EP4206374A1 - Chemisch gebundene vliesstoffsubstrate - Google Patents

Chemisch gebundene vliesstoffsubstrate Download PDF

Info

Publication number
EP4206374A1
EP4206374A1 EP21306964.4A EP21306964A EP4206374A1 EP 4206374 A1 EP4206374 A1 EP 4206374A1 EP 21306964 A EP21306964 A EP 21306964A EP 4206374 A1 EP4206374 A1 EP 4206374A1
Authority
EP
European Patent Office
Prior art keywords
acid
resin
polyester resin
chemically bonded
fibers
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.)
Withdrawn
Application number
EP21306964.4A
Other languages
English (en)
French (fr)
Inventor
Filippo FINETTI
Maria-Chiara PICCININI
Daniel Stark
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.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Priority to EP21306964.4A priority Critical patent/EP4206374A1/de
Priority to EP22844169.7A priority patent/EP4457392A1/de
Priority to CN202280086523.5A priority patent/CN118525116A/zh
Priority to MX2024007844A priority patent/MX2024007844A/es
Priority to PCT/EP2022/087823 priority patent/WO2023126374A1/en
Publication of EP4206374A1 publication Critical patent/EP4206374A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—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 relates to chemically bonded nonwoven substrates and to polyester binders for chemically bonding nonwoven fibers of a nonwoven substrate.
  • Nonwoven substrates relate to fabric-like materials made from fibers or filaments arranged into a web.
  • the web may be formed by a dry-laid or wet-laid process.
  • the web is then consolidated by bonding the fibers, in other words by forming attachment points between the fibers.
  • Chemical bonding is a consolidation method involving the use of an aqueous dispersion of polymer particles (also referred to as a latex) to bond the fibers.
  • Nonwoven substrates are therefore distinct from knitted substrates or woven substrates in that the substrate is formed by directly bonding the fibers to one another without any interlacing or stitching step.
  • EVA ethylene-vinyl acetate
  • ACR acrylic
  • binders In the field of durable (i.e. reusable) nonwovens, such as technical nonwovens or composite materials, other polymers may be used as binders.
  • acrylic modified polymeric dispersions such as vinyl acrylic dispersions, as well as SBR latexes and vinyl acetate homo-polymers can be used.
  • N-MA N-methylolacrylamide
  • US patent number 4,455,342 discloses an aqueous dispersion of an acrylic resin, which is suitable for the reinforcement of fibrous articles, such as nonwovens, while being free of formaldehyde or formaldehyde-releasing substances.
  • Acrylic binders are mostly made from petroleum-based materials. Also, acrylic dispersions are prone to the development of bacteria and require the use of antimicrobial substances.
  • the mechanical properties in dry and wet conditions are a key parameter.
  • the nonwoven producers are still interested in new polymers having formaldehyde free crosslinking functionalities, good mechanical applicative properties but also exhibiting a high bio-sourced content.
  • a polyester resin can be used as a non-formaldehyde-releasing binder for chemically bonding nonwoven fibers to provide nonwoven substrates with good water absorbency and good mechanical properties, in particular the wet tensile strength.
  • the alkyd resin according to the invention can be bio-sourced and optionally biodegradable.
  • the present invention thus relates to a chemically bonded nonwoven substrate comprising nonwoven fibers bonded by a binder comprising a polyester resin.
  • the present invention also relates to a method for chemically bonding fibers of a nonwoven substrate comprising:
  • the present invention also relates to a use of a polyester resin for chemically bonding nonwoven fibers.
  • the word “comprising” is synonymous to "include” or “contain”.
  • a subject-matter is said to comprise one or several features, it is meant that other features than those mentioned can be comprised in the subject-matter.
  • a subject-matter is said to consist of one or several features, it is meant that no other features than those mentioned are comprised in the subject-matter.
  • a subject-matter is said to consist essentially of one or several features, it is meant that other features than those mentioned may be comprised in the subject-matter in minor proportion (for example a composition consisting essentially of Z means a composition comprising more than 90%, more than 95%, more than 98%, more than 99%, more than 99.5%, more than 99.9% or even 100%, by weight of Z based on the weight of the composition).
  • Nonwoven fibers according to the invention relate to any fiber suitable to prepare nonwoven substrates.
  • the nonwoven fibers may be selected from natural fibers, modified natural fibers, synthetic fibers, inorganic fibers and mixtures thereof.
  • Natural fibers are bio-sourced fibers derived from plants or animals.
  • Animal fibers are fibers made of proteins, which can be obtained from the hair, fur, wool or silk of animals, such as sheep, alpaca, rabbits, goats, horses, llamas, minks or camels.
  • Plant fibers also referred to as cellulosic fibers, are fibers made with ethers or esters of cellulose, which can be obtained from the bark, wood, stem, leaves, flowers or fruits of plants, such as cotton, flax, jute, hemp, sisal, kenaf, nettle, ramie or abaca.
  • the fibers may also contain hemicellulose and lignin, with different percentages of these components altering the mechanical properties of the fibers.
  • Modified natural fibers also referred to as artificial fibers, are natural fibers that have been modified by one or more chemical treatments, such as enzymatic treatment, maleinization, epoxidation, esterification, anhydridation or alkoxylation, and/or physical treatments, such as heating or applying steam.
  • suitable modified natural fibers include viscose, modal, and lyocell.
  • Synthetic fibers are fibers made by humans through polymerization, mainly of petroleum-based raw materials. Synthetic fibers may be created by extruding fiber-forming materials through spinnerets. Examples of suitable synthetic fibers include polyester, polyamide, acrylic, aramid or olefin (such as polyethylene, or polypropylene).
  • Inorganic fibers are fibers made of inorganic material.
  • Inorganic fibers can be obtained from inorganic substances such as rock, slag, clay or glass, or from organic material such as pitch, tar or synthetic fibers.
  • suitable inorganic fibers include mineral wool, glass fibers, basalt fibers, carbon fibers, ceramic fibers or metal fibers.
  • the nonwoven fibers may be natural fibers, in particular cellulosic fibers.
  • the nonwoven fibers have a diameter of from about 500 nm to about 100 ⁇ m, more preferably of about 1 ⁇ m to about 50 ⁇ m, most preferably of about 1 ⁇ m to about 10 ⁇ m.
  • the polyester resin according to the invention may be based on:
  • a polyester resin based on component X or "a polyester resin comprising component X” means a polyester resin obtained by polymerization of a composition comprising component X, in other words a polyester resin comprising units derived from the polymerization of component X.
  • the polyester resin according to the invention is at least partially bio-sourced.
  • the polyester resin according to the invention may be based on at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 97%, at least 98%, at least 99% or even 100%, by weight of bio-sourced components based on the total weight of the polyester resin.
  • the polyester resin according to the invention are said to be "bio-sourced” when they originate from plants or animals, optionally after chemical modifications, such as hydrogenation, hydroxylation, maleinization, epoxidation, esterification, anhydridation or alkoxylation, or after physical treatments, such as heating.
  • suitable bio-sourced components include rosin, glycerol, naturally occurring oils and fats (i.e. triglycerides extracted from plants, animals or milk), naturally occurring fatty acids, mono- or di-glycerides of naturally occurring fatty acids, naturally occurring polyacids, as well as dimers or trimers thereof and alkyl esters thereof.
  • the polyester resin may be based on a fatty component.
  • an alkyd resin may correspond to a polyester resin based on:
  • an alkyd resin may correspond to a polyester resin based on:
  • fatty component means a component comprising at least one fatty acid or a derivative thereof.
  • fatty acid means a compound of formula R-COOH wherein R is an aliphatic hydrocarbon chain bearing from 7 to 36 carbon atoms, preferably 16 to 24 carbon atoms, which may optionally be substituted by one or more substituents such as methyl or hydroxyl.
  • a fatty acid may be saturated or unsaturated. When a fatty acid is unsaturated it may comprise one or more carbon-carbon double bonds.
  • An unsaturated fatty acid may also be referred to as an oxidizable fatty acid as the unsaturations may be oxidized in the presence of air, optionally in the presence of a drier catalyst, to provide crosslinked structures during curing of the alkyd resin.
  • fatty acid derivative means a fatty acid that has been modified, for example by one or more of the following reactions:
  • the fatty component may comprise at least one fatty acid selected from caprylic acid (8:0), capric acid (10:0), lauric acid (12:0), myristic acid (14:0), palmitic acid (16:0), stearic acid (18:0), 12-hydroxystearic acid (18:0), arachidic acid (20:0), behenic acid (22:0), lignoceric acid (24:0), cerotic acid (26:0), myristoleicacid (14:1), palmitoleic acid (16:1), sapienic acid (16:1), oleic acid (18:1), elaidic acid (18:1), vaccenic acid (18:1), linoleic acid (18:2), linoelaidic acid, (18:2), alpha-linolenic acid (18:3), arachidonic acid (20:4), eicosapentaenoic acid (20:5), erucic acid (22:1), docosahexaenoic acid (22:3)
  • the fatty component may comprise a mixture of fatty acids or derivatives thereof, for example a mixture of monoacids derived from plants or animals, preferably plants.
  • mixtures include soybean oil fatty acids (SOFA), sunflower oil fatty acids, tall oil fatty acids (TOFA), castor oil fatty acids (COFA), dehydrated castor oil fatty acids (DCOFA), linseed oil fatty acids (LOFA), rapeseed oil fatty acids, palm oil fatty acids, palm kernel oil fatty acids, coconut oil fatty acids, safflower oil fatty acids, derivatives thereof and mixtures thereof.
  • the fatty acid component has an average iodine value of from 100 to 200 mg of iodine per gram of fatty acid component.
  • the weight ratio between unsaturated fatty acids and total fatty acid of the fatty component according to the invention is of 0, of 1, or of from 0 to 1, from 0 to 0.5, or from 0.5 to 1.
  • the polyester resin according to the invention has an oil length of from 5% to 40%, in particular of from 10% to 35%, more particularly of from 15% to 30% by weight based on the total weight of the polyester resin.
  • the "oil length" of the polyester resin according to the invention relates to the weight percentage of the fatty component, relative to the total weight of the resin. If the polyester resin is based on a rosin component comprising tall-oil fatty acids, said tall-oil fatty acids are included in the weight percentage of the fatty component. If the polyester resin is based on a polyacid component comprising a fatty acid dimer or trimer, said fatty acid dimer or trimer is included in the weight percentage of the fatty component. If the polyester resin does not comprise a fatty component, then the oil length of the polyester resin is 0%. Such a polyester may also be referred to as an oil-free polyester.
  • the polyester resin according to the invention has an oxidizable unsaturation content of from 0 mmol to 0.25 mmol, in particular of from 0 mmol to 0.15 mmol, more particularly of from 0 mmol to 0.05 mmol, of oxidizable unsaturations per g of dry resin.
  • the polyester resin may be based on a rosin component. Suitable rosin-based polyester resins according to the invention are notably described in International publication WO 2012/042153 which is incorporated herein by reference.
  • rosin component means a component comprising rosin or a derivative thereof.
  • rosin also referred to as colophony
  • Rosin is a natural resin derived from resinous trees, in particular conifers, such as pines, cedars, firs, hemlocks, larches, spruces. Rosin may be produced by heating conifer oleoresin (i.e. gum tapped from living conifers) to eliminate the volatile liquid terpene components, also referred to as turpentine. Rosin produced with this process may be referred to as gum rosin. Gum rosin generally comprises resin acids and is substantially exempt of fatty acids. Alternatively, rosin may be produced from the distillation of crude tall-oil (CTO).
  • CTO crude tall-oil
  • Rosin produced with this process may be referred to as tall-oil rosin (TOR) or tall-oil pitch and is referenced under CAS No. [8016-81-7 ].
  • Crude tall-oil is a by-product resulting from the manufacture of paper pulp by the Kraft process.
  • the lignin and the hemicellulose degrade and dissolve in the liquor, whereas the cellulose can be recovered in the form of pulp and then washed.
  • the liquor which also contains resin acids and fatty acids in the form of sodium carboxylates, may be recovered and concentrated.
  • the foam which forms at the surface of the concentrated liquor also referred to as kraft soap or resin soap, may be recovered and acidified under hot conditions with sulfuric acid so as to provide crude tall-oil. Crude tall-oil may then be distilled at reduced pressure to provide tall-oil rosin as the residual non-volatile fraction.
  • Tall-oil rosin generally comprises resin acids and tall-oil fatty acids (mainly palmitic acid, oleic acid and linoleic acid).
  • rosin encompasses gum rosin and tall-oil rosin.
  • the composition of rosin varies depending on the resinous tree used and where it comes from.
  • rosin derivative means a rosin that has been modified, for example by one or more of the reactions described above for the modification of a fatty acid.
  • the rosin component may comprise at least one resin acid or a derivative thereof.
  • the rosin component of the polyester resin may comprise a mixture of resin acids or derivatives thereof.
  • a “resin acid”, also called a “resinous acid” or “rosin acid” refers to a polycyclic compound, in particular a terpenoid, bearing one carboxylic acid group which can be derived from resinous trees, in particular conifers.
  • the term “resin acid derivative” means a resin acid that has been modified, for example by one or more of the reactions described above for the modification of a fatty acid.
  • the rosin component comprises at least one resin acid selected from the group consisting of abietic acid, pimaric acid, levopimaric acid, dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, palustric acid, neoabietic acid, isopimaric acid, sandaracopimaric acid, derivatives thereof and mixtures thereof.
  • the polyester resin according to the invention may be based on from 20% to 85%, in particular from 25% to 80%, more particularly from 30% to 75%, even more particularly from 35% to 70%, by weight of resin acid or derivative thereof, based on the total weight of the polyester resin.
  • the polyester resin may be based on a polyacid component.
  • polyacid component means a component comprising a polyacid or a derivative thereof.
  • the polyacid component may comprise a mixture of polyacid or derivatives thereof.
  • a polyacid is a compound bearing at least two -COOH groups, in particular from 2 to 3 -COOH groups.
  • the term "polyacid derivative" is a compound capable of yielding a polyacid in situ, for example by hydrolysis or ring opening. Examples of suitable polyacid derivatives include alkyl esters of a polyacid and cyclic anhydrides.
  • the polyacid may preferably be an aromatic polyacid or an aliphatic polyacid (i.e. a non-aromatic polyacid).
  • Suitable polyacids include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, adipic acid, azelaic acid, glutaric acid, 3,3-diethylglutaric acid, malonic acid, pimelic acid, sebacic acid, suberic acid, succinic acid, 2,2-dimethylsuccinic acid, 2-methylsuccinic acid, dodecenylsuccinic, acid, dodecanedioic acid, citric acid, a fatty acid dimer, a fatty acid trimer, itaconic acid, fumaric acid, maleic acid, citraconic acid, trimellitic acid, derivatives thereof and mixtures thereof.
  • the polyester resin according to the invention may be based on 10% to 55%, in particular from 15% to 50%, more particularly from 20% to 45%, even more particularly from 25% to 40%, by weight of polyacid or derivative thereof, based on the total weight of the polyester resin.
  • the polyester resin may be based on a polyol component.
  • polyol component means a component comprising a polyol or a derivative thereof.
  • the polyol component may comprise a mixture of polyols.
  • polyol means a compound bearing at least two hydroxyl (OH) groups.
  • a polyol may have an OH functionality ranging from 2 to 10, preferably from 3 to 6.
  • the polyol may bear from 2 to 10, preferably from 3 to 6 OH groups.
  • the polyol component may comprise a polyol having an OH functionality of at least 3.
  • the polyol component according to the invention comprises at least one polyol selected from the group consisting of ethylene glycol, polyethylene glycol (preferably with a number-average molecular mass Mn ranging from 300 to 6,000 g/mol), propylene glycol (1,2-propanediol), 1,3-propanediol, dipropylene glycol, triethylene glycol, glycerol, diglycerol, trimethylolpropane, di(trimethylolpropane), trimethylolethane, pentaerythritol, dipentaerythritol, sorbitol, mannitol, methyl glucoside, polyglycerol (in particular glycerol oligomers, such as Polyglycerol-3 and decaglycerol) as well as the alkoxylated (i.e. ethoxylated and/or propoxylated derivatives thereof) and mixtures thereof.
  • polyglycerol in particular gly
  • polyglycerol-3 is a mixture of glycerol oligomers, i.e. glycerol oligomerized in the presence of oligomers containing 30% to 55% by weight of glycerol trimer constituting the predominant oligomer.
  • the polyol component comprises, or consists of, polyglycerol-3, in particular with a -OH functionality ranging from 5 to 6.
  • the polyester resin according to the invention has an acid number of 2 to 15, preferably from 5 to 12 mg KOH/g.
  • the polyester resin according to the invention has a hydroxyl number of 30 to 120, preferably from 40 to 100 mg KOH/g.
  • the polyester resin according to the invention has a number-average molecular mass Mn, measured by GPC as polystyrene equivalents in THF, of from 1000 to 10 000, in particular of from 1100 to 5000, more particularly of from 1200 to 3500.
  • the polyester resin according to the invention has a Tg, measured by DSC, ranging from -40°C to 50°C and more preferably from -20°C to 35°C.
  • a particularly preferred polyester resin is a rosin-based alkyd resin marketed under trade name SYNAQUA ® 4856 by Arkema.
  • the preparation of the polyester resin according to the invention in particular the alkyd resin according to the invention, can be performed by polycondensation reaction under inert atmosphere at a temperature of between 180°C and 300°C, preferably between 250°C and 270°C, preferentially with removal of the water formed during condensation.
  • a vacuum (reduced pressure) of moderate level ranging from 50 to 250 mmHg may be applied at the end of the polycondensation in order to reduce the reaction times.
  • additives in particular antioxidants, as employed in the preparation of rosin esters used in particular for adhesives: phenol sulfites, paraformaldehyde, hypophosphorous acid, trialkyl or triphenyl phosphites.
  • antioxidants as employed in the preparation of rosin esters used in particular for adhesives: phenol sulfites, paraformaldehyde, hypophosphorous acid, trialkyl or triphenyl phosphites.
  • the polyester resin is subsequently emulsified to provide an aqueous emulsion of polyester resin.
  • the emulsion may be obtained by phase inversion in the presence of one or more surfactants or by self-emulsification without any surfactant, preferably by phase inversion in the presence of one or more surfactants.
  • the emulsification may be carried out at a temperature of from 30 to 90°C and preferably from 50 to 85°C.
  • the emulsification may be carried out in a reactor stirred via a dual-flow stirring system.
  • the resin may be emulsified, at neutral or slightly alkaline pH.
  • the resin may be emulsified in the presence of a surfactant or a mixture of surfactants.
  • a surfactant improves the stability of the dispersion, thus preventing sedimentation and/or coalescence during the emulsification and storage/use of the product.
  • a selection criterion for a nonionic surfactant is the HLB index (hydrophilic-lipophilic balance) representing the ratio of hydrophilic and hydrophobic characters in the surfactant.
  • the surfactant may comprise a surfactant selected from an ionic surfactant (preferably anionic surfactant), a nonionic surfactant, a hybrid surfactant of mixed structure and combinations thereof.
  • an ionic surfactant preferably anionic surfactant
  • a nonionic surfactant preferably anionic surfactant
  • a hybrid surfactant of mixed structure and combinations thereof preferably anionic surfactant
  • anionic surfactants that are suitable for this invention, mention may be made of sodium, lithium, potassium, ammonium or magnesium salts of alkyl ether sulfates (in particular with alkyl ranging from C 8 to C 18 or C 12 ), alkyl benzene sulfates, alkyl sulfates, alkyl phosphates, dialkyl sulfosuccinate esters or even soaps obtained from the corresponding fatty acids.
  • the anionic surfactant is preferably used in combination with at least one nonionic surfactant.
  • a hybrid surfactant of mixed structure is a surfactant which comprises both a nonionic structure, such as a polyoxyalkylene segment (more particularly oxyethylene and/or oxypropylene units) and an anionic structure (for instance a sulfonate or sulfate or phosphate or phosphonate group) on the same molecule or molecular chain.
  • the hybrid surfactant of mixed structure may be a sulfonate, sulfate, phosphate or phosphonate ester of a polyether alcohol or of an alkoxylated fatty alcohol.
  • Another example of a hybrid mixed surfactant is an alkoxylated alkyl phenol sulfonate or phosphonate.
  • nonionic surfactants examples include: ethoxylated C 12 -C 18 fatty alcohols (6 to 50 OE), ethoxylated iso-C 10 fatty alcohols (6 to 50 OE), ethoxylated mono-branched C 10 -C 18 fatty alcohols (6 to 50 OE), sorbitol fatty esters, ethoxylated sorbitol esters (5-50 OE), alkyl polyglucosides, glucamides, glycerol, diglycerol or polyglycerol fatty esters, ethoxylated fatty acids (7-100 OE), ethoxylated castor oil (hydrogenated or non-hydrogenated) (30-40 OE), glycol or polyethylene glycol fatty acids, nonionic polymers and other block copolymers, for instance poly(propylene glycol)-poly(ethylene glycol) block copolymer.
  • the nonionic surfactant is preferably combined with an anionic surfact
  • a combination of a nonionic surfactant and of an anionic surfactant is used.
  • the weight ratio of the ionic surfactant to nonionic surfactant may be from 25/75 to 50/50.
  • Such a combinations advantageously provides stable emulsions with a small particle size, preferably less than 300 nm.
  • the total amount of surfactant may be from 2% to 15%, preferably from 5% to 10%, by weight based on the weight of the polyester resin.
  • the pH of the medium is preferably adjusted as a function of the acidity of the resin. This is why a basic aqueous solution, of from 1% to 50% and preferably from 10% to 20% by weight of base, may be introduced after the addition of the surfactants, at the emulsification temperature.
  • basic (alkaline) aqueous solutions may be used, such as aqueous LiOH, NaOH or KOH solutions, aqueous ammonia or amines, preferably tertiary or hindered amines, such as diethanolamine, triethanolamine, aminomethylpropane or triethylamine.
  • the aqueous dispersion of the resin may also be obtained by self-emulsification of the resin without any surfactant after at least partial neutralization of the carboxylic functions of the resin.
  • the binder according to the invention comprises at least one polyester resin according to the invention.
  • the binder according to the invention may be contacted with the nonwoven fibers in an uncured (i.e. liquid) state.
  • the binder may be in a cured state forming a cured (i.e. solid) polymer matrix interconnecting the nonwoven fibers.
  • the term "binder" may thus indifferently refer to an uncured binder (prior to curing) or to a cured binder (after curing).
  • the cured binder may be obtained by curing the uncured binder.
  • the uncured binder may be in the form of an aqueous emulsion of the polyester resin as defined above, preferably an oil-in water emulsion of the polyester resin.
  • the uncured binder may comprise polyester resin droplets dispersed in an aqueous phase. During curing, the aqueous phase of the emulsion may be removed and the polyester resin droplets may coalesce to form a continuous polymer matrix.
  • the aqueous emulsion may have a solids content relative to the weight of the aqueous emulsion ranging from 30% (w/w) to 70% (w/w) and preferably from 40% (w/w) to 60% (w/w).
  • the mean particle size of the polymer droplets of the aqueous emulsion according to the invention ranges from 100 to 500 nm.
  • the aqueous emulsion according to the invention may be free of any organic solvent, this meaning a corresponding content of volatile organic compounds (VOC) in said emulsion of less than 2000 ppm, preferably less than 1000 ppm and more preferentially less than 500 ppm.
  • VOC volatile organic compounds
  • the binder according to the invention may further comprise at least one moisture-retaining additive, such as a glycol, in particular a polyethylene glycol (PEG).
  • a moisture-retaining additive such as a glycol, in particular a polyethylene glycol (PEG).
  • the binder according to the invention may also comprise at least one surfactant or a mixture of surfactants as described above.
  • the binder of the invention may comprise a second resin which is distinct from the polyester resin as defined above.
  • the binder according to the invention comprises at least one ethylenically unsaturated resin, more preferably an aqueous dispersion of an ethylenically unsaturated resin.
  • the ethylenically unsaturated resin may be simply admixed with the polyester resin, i.e. the ethylenically unsaturated resin and the polyester resins are prepared separately and are mixed together after they have been polymerized.
  • the ethylenically unsaturated resin and the polyester resin may not be in a co-polymerized form.
  • the binder may thus be an aqueous composition comprising emulsified droplets of polyester resin and ethylenically unsaturated resin particles which are distinct from one another.
  • the ethylenically unsaturated resin and the polyester resin may not be bonded to one another by chemical covalent bonds or strong physical intermolecular interactions such as hydrogen bonding or electrostatic interactions.
  • the ethylenically unsaturated resin and the polyester resins may be co-polymerized or form a hybrid polymer.
  • a multistage polymerization process can be used wherein a first resin is prepared in a first step and, in a subsequent step, one or more monomers of a second resin are added and polymerized in the presence of the first resin.
  • the polyester resin and the ethylenically unsaturated resin may be prepared separately and subsequently bonded to one another by chemical covalent bonds or strong physical intermolecular interactions.
  • the ethylenically unsaturated resin comprises carboxylic acid groups, they can react with the hydroxyl groups of the polyester resin by heating.
  • the binder may thus be an aqueous dispersion of particles comprising both the ethylenically unsaturated resin and the polyester resin.
  • the presence of at least one ethylenically unsaturated resin in the binder improves the mechanical properties of the resulting chemically bonded nonwoven substrates.
  • the ethylenically unsaturated resin may be selected from a (meth)acrylic resin, a vinylic resin, a styrenic resin, an olefinic resin and mixtures thereof.
  • a (meth)acrylic resin is a polymer comprising monomeric units derived from the polymerization of one or more (meth)acrylic monomers, such as alkyl (meth)acrylates (in particular methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate or 2-ethylhexyl (meth)acrylate), hydroxyalkyl (meth)acrylates (in particular 2-hydroxyethyl (meth)acrylate), (meth)acrylic acid, (meth)acrylamide, (meth)acrylonitrile or mixtures thereof; and optionally one or more ethylenically unsaturated co-monomers, such as vinyl aromatic monomers (in particular styrene), vinyl monomers, unsaturated polyacids, unsaturated polyacid derivatives, or mixtures thereof.
  • alkyl (meth)acrylates in particular methyl (meth)acrylate
  • the resin when the (meth)acrylic resin comprises monomeric units derived from vinyl co-monomers as described below, the resin may be referred to as a vinyl-(meth)acrylic resin.
  • the resin when the (meth)acrylic resin comprises monomeric units derived from vinyl aromatic co-monomers as described below, the resin may be referred to as a styrene-(meth)acrylic resin.
  • a vinylic resin is a polymer comprising monomeric units derived from the polymerization of one or more vinyl monomers, such as vinyl halides (in particular vinyl chloride), vinyl esters (in particular vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl pentanoate, vinyl hexanoate, vinyl octanoate, vinyl 2-ethylhexanoate, vinyl pelargonate, vinyl laurate, vinyl stearate, and vinyl versatate, i.e.
  • vinyl halides in particular vinyl chloride
  • vinyl esters in particular vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl pentanoate, vinyl hexanoate, vinyl octanoate, vinyl 2-ethylhexanoate, vinyl pelargonate, vinyl laurate, vinyl stearate, and vinyl versatate,
  • esters of branched monocarboxylic acids having 6, 9, 10 or 11 carbon atoms available under references VeoVa ® EH, VeoVa ® 9, VeoVa ® 10 or VeoVa ® 11 from Hexion), vinyl ethers (in particular methyl-, ethyl-, butyl- or iso-butyl vinyl ether) or mixtures thereof; and optionally one or more ethylenically unsaturated co-monomers, such as olefins, (meth)acrylic monomers, unsaturated polyacids, unsaturated polyacid derivatives, or mixtures thereof.
  • the resin When the vinylic resin is a vinyl ester resin that comprises monomeric units derived from (meth)acrylic co-monomers as described above, the resin may be referred to as a vinyl ester-(meth)acrylic resin.
  • the vinylic resin is a vinyl ester resin (in particular a vinyl acetate resin) that comprises monomeric units derived from an ethylene co-monomer, the resin may be referred to as an ethylene-vinyl ester resin (in particular an ethylene-vinyl acetate resin (EVA)).
  • EVA ethylene-vinyl acetate resin
  • a styrenic resin is a polymer comprising monomeric units derived from the polymerization of one or more vinyl aromatic monomers, such as styrene, alpha-methylstyrene, tert-butylstyrene, ortho-, meta- or para-methylstyrene, ortho-, meta- or para-ethylstyrene, o-methyl-p-isopropylstyrene, p-chlorostyrene, p-bromostyrene, o,p-dichlorostyrene, o,p-dibromostyrene, ortho-, meta- or para-methoxystyrene, optionally substituted indenes, optionally substituted vinylnaphthalenes, acenaphthylene, diphenylethylene, vinyl anthracene or mixtures thereof; and optionally one or more ethylenically unsaturated co-monomers such as st
  • the resin when the styrenic resin comprises monomeric units derived from (meth)acrylic co-monomers as described above, the resin may be referred to as a styrene-(meth)acrylic resin.
  • the resin when the styrenic resin comprises monomeric units derived from a butadiene co-monomer, the resin may be referred to as a styrene-butadiene resin (SBR).
  • SBR styrene-butadiene resin
  • an olefinic resin is a polymer comprising monomeric units derived from the polymerization of one or more olefin monomers, such as ethylene, propene, 1-butene, isobutylene, diisobutylene, 1-nonene, 1-decene or mixtures thereof; and optionally one or more ethylenically unsaturated co-monomers such as (meth)acrylic monomers, vinyl esters, unsaturated polyacids, unsaturated polyacid derivatives, or mixtures thereof.
  • olefin monomers such as ethylene, propene, 1-butene, isobutylene, diisobutylene, 1-nonene, 1-decene or mixtures thereof
  • ethylenically unsaturated co-monomers such as (meth)acrylic monomers, vinyl esters, unsaturated polyacids, unsaturated polyacid derivatives, or mixtures thereof.
  • the ethylenically unsaturated resin according to the invention is selected from a (meth)acrylic resin, a styrene-(meth)acrylic resin, a vinyl ester-(meth)acrylic resin, an ethylene-vinyl ester resin, a vinyl ester resin, a styrene-butadiene resin and combinations thereof. More preferably, the ethylenically unsaturated resin is a (meth)acrylic resin, a styrene-(meth)acrylic resin or a vinyl ester-(meth)acrylic resin.
  • the ethylenically unsaturated resin according to the invention comprises monomeric units derived from the polymerization of at least one unsaturated polyacid or derivative thereof.
  • unsaturated polyacid derivative means a compound capable of yielding a unsaturated polyacid in situ, for example by hydrolysis or ring opening.
  • suitable unsaturated polyacid derivatives include alkyl esters of unsaturated polyacids and cyclic anhydrides.
  • the unsaturated polyacid or derivative thereof is selected from the group consisting of fumaric acid, maleic acid, itaconic acid, aconitic acid, mesaconic acid, anhydrides thereof and mixtures thereof.
  • the unsaturated polyacid is itaconic acid.
  • the presence of an unsaturated polyacid or derivative thereof in the ethylenically unsaturated resin according to the invention provides chemically bonded nonwoven substrates with enhanced wet tensile strength (WTS).
  • WTS wet tensile strength
  • the ethylenically unsaturated resin is a (meth)acrylic resin, a styrene-(meth)acrylic resin or a vinyl ester-(meth)acrylic resin obtained from a monomeric composition comprising:
  • the ethylenically unsaturated resin may be a (meth)acrylic resin obtained from a monomeric composition comprising:
  • the ethylenically unsaturated resin may be a styrene-(meth)acrylic resin obtained from a monomeric composition comprising:
  • the weight ratio between the polyester resin according to the invention and the ethylenically unsaturated resin according to the invention is from 1:10 to 10:1, in particular from 1:5 to 5:1, more particularly from 1:2 to 2:1.
  • the binder of the invention may comprise a catalyst.
  • a catalyst may be used to facilitate curing and to promote cross-linking.
  • suitable catalysts include metal salts (in particular metal soap carboxylates) or metal complexes (in particular metals complexed with nitrogen-containing ligands) based on cobalt, iron, manganese, vanadium, calcium, zirconium, or barium.
  • the binder of the invention may comprise a cross-linker.
  • a cross-linker may be used to provide cross-links with the polyester resin to enhance the mechanical properties of the resulting chemically bonded nonwoven substrate.
  • a "chemically bonded nonwoven substrate” relates to an interconnected web of nonwoven fibers bonded together by a binder.
  • the binder may create a network of interlocked fibers throughout the nonwoven structure.
  • a chemically bonded nonwoven substrate according to the invention preferably does not encompass webs of nonwoven fibers bonded solely by means other than chemical bonding, for example mechanical, solvent and/or thermal bonding.
  • the web of nonwoven fibers may be subjected to other bonding techniques, for example mechanical bonding, prior to the chemical bonding with the binder of the invention.
  • Mechanical bonding includes needlefelting, stitchbonding, and hydroentangling.
  • Solvent bonding involves softening or partially dissolving fibers with a solvent to provide self-bonding surfaces.
  • Thermal bonding involves the use of heat and often pressure to fuse or weld fibers together at points of intersection or in patterned bond sites.
  • a chemically bonded nonwoven substrate according to the invention preferably does not encompass webs of nonwoven fibers that are only superficially coated with a layer of cured binder.
  • the binder may not be present only on the surface of the web of nonwoven fibers, i.e. as a finish coating resulting from a chemical finishing treatment, but may at least partially penetrate into the web of nonwoven fibers.
  • the binder may penetrate the web of nonwoven fibers in an amount of at least 50%, at least 60%, or least 70%, at least 80%, at least 90%, at least 95%, at least 99% or even 100% of the thickness of the web of nonwoven fibers.
  • the chemically bonded nonwoven substrate according to the invention is selected from abrasives and sheets for scouring, agricultural coverings, agricultural seed strips, apparel linings, automobile headliners, automobile upholstery, bed linen, bibs, blinds/curtains, cheese wraps, civil engineering fabrics, civil engineering geotextiles, coffee filters, cosmetic removers and applicators, covering and separation material, detergent pouches/fabric softener sheets, diapers, envelopes, filters, flooring, garment bags, household cleaning wipes, house wraps, hygiene products, insulation, labels, laundry aids, laundry bags, medical nonwovens, such as bandages, cast paddings and covers, dressings, packs, sterile overwraps, sterile packaging, surgical drapes, surgical gowns, swabs or under-pads, mops, personal wipes, reusable bags, roofing undercoverings and products, table linen, tags, tea and coffee bags, toilet paper, upholstery, vacuum cleaning bags, wallcoverings, wipes, in particular for household care, floor care, cleaning or
  • the chemically bonded nonwoven substrate of the invention may be prepared according to the method described hereinafter.
  • the invention also relates to a method for chemically bonding fibers of a nonwoven substrate.
  • the method of the invention comprises the following step:
  • the method of the invention may be carried out as a separate and distinct operation or it may be carried out as a sequential operation in tandem with formation of a web of nonwoven fibers.
  • the web of nonwoven fibers used in step i) may be obtained by an airlaying, wetlaying or drylaying web formation process.
  • the method of the invention may be repeated to enhance physical or chemical properties of the chemically bonded nonwoven substrate.
  • the binder can be contacted with/applied to the web of nonwoven fibers by numerous methods well-known to the person skilled in the art, such as spraying, impregnation (also referred to as saturation), padding or foaming.
  • the nonwoven web may be impregnated with the binder, for example by immersing the web in a binder bath or by flooding the web as it enters the nip point of a set of pressure rolls.
  • the nonwoven web may be sprayed with the binder, i.e. by dispensing the binder in fine droplet form through a system of nozzles.
  • the amount of binder applied on the web may be from 2 to 40%, in particular from 5 to 30%, more particularly from 10 to 25%, by weight of dry binder based on the weight of the dry nonwoven fibers.
  • the method of the invention may comprise a drying step between steps i) and ii).
  • drying means removing the water or solvent contained in the binder.
  • the web of nonwoven fibers may first be heated at a temperature and for a time sufficient to remove most of the water but not to substantially cure the binder.
  • Other drying methods include removal of water by vacuum or roll pressure.
  • the drying step and curing step may be carried out simultaneously.
  • curing means chemically altering the binder for example crosslinking through formation of covalent bonds between the various functional groups of the binder, formation of ionic interactions and clusters, and/or formation of hydrogen bonds. Furthermore, the curing can be accompanied by physical changes in the binder, for example phase transitions or phase inversion.
  • the curing step ii) may be carried out by heating the web of nonwoven fibers at a temperature and/or for a period of time to effect curing (crosslinking).
  • the binder may be cured at a temperature of at least 80°C, at least 90°C, at least 100°C, at least 110°C, at least 120°C, at least 130°C, at least 140°C, at least 150°C, at least 160°C, or at least 170°C.
  • the binder may be cured at a temperature below 200°C, 190°C, 180°C, 170°C, 160°C, 150°C, 140°C, 130°C, 120°C or 110°C.
  • the binder is cured at a temperature of from 140°C to 180°C.
  • Curing can in particular be carried in a ventilated oven or an industrial drying line.
  • Curing may be carried out for a period of time of 5 seconds to 2 hours, in particular 1 minute to 20 minutes.
  • the curing step may be a multistage curing step with at least two curing steps.
  • the curing speed can be promoted by the addition of a cross-linker or catalyst in the binder.
  • the polymer-based binders used for the comparative evaluation below are characterized for their bonding properties without further formulation (neat polymer) by applying the polymer on a cellulosic substrate at a dry pick up of indicatively 25% (by weight of dry binder based on the weight of dry fibers).
  • the binder according to the invention is a bio-sourced alkyd emulsion (Synaqua ® 4856, Arkema).
  • the (meth)acrylic dispersion used in Comparative Example 2 is a formaldehyde-free (meth)acrylic dispersion (ENCOR 1130 S from Arkema).
  • the substrate is a mechanically bonded mono-layer cellulosic nonwoven.
  • the measurements used for the evaluation are the Dry Tensile Strength (DTS), the Wet Tensile Strength (WTS) as well as the Liquid absorptive capacity (LAC).
  • DTS Dry Tensile Strength
  • WTS Wet Tensile Strength
  • LAC Liquid absorptive capacity
  • the test was carried out according to the procedure described in standard ISO 9073-3:1989.
  • the nonwoven substrate Prior to the application of the binder, the nonwoven substrate was conditioned in a climatic chamber at 23°C and 50% of Relative Humidity (RH), and then weighed.
  • the application of the binder was carried out in a foulard by applying the binder at 25% of solids on the cellulosic substrate (21 x 29 cm) which was first dried in a ventilated oven at 130°C for 5 minutes and then cured by increasing the temperature of the oven up to 160°C for 90 seconds. After drying, the finished nonwoven was weighed for the measure of the applicative "dry pickup" and further conditioned for 24 hours before proceeding with the mechanical tests.
  • the DTS was measured at 23°C and the specimens (5 x 15 cm) were pulled with a dynamometer in the cross direction of the nonwoven taken from the previously prepared substrate. Results were reported in N/m.
  • test was carried out following the procedure described in standard ISO 9073-3:1989 using a tearing speed of 100 mm/min. Specimens for measuring WTS were prepared as indicated above for DTS with the difference that, before measurement, the specimens were soaked for 10 minutes in deionized water at 23°C. Results were reported in N/m.
  • LAC Liquid absorptive capacity
  • LAC Liquid absorptive capacity
  • the nonwoven substrate chemically bonded with the bio-sourced alkyd emulsion according to the invention had higher DTS and LAC and similar WTS compared to those of the nonwoven substrate bonded with the comparative acrylic dispersion. Both chemically bonded nonwoven substrates had good hand softness and flexibility (determined qualitatively by touching the nonwoven substrate).
  • the nonwoven substrate chemically bonded with the bio-sourced alkyd emulsion of the invention may be at least partly biodegradable and can be marketed as a bio-sourced product.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Nonwoven Fabrics (AREA)
  • Multicomponent Fibers (AREA)
EP21306964.4A 2021-12-31 2021-12-31 Chemisch gebundene vliesstoffsubstrate Withdrawn EP4206374A1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP21306964.4A EP4206374A1 (de) 2021-12-31 2021-12-31 Chemisch gebundene vliesstoffsubstrate
EP22844169.7A EP4457392A1 (de) 2021-12-31 2022-12-23 Chemisch gebundene vliesstoffsubstrate
CN202280086523.5A CN118525116A (zh) 2021-12-31 2022-12-23 化学粘合的非织造基材
MX2024007844A MX2024007844A (es) 2021-12-31 2022-12-23 Sustratos no tejidos unidos quimicamente.
PCT/EP2022/087823 WO2023126374A1 (en) 2021-12-31 2022-12-23 Chemically bonded nonwoven substrates

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP21306964.4A EP4206374A1 (de) 2021-12-31 2021-12-31 Chemisch gebundene vliesstoffsubstrate

Publications (1)

Publication Number Publication Date
EP4206374A1 true EP4206374A1 (de) 2023-07-05

Family

ID=79830788

Family Applications (2)

Application Number Title Priority Date Filing Date
EP21306964.4A Withdrawn EP4206374A1 (de) 2021-12-31 2021-12-31 Chemisch gebundene vliesstoffsubstrate
EP22844169.7A Pending EP4457392A1 (de) 2021-12-31 2022-12-23 Chemisch gebundene vliesstoffsubstrate

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP22844169.7A Pending EP4457392A1 (de) 2021-12-31 2022-12-23 Chemisch gebundene vliesstoffsubstrate

Country Status (4)

Country Link
EP (2) EP4206374A1 (de)
CN (1) CN118525116A (de)
MX (1) MX2024007844A (de)
WO (1) WO2023126374A1 (de)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB564570A (en) * 1941-11-18 1944-10-04 Hercules Powder Co Ltd Heat-insulating products having hydrogenated rosin or its derivatives as binding media
US4455342A (en) 1982-01-23 1984-06-19 Rohm Gmbh Acrylic resin dispersions
US4535013A (en) * 1983-08-15 1985-08-13 Hercules Inc Addition of resins to latex bonded nonwoven fabrics for improved strength
US4744925A (en) 1985-05-09 1988-05-17 Westvaco Corporation Method for producing modified rosin & ester
WO2003106561A1 (en) * 2002-06-18 2003-12-24 Georgia-Pacific Resins, Inc. Polyester-type formaldehyde free insulation binder
WO2005087837A1 (en) * 2004-03-11 2005-09-22 Knauf Insulation Gmbh Binder compositions and associated methods
US20080038977A1 (en) * 2006-08-09 2008-02-14 Dynea Oy Alkyd resins as non-formaldehyde binders for nonwoven products
EP2202251A1 (de) * 2008-12-29 2010-06-30 Celanese Emulsions GmbH Vinylacetat-/Vinyl-2-Ethylhexonoat-Copolymer-Binderharze
WO2012042153A1 (fr) 2010-09-27 2012-04-05 Arkema France Resines polyesters a base d'acides gras de longueur en huile courte,dispersions aqueuses et revêtements lies

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB564570A (en) * 1941-11-18 1944-10-04 Hercules Powder Co Ltd Heat-insulating products having hydrogenated rosin or its derivatives as binding media
US4455342A (en) 1982-01-23 1984-06-19 Rohm Gmbh Acrylic resin dispersions
US4535013A (en) * 1983-08-15 1985-08-13 Hercules Inc Addition of resins to latex bonded nonwoven fabrics for improved strength
US4744925A (en) 1985-05-09 1988-05-17 Westvaco Corporation Method for producing modified rosin & ester
WO2003106561A1 (en) * 2002-06-18 2003-12-24 Georgia-Pacific Resins, Inc. Polyester-type formaldehyde free insulation binder
WO2005087837A1 (en) * 2004-03-11 2005-09-22 Knauf Insulation Gmbh Binder compositions and associated methods
US20080038977A1 (en) * 2006-08-09 2008-02-14 Dynea Oy Alkyd resins as non-formaldehyde binders for nonwoven products
EP2202251A1 (de) * 2008-12-29 2010-06-30 Celanese Emulsions GmbH Vinylacetat-/Vinyl-2-Ethylhexonoat-Copolymer-Binderharze
WO2012042153A1 (fr) 2010-09-27 2012-04-05 Arkema France Resines polyesters a base d'acides gras de longueur en huile courte,dispersions aqueuses et revêtements lies

Also Published As

Publication number Publication date
EP4457392A1 (de) 2024-11-06
WO2023126374A1 (en) 2023-07-06
CN118525116A (zh) 2024-08-20
MX2024007844A (es) 2024-07-04

Similar Documents

Publication Publication Date Title
AU694136B2 (en) Method for strengthening cellulosic substrates
US20090048371A1 (en) Roofing membranes
KR101374640B1 (ko) 섬유 처리제 및 그 응용
US20210054548A1 (en) Modified Cellulose-Based Natural Binder for Nonwoven Fabrics
CN114214783A (zh) 一种可降解的去油污湿巾及其制备方法
EP4206374A1 (de) Chemisch gebundene vliesstoffsubstrate
CN102939411A (zh) 由非交联的醇酸低聚物制成的纤维和非织造材料
EP3752541A1 (de) Formaldehydfreie bindemittel-zusammensetzung
EP3966379B1 (de) Bituminöse membranen mit biologisch abbaubarem bindemittel
US20220220646A1 (en) Formaldehyde-free binder composition
JP4602001B2 (ja) 極細長繊維絡合シートの製造方法
JP5813360B2 (ja) 不織布製造用繊維処理剤およびその応用
EP2863785A1 (de) Bindemittel für spülbaren vliesstoff
TWI772186B (zh) 聚烯烴系合成纖維製不織布用處理劑、聚烯烴系合成纖維、及聚烯烴系合成纖維製紡黏不織布
JP4602002B2 (ja) 皮革様シートの製造方法
EP3781741B1 (de) Formaldehydfreie bindemittel-zusammensetzung
CA3169143A1 (en) Bituminous membranes with biodegradable binder
AU2022210861A1 (en) Hydrophobic cellulosic fiber
EP4244419A1 (de) Bituminöse membranen mit biologisch abbaubarem bindemittel
CN115917068A (zh) 用生物基结合剂聚合物固结纤维性材料的方法、固结的纤维性材料以及水性结合剂溶液
CN118647763A (zh) 非织造布用加工剂和含有其的非织造布
CN115992452A (zh) 拨水剂组合物
AU5946300A (en) Nonwoven materials comprising biodegradable copolymers

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20240106