CN1280635A - Process for extruding fibers - Google Patents

Process for extruding fibers Download PDF

Info

Publication number
CN1280635A
CN1280635A CN 98811851 CN98811851A CN1280635A CN 1280635 A CN1280635 A CN 1280635A CN 98811851 CN98811851 CN 98811851 CN 98811851 A CN98811851 A CN 98811851A CN 1280635 A CN1280635 A CN 1280635A
Authority
CN
China
Prior art keywords
fiber
giving
hydrophilic compounds
fluorine
spinning oil
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.)
Pending
Application number
CN 98811851
Other languages
Chinese (zh)
Inventor
B·戈曼
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.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
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 Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of CN1280635A publication Critical patent/CN1280635A/en
Pending legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Abstract

The present invention provides a process for obtaining a fiber comprising the steps of (a) melt extruding a mixture of a thermoplastic polymer and hydrophilicity imparting compound to form a plurality of filaments; (b) applying a spin finish to said filaments; and (c) spinning said filaments into a fiber; wherein said spin finish comprises fluorochemical. The invention also provides fibers, textiles and carpet prepared in accordance with the invention.

Description

The extrusion method of fiber
FIELD OF THE INVENTION
The present invention relates to the manufacturing of fiber and the processing of fiber, make fiber have antifouling, grease proofing and/or water proofing property.
The background of invention
When making fabric with the thermoplastic polymer of extruding (as polypropylene), the method for standard is that spinning oil (spin oil) is applied on the long filament.The spinning oil that comprises spinning oil is a kind of lubricating composition that is deposited on the fiber surface, the friction when being used to reduce the friction between fiber-fiber and reducing yarn by the metal mechanical surface.Spinning oil contains a large amount of chemical constituents usually, and its key component is lubricant, antistatic additive and emulsifying agent.The amount of required spin finishing depends on manufacturer and manufacture method, and the amount of residual spinning oil is generally 0.7%-5% on fiber.The major defect that use contains the spinning oil of spinning oil is to remain in the spinning oil of extruding on the fiber and can adsorbs dirt.And can reduce the effect of fiber being protected processing, thereby reduce the soil resistance of product.
When industrial manufacturing fabric (as carpet and clothing), use this fabric of a kind of compositions-treated usually, make it to have required performance (as preventing that particle or dried dirt from staiing).Industrial fluorine-containing Chemical composition that is used for this purposes.Can for example utilize to spray, bubble, pad and cover with paint, lacquer, colour wash, etc. and bathe immersion process it is applied on the various fabrics.
United States Patent (USP) 4,264,484 disclose a kind of liquid carpet treatment compositions, it comprises a kind of water-fast addition polymer and a kind of water-fast ester that contains fluorine-containing aliphatic group and chloride aliphatic group, described polymer is made by the polymerisable ethylene linkage unsaturated monomer that does not contain non-vinyl fluoride and at least one main transition temperature is higher than about 25 ℃, and the main transition temperature of at least one of described ester is higher than about 25 ℃.
United States Patent (USP) 4,107,055 discloses a kind of textile coating composition, and it comprises that a kind of vitrification point is higher than the polymer of room temperature, a kind of ionic surface active agent of fluoridizing and a kind of carrier.The amount of application of described polymer on fabric better makes dried solids content be about 0.25-10%, to give anti-dried dirt performance.
United States Patent (USP) 4,043,964 disclose a kind of coating that can form the carpet of durable pollution resistance, it contains: (a) at least a special water-fast addition polymer phase, described polymer is made by the polymerizable ethylene linkage unsaturated monomer that does not contain non-vinyl fluoride, and (b) at least a special water-fast fluorine component, it contains the fluorine-containing aliphatic group of at least 3 carbon atoms.The monomer that forms fluorine component can comprise dicarboxylic acids, dihydroxylic alcohols, diamine, azanol etc.
A common trait of the treatment compositions of above-mentioned U.S. Patent Publication or coating composition is that they are to be applied on carpet or the fabric in the independent step after making carpet or fabric.Equipment that applies that this treatment step is required and time have increased the cost of final products.
As United States Patent (USP) 4,190,545 and 4,192,754 is described, also can handle fabric fibre and yarn by adding the fluorochemical protective agent for surface treatment in spin finishing is bathed.A shortcoming of this method is that the precipitation of the mixture of fluorochemical oil and waterproofing agent/spinning oil can be deposited on the roller.Deposition on the roller can cause fibrous fracture, need often remove this deposit.It is consuming time and expensive to carry out this processing, no longer is accepted as method of application by fiber manufacturers.Usually, the spinning oil that adds in the fluorochemical finishing agent is many more, and the deposition on roller is just serious more, descends just serious more owing to a large amount of spinning oils stockpile the barrier propterty that makes end product on treated fabric.
Perhaps, can make treated textile fabric and yarn by melt extruding the polymer of making synthetic fiber and the blend of fluorochemical component.This melt extrude for example be described in the United States Patent (USP) 3,839,312.This patent disclosure have the amphipathic compound that contain fluoroalkyl of 1-4 side joint on organic group by in resin, adding a small amount of (about 1%), can improve the soil resistance of extruding long filament and the anti-spot of synthetic resin.Soil resistance and anti-spot provide by containing fluoroalkyl, and this group can be enriched on the fiber surface.
WO 92/18569 and WO 95/01396 disclose permanent antifouling polymer composition (as fiber and yarn), are dispersed with fluorochemical in whole polymer.These polymer compositions are extruded fluorochemical and required polymer melt together and are made.Can comprise polyester, polypropylene, polyethylene and polyamide with the polymer that fluorochemical uses.
United States Patent (USP) 5,025,052 discloses and has contained some fluorine-containing aliphatic group De oxazolidone composition.This patent also discloses for example by making synthetic organic polymer and the blend of some Han Fu oxazolidone compound or fiber, film and the moulding article that the mixture injection mo(u)lding makes of fiber or manufacturing film.It is said that the fiber, film and the moulding article that form have low surface energy, have grease proofing and water proofing property and pollution resistance.
Europe publication 0516271 discloses durable hydrophily thermoplastic fibre, and it comprises thermoplastic polymer and contains the non-ionic compound of fluorine-containing aliphatic group.
Although above-mentioned open source literature (United States Patent (USP) 3,839,312, WO 92/18569 and WO 95/01396) successfully make yarn or fiber have antifouling and anti-spot performance and confirmed that many fluorochemical components of using at present can make carpet have soil resistance, but be difficult to a large amount of carpets or the fabric that makes are handled to obtain required performance.Reason is that the spinning oil of a large amount of and different amounts can remain on fiber or the yarn usually, has reduced its soil resistance, perhaps influences the processing of fluorochemical as dirt, and reduction or prevention obtain required result.
WO 97/33019 discloses a kind of carpet yarn, and it contains to be scattered in and gives hydrophilic compounds in the filament thermoplastic polymer.Also disclosing the fluorine-containing hydrophilic compounds of giving is to give hydrophilic compounds preferably.It has reported in yarn filament and to have used the result who gives hydrophilic compounds seldom to need or need not spinning oil that carpet is difficult for staiing as a result in spin finishing is bathed.Although this method is successful, the grease proofness of the fiber that makes and/or water proofing property are totally relatively poor, therefore still need to improve antifouling property.
The general introduction of invention
One aspect of the present invention provides a kind of manufacture method of fiber, and it comprises the following steps:
Thermoplastic polymer is melt extruded into many long filaments with the mixture of giving hydrophilic compounds;
Apply spinning oil to described long filament; With
With described long filament drawing fiber,
It is characterized in that described spinning oil comprises fluorochemical.In example preferably, described fluorochemical is a kind of effectively grease proofing and/or waterproofing agent, and it makes fiber have good grease proofness and water proofing property.
An advantage of the invention is:, on the fiber that the inventive method makes, can not produce roller and deposit although will comprise that the spinning oil of fluorochemical is applied to can produce roller deposition usually on the thermoplastic fibre.Simultaneously, the fiber of formation generally demonstrates good grease proofness, water proofing property and soil resistance.In addition, can on the fiber that makes with the inventive method, use a small amount of spinning oil, and can not influence its antistatic property.
On the other hand, the invention provides and a kind ofly contain many filament thermoplastic polymer and wherein be dispersed with the fiber of giving hydrophilic compounds, it is characterized in that comprising fluorochemical at least a portion surface of described long filament.As mentioned above, described fluoride better is a kind of effectively grease proofing and/or waterproof finishing agent, and it makes fiber have good grease proofness and water proofing property.Further aspect of the present invention provides a kind of carpet or fabric that contains described fiber.
The detailed description of invention
Be applicable to that thermoplastic polymer of the present invention comprises poly alpha olefin, polyester and the polyamide of making fiber.Thermoplastic polymer is a poly alpha olefin preferably.Be applicable to that poly alpha olefin of the present invention comprises common solid-state homopolymers, copolymer and the ter-polymers of aliphatic series list-1-alkene known in the art (alpha-olefin).Usually, each molecule of monomer that is used for making this poly alpha olefin contains 2 to about 10 carbon atoms, although the monomer that also uses higher molecular weight sometimes is as comonomer.Also can use mechanically or the polymer that original position makes or the blend of copolymer.The example that is applicable to monomer of the present invention comprises independent ethene, propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene and 1-octene, its mixture or be used for above-mentioned monomer or its mixture of sequential polymerization system.
The example of thermoplastic poly alpha-olefine polymers comprises polyethylene, polypropylene, ethylene/propene copolymer, polybutene and blend thereof preferably.Polypropylene is best suited for the present invention.
It is well-known being used to make the method that is applicable to thermoplastic polymer of the present invention, the invention is not restricted to the polymer that makes with specific catalyst or method.
Be applicable to that of the present invention to give hydrophilic compounds can be fluorochemical or do not have fluorine compounds, the mixture of the mixture of described compound or fluorochemical and no fluorine compounds.Giving hydrophilic floride-free compound, not fluorine-containing substantially (fluorinated volume is better less than about 10 weight %, preferably less than about 5 weight %), and be hydrophilic generally or contain the hydrophilic parts of capacity at least, thereby make the surperficial possess hydrophilic property or the wettability of filament thermoplastic polymer.Described compound comprises low molecular weight compound, oligomer and copolymer.It is suitable that to give hydrophilic no fluorine compounds better incompatible with melt of thermoplastic polymers and to be preferably under the required extrusion temperature be stable.
The suitable hydrophilic no fluorine compounds of giving can be anionic, cationic, non-ionic or both sexes.Compound comprises known compound as surfactant preferably.Better giving hydrophilic no fluorine compounds is the compounds that contain a polyalkylene oxide groups at least.
Be applicable to that of the present invention to give hydrophilic fluoride be hydrophilic and can comprise compound, oligomer and polymer.This material can contain the fluorine fluorine of bond with carbon (promptly with) of the 10 weight % that have an appointment at least.They contain one or more fluorine-based (R that contain f) and one or more dissolubility polar group (Z) of surging, fluorine-based link to each other by suitable linking group (Q) usually with polar group described containing.
In giving hydrophilic fluorochemical, contain fluorine-based R fUsually can fluoridize, better be the saturated unit price base that has about 4 carbon atoms at least.This fluoro-containing group better is fluorine-containing aliphatic series but not aromatic group.Aliphatic chain can be straight chain, side chain or (enough big time) is ring-type, and it only can contain oxygen, divalence or sexavalence sulphur or trivalent nitrogen atom with carbon atom bonding.Be more preferably fluoridized group, but can exist hydrogen or chlorine atom, as long as this replacement atom is no more than one in per two carbon atoms as substituting group.Fluorine-containing aliphatic group with about 5-12 carbon atom is best.
Give in the hydrophilic fluorochemical, surge dissolubility polar group or part Z can be nonionic, anion, CATION or both sexes part, or the mixing of these identical or different groups or part.Be preferably, this dissolubility group of surging comprises polyalkylene oxide groups (OR ') x, wherein R ' has 2 alkylidenes to about 4 carbon atoms, as-CH 2CH 2-,-CH 2CH 2CH 2-,-CH (CH 3) CH 2-and-CH (CH 3) CH (CH 3)-or its mixed base, x is the integer of about 6-20.Oxyalkylene units in described polyoxyalkylene can be identical (as in polyoxypropylene), perhaps the form with mixed base exist (as mixing (heteric), the ethylene oxide of straight or branched random and propylene oxide unit (for example poly-(ethylene oxide-copolymerization-propylene oxide)) or exist with the ethylene oxide unit block of straight or branched and the form of propylene oxide unit block.Polyoxyalkylene chain also can be embedded with or contain one or more stretched wire keys, as long as this key can obviously not change the dissolubility characteristic of surging of this polyoxyalkylene chain.The Z group with hydroxyl or lower alkyl ether (as-OCH 3Or-OCH 2CH 3) end-blocking.Anionic group generally includes CO 2H, CO 2M, SO 3H, SO 3M, OSO 3H, OSO 3M, OPO (OH) 2And OPO (OM) 2, wherein M is metal ion (as sodium or potassium) or ammonium ion or other amine CATION.Cation group generally includes NR 3 +A -, wherein R is a low alkyl group, as methyl, ethyl, butyl, ethoxy or hydrogen, A is an anion, as chlorion, sulfate radical, phosphate radical, hydroxyl or iodide ion.Mix or amphiprotic group generally includes N +(CH 3) 2C 2H 4COO -, N +(CH 3) 2C 3H 6SO 3 -Or amine oxide.
Linking group Q is multivalence (normally two a valencys) linking group, contains heteroatomic group as alkylidene, arlydene, sulfonamido alkylidene, acylamino-alkylidene and other, as siloxanes, comprises the mixing of these groups.In some cases, can will be connected on the single linking group more than a fluorine-containing aliphatic group.In other cases, can a fluorine-containing aliphatic group be connected more than a polarity by a linking group and surge on the dissolubility group.Q can also be a covalent bond.
One class is specially suitable gives hydrophilic fluorochemical and can be represented by the formula:
R f-Q-Z is R wherein fBe described fluorine-containing aliphatic group, Q is described linking group, and Z is the described dissolubility group of surging.
Be applicable to that the present invention gives hydrophilic fluorine-containing non-ionic compound and can make with known method, as using the described method of United States Patent (USP) 2,915,554 (Albrecht etc.).The patent of Albrecht has been described by the fluoro-containing intermediate that contains reactive hydrogen (as fluorine-containing fatty alcohol (as R fC 2H 4OH), acid is (as R fSO 2N (R ") CH 2COOH) and sulfonamide (as R fSO 2N (R ") H)) by this intermediate and for example reacting ethylene oxide, make R respectively fC 2H 4O (C 2H 4O) nH, R fSO 2N (R ") CH 2CO 2(C 2H 4O) nH and R fSO 2N (R ") (C 2H 4O) nH and make the non-ionic compound that contains fluorine-containing aliphatic group, wherein n is approximately greater than 3 number, R " be hydrogen or the low alkyl group alkyl of 1-6 carbon atom (as have).Can make similar compounds by this intermediate of mixture process with expoxy propane or oxirane and expoxy propane.Also can be referring to United States Patent (USP) 3,787, the condensation product of disclosed fluorine-containing aliphatic oligomer of 351 (Olson) and disclosed some the fluorine-containing alcohol-oxirane of United States Patent (USP) 2,723,999 (Cowen etc.).
By the gross weight of thermoplastic polymer, give the about usually 0.05-5 weight of the addition % of hydrophilic compounds, better about 0.5-1.5 weight %.
Some examples of giving hydrophilic compounds comprise:
C 8F 17SO 2N(C 2H 5)CH 2CH 2O(CH 2CH 2O) 7CH 3
2C 8F 17SO 3H
Jeffamine TMED-600 disalt (Jeffamine TMED 600 is amino-terminated PEP-101)
The copolymer of fluorinated acrylate or methacrylate
The mono acrylic ester of poly(ethylene oxide) or monomethacrylates
C 8H 17SO 2N(C 2H 5)(CH 2CH 2O) 2-(CH(CH 3)CH 2O) 6H
Poly(ethylene oxide)
The copolymer of oxirane and expoxy propane
The alkyl phenol of ethoxylation is (as Triton TMX-100, available from Union Carbide, Danbury, Connecticut)
Contain thermoplastic polymer according to the present invention by use and can make fiber or yarn with one or more mixtures of giving hydrophilic compounds.This mixture can be extruded into long filament, better cool off this long filament subsequently.Then in bathing, spin finishing handles endless tow usually.After the spinning oil processing, this long filament usually stretches.Described stretching is carried out on a series of rollers, and the temperature of described roller is enough to softening this thermoplastic polymer.By making roller, can stretch to long filament with different speed rotations.Although can finish stretching by a step, should use the two-step stretch long filament.Usually, with long filament by extruding length stretching 3-4 doubly.After the stretching,, should at high temperature make this yarn have texture usually, and make it to tangle with compressed air or steam jet in order to obtain carpet yarn.
According to the present invention, spinning oil comprises fluorochemical.This fluorochemical better is a kind of effective oil-proofing agent and/or waterproofing agent.The about usually 0.1-5 weight of the content of fluorochemical % in spinning oil, better about 0.5-3 weight %.In general, being applicable to that fluorochemical of the present invention comprises becomes known for handling fabric to obtain the reagent that contains fluorine-containing aliphatic group of grease proofness and water proofing property.Selection contains fluorine-based reagent, for example as this condensation polymer of polyester, polyamide or polyepoxide be effective as this polyvinyl of polyacrylate, polymethacrylates or polyvingl ether.This known reagent comprises for example United States Patent (USP) 3,546,187,3,544,537,3,470,124,3,445,491,3,341,497 and 3,420,697 described reagent.
Other example of the reagent that imparting water repellency that is suitable for and grease proofness contain fluorine-containing aliphatic group comprises forming by perfluor aliphatic diol or sulphur glycol and di-isocyanate reaction and contains the reagent that polyurethane that perfluoroaliphatic group rolls into a ball obtains.These products are applied on the fiber with the form of aqueous liquid dispersion usually.This product for example is described in the United States Patent (USP) 4,054,592.The fluorochemical that another group is suitable for is the N-methylol condensation product that contains fluorine-containing aliphatic group.These compounds are described in United States Patent (USP) 4,477, in 498.Other example of the fluorochemical that is suitable for comprises the poly-carbodiimide that contains fluorine-containing aliphatic group, and it can for example obtain by perfluor aliphatic series sulfonamido alkanol and polyisocyanates reaction in the presence of appropriate catalyst.
Described fluorochemical can be one or more copolymers that contain the ethylene linkage unsaturated comonomer of the acrylate of fluorine-containing aliphatic group or methacrylate monomers and one or more free-florides (or hydrocarbon) end-blocking.The representative example of this fluorochemical monomer comprises: CF 3(CF 2) 4CH 2OC (O) C (CH 3)=CH 2CF 3(CF 2) 6(CH 2) 2OC (O) C (CH 3)=CH 2CF 3(CF 2) 6(CH 2) 2OC (O) CH=CH 2CF 3(CF 2) 7(CH 2) 2OC (O) CH=CH 2CF 3(CF 2) 7SO 2N (C 2H 5) (CH 2) 2OC (O) CH=CH 2CF 3CF 2(CF 2CF 2) 2-8CH 2CH 2OC (O) CH=CH 2CF 3(CF 2) 7SO 2N (C 2H 5) (CH 2) 2OC (O) C (CH 3)=CH 2CF 3(CF 2) 7CH 2CH 2SO 2N (CH 3) CH 2CH 2OC (O) C (CH 3)=CH 2
Comprise the monomer that is selected from methacrylic acid octadecane ester, 1,4 butanediol diacrylate, lauryl methacrylate, butyl acrylate, N hydroxymethyl acrylamide, isobutyl methacrylate, EHA, ethylhexyl methacrylate, vinyl chloride and vinylidene chloride with the above-mentioned better monomer that contains the monomer copolymerization of fluorine-containing aliphatic group.Can have different weight ratios between fluorine-containing aliphatic monomers and the hydrocarbon comonomer, this weight ratio is known in the art.
Other example of the fluorochemical that is suitable for comprises, for example the carbamate of fluorinated group, urea, ester, amine (and salt), acid amides, acid (and salt), carbodiimide, guanidine, allophanate, biuret, oxazolidone and other contain the material and composition thereof and the blend of one or more fluoro-containing groups.These reagent are well-known to those of ordinary skill in the art, for example can be referring to Kirk-Othmer encyclopedia of chemical technology, 3 RdEd., Vol.24, pp448-451, many reagent wherein are (as SCOTCHGARD Fabric Protector, form that 3M) can ready-made preparation is buied from the market.
Except fluorochemical, this spinning oil also comprises the spinning oil commonly used that is used for the extruded thermoplastic polymer usually.But spinning oil can be a water-based, does not contain spinning oil.Can use methods known in the art to apply spinning oil.An example that applies comprises that the kiss roller applies.The bottom that kiss is coated with roller is immersed in the finish application bath, and yarn tangentially is coated with the top of roller through kiss.Can change the last oil mass of spinning oil by control Several Parameters (for example the geometrical condition between yarn and the roller, roller speed and in spin finishing is bathed the concentration of spinning oil).When using spinning oil, customized parameter makes the residual quantity of gross weight spinning oil on long filament by long filament and spinning oil be about 0.01-1.2 weight %, better about 0.01-0.6 weight %.Best is that the residual quantity of spinning oil is less than about 0.4%.
The following example is used to further specify the present invention, but it is not construed as limiting.
Embodiment
Except as otherwise noted, all parts, percentage etc. are all calculated by weight otherwise in embodiment and comparative example.
Each grease proofness in embodiment and the comparative example and water proofing property and soil resistance data all record with following method.
Water proofing property (WR) uses a series of water-isopropanol test liquid to measure the water proofing property of substrate.The water proofing property of substrate is represented with the WR rank.The ER rank is equivalent to the permeability test liquid to substrate effect maximum of impermeable or moistening this substrate surface after 15 seconds.To be decided to be 0 with the rank of the substrate of 100% water (0% isopropyl alcohol) (minimum permeability test liquid) infiltration or anti-100% water (0% isopropyl alcohol).The rank of the substrate of anti-100% isopropyl alcohol (0% water) (maximum permeability test liquid) is decided to be 10.Isopropyl alcohol percentage in the experimental liquid is calculated rank in the middle of other divided by 10, for example a kind of test substrate ability 70%/30% isopropanol blend, but ability 80%/20% blend not, then its rank is 7.
Grease proofness (OR) is used the grease proofness of the AATCC step measurements substrate of standard test method 118-1983.The grease proofness of substrate is represented with the OR rank.
The anti-anti-dried dirt of doing dirt use United States Patent (USP) 5,370,919 described methods mensuration substrates.Numerical value 5 expressions are compared pollution with nonstaining sample not to be increased.Doing dirty rank 1 expression substrate seriously stains.
Measure the fluorine in the fiber
Use following method to measure the described fluorine content of extruding in the fiber of embodiment.The sample of known weight is placed in the calcination basket that platinum filament makes.Subsequently sample is decomposed.After fluorine ion is absorbed in the cushioning liquid, use Orion 9409 electrodes (to the electrode of fluorine ion sensitivity) that link to each other with pH meter to measure fluorine ion with the mV operator scheme.The curve that the data that use records with the standard fluorine solion are done is calculated the content of fluorine ion by the mV reader.All samples are all analyzed two parts and consistent less than just thinking at result error at 10% o'clock.After suitably proofreading and correct, the reappearance deviation of electrode measurement is about 2%.
The deposition that roller is deposited on the process equipment that detects by an unaided eye in the described manufacturing experiment of embodiment records the roller deposition.Use 0 to 5 grade of observed deposition of expression, deposition is not observed in 0 expression, the serious deposition of 5 expressions.The acceptable roller deposition of 0 and 1 expression.
Abbreviation
Use following abbreviation and trade name in an embodiment:
PP polypropylene HG 235 J, a kind of MFI is 25 polypropylene, available from Borealis;
Genapol TMUD 080 C 11H 23(OCH 2CH 2) 100H (55% straight chain, 45% side chain) is available from BASF;
Alfonic TM6-8.5 C 6H 13(OCH 2CH 2) 8.5OH, available from Condea-Vista, Austin;
PMA polymer melt additive;
PMA-1?C 8F 17SO 2N(C 2H 5)CH 2CH 2O(CH 2CH 2O) 7CH 3；
PMA-2 Genapol TMUD 080 and MEFOSA/Alfonic TM6-8.5 1: 1 blend, it is according to United States Patent (USP) 5,804, the synthetic method of fluorochemical F-18 makes in 625, but is to use Alfonic TM6-8.5 replace Triton TMX-100;
MEFOSA?C 8F 17SO 2N(CH 3)H；
PMA-3?Genapol TM?UD?080
ETFOSE N-ethyl perfluoro capryl sulfonamido ethanol;
PAPI Voronate M220, many aromatics polymethylene polyisocyanates is available from Dow Chemical (Holland);
OWR is used for the fluorochemical of spin finishing;
OWR-1 FC 398 and FC 399 Scotchgard TMProtectant 50/50 blend of carpet, 24% solid is all available from 3M;
OWR-2 Scotchgard TMProtective agent FC 248,30% solids are available from 3M;
OWR-3 Scotchgard TMProtective agent FC 3548,30% solids are available from 3M;
OWR-4 Scotchgard TMProtective agent FC 5102,30% solids are available from 3M;
OWR-5 Scotchgard TMProtective agent FC 3860,15% solids are available from 3M;
OWR-6 Scotchgard TMProtective agent FC 3583,20% solids are available from 3M;
OWR-7 PAPI/ETHYLFOSE 1/3, it is by heating PAPI and ETFOSE at 60 ℃ in ethyl acetate, making fully until isocyanate reaction.Product with Rew IM/OA (6% on the solid) and Atpol E 5721 (2% on solid) with 20% solids content emulsification;
OWR-8 Scotchgard TMProtective agent FC 1374,20% solids are available from 3M;
Rewopon IM/OA Imidazoline Surfactants, available from Rewo, Germany;
Atpol 5721 alkyl ethoxylates, available from ICI, Wilton, UK;
The SF spinning oil;
FA 2820 spinning oils are available from Zschimmer und Schwartz (Germany);
FA 2825 spinning oils are available from Zschimmer und Schwartz (Germany);
Lurol TMThe NF-6239-20 spinning oil is available from Devan NV (Belgium);
Lurol TMThe PP-3919 spinning oil is available from Devan NV (Belgium);
The rpm revolutions per minute;
Ex. embodiment.
Make the general step of yarn
The first step makes and contained for 25% (except as otherwise noted) and give the polypropylene masterbatch of hydrophilic compounds, and is extruded into particle.This particle is mixed with other polypropylene, obtain containing the extrudable polypropene composition of giving hydrophilic compounds of desired content.Extrude on the spinning plate of trilobal section at about 230 ℃ of blends that will so form with Thermol Alfa single screw extrusion machine (triple extruders-an end).After leaving extruder, long filament is coated with on the roller through a cooling zone at kiss, applies the aqueous mixture (spin finishing bath) of spinning oil and fluorochemical at this roller place.Regulate kiss be coated with the speed of roller and spin finishing bathe in compound concentrations change the spinning oil that is applied on the yarn and the amount of fluorochemical.Then this carpet yarn is stretched to its about 3-4 that extrudes length doubly, obtains about 165 spies (yarn of weight (gram)/1000m).In making the process of yarn, after will giving hydrophilic compounds and adding in the extrudable composition, on the roller seldom or do not have a deposition.Do not use and give hydrophilic compounds, the layer that deposition one deck is clamminess on the guide reel of cooling unit, it produces very big problem and prolongs and makes the required time of treated yarn.Make this yarn have texture at about 140-180 ℃, make the varicosity yarn that is particularly useful for carpet.The mechanical quality of this varicosity yarn of range estimation after spinning and texture, the varicosity yarn that the present invention makes is not observed the long filament of fracture.In order to make substrate to measure waterproof and grease proofness and soil resistance, yarn closely is wrapped on a slice cardboard, so that tight between yarn, obtain the plane surface of one deck yarn.
Embodiment 1-3 and comparative example C-1
Use 0.4%PMA-1 as giving the sample that hydrophilic compounds makes embodiment 1-3.The waterproof finish application bath contains the FA 2820 and the OWR-1 of different amounts.Comparative example 1 does not use PMA-1.In this case, needing should note the spinning oil of high consumption to avoid too much electrostatic accumulation.Fibrous and the parameter of extruding fiber is listed in table 1.Table 1: the composition of polypropylene fibre and extrude parameter
Embodiment ??SF *(％) ??OWR-1(％) Screw speed (rpm) The roller deposition
????1 ????7 ????8 ????85 ????1
????2 ????7 ????12 ????85 ????0
????3 ????5 ????8 ????85 ????1
????C-1 ????10 ????8 ????52 ????5
The percentage that * should be worth representative spinning oil of use in spin finishing is bathed, but not the residual quantity of spinning oil on the fiber.
Data show that the sample that uses PMA-1 to make has seldom or do not have the roller deposition, although the concentration of the PMA-1 that uses is very low.When the sample of manufacturing comparative example C-1, serious roller deposition almost takes place immediately, problem is more serious than anticipation, in fact makes the employed amount of the only a little higher than manufacturing embodiment of amount 1-3 fiber of the spinning oil of C-1 fiber use.
The grease proofness of test thread, water proofing property and anti-dried dirt.The results are shown in table 2.Table 2: the performance of polypropylene fibre
Embodiment ??OR ????WR Anti-dried dirt Fluorine (ppm)
??1 ????3 ????5 ????3 ?1652
??2 ????3 ????3 ????3．5 ?2663
??3 ????1 ????0 ????3．5 ?1878
??C-1 ????3 ????5 ????3 ??707
Although the barrier propterty of C-1 also is acceptable, it produces serious roller deposition in manufacture process, and this method is unacceptable for the industry manufacturing.Embodiment 1 and 2 has good anti-dirty data and acceptable grease proofness and the water proofing property done.Embodiment 3 has quite low grease proofness and water proofing property, but has good anti-dried dirt
Embodiment 4-11 and comparative example C-2 to C-6
In embodiment 4-11, extrude the PP that contains 0.45%PMA-1.In bathing, spin finishing adds the different spinning oils and the OWR-1 of different amounts.Comparative example C-2 to C-6 adds 0.45%PMA-1 in melt, but does not use fluorochemical in spin finishing is bathed.The degree of used spinning oil and the kind of OWR-1 and consumption, roller deposition, water proofing property, grease proofness and anti-dried dirt and fluorine content are listed in table 3 and table 4.Table 3: the composition of polypropylene fibre and extruding
Embodiment Spinning oil (%) ???OWR-1(％) The roller deposition
??4 ????7％FA?2825 ????8 ????0
??5 ????7％FA?2820 ????8 ????0
??6 ????7％FA?2820 ????12 ????0
??7 ?7％Lurol TM?NF-6239-20 ????12 ????0
??8 ?12％Lurol TM?NF-6239-20 ????12 ????0
??9 ?20％Lurol TM?NF-6239-20 ????12 ????1
?10 ** ????7％Lurol TM?PP-3919 ????12 ????0
??11 ????7％Lurol TM?PP-3919 ????12 ????0
??C-2 ????7％FA?2825 ????- ????0
??C-3 ????7％FA?2820 ????- ????0
??C-4 ????7％Lurol TM?NF-6239-20 ????- ????0
???C-5 ?20％Lurol TM?NF-6239-20 ????- ????0
???C-6 ????7％Lurol TM?PP-3919 ????- ????0
The speed that kiss was coated with roller during * should test is 18rpm and non-standard 13.5rpm.Speed rises and does not produce big problem, shows that the inventive method is not so good as not use the spinning process of giving hydrophilic compounds so responsive to the rising of spinning oil coated weight.
Table 4: estimate grease proofness, water proofing property and anti-dried dirt
Embodiment ?OW ????WR Anti-dried dirt Fluorine
??4 ?4 ????2 ????3．5 ?2243
??5 ?3 ????4 ????2 ?2512
??6 ?2 ????2 ????2．5 ?2910
??7 ?3 ????7 ????3．5 ?2442
??8 ?3 ????6 ????4 ?2258
??9 ?3 ????7 ????3．5 ?2613
??10 ?1 ????0 ????1．5 ?3122
??11 ?2 ????1 ????2．5 ?2524
??C-2 ?0 ????0 ????3．5 ?1574
??C-3 ?0 ????0 ????3 ?1474
??C-4 ?0 ????0 ????3．5 ?1898
??C-5 ?0 ????0 ????4 ??1827
??C-6 ?0 ????0 ????2．5 ??1871
Data show that in most of the cases, the fiber that uses PMA-1 and OWR-1 to make has acceptable grease proofness and water proofing property and the goodish anti-dirt of doing, and seldom or not produces the roller deposition simultaneously.
Embodiment 12-15 and comparative example C-7
Use the different PMA-1 that measure to make the sample of embodiment 12-15.Spin finishing is bathed spinning oil Lurol NF-6239-20 and the 12%OWR-1 that contains different amounts.The composition of embodiment and extrude parameter and list in table 5, fibre property is listed in table 6.Comparative example C-7 does not add PMA.Table 5: the composition of polypropylene fibre and extrude parameter
Embodiment ??SF *(％) ??PMA(％) Screw speed (rpm) The roller deposition
????12 ????20 ????0．1 ????48 ????3
????13 ????20 ????0．2 ????63 ????1
????14 ????10 ????0．2 ????63 ????2
????15 ????10 ????0．3 ????79 ????1
????C-7 ????20 ????0 ????50 ????5
The percentage that * should be worth representative spinning oil of use in spin finishing is bathed, but not the residual quantity of spinning oil on the fiber.
Even showing, data in melt, use very the PMA-1 of low concentration also can reduce the roller deposition.Table 6: the performance of polypropylene fibre
Embodiment ????OR ????WR Anti-dried dirt
????12 ????2 ????5 ????3．5
????13 ????1 ????3 ????3
????14 ????2 ????5 ????3
????15 ????2 ????5 ????3
????C-7 ????1 ????6 ????3．5
Although C-7 has part favorable protection performance, its serious roller deposition makes it to be difficult to be accepted as the method for making fiber.Embodiment 12-15 has suitable acceptable grease proofness government office in feudal China water proofing property, sends out and the good anti-dirty data of doing.
Embodiment 16-26 and comparative example C-8
In these embodiments, use is made fiber than the PMA/PP masterbatch of other enforcement rarer (3%).The PMA-1 total amount for preparing each sample is listed in table 7.Spin finishing is bathed content and the kind contain 8%OWR-1 and to spin agent and is listed in table 7.Comparative example C-8 sample does not contain PMA-1.Fibrously list in table 7 and fibre property is listed in table 8.Table 7
Embodiment Spinning oil ??SF *(％) ??PMA-1(％) The roller deposition
????16 ?Lurol?NF?6239-20 ????20 ????0．13 ????1
????17 ?Lurol?NF?6239-20 ????20 ????0．26 ????2
????18 ?Lurol?NF?6239-20 ????15 ????0．26 ????0
????19 ?Lurol?NF?6239-20 ????15 ????0．34 ????0
????20 ?Lurol?NF?6239-20 ????15 ????0．45 ????0
????21 ????FA?2825 ????10 ????0．13 ????3
????22 ????FA?2825 ????10 ????0．26 ????4
????23 ????FA?2825 ????10 ????0．34 ????3
????24 ????FA?2820 ????10 ????0．34 ????3
????25 ????FA?2820 ????10 ????0．45 ????0
????26 ????FA?2820 ????7 ????0．45 ????1
???C-8 ?Lurol?NF?6239-20 ????20 ????0 ????5
The percentage that * should be worth representative spinning oil of use in spin finishing is bathed, but not the residual quantity of spinning oil on the fiber.Table 8: the performance of polypropylene fibre
Embodiment ??OR ????WR Anti-dried dirt
????16 ????1 ????3 ????3
????17 ????2 ????1 ????1
????18 ????1 ????2 ????2．5
????19 ????1 ????3 ????3
????20 ????1 ????4 ????4
????21 ????3 ????5 ????2
????22 ????3 ????3 ????2
????23 ????2 ????3 ????2
????24 ????2 ????1 ????2
????25 ????2 ????1 ????3
????26 ????2 ????3 ????3．5
????C-8 ????1 ????3 ????3
Data show that the inventive method can reduce to minimum with the roller deposition well by consumption and the PMA concentration of suitably selecting spinning oil, spinning oil.
Embodiment 27-34 and comparative example C-9
In embodiment 27-34, use 0.4%PMA-1 to extrude the PP fiber.Spin finishing is bathed and is contained 15%Lurol NF 6239-20 and the listed fluorochemical of various table 9.Comparative example C-9 does not use and gives hydrophilic compounds or fluorochemical.The composition of fiber and roller deposition data are listed in table 9, and fibre property is listed in table 10.Table 9: the composition of polypropylene fibre and extrude parameter
Embodiment Fluorochemical Fluorochemical (%) The roller deposition
??27 ????OWR-1 ????8 ????2
??28 ????OWR-2 ????6．7 ????0
??29 ????OWR-3 ????6．7 ????0
??30 ????OWR-4 ????10 ????0
??31 *** ????OWR-5 ????6．7 ????0
??32 *** ????OWR-6 ????10 ????0
??33 ????OWR-7 ????10 ????1
??34 ????OWR-8 ????10 ????0
??C-9 ????- ????0 ????0
* * observes slight electrostatic precipitation in manufacture process.Table 10: the performance of polypropylene fibre
Embodiment ????OR ????WR
????27 ????2 ????5
????28 ????1 ????0
????29 ????1 ????0
????30 ????5 ????4
????31 ????0 ????0
????32 ????0 ????1
????33 ????2 ????6
????34 ????0 ????0
????C-9 ????0 ????0
Data show, the water proofing property that various spin finishing bath compositions obtain and the grease proofness type of the fluorochemical used with making finish application bath to a certain extent are relevant.
Embodiment 35-38 and comparative example C-10
In embodiment 35-38, listed as table 11, working concentration is that 0.4% or 0.8% PMA-2 is as giving hydrophilic compounds.Spin finishing is bathed and is contained 15%Lurol NF 6239-20 and type and consumption fluorochemical as described in Table 11.Fibrous and roller deposition value is listed in table 11, and fibre property is listed in table 12.Table 11
Embodiment Fluorochemical Fluorochemical (%) ??PMA(％) The roller deposition
????35 ????OWR-1 ????8 ????0．4 ????3
????36 *** ????0WR-1 ????8 ????0．8 ????0????
????37 ????OWR-3 ????6．7 ????0．4 ????0
????38 ????OWR-3 ????6．7 ????0．8 ????0
* * observes some electrostatic precipitation in manufacture process.Table 12: the performance of polypropylene fibre
Embodiment ????OR ??WR
????35 ????2 ??1
????36 ????2 ??3
????37 ????1 ??0
????38 ????1 ??1
Data show, can make roller deposition and grease proofness and water proofing property optimization by the suitable type and the consumption of PMA type and consumption and fluorochemical selected.
Embodiment 39 and 40
Use 0.4%PMA-3 to make the sample of embodiment 39 and 40.Spin finishing is bathed and is contained 15%Lurol NF6239-20 and type and consumption fluorochemical as described in Table 13.Fibrous and roller deposition value is listed in table 13, and fibre property is listed in table 14.Table 13
Embodiment Fluorochemical Fluorochemical (%) The roller deposition
??39 ???OWR-1 ???8 ???2
??40 ???OWR-3 ???6．7 ???0
Table 14: the performance of polypropylene fibre
Embodiment ???OR ???WR
????39 ????1 ???4
????40 ????1 ???2

Claims (19)

1. the manufacture method of a fiber, it comprises the following steps:
(a) thermoplastic polymer is melt extruded into many long filaments with the mixture of giving hydrophilic compounds;
(b) apply spinning oil to described long filament; With
(c) with described long filament drawing fiber,
Wherein said spinning oil comprises fluorochemical.
2. the method for claim 1 is characterized in that the described hydrophilic compounds of giving comprises the fluorine-containing hydrophilic compounds of giving.
3. the method for claim 1 is characterized in that the described hydrophilic compounds of giving is made up of the fluorine-containing hydrophilic compounds of giving.
4. as the described method of above-mentioned any one claim, it is characterized in that the described hydrophilic compounds of giving is a non-ionic compound.
5. the method for claim 1 is characterized in that the described hydrophilic compounds of giving represents with following formula:
R f-Q-Z
R wherein fBe the fluorine-containing unit price residue that has 4 carbon atoms at least, Q is linking group or covalent bond, and Z is the dissolubility group of surging.
6. method as claimed in claim 5 is characterized in that Z comprises polyalkylene oxide groups.
7. the method for claim 1, the content that it is characterized in that giving hydrophilic compounds in described mixture is about 0.05-5% weight by the weight of described thermoplastic polymer.
8. as the described method of above-mentioned any one claim, it is characterized in that described thermoplastic polymer is a poly alpha olefin.
9. method as claimed in claim 8 is characterized in that described poly alpha olefin is a polypropylene.
10. as the described method of above-mentioned any one claim, it is characterized in that described spinning oil also comprises spinning oil.
11. a fiber, it contains many filament thermoplastic polymer and wherein is dispersed with and gives hydrophilic compounds, it is characterized in that comprising fluorochemical at least a portion surface of described long filament.
12. fiber as claimed in claim 11 is characterized in that the described hydrophilic compounds of giving comprises the fluorine-containing hydrophilic compounds of giving.
13., it is characterized in that the described hydrophilic compounds of giving is a non-ionic compound as claim 11 or 12 described fibers.
14. fiber as claimed in claim 11 is characterized in that the described hydrophilic compounds of giving represents with following formula:
R f-Q-Z is R wherein fBe the fluorine-containing unit price residue that has 4 carbon atoms at least, Q is linking group or covalent bond, and Z is the dissolubility group of surging.
15. fiber as claimed in claim 14 is characterized in that Z comprises polyalkylene oxide groups.
16. fiber as claimed in claim 11, the content that it is characterized in that giving hydrophilic compounds in described fiber is about 0.05-5% weight by the weight of described thermoplastic polymer.
17., it is characterized in that described thermoplastic polymer is a polyalphaolefin as the described fiber of any one claim among the claim 11-16.
18. fiber as claimed in claim 17 is characterized in that described poly alpha olefin is a polypropylene.
19. fabric or carpet, it comprises as any one described fiber among the claim 11-18.
CN 98811851 1997-12-05 1998-12-02 Process for extruding fibers Pending CN1280635A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP97203812.9 1997-12-05
EP97203812A EP0921216A1 (en) 1997-12-05 1997-12-05 Process for extruding fibers

Publications (1)

Publication Number Publication Date
CN1280635A true CN1280635A (en) 2001-01-17

Family

ID=8229015

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 98811851 Pending CN1280635A (en) 1997-12-05 1998-12-02 Process for extruding fibers

Country Status (6)

Country Link
EP (2) EP0921216A1 (en)
JP (1) JP2001526326A (en)
CN (1) CN1280635A (en)
AU (1) AU742193B2 (en)
DE (1) DE69817014T2 (en)
WO (1) WO1999029936A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI623666B (en) * 2016-11-30 2018-05-11 Modified water-repellent fiber and preparation method thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6537662B1 (en) * 1999-01-11 2003-03-25 3M Innovative Properties Company Soil-resistant spin finish compositions
DE102014014479A1 (en) * 2014-04-16 2015-10-22 Perlon Nextrusion Monofil GmbH Monofilaments with high abrasion and dimensional stability, low sliding friction and soiling tendency, textile fabrics containing these and their use

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5244951A (en) * 1991-05-02 1993-09-14 Minnesota Mining And Manufacturing Company Durably hydrophilic, thermoplastic fiber
CA2247272A1 (en) * 1996-03-07 1997-09-12 Bart O. Goeman Carpet yarn having high soil resistance
US5804625A (en) * 1996-05-21 1998-09-08 Minnesota Mining And Manufacturing Company Fluorochemical and hydrocarbon surfactant blends as hydrophilic additives to thermoplastic polymers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI623666B (en) * 2016-11-30 2018-05-11 Modified water-repellent fiber and preparation method thereof

Also Published As

Publication number Publication date
AU1617599A (en) 1999-06-28
WO1999029936A1 (en) 1999-06-17
EP0921216A1 (en) 1999-06-09
DE69817014T2 (en) 2004-06-09
EP1036223A1 (en) 2000-09-20
JP2001526326A (en) 2001-12-18
EP1036223B1 (en) 2003-08-06
DE69817014D1 (en) 2003-09-11
AU742193B2 (en) 2001-12-20

Similar Documents

Publication Publication Date Title
CN1130400C (en) Polymeric compositions for soil release on fabrics
CN1239777C (en) High-durability low-yellowing water-and oil-repellent for textiles
EP1838773B1 (en) Fluorochemical diesters as repellent polymer melt additives
CN1856396A (en) Treated textiles and compositions for treating textiles.
CN108699426B (en) Surface treating agent
CN1505562A (en) Condrapable hydrophobic nonwoven web and method of making same
CN1195919C (en) Spin finish
CN1444673A (en) Spunbonded nonwoven fabric and absorbent article
TW201917193A (en) Water repellent agent composition
US4565717A (en) Antisoiling treatment of synthetic filaments
KR20070103002A (en) Fluorochemical esters blends as repellent polymer melt additives
CN1867728A (en) Product comprising a fibrous support and a hydrophilic and/or permeabilizing coating, preparation method thereof and use of same
CN1114006C (en) Synthetic fiber treating agent and synthetic fiber treating method
KR100689941B1 (en) Aqueous Dispersion Composition Comprising Agent Repelling Water and Oil
CN1280635A (en) Process for extruding fibers
EP0904432B1 (en) Carpet yarn having high soil resistance
US6426025B1 (en) Process for extruding fibers
TW202110902A (en) Water repellent polymer and water repellent composition
JP3852156B2 (en) Antifouling synthetic fiber fabric and method for producing the same
JP2007039833A (en) Method for producing modified polyester fiber
EP1556421B1 (en) Ethylene copolymer with fluorine-containing graft and a process for preparing the same
CN1084814C (en) Fiber product processing method
CN101057022A (en) Latently functional polyolefin article, process for producing the same, and process for producing polyolefin article whose function has actualized
KR102068478B1 (en) Stain-proofing Agent Composition and Fabric Article Processed With the Same
CN1205684A (en) Fluorinated dieaster

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication
REG Reference to a national code

Ref country code: HK

Ref legal event code: GR

Ref document number: 1068954

Country of ref document: HK