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 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, a urea resin and the like.
• 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 Kokai 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.
• 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 also provide a textile treated by the above method for treatment.
• treatment means that a textile is contact 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, a coating method and the like.
• 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, a lithium salt, etc.; an organic amine salt such as a diethanolamine salt, a triethylamine salt, a propylamine salt, a morpholine salt, etc.; 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, aluminum and the like are preferred.
• the metal salt compound is water-soluble one.
• chloride, nitrate, sulfate, hydroxide and the like 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, glyoxal and the like.
• 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, isopropyl alcohol and the like.
• 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.
• a carboxylic acid-metal complex is obtained by reacting the metal salt compound with the carboxylic acid.
• a chromium complex is obtained by reacting a carboxylic acid with a chromium compound.
• the chromium compound is a compound represented by the formula: Cr(OH)Cl 2 ⁇ 6H 2 O.
• the chromium complex is, for example, wherein R 3 is as defined above.
• the chromium complex is obtained by heating the carboxylic acid together with the chromium compound in the presence or absence of a solvent.
• carboxylic acid examples include the followings, but are not to be limited thereto.
• the metal salt compound in the metal complex may be the metal salt compound described above as in the fixing agent.
• the textile is firstly treated with a treating agent comprising the metal complex of carboxylic acid, in the first stage of treatment.
• a treating agent comprising the metal complex of carboxylic acid
• the textile is immersed in an aqueous solution (liquid temperature: 20 to 70°C, preferably from 30 to 50°C) containing the metal complex of carboxylic acid in an amount of 0.01 to 30% by weight, preferably from 0.1 to 10% by weight, for at least 10 seconds, preferably from 1 to 120 minutes, removed from the bath, swished for removing water and then dried.
• a drying temperature can be adjusted within the range from 10 to 140°C, but it is practically sufficient to air-dry at room temperature.
• the aqueous solution may contain an acid.
• the acid include mineral acids such as hydrochloric acid and sulfuric acid and organic acids such as formic acid, acetic acid and propionic acid.
• the textile which has already been subjected to the first stage of treatment is treated with a usual fluorine-containing water- and oil-repellent as described hereinafter, in the second stage (B) of treatment.
• the method 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
• 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 oil-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 or carboxylic-metal complex 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 yarn, 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 denier, preferably not more than 0.8 denier, more preferably from 0.8 to 0.0001 denier, most preferably from 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.
• Example 1 (in case (i) that the treatment is conducted using a phosphoric acid derivative and a fixing agent)
• 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.
• a dyeing test machine manufactured by TSUZII SENKI KOGYO CO., LTD.
• 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 bean subjected to the first stage of treatment was immersed in the resultant treating liquid, squeezed with a mange 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. Table 5 Feeling Water repellency Oil repellency Water absorption property (%) Water resistance (cm)
• Example 1 L0 O 100+ 4 5.8 140 L20 O 70 1 29.4 114 Com.
• Ex. 2 L0 O 70+ 0 10.4 76 L20 O 50 0 79.0 71 (Note)
• L0 and L20 respectively indicate "before washing” and "after washing 20 times".
• Example 2 (in case (ii) that the treatment is conducted using a carboxylic acid-metal complex)
• a fabric consisting of supertine fibers (Artificial Leather SOFRINATIAL (trade name) manufactured by KURARAY CO., LTD) was immersed in an aqueous solution (bath ratio: 250%) containing 2% (solid content) of a perfluoroalkyl group-containing carboxylic acid-chromium complex (SCOTCHGUARD 233A manufactured by 3M CO.) of the formula: and 0.4% of formic acid and then subjected to a rotating treatment at 40°C using a dyeing test machine (manufactured by TSUZII SENKI KOGYO CO., LTD.) for 30 minutes. Aftter swish off of water, the fabric was squeezed so that a wet pickup was 80%, and then the fabric was air-dried at room temperature.
• a perfluoroalkyl group-containing carboxylic acid-chromium complex (SCOTCHGUARD 233A manufactured by 3M CO.) of the formula: and 0.4% of formic acid
• a fluorine-containing water- and oil-repellent (TEXGUARD TG-520 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 2 The textile sample used in Example 2 was subjected to only the same treatment as the second stage of treatment used in Example 2, except that the solid content of the fluorine-containing water- and oil-repellent in the liquid was increased to two times that of Example 2. The feeling, water repellency, oil repellency, water absorption property and water resistance before and after washing were measured. The results are shown in Table 6.
• Example 2 The textile sample used in Example 2 was subjected to only the same treatment as the first stage of treatment used in Example 2, except that the solid content of the carboxylic acid-chromium complex in the solution was increased to two times that of Example 2.
• the feeling, water repellency, oil repellency, water absorption property and water resistance before and after washing were measured. The results are shown in Table 6.
• Table 6 Water repellency Oil repellency Water absorption property (%) Water resistance (cm)
• Example 2 L0 100+ 4 5.3 150 L20 70 1 6.8 112 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.

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• 1993
  • 1993-12-28 JP JP5353613A patent/JPH07197377A/ja active Pending
• 1994
  • 1994-12-27 WO PCT/JP1994/002223 patent/WO1995018258A1/ja active IP Right Grant
  • 1994-12-27 DE DE69430873T patent/DE69430873T2/de not_active Expired - Fee Related
  • 1994-12-27 CN CN94194723A patent/CN1096522C/zh not_active Expired - Fee Related
  • 1994-12-27 EP EP00110985A patent/EP1039018A1/de not_active Withdrawn
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  • 1994-12-27 EP EP95903962A patent/EP0737773B1/de not_active Expired - Lifetime
• 1995
  • 1995-02-07 TW TW084100982A patent/TW327198B/zh active

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