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
  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus 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
  • D06M15/21—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
• • 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
  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
  • D06M15/3564—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing phosphorus
• • 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
  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
  • D06M15/3566—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing sulfur

Definitions

• the present invention relates to a method for treating a textile. Particularly, it relates to a textile treatment method which can give excellent initial water- and oil-repellency and excellent durable water- and oil-repellency when a textile, especially a hydrophilic textile is treated for modification.
• a fluorine-containing compound has an excellent property of a water- and oil-repellent.
• a treatment agent comprising a polymer of a fluoroalkyl group-containing vinyl monomer has been practically used.
• Such polymer is sometimes a homopolymer of a fluoroalkyl group-containing vinyl monomer.
• it is a copolymer with various fluorine-free vinyl monomers.
• the used fluorine-free vinyl monomers include a hydrophilic monomer.
• Japanese Patent Kokoku Publication JP-B-62047466 discloses a water- and oil repellent comprising a phosphoric acid group-containing monomer and a perfluoroalkyl group-containing vinyl monomer.
• the use of the copolymer with the hydrophilic vinyl monomer such as the phosphoric acid group-containing monomer gives poor adhesion to a hydrophilic textile such as nylon because of an electrical charge of the polymer from an electrical property of functional group and a hydrophilic property of the polymer, and sometimes gives no water- and oil-repellency.
• FR-A-2270364 discloses a method for treating hydrophilic fibrous textile materials comprising the treatment of fibrous materials in a bath containing (a) a salt of the 2 to 4 valent metal and (b) a fluorine containing polymer.
• This fluorine containing polymer comprises moieties of a monomer containing fluoroalkyl groups of the formula X-C a F 2a wherein X is H or F and a is 4 to 14, and a moiety representing phosphoric acid ester salt and/or an oxyalkylation reaction product moiety which may comprise a sulfuric acid ester group.
• US 3467612 concerns a textile treated composition containing fluorinated acrylic polymers together with polyvalent metal salts of weak acids.
• the fibrous material is treated with a metal salt of (in)organic acid and subsequently with a water-repellent copolymer of perfluoroalkyl(meth)acrylate and an ethylenically unsaturated monomer.
• An object of the present invention is to give excellent initial water- and oil-repellency and excellent durable water- and oil-repellency to a textile, particularly a hydrophilic textile due to the stabilized exhibition of water- and oil-repellency of a fluorine-containing polymer.
• the present invention provides a method for treating a textile, comprising treating the textile with a salt of a metal having a valency of at least two and then treating the textile with a fluorine-containing polymer having a hydrophilic functional group selected from a phosphoric acid group and a sulfonic acid group capable of coordinating with said metal.
• the present invention provides a textile treated by the above treatment method.
• treatment used in the present specification means that the textile is contacted with a treatment liquid containing the metal salt or the fluorine-containing polymer.
• the “treatment” includes a dip process, an impregnation process, a padding process, and a coating process.
• the hydrophilic functional group is preferably selected from the group consisting of a phosphoric acid group and a sulfonic acid group.
• the fluorine-containing polymer is preferably a copolymer having
• the fluorine-containing vinyl monomer (a) is a compound having both of a polyfluoroalkyl group (particularly a perfluoroalkyl group) or a polyfluoroalkenyl group (particularly a perfluoroalkenyl group) and a polymerizable unsaturated double bond (particularly a carbon-carbon double bond).
• Specific examples of the fluorine-containing vinyl monomer (a) are following compounds: wherein R 11 is a hydrogen atom or a methyl group, R 12 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.
• the carbon number of R 12 is usually from 1 to 6.
• Examples of X are a C 1 -C 10 alkyleneoxy group, an oxygen atom, a sulfur atom, an amino group optionally substituted with a C 1 -C 6 lower alkylene group and the like.
• the acid group-containing monomer (b) has an anionic functional group capable of coordinating with the metal.
• the functional group is a phosphoric acid group or a sulfonic acid group.
• Specific examples of the acid group-containing monomer (b) are the following compounds:
• the copolymerization ratio of the fluorine-containing vinyl monomer (a) to the acid group-containing monomer (b) is in a range giving no adverse effect on the water- and oil-repellency.
• the amount of the acid group-containing monomer (b) is usually at most 50 parts by weight, preferably from 0.2 to 30 parts by weight per 100 parts by weight of the fluorine-containing vinyl monomer (a).
• the fluorine-containing polymer may contain at least one fluorine-free monomer (c) having neither of the phosphoric acid group nor the sulfonic acid group.
• the amount of the fluorine-free monomer (c) is usually smaller than 100 parts by weight, preferably from 0 to 50 parts by weight per 100 parts by weight of the fluorine-containing vinyl monomer (a).
• fluorine-free monomer (c) are a lower olefinic halogenated or non-halogenated hydrocarbon such as ethylene, propylene, isobutene, 3-chloro-1-isobutene, butadiene, isoprene, chloro- and dichloro-butadiene, 2,5-dimethyl-1,5-hexadiene and diisobutylene;
• a lower olefinic halogenated or non-halogenated hydrocarbon such as ethylene, propylene, isobutene, 3-chloro-1-isobutene, butadiene, isoprene, chloro- and dichloro-butadiene, 2,5-dimethyl-1,5-hexadiene and diisobutylene;
• the method for preparing the fluorine-containing polymer is not limited and may be a conventionally used solution polymerization, emulsion polymerization or the like.
• a radical initiator may be used for the polymerization.
• the molecular weight of the fluorine-containing polymer used in the present invention is usually from 1,000 to 1,000,000.
• the metal salt treatment means that the textile is dipped in a liquid containing the salt of metal having the valency of at least two, and it is used as the first step in the method of the present invention.
• the metal are chromium, zirconium, titanium, aluminum and the like.
• the metal salt are a sulfate salt, a nitrate salt, a chloride and the like. Among them, basic chromium sulfate is recommendable, since it has a particularly strong strength of bonding to an anionic functional group.
• the textile is dipped in a liquid containing the metal salt (the liquid temperature: 20-70°C), a pH value of the liquid is optionally adjusted to a range between 5 and 7, preferably between 5.5 and 6.5 and then the textile is washed with water.
• the metal salt liquid is an aqueous solution or aqueous suspension containing 0.01 to 50 % by weight, preferably 0.5 to 10 % by weight, based on the weight of the textile, of the metal salt.
• the time for dipping the textile is usually at least 10 seconds, preferably from 1 minute to 120 minutes.
• the pH adjustment can be conducted by using sodium acetate, sodium formate, sodium hydrogen carbonate and the like.
• the dried textile is treated with the fluorine-containing polymer.
• the treatment with the fluorine-containing polymer is a second step in the present invention.
• Said treatment may be a conventionally conducted process, for example, an impregnation process, a padding process, a coating process and the like.
• the textile is dried.
• the textile can be treated with the fluorine-containing polymer in the same bath.
• the fluorine-containing polymer in the amount of 0.01 to 50 % by weight, preferably 5 to 25 % by weight in solid, of the textile weight is added to the bath and textile is dipped for at least 10 seconds, preferably 1 minute to 120 minutes.
• an organic base such as ammonia and triethylamine, or an inorganic base such as sodium hydroxide and potassium hydroxide is particularly effective on the treatment of the textile having a large thickness.
• a 0.1 to 5 % aqueous solution of a mineral acid such as hydrochloric acid and sulfuric acid or an organic acid such as formic acid, acetic acid and propionic acid is preferably added to the bath so as to adjust the pH value of the bath to a range between 1 and 4, more preferably between 2.5 and 3.5.
• a mineral acid such as hydrochloric acid and sulfuric acid or an organic acid such as formic acid, acetic acid and propionic acid
• the weight ratio of the metal salt and the fluorine-containing polymer is usually from 1:10 to 10:1.
• the fluorine-containing polymer may be used together with various combination agents.
• the combination agent are a melamine resin, a urea resin, a blocked isocyanate, glyoxal and the like. If necessary, a thermal treatment and/or a calendaring process may be conducted.
• a treatment agent other than a fluorine-containing compound, for example, a silicone compound may combined.
• the textile treated with the metal salt/fluorine-containing copolymer according to the present invention may be treated with other water- and oil-repellent, preferably a fluorine-containing water- and oil-repellent.
• a homopolymer or copolymer of a fluorine-containing monomer having no anionic functional group is preferable for the improvement of the textile durability.
• the treated textile includes one in the form of a fiber, and a yarn, a woven fabric, a knitted fabric, a non-woven fabric and the like prepared from the fiber.
• the fiber are a natural fiber such as cotton, wool and silk; and a chemical fiber including a synthetic fiber such as acryl, a polyamide, a cellulose and a polyester.
• a textile blend of the natural fiber and the synthetic fiber may be used.
• the textile is preferably hydrophilic. Particularly preferable examples of the hydrophilic textile are a polyamide and a polyester.
• the woven fabric and artificial leather comprising a recently remarkably developed ultra-thin fiber are a preferable textile.
• the ultra-thin fiber has usually at most 1 Denier, preferably 1 to 0.0001 Denier, more preferably 0.1 to 0.001 Denier.
• the water repellency shown in Examples and Comparative Examples is determined according to JIS-L-1092-1977, and is indicated by the numeral figure shown in Table 1.
• the oil repellency is determined by, according to AATCC-TM-118-1966, dropping several drops of the following test solutions having different surface tensions shown in Table 2, and observing the penetration state of the drops after 30 seconds, and the maximum value of oil repellency of the test solution having no penetration is expressed as the oil repellency.
• the wash durability was measured according to JIS-L-0217-103 and is shown by the water repellency and oil repellency before and after the ten times of washing.
• the suffix "+" to the numeral value in the water repellency and oil repellency represents that the performance is slightly better than said numeral value and the suffix "-" to the numeral value represents that the performance is slightly worse than said numeral value.
• Azobisisobutylamidine hydrochloride (0.51 g) was added to the emulsion, the vapor atmosphere was replaced with the nitrogen gas and the polymerization was conducted at 55°C for 5 hours.
• the resultant emulsion was diluted with the deionized water (229.8 g) to give a fluorine-containing copolymer emulsion having a solid content of 20%.
• Structure a (a mixture of compounds in which n is 3, 4, 5 and 6 in a molar ratio of 5:3:2:1)
• 6-Nylon taffeta for a dyeing test was dipped in a 30°C aqueous solution (bath ratio 10:1) containing basic chromium sulfate (trade name: Baychrom F (manufactured by Bayer AG) in amount of 5 wt %, based on the test fabric weight, and rotary-treated by a dyeing test machine (manufactured by Tsujii Senki Kogyo Co., Ltd.) for 120 minutes, and then each of sodium formate and sodium hydrogen carbonate in an amount of 0.2 wt% based on the test fabric weight was added to conduct the neutralization. Then, the fabric was rotary-treated at 40°C for 20 minutes, hydro-extracted, washed with water, and dried at a room temperature to give a sample.
• bath ratio 10:1 basic chromium sulfate
• Baychrom F manufactured by Bayer AG
• a dyeing test machine manufactured by Tsujii Senki Kogy
• Each of the fluorine-containing copolymer emulsions prepared in Preparative Examples 1 to 4 was diluted with the tap water to the solid content of 1 %. Then 3 % of isopropyl alcohol was added to give a treatment liquid.
• the test fabric prepared in Example 1 of preparing fabric treated with metal salt was dipped in said treatment liquid, and was squeezed with a mange to give a wet pickup of 25%.
• the test fabric was dried at 110°C for 3 minutes and thermally treated at 160°C for 1 minute.
• the water repellency and the oil repellency of the sample were measured before and after the ten times washing with water. The results are shown in Table 4.
• Example 5 The same process till the neutralization as in Example 1 of preparing test fabric treated with metal salt was repeated, and then the liquid was removed, the 6-nylon taffeta was dipped in a 50°C diluted liquid (bath ratio 10:1) containing 15 %, based on the test fabric weight, of the emulsion of Preparative Example 1 or 2 (corresponding to Example 5 and 6, respectively), and the rotary-treatment was conducted for 60 minutes. After 3 %, based on the test fabric weight, of formic acid was added, the rotary-treatment was conducted at 40°C for 20 minutes. After the liquid was removed, the fabric was washed with water, hydro-extracted, dried at 110°C for 3 minutes and thermally treated at 160°C for 1 minute. The water-repellency and the oil-repellency of the resultant sample were measured before and after the ten times of wash. The results of Examples 5 and 6 are shown in Table 5.
• a fluorine-containing water- and oil-repellent (Texguard TG-5431 manufactured by Daikin Industries Ltd.) was diluted with the tap water to the solid content of 1%, and 3% of isopropyl alcohol was added to give a treatment liquid.
• the test fabric prepared in each of Examples 5 and 6 was dipped in the treatment liquid, and squeezed with a mangle to give a wet pickup of 25%.
• the test fabric was dried at 110°C for 3 minutes and thermally treated at 160°C for 1 minute.
• the water repellency and the oil repellency of the resultant sample were measured before and after the ten times of wash.
• the results of Examples 7 and 8 are shown in Table 5.
• a fluorine-containing water- and oil-repellent (Texguard TG-5431 manufactured by Daikin Industries Ltd.) was diluted with the tap water to the solid content of 1%, and 3 % of isopropyl alcohol was added to give a treatment liquid.
• An untreated 6-nylon taffeta for the dyeing test was dipped in the treatment liquid, and squeezed with a mange to give a wet pickup of 25%.
• the test fabric was dried at 110°C for 3 minutes and thermally treated at 160°C for 1 minute.
• the water repellency and the oil repellency of the resultant sample were measured before and after the ten times of wash. The results are shown in Table 5.
• Water repellency Oil repellency Ex. 5 100+ 6 100 3 Ex. 6 100+ 5 100 2 Ex. 7 100+ 6 100 3 Ex. 8 100+ 5 100 2 Com.
• Example 2 The same procedure as in Example 1 of preparing test fabric treated with metal salt was repeated, except that basic zirconium sulfate (trade name: Zircotan (manufactured by Rohm & Haas Co.)) was used instead of basic chromium sulfate.
• basic zirconium sulfate trade name: Zircotan (manufactured by Rohm & Haas Co.)
• Example 2 The same procedure as in Example 1 was repeated, except that the fluorine-containing copolymer emulsion prepared in Preparative Example 4 was used and the test fabric prepared in Example 2 of preparing test fabric treated with metal salt was used.
• the water repellency and the oil repellency of the sample were measured before and after the ten times of wash. The results are shown in Table 6.
• the present invention can give the excellent initial water- and oil-repellency to a textile, particularly a hydrophilic textile.
• the present invention can easily and stably give the permanent water- and oil-repellency which can endure a long-term use including the wash, the rubbing and like.

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

Applications Claiming Priority (4)

Publications (3)

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Family Applications (1)

Country Status (7)

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• 1993
  • 1993-07-22 JP JP18125693A patent/JP3284672B2/ja not_active Expired - Fee Related
• 1994
  • 1994-07-18 KR KR1019960700104A patent/KR100322937B1/ko not_active IP Right Cessation
  • 1994-07-18 CN CN94192838A patent/CN1084814C/zh not_active Expired - Fee Related
  • 1994-07-18 DE DE69426025T patent/DE69426025T2/de not_active Expired - Fee Related
  • 1994-07-18 EP EP94921106A patent/EP0710738B1/en not_active Expired - Lifetime
  • 1994-07-18 WO PCT/JP1994/001171 patent/WO1995003445A1/ja active IP Right Grant
  • 1994-07-28 TW TW083106910A patent/TW278104B/zh active

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