EP0737773B1 - Procede de traitement de produits textiles et produits textiles ainsi traites - Google Patents

Procede de traitement de produits textiles et produits textiles ainsi traites Download PDF

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Publication number
EP0737773B1
EP0737773B1 EP95903962A EP95903962A EP0737773B1 EP 0737773 B1 EP0737773 B1 EP 0737773B1 EP 95903962 A EP95903962 A EP 95903962A EP 95903962 A EP95903962 A EP 95903962A EP 0737773 B1 EP0737773 B1 EP 0737773B1
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EP
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Prior art keywords
textile
water
treatment
fluorine
oil
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EP95903962A
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German (de)
English (en)
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EP0737773A1 (fr
EP0737773A4 (fr
Inventor
Yasuo Itami
Tetsuya Masutani
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to EP00110985A priority Critical patent/EP1039018A1/fr
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Publication of EP0737773A4 publication Critical patent/EP0737773A4/fr
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/203—Unsaturated carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/2035—Aromatic acids
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/1845—Aromatic mono- or polycarboxylic acids
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/213—Perfluoroalkyl carboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/2243—Mono-, di-, or triglycerides
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/425—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes
    • D06M13/428—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes containing fluorine atoms
    • 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
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • 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
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk
    • 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
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • 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
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • 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
    • D06M2200/50—Modified hand or grip properties; Softening compositions

Definitions

  • the present Invention relates to a method for treatment of a textile, and a treated textile. More particularly, it relates to a method for treatment of a textile, which method maintains durable water- and oil-repellency even after long-term use including the washing and the like and further maintains a touch, a feeling and a flexibility of fiber Itself, by a modification treatment of the textile.
  • a fluorine-containing compound having a fluoroalkyl group gives excellent water- and oil-repellency to a textile.
  • an acrylic polymer treating agent having a fluoroalkyl group has been practically used.
  • a disadvantage that a touch, a feeling and a flexibility of the treated textile are remarkably deteriorated and the resultant water repellency Is remarkably deteriorated by the washing or abrasion.
  • a combined agent has been used on the treatment, together with the acrylic polymer having the fluoroalkyl group.
  • Examples of combined agent include a melamine resin or a urea resin.
  • these resins are used in combination, the durability is improved in comparison with the case when using the polymer alone, but the touch, feeling and flexibility of fiber itself are liable to be deteriorated. Accordingly, it can be said that the durability and the touch, feeling and flexibility of fiber itself are contrary each other when using the fluorine-containing polymer.
  • Japanese Patent Kokal Publication No. 98568/1993 discloses that animal hair fibers are treated with an alkylphosphate salt to impart the water repellency and flexibility to the animal hair fibers. However, the treated fibers are inferior in durability because they are not treated with a fluorine-containing water- and oil-repellent.
  • EP-A-0 624 680 reveals an agent for treating a textile comprising a modifying agent which is a fluorine-containing phosphoric acid derivative having the formula (I) as defined below, wherein R 1 and R 2 are, same or different, a hydrogen atom or R f -(CH 2 ) m -, wherein R f is a saturated or unsaturated, linear or branched fluorine-containing aliphatic group having 4 to 20 carbon atoms in which an oxygen atom, a nitrogen atom, a sulfonyl group and/or an aromatic ring may be present between carbon atoms; and m is 1 or 2; A is an oxygen atom, a sulfur atom or a direct bond, and n is 1 or 2.
  • the treating agent further comprises a metal salt compound. After treating the textile with said treating agent, the textile is treated with a fluorine-containing water- and oil-repellent or a fluorine-containing stain-proofing agent.
  • a chromium complex of carboxylic acid has also been used as a processing agent for a textile or paper for the purpose of Imparting a water repellency.
  • a chromium complex of carboxylic acid having a perfluoroalkyl group has been used for the purpose of Imparting an oil repellency In addition to the water repellency (cf. Japanese Patent Kokoku Publication Nos. 466/1958 and 3274/1969).
  • an effect of these chromium complexes Is not always sufficient, and a further enhancement in effect has been required.
  • An object of the present invention Is to maintain a durable water- and oil-repellency even after long-term use including the washing and the like, and to maintain a touch, a feeling and a flexibility of fiber Itself even after the treatment of textile.
  • the present invention provides a method for treatment of a textile, which comprises:
  • the present invention also provides a textile treated by the above method for treatment.
  • treatment means that a textile is contacted with a treating liquid containing the modifier the fixing agent the metal complex or the fluorine-containing water- and oil-repellent.
  • the treatment may be conducted, for example, by an Immersion, an impregnation, a pad method or a coating method.
  • the textile may be treated with the modifier after treated with the fixing agent.
  • a textile may be treated with the fixing agent after treated with the modifier.
  • the modifier used in the first stage of treatment is the phosphoric acid derivative represented by the above general formula (I) or the salt thereof.
  • the phosphoric acid derivative is a compound having a P-OH bond and a hydrocarbon group.
  • the hydrocarbon group usually means a saturated or unsaturated straight-chain or branched aliphatic hydrocarbon group, and includes those in which an oxygen atom, a nitrogen atom, a sulfonyl group or an aromatic ring exists in a carbon-carbon bond. It is preferred that the hydrocarbon group is an alkyl group.
  • Examples of the salt of the phosphoric acid derivative include a monovalent metal salt such as a sodium salt, a potassium salt, or a lithium salt; an organic amine salt such as a diethanolamine salt, a triethylamine salt, a propylamine salt, or a morpholine salt; and an ammonium salt.
  • a molecular weight of the phosphoric acid derivative or the salt thereof varies depending on the general formula, but is preferably not more than 2000.
  • the metal In the metal salt compound as the fixing agent used in the first stage of treatment may be a polyvalent (divalent or more) metal which bonds ionically to a hydroxyl group bonding to a phosphoric atom.
  • chromium, zirconium, titanium, or aluminum are preferred.
  • the metal salt compound is water-soluble one.
  • chloride, nitrate, sulfate, or hydroxide are preferred.
  • basic chromium sulfate and basic zirconium sulfate are particularly preferred in view of durability.
  • the fluorine-containing water- and oil-repellent used in the second step of treatment is a fluorine-containing compound having a perfluoroalkyl group.
  • the fluorine-containing compound may be a known fluorine-containing polymer having a side chain of a perfluoroalkyl group.
  • the following monomers forming polymers or copolymer can be used. wherein R 1 is a hydrogen atom or a methyl group; R 2 Is a lower alkyl group; X Is a divalent organic group; m Is an integer of 1 to 4; and n is an integer of 5 to 21.
  • An average molecular weight of the fluorine-containing polymer is usually from 5,000 to 500,000.
  • the fluorine-containing compound may be a fluorine-containing urethane compound or a fluorine-containing ester compound, and examples thereof include the followings.
  • Rf is C m F m+1 (m is an integer of 5 to 21); and n is 0 to 4.
  • the fluorine-containing water- and oil-repellent may be used in combination with various combined agents, and examples of the combined agent include a melamine resin, a urea resin, a blocked isocyanate, or glyoxal.
  • the textile is treated with the modifier and the fixing agent.
  • the use order of the modifier and fixing agent may be freely selected as described hereinafter.
  • Examples of the method for treatment using the modifier and the fixing agent include the following methods (1), (2) and (3).
  • the solution of the metal salt compound as the fixing agent is an aqueous solution of 0.01 to 10% by weight, preferably from 0.03 to 3% by weight.
  • a temperature of the fixing agent solution is usually from 20 to 70°C.
  • a solution of the phosphoric acid derivative as the modifier is an aqueous solution or a lower alcohol solution of 0.01 to 10% by weight, preferably from 0.03 to 3% by weight. Examples of the lower alcohol include methanol, ethanol, or isopropyl alcohol.
  • a temperature of the modifier solution is usually from 5 to 90°C, preferably from 20 to 70°C.
  • the acid solution used for the immersion or the adjustment of pH is a solution, preferably aqueous solution, containing a mineral acid such as hydrochloric acid and sulfuric acid or an organic acid such as formic acid, acetic acid and propionic acid.
  • a concentration of the acid solution is not specifically limited, but is usually from 0.05 to 30% by weight, preferably from 0.1 to 5% by weight.
  • a temperature of the acid solution is usually from 5 to 90°C, preferably from 20 to 70°C.
  • An immersion time in each of the fixing agent solution, the modifier solution and the acid solution Is usually at least 10 seconds, preferably from 1 to 120 minutes, more preferably from 1 to 30 minutes.
  • a retention time in the bath adjusted to the pH of 1 to 5 is usually at least 10 seconds, preferably from 1 to 30 minutes.
  • a drying temperature is usually from 10 to 70°C, preferably room temperature.
  • the drying time varies depending on the drying condition (particularly, the drying temperature), but is usually within 24 hours, preferably from 0.1 to 10 hours.
  • a weight ratio of the fixing agent to the modifier in the bath is usually from 0.1:1 to 10:1.
  • the method of the second stage (B) may be a method which has hitherto been used.
  • the treatment is conducted by an immersion, a pad method, a coating method or the like, followed by drying.
  • the combined agent such as the melamine resin and the urea resin may be used in combination.
  • a heat treatment, a calendering and the like may be conducted.
  • a treating agent e.g. a silicon compound, other than the fluorine-containing compound in combination.
  • the form of the fluorine-containing water- and oil-repellent may be an emulsion or a solution in an organic solvent.
  • a water-soluble lower alcohol or ketone isopropyl alcohol is particularly preferred
  • an amount of 0.1 to 10% by weight preferably from 1 to 5% by weight based on the emulsion, in view of penetration of the fluorine-containing water- and oll-repellent.
  • the second stage of treatment can be applied to any textile.
  • a resultant carpet or fabric
  • the second stage of treatment can be conducted on raw yarns or raw hairs used for the carpet, and the carpet can be produced by using the treated raw yarns or raw hairs.
  • the raw yarns and raw hairs may be subjected to the first stage of treatment and then the resultant carpet may be subjected to the second stage of treatment.
  • the water- and oil-repellency is obtained only at the surface of the textile fabric because the phosphoric acid derivative is penetrated into the interior of a fiber bundle and then fixed. It is possible to impart the advantageous effect in the interior of textile even if the textile has a large thickness. Since the second stage of treatment is further conducted by using the fluorine-containing water- and oil-repellent, the durability becomes stronger. When using the phosphoric acid derivative, the deterioration of the feeling and flexibility of the textile which has not hitherto been avoided by using the fluorine-containing water- and oil-repellent alone, is improved surprisingly.
  • the textile to be treated includes a yam, a woven fabric, a knitted fabric, a nonwoven fabric, an artificial leather and the like which are formed from the fiber, in addition to the textile having the form of the fiber as such.
  • the fiber there can be used chemical fibers including synthetic fibers such as polyester and nylon in addition to natural fibers such as cotton, wool and silk. It is also possible to use a textile blend of natural fibers and synthetic fibers.
  • the woven fabric and artificial leather comprising superfine fibers, which have recently been remarkably developed, are suitable for the present invention in view of the fact that the feeling and touch are considered to be Important.
  • the superfine fibers usually have a fineness of not more than 1.1 dtex (1 denier), preferably not more than 0.89 dtex (0.8 denier), more preferably from 0.89 to 0.00011 dtex (0.8 to 0.0001 denier), most preferably from 0.1 to 0.0011 dtex (0.1 to 0.001 denier).
  • the textile obtained by the present Invention has the above excellent advantages and, therefore, it is suitably used for applications where water and oil repellency as well as stainproofing properties are required.
  • the textile which Is suitable for the present invention may be, for example, a carpet.
  • the material of the carpet may be a polyamide such as nylon, a polyester, an acryl, a wool and the like, and is not specifically limited.
  • the present invention is particularly effective for a nylon carpet which is usually used under a severe condition.
  • the structure, the weaving type, the pile length of the carpet are not specifically limited.
  • the textile obtained according to the present invention can be used for outdoor applications exposed to rainwater.
  • Examples thereof include a tent, an automobile cover, a motorbike cover, a hood for rear deck of track, a coated sheet for construction, an umbrella and clothes (particularly, rainwears such as a raincoat and a poncho).
  • the present invention can be used for the textiles used for a cover of a cap, a foot wear (e.g. shoes, slippers), a bag, a pouch or a seat (e.g. a car seat, a seat, a sofa and a chair), interior goods such as a curtain, a carpet, a wall and ceiling of buildings and vehicles (e.g. an automobile, a train, an aircraft and a ship) and various displays.
  • a foot wear e.g. shoes, slippers
  • a bag e.g. a bag, a pouch or a seat
  • interior goods such as a curtain, a carpet, a wall and ceiling of buildings and vehicles (e.g. an automobile, a train, an aircraft and a ship) and various displays.
  • the water repellency shown in the Examples and Comparative Examples is measured according to JIS-L-1092-1977 and expressed by the numeral shown in Table 1,
  • the oil repellency is measured by a method according to AATTC TM-118-1975, and a maximum number of oil wherein no penetration is observed after 30 minutes from dropping several drops of oils having different surface tensions shown in Table 2 is expressed as the oil repellency.
  • the washing resistance was measured according to JIS-L-0217-103 and was expressed by the water repellency and oil repellency before and after washing 20 times.
  • the superscript "+" to the water repellency and oil repellency represents that the result is slightly better than said water repellency and said oil repellency.
  • the water absorption properties are measured according to JIS-K-6550-1976. That is, each sample Is immersed in a distilled water for 30 minutes and the water absorption properties are represented by an increase in weight (%) before and after immersion.
  • the water resistance is measured according to JIS-K-6550-1976. That Is, a sample is attached to a water resistance test machine (manufactured by YASUDA SEIKI SEISAKUSHO CO., LTD.) having a structure that a constant pressure is applied to a bore having a diameter of 50 mm, and then a water column is gradually increased.
  • the water resistance is represented by a height of the water column at which water leaks onto the surface of the sample.
  • a fabric consisting of superfine fibers (Artificial Leather SOFRINATIAL (trade name) manufactured by KURARAY CO., LTD) was immersed at 30°C In an aqueous 0.5% solution (bath ratio: 10:1) of basic chromium sulfate (BAYCHROME F (trade name) manufactured by BAYER AG) and then subjected to a rotating treatment using a dyeing test machine (manufactured by TSUZII SENKI KOGYO CO., LTD.) for 30 minutes.
  • BAYCHROME F basic chromium sulfate
  • the fabric After swish off of water, the fabric was immersed at 50°C in an aqueous 0.5% solution (bath ratio: 10:1) of a compound 1 (phosphoric acid derivative) shown In Table 4 and then subjected to a rotating treatment for 30 minutes. After the pH was adjusted to 3 by adding a 0.3% aqueous formic acid solution to the bath, the fabric was rotated for 30 minutes, swished to remove water, washed with water at 40°C and then dried at room temperature.
  • aqueous 0.5% solution bath ratio: 10:1
  • a compound 1 phosphoric acid derivative
  • a fluorine-containing water- and oil-repellent (TEXGUARD TG-520 (trade name) manufactured by DAIKIN INDUSTRIES, LTD.) was diluted with tap water so that a solid content was 1%. Further 2% of a blocked isocyanate (ELASTRON BN-69 manufactured by DAIICHI KOGYO SEIYAKU CO., LTD.) as a combined agent, 0.2% of a catalyst (ELASTORON CATALYST manufactured by DAIICHI KOGYO SEIYAKU CO., LTD.) and 3% of isopropyl alcohol were added to prepare a treating liquid.
  • a blocked isocyanate ELASTRON BN-69 manufactured by DAIICHI KOGYO SEIYAKU CO., LTD.
  • a catalyst EASTORON CATALYST manufactured by DAIICHI KOGYO SEIYAKU CO., LTD.
  • test fabric which had already been subjected to the first stage of treatment was immersed in the resultant treating liquid, squeezed with a mangle to adjust a wet pickup to 50%, dried at 110°C for 3 minutes and then heat-treated at 160°C for one minute.
  • Example 1 The textile sample used in Example 1 was subjected to only the same treatment as the second stage of treatment used in Example 1. The feeling, water repellency, oil repellency, water absorption property and water resistance before and after washing were measured. The results are shown in Table 5.
  • Example 1 The textile sample used in Example 1 was subjected to only the same treatment as the first stage of treatment used in Example 1. The feeling, water repellency, oil repellency, water absorption property and water resistance before and after washing were measured. The results are shown in Table 5. Feeling Water repellency Oil repellency Water absorption property (%) Water resistance (cm)
  • Example 1 L0 ⁇ 100+ 4 5.8 140 L20 ⁇ 70 1 29.4 114 Com.
  • L0 and L20 respectively indicate "before washing” and "after washing 20 times".
  • the durable water repellency can be maintained even after a long-term use including washing and friction and, furthermore, the touch, the feeling and the flexibility of fiber itself can be maintained even after a treatment of a textile when treated with a phosphoric acid derivative and a fixing agent.
  • the present invention solves the problem of durability and the problem of flexibility which were contrary each other, while said problems occurs when using a conventional fluorine-containing water- and oil-repellent.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (4)

  1. Procédé de traitement d'un textile, qui comprend les étapes consistant à
    (A) appliquer à un textile un agent de modification à base d'un dérivé d'acide phosphorique représenté par la formule générale :
    Figure 00230001
    dans laquelle R1 et R2 sont identiques ou différents et sont un atome d'hydrogène ou un groupe hydrocarbure à chaíne droite ou ramifiée, saturé ou non, ayant 4 à 20 atomes de carbone (un atome d'oxygène, un atome d'azote, un groupe sulfonyle ou un cycle aromatique peut être présent entre les atomes de carbone), à condition que R1 et R2 ne soient pas simultanément un atome d'hydrogène ;
       A est un atome d'oxygène, un atome de soufre ou une liaison directe ; et
       n vaut 1 ou 2,
       ou un sel de celui-ci, avant ou après traitement du textile avec un agent de fixation ou un sel métallique,
       et traiter le textile avec une solution acide ayant un pH de 1 à 5, puis
    (B) appliquer au textile un agent hydro- et oléophobe fluoré qui est un composé fluoré contenant un groupe perfluoroalkyle.
  2. Procédé de traitement d'un textile selon la revendication 1, dans lequel le sel métallique est un sel de chrome, de zirconium, de titane ou d'aluminium.
  3. Textile pouvant être obtenu par le procédé selon la revendication 1, et comprenant l'agent de modification textile fixé et l'agent hydro- et oléophobe appliqués comme indiqué dans le procédé selon la revendication 1.
  4. Textile selon la revendication 3, comprenant une fibre superfine ayant une finesse d'au plus 0,89 dtex (0,8 denier).
EP95903962A 1993-12-28 1994-12-27 Procede de traitement de produits textiles et produits textiles ainsi traites Expired - Lifetime EP0737773B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP00110985A EP1039018A1 (fr) 1993-12-28 1994-12-27 Procédé de traitement de produits textiles et produits textiles ainsi traités

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP35361393 1993-12-28
JP353613/93 1993-12-28
JP5353613A JPH07197377A (ja) 1993-12-28 1993-12-28 繊維製品の処理方法および処理された繊維製品
PCT/JP1994/002223 WO1995018258A1 (fr) 1993-12-28 1994-12-27 Procede de traitement de produits textiles et produits textiles ainsi traites

Related Child Applications (1)

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EP00110985A Division EP1039018A1 (fr) 1993-12-28 1994-12-27 Procédé de traitement de produits textiles et produits textiles ainsi traités

Publications (3)

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EP0737773A1 EP0737773A1 (fr) 1996-10-16
EP0737773A4 EP0737773A4 (fr) 1998-06-10
EP0737773B1 true EP0737773B1 (fr) 2002-06-26

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EP95903962A Expired - Lifetime EP0737773B1 (fr) 1993-12-28 1994-12-27 Procede de traitement de produits textiles et produits textiles ainsi traites

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EP (2) EP1039018A1 (fr)
JP (1) JPH07197377A (fr)
CN (1) CN1096522C (fr)
AT (1) ATE219804T1 (fr)
DE (1) DE69430873T2 (fr)
TW (1) TW327198B (fr)
WO (1) WO1995018258A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7931944B2 (en) 2003-11-25 2011-04-26 Kimberly-Clark Worldwide, Inc. Method of treating substrates with ionic fluoropolymers
US7811949B2 (en) 2003-11-25 2010-10-12 Kimberly-Clark Worldwide, Inc. Method of treating nonwoven fabrics with non-ionic fluoropolymers
EP2302130A1 (fr) * 2009-09-26 2011-03-30 Huntsman Textile Effects (Germany) GmbH Composition pour l'équipement oléofuge et/ou hydrofuge de matériaux en fibres
FR2954454B1 (fr) * 2009-12-23 2012-02-10 Vallourec Mannesmann Oil & Gas Composant filete tubulaire resistant au grippage et procede de revetement d'un tel composant
CN102797148A (zh) * 2012-08-30 2012-11-28 源达日化(天津)有限公司 一种针对纺织产品的防蛀剂
CN111041834B (zh) * 2019-12-10 2022-09-23 上海驰纺材料科技有限公司 一种多功能超柔软含棉针织面料的制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3061473A (en) * 1960-06-23 1962-10-30 Stevens & Co Inc J P Process of and composition for producing improved textile materials having oil and water repellent and antistatic properties
GB1296255A (fr) * 1970-03-26 1972-11-15
NL7505229A (nl) * 1974-05-07 1975-11-11 Hoechst Ag Werkwijze en middel voor het vuilafstotend en antistatisch afwerken van vezelmateriaal.
JPS598568A (ja) * 1982-07-07 1984-01-17 Nissan Motor Co Ltd キツキングプレ−ト
JPS63105175A (ja) * 1986-10-23 1988-05-10 カネボウ株式会社 合成繊維構造物を帯電防止ならびに撥水加工する方法
JP2796385B2 (ja) * 1989-12-22 1998-09-10 ミネソタ マイニング アンド マニユフアクチユアリング カンパニー 撥水撥油処理剤
JPH03193975A (ja) * 1989-12-22 1991-08-23 Minnesota Mining & Mfg Co <3M> 撥水撥油処理剤
JPH0598568A (ja) * 1991-10-09 1993-04-20 Senka Kk 獣毛繊維の処理方法
ES2185626T3 (es) * 1992-01-27 2003-05-01 Daikin Ind Ltd Utilizacion de un agente de tratamiento para productos fibrosos, procedimiento de tratamiento de productos fibrosos tratados segun este procedimiento.

Also Published As

Publication number Publication date
DE69430873T2 (de) 2002-11-28
EP0737773A1 (fr) 1996-10-16
WO1995018258A1 (fr) 1995-07-06
TW327198B (en) 1998-02-21
EP1039018A1 (fr) 2000-09-27
CN1096522C (zh) 2002-12-18
DE69430873D1 (de) 2002-08-01
ATE219804T1 (de) 2002-07-15
JPH07197377A (ja) 1995-08-01
CN1139965A (zh) 1997-01-08
EP0737773A4 (fr) 1998-06-10

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