C ; et à sécher et durcir les fibres traitées par le liant, dans des conditions de chauffage telles qu'il y ait production de l'étoffe non tissée, caractérisé en ce que le polymère est présent sous forme d'un polymère réticulé, et que la réticulation est effectuée par un monomère de réticulation présent en une quantité comprise dans l'intervalle de 0,1 à 20 parties en poids.
  9. Procédé selon la revendication 8, dans lequel le monomère de réticulation est choisi parmi l'ensemble comprenant le N-méthylolacrylamide et le carbamate de bis-(N-méthylol)allyle, le N-méthylolacrylamide éthérifié par un alcanol en C₁-C₄ et le carbamate de bis-(N-méthylol)allyle éthérifié avec un alcanol en C₁-C₄.
  10. Procédé selon la revendication 8, dans lequel les chaînes polymères comprennent des motifs répétitifs d'un monomère copolymérisé choisi parmi l'ensemble comprenant les acrylates d'alkyle, les monomères diacrylates et diméthacrylates ; les monooléfines en C₂-C₁₀, les acétates de vinyle et d'allyle en C₂-C₁₀, les vinylcétones en C₄-C₂₀, les oxydes d'allyle en C₄-C₂₀, les vinylaromatiques en C₈-C₂₀, les vinylnitriles en C₃-C₆, les vinylamides en C₄-C₂₀, les diènes et divinyles en C₄-C₂₀ ; les monomères en C₂-C₂₀ contenant un halogène ; les monomère sulfonates insaturés ; les esters d'acides carboxyliques insaturés et les amides insaturés en C₄-C₂₀ ; et les acides monocarboxyliques insaturés en C₃-C₅.
  11. Procédé selon la revendication 8 ou 10, dans lequel le monomère copolymérisé est l'acrylate de n-butyle, et l'acide itaconique est présent en une quantité comprise dans l'intervalle de 2 à 8 parties en poids.
  12. Procédé selon la revendication 8, dans lequel le monomère de réticulation est le N-méthylolacrylamide, présent en une quantité comprise dans l'intervalle de 0,5 à 10 parties en poids.
  13. Procédé selon la revendication 8, dans lequel l'étape d'association comprend l'étape consistant à doser le latex dans le réacteur, un prémix comprenant le monomère copolymérisable et jusqu'à la moitié de l'acide itaconique, le réacteur contenant au moins une moitié de l'acide itaconique, à ajouter l'agent de réticulation à l'acide itaconique puis à mettre en oeuvre la polymérisation dans le réacteur à une température de 0 à 100°C.
  14. Procédé selon la revendication 13, dans lequel la totalité de l'acide itaconique est introduite initialement dans le réacteur, le prémix ne contenant pas d'acide itaconique.
EP87115223A 1986-10-20 1987-10-17 Etoffe non tissée avec un interpolymère d'acrylate comme liant, et procédé pour la fabriquer Revoked EP0264869B1 (fr)

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AU643014B2 (en) 1990-07-31 1993-11-04 Kimberly-Clark Worldwide, Inc. Elastomeric saturated nonwoven material
EP0510153A1 (fr) * 1990-11-14 1992-10-28 Vinamul Ltd. Ameliorations relatives a des matieres fibreuses non-tissees
US5143582A (en) * 1991-05-06 1992-09-01 Rohm And Haas Company Heat-resistant nonwoven fabrics
AU6666996A (en) * 1995-08-29 1997-03-19 Rhone-Poulenc, Inc. Aqueous polymer emulsions useful as wallcovering prepaste adhesives
CN1325713C (zh) * 2003-09-02 2007-07-11 徐方坤 一种硬质无纺棉的制造方法
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CN100453625C (zh) * 2006-03-07 2009-01-21 路俊杰 合成环保甲醇燃料
JP5241901B2 (ja) * 2010-10-28 2013-07-17 ローム アンド ハース カンパニー 水性不織物バインダーおよびこれから製造された処理された不織物
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CN113308903B (zh) * 2021-05-26 2022-09-06 成都德美精英化工有限公司 一种水性丙烯酸酯涂层胶及其制备方法

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MX169303B (es) 1993-06-29
CA1332901C (fr) 1994-11-08
DE3750209T2 (de) 1994-11-17
AU7959687A (en) 1988-04-21
CN87107050A (zh) 1988-06-29
CN1012086B (zh) 1991-03-20
JP2559427B2 (ja) 1996-12-04
ES2059341T3 (es) 1994-11-16
JPS63165563A (ja) 1988-07-08
ATE108496T1 (de) 1994-07-15
AU612600B2 (en) 1991-07-18
KR880005305A (ko) 1988-06-28
DE3750209D1 (de) 1994-08-18
EP0264869A3 (en) 1990-02-14
EP0264869A2 (fr) 1988-04-27

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