WO1999047579A1 - Resine polyester sulfonee, fibre polyester facile a teindre, matiere antistatique et procede de preparation associe - Google Patents

Resine polyester sulfonee, fibre polyester facile a teindre, matiere antistatique et procede de preparation associe Download PDF

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Publication number
WO1999047579A1
WO1999047579A1 PCT/JP1999/000993 JP9900993W WO9947579A1 WO 1999047579 A1 WO1999047579 A1 WO 1999047579A1 JP 9900993 W JP9900993 W JP 9900993W WO 9947579 A1 WO9947579 A1 WO 9947579A1
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WO
WIPO (PCT)
Prior art keywords
polyester resin
sulfonated polyester
fiber
sulfonated
antibacterial
Prior art date
Application number
PCT/JP1999/000993
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English (en)
Japanese (ja)
Inventor
Kazuhiro Tachibana
Original Assignee
Riverson & Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP08922998A external-priority patent/JP2002179503A/ja
Priority claimed from JP17064298A external-priority patent/JP2002180373A/ja
Application filed by Riverson & Co., Ltd. filed Critical Riverson & Co., Ltd.
Publication of WO1999047579A1 publication Critical patent/WO1999047579A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • 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
    • D06M15/507—Polyesters
    • D06M15/5075—Polyesters containing sulfonic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material

Definitions

  • the present invention relates to a sulfonated polyester resin, an easily dyeable polyester fiber, an antibacterial material, an antistatic material, and a method for producing these.
  • the present invention particularly provides a sulfonated polyester resin having a sulfone group introduced therein without impairing the properties of the polyester resin, an easily dyeable polyester fiber which can be easily dyed with a cationic dye, and a high antibacterial property over a long period of time.
  • Antimicrobial material that hardly elutes during use, has little antibacterial toxicity and skin irritation, and antistatic material that can maintain high antistatic properties for a long time About. Background art
  • Polyester fiber is widely used in various kinds of clothing such as suits, shirts, blouses, dresses, trousers, slacks, and socks because it is resistant to wrinkling, has excellent heat resistance and abrasion resistance, and has a good texture. .
  • polyester fibers are fibers that are difficult to dye, and it is extremely difficult to dye with a cationic dye widely used for dyeing cotton and the like.
  • polyester fiber obtained by the above method not all the sulfone groups in the copolymerized polyester are necessarily exposed on the surface of the polyester fiber, so that it is necessary to impart sufficient hydrophilicity and antibacterial property to the polyester fiber.
  • the polyester resin is sulfonated with concentrated sulfuric acid, fuming sulfuric acid, and sulfuric acid sulfuric acid, which are known as sulfonating agents for polyolefins such as polyethylene and polypropylene
  • the polyester resin is significantly hydrolyzed, and the texture and The present inventors have found that the strength and the like are remarkably deteriorated, that is, the conventional sulfonating agent is unsuitable for sulfonation of a polyester resin.
  • polyester fibers are much less hydrophilic than natural fibers such as cotton, wool, and silk, as well as other synthetic fibers such as nylon and acryl fibers. Therefore, clothing made of polyester fiber was easily stuffy in hot and humid summer. Then, metabolites such as sweat, sebum, and dirt secreted from the skin adhere to the clothes, and they are spoiled by various bacteria and fungi in the living environment, causing a bad smell. Furthermore, the clothing made of polyester fiber was easily charged during low-temperature drying in winter.
  • the present invention relates to a method for sulfonating a polyester resin capable of directly introducing a sulfone group into a polyester resin by post-treatment without impairing the properties of the polyester resin, that is, a method for producing a sulfonated polyester resin, and a method for sulfonating the polyester resin. It is an object to provide the resulting sulfonated polyester resin.
  • the present invention also provides a polyester fiber excellent in hygroscopicity and dyeability, and a method for producing the same.
  • the purpose is to provide the law.
  • Another object of the present invention is to provide a polyester fiber product containing the polyester fiber, such as a yarn, a woven fabric, a nonwoven fabric, and a knitted fabric.
  • the present invention further has long-lasting high antibacterial and antistatic properties without being impaired by washing and dry cleaning, has a good texture, and has toxicity and skin irritation due to antibacterial agents and antistatic agents. It is intended to provide antibacterial materials and antistatic materials that do not have any.
  • Another object of the present invention is to provide a method for producing the antibacterial material and the antistatic material, which can extremely easily produce the antibacterial material and the antistatic material. Disclosure of the invention
  • the present invention for solving the above-mentioned problem is characterized in that a polyester resin is formed by bringing a polyester resin into contact with a sulfuric anhydride-containing gas containing sulfuric anhydride in a dry atmosphere,
  • the present invention relates to a sulfonated polyester resin having the following.
  • the sulfonated polyester resin has any form of fiber, yarn, woven fabric, knitted fabric, non-woven fabric, cotton-like material, film, and sheet,
  • the polyester resin has any form of a fiber, a yarn, a woven fabric, a knitted fabric, a nonwoven fabric, a floc, a film, and a sheet;
  • the sulfuric anhydride-containing gas is sulfuric anhydride diluted with an inert gas, and the inert gas is at least one selected from dry air, dry nitrogen, and dry argon gas,
  • the addition amount of the sulfone group present on the surface of the sulfonated polyester resin is 0.1 to: L 0 meqZm 2 .
  • the present invention for solving the above problems also includes an invention relating to an easily dyeable polyester fiber, which comprises the sulfonated polyester resin.
  • the present invention further includes an invention related to an antibacterial material, which comprises the sulfonated polyester resin and an organic base ionically bonded to a sulfone group of the sulfonated polyester resin.
  • the organic base is one or both of a low molecular weight quaternary ammonium compound and a quaternary phosphonium compound,
  • the antibacterial material has any form of fiber, yarn, woven fabric, nonwoven fabric, cotton, knit, film, and sheet.
  • the present invention further includes an invention relating to a method for producing the antibacterial material, wherein the sulfonated polyester resin is treated with the organic base.
  • the present invention also includes an invention related to an antistatic material, comprising: the sulfonated polyester resin; and an organic base ionically bonded to a sulfone group of the sulfonated polyester resin. .
  • the organic base is one or both of a polymer type quaternary ammonium compound and an amidine base compound,
  • the antistatic material has any form of a fiber, a yarn, a woven fabric, a nonwoven fabric, a floc, and a knit.
  • the present invention further includes an invention relating to a method for producing the antistatic material, wherein the sulfonated polyester resin is treated with the organic base.
  • the sulfonated polyester resin can take include a fiber, a yarn, a woven fabric, a nonwoven fabric, a knit, a cotton-like material, a sheet, and a film.
  • the yarn, the woven fabric, the nonwoven fabric, the knitted fabric, and the cotton-like material may be collectively referred to as “fiber products”.
  • the sheet usually has a thickness of 250 / m or more, and the film has a thickness of 25 to 250 m.
  • the polyester sheet or the polyester film and a sheet or film formed from another synthetic resin were bonded.
  • Laminated sheets and films can be mentioned.
  • the “other synthetic resin” include polyamide, polystyrene, polyolefin, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, and cellulose derivative.
  • the addition amount of sulfone groups in the sulfonated polyester resin is usually 0.1 to 10 O meq / m 2 , preferably 0.5 to 5 O meq / m 2 , in terms of potassium ion exchange amount per area. And particularly preferably 1 to 20 meqZm 2 .
  • the sulfonated polyester resin in which the sulfone group addition amount is within the above range hardly causes coloring and physical property deterioration due to sulfonation, and is strongly bonded to a cationic dye, and has high hygroscopicity.
  • the sulfone group density in the sulfonated polyester resin can be obtained as a potassium ion exchange amount.
  • the amount of potassium ion exchange can be determined according to the procedure shown in the Examples section described later.
  • the sulfone group may be a free sulfone group, or may form a salt with a metal element selected from the group consisting of alkali metals and alkaline earth metals. However, if a salt is formed with the metal element, the sulfone group becomes more stable to heat, so that it is preferable to form a salt with the metal element.
  • alkali metal examples include sodium, potassium, ammonium, and lithium.
  • alkaline earth metal examples include calcium and magnesium.
  • the addition amount of the alkali metal and Z or the alkaline earth metal to the sulfone group of the sulfonated polyester resin is usually 5 to 100 mol%, preferably 50 to 100 mol%. %.
  • polyester resin used for the production of the sulfonated polyester resin examples include a polyester resin obtained by condensation of an aromatic dicarboxylic acid such as terephthalic acid and a diol such as ethylene glycol.
  • aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, naphthylene dicarboxylic acid, biphenyldicarboxylic acid, and diphenoxenedicarboxylic acid.
  • diol examples include ethylene glycol, trimethylene glycol,
  • a small amount of a third component other than the aromatic dicarboxylic acid and the diol may be included as a copolymerization component.
  • the amount of the third component is usually 15 mol% or less.
  • Examples of the third component include aliphatic dicarboxylic acids and oxycarboxylic acids.
  • a polycarboxylic acid and a polyol may be used as a copolymerization component in addition to the third component.
  • the polyester resin can be produced by a conventional method.
  • the polyester resin may be in the form of, for example, fibers, fiber products, sheets, films, and the like.
  • the sulfuric anhydride containing sulfuric acid which can be used for producing the sulfonated polyester resin of the present invention is used.
  • the gas include sulfuric anhydride in a gaseous state and sulfuric anhydride diluted with an inert gas.
  • the polyester resin may be hydrolyzed, and the strength and hand of the polyester resin may be significantly reduced. Therefore, the mixed gas containing the sulfonating agent is not preferable as the sulfuric anhydride-containing gas.
  • sulfuric anhydride-containing gas sulfuric anhydride diluted with an inert gas is preferable because the ratio of sulfuric anhydride to the polyester resin can be strictly controlled.
  • the inert gas examples include a gas that does not substantially react with any of sulfuric anhydride and the polyester resin under the sulfonation conditions described below. Specifically, dry air, dry nitrogen, and dry argon gas , And mixtures thereof.
  • the dilution degree of sulfuric anhydride is usually in the range of 2 to 100 times, and preferably in the range of 2 to 20 times.
  • sulfuric anhydride-containing gas examples include a mixture of a gaseous Lewis base and sulfuric anhydride, and a mixture of a gaseous Lewis base, sulfuric anhydride and the inert gas.
  • Lewis base for example, amines, ethers, phosphates, phosphonates and the like can be used.
  • amines examples include methylamine, dimethylamine, trimethylamine, ethylamine, getylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, butyramine, isobutylamine, sec-butylamine, and tert-butylamine. I can do it.
  • ether compound examples include dioxane, furan, 2-methylfuran, tetrahydrofuran, and tetrahydrosilane.
  • Examples of the phosphate include trimethyl phosphate and triethyl phosphate. Can be.
  • phosphonate examples include dimethyl phosphonate, getyl phosphonate, trimethyl phosphonate, and triethyl phosphonate.
  • Lewis bases getylamine and dioxane are particularly preferred.
  • the molar ratio between sulfuric anhydride and Lewis base in the sulfuric anhydride-containing gas is usually in the range of 3: 1 to 1: 1.
  • Examples of the method for bringing the polyester resin into contact with sulfuric anhydride include, for example, a polyester product containing the polyester resin, such as a fiber, a yarn, a woven fabric, a nonwoven fabric, a cotton, a knit, a film, and a sheet.
  • a polyester product containing the polyester resin such as a fiber, a yarn, a woven fabric, a nonwoven fabric, a cotton, a knit, a film, and a sheet.
  • a batch method in which the sulfuric acid-containing gas is introduced into the closed container to perform sulfonation in a closed container, and the sulfonation chamber in which the anhydrous sulfuric acid-containing gas flows inside is continuously used to feed the polyester product.
  • a continuous method of performing sulfonation by passing through is
  • the amount of sulfuric anhydride contained in the sulfuric anhydride-containing gas filled in the container is 50% by weight or less based on the weight of the polyester product contained in the container. Is preferred.
  • the flow rate (weight) of sulfuric anhydride per unit time in the sulfonation chamber is 50% of the flow rate (weight) of the polyester product per unit time in the sulfonation chamber. It is preferable to adjust the flow rate of the sulfuric anhydride-containing gas in the sulfonation chamber as described below.
  • the sulfonation time that is, the contact time between the polyester product and the sulfuric anhydride-containing gas, is determined so that the amount of sulfone groups added to the obtained sulfonated polyester resin falls within the above range. be able to.
  • the sulfonation time is usually in the range of 0.1 seconds to 30 minutes, preferably in the range of 1 second to 10 minutes.
  • the sulfonation temperature is usually equal to or higher than the temperature at which sulfuric anhydride is gasified, preferably in the range of room temperature (25 ° C) to 80 ° C, more preferably in the range of room temperature to 60 ° C, and particularly preferably in the range of room temperature to A range of 40 is particularly preferred.
  • the sulfonation pressure is usually set at the sulfonation temperature by using a sulfuric anhydride-containing gas.
  • the pressure is within a range in which sulfuric anhydride does not precipitate as a liquid or a solid, specifically, about 0.1 to 2 atm.
  • the polyester resin is pretreated, dried, and then brought into contact with the sulfuric anhydride-containing gas. This is because if even a small amount of water is present in the system, the sulfuric anhydride in the sulfuric anhydride-containing gas may change to concentrated sulfuric acid.
  • Examples of the pretreatment method of the polyester resin include hot air drying and corona treatment.
  • the corona treatment time is usually several seconds.
  • a post-treatment is immediately performed to remove sulfuric anhydride remaining on the surface of the polyester product.
  • post-treatment examples include washing with water, treatment with an alkaline solution such as an aqueous solution of sodium bicarbonate and lime, and treatment with the inert gas described in the above section “(2) Gas containing sulfuric anhydride”.
  • the sulfonated polyester resin of the present invention is strongly bonded to a cationic dye, a sulfonated polyester fiber having a fiber form, and a sulfonated polyester fiber product having a fiber form are formed by a cationic dye. It can be dyed easily and vividly. Furthermore, the sulfonated polyester fiber and the sulfonated polyester fiber product can be referred to as an easily dyeable polyester fiber and an easily dyeable polyester fiber product, respectively.
  • examples of the yarn include a sulfonated polyester fiber alone, or a sulfonated polyester yarn twisted from the sulfonated polyester fiber and other synthetic fibers and / or natural fibers. it can.
  • “other synthetic fibers” include synthetic fibers such as non-sulfonated polyester fiber, polyamide fiber, polyolefin fiber, polyacryl fiber, polyvinyl chloride fiber, and polyvinylidene chloride fiber.
  • polyamide fiber examples include nylon 6 fiber, nylon 66 fiber, Nylon 610 fiber, Nylon 11 fiber, Nylon 12 fiber, Nomex (trade name) fiber, and Nylon 6T fiber.
  • polyolefin fibers examples include polyethylene fibers and polypropylene fibers.
  • Examples of the natural fibers include cotton, hemp, silk, and wool.
  • Examples of the woven fabric include a woven fabric woven only from the sulfonated polyester yarn, and a woven fabric woven from the sulfonated polyester yarn and a non-sulfonated yarn obtained by twisting non-sulfonated fibers. Can be.
  • the woven cloth can be used for cloths of various clothes such as suits, shirts, trousers, open-collared shirts, dresses, blouses, and sleepwear, and sheets, blanket covers, blankets, blankets, pillow covers, and the like. Can also be used for bedding.
  • the woven fabric is also preferably used for building materials such as curtains.
  • nonwoven fabric examples include a nonwoven fabric manufactured only from the sulfonated polyester fiber, and a nonwoven fabric manufactured from the sulfonated polyester fiber and the “other synthetic fiber and Z or natural fiber”. .
  • nonwoven fabric examples include a dry nonwoven fabric manufactured by a dry process, a wet nonwoven fabric manufactured by a wet process, a needle punched nonwoven fabric manufactured by a needle punch method, a spray fiber nonwoven fabric manufactured by a spray fiber method, and a nonwoven fabric manufactured by a spray fiber method.
  • Spunbonded nonwoven fabrics manufactured by the panbonding method, and meltblown nonwoven fabrics manufactured by the meltflowing method can be exemplified.
  • the nonwoven is usually processed into carpets, wall cloth, and other building materials.
  • the knitted fabric include a knitted fabric obtained by knitting or lace-knitting the sulfonated polyester yarn, and a knitted fabric formed by knitting or lace-knitting the sulfonated polyester yarn with the non-sulfonated yarn.
  • the knitting includes various types of underwear, pants, socks, jerseys, and the like.
  • the cotton-like material include a sulfonated polyester fiber alone, or a sulfonated polyester cotton in which the polyester fiber and the “other synthetic fiber and Z or natural fiber” are formed into a floc. 4.
  • Antibacterial and antistatic materials include a sulfonated polyester fiber alone, or a sulfonated polyester cotton in which the polyester fiber and the “other synthetic fiber and Z or natural fiber” are formed into a floc. 4.
  • the antibacterial material and the antistatic material of the present invention contain the sulfonated polyester resin and an organic base that ionically bonds to a sulfone group of the sulfonated polyester resin.
  • Addition amount of your Keru sulfone group sulfonated polyester ⁇ used for the antibacterial material and antistatic material 2 ⁇ 1 0 O meq / m 2 in the range of preferably in the range of 2 ⁇ 5 0 meqZin 2 is Particularly preferred, a range of 4 to 2 O meq / m 2 is most preferred.
  • the organic base include an organic compound capable of forming a salt with a sulfone group. Specifically, a low molecular weight quaternary ammonium compound, a polymer type quaternary ammonium compound, and a quaternary phosphonium compound , An amidine base compound, and a guanidine base compound.
  • Examples of the low molecular weight quaternary ammonium compound include a quaternary ammonium compound having a molecular weight of 1,000 or less, and specifically, tetraalkyl quaternary ammonium salt, alkyltrimethyl quaternary ammonium compound.
  • Quaternary ammonium salts having an alkyl group such as salts, dialkyl dimethyl quaternary ammonium salts, and trialkylmethyl quaternary ammonium salts; and quaternary ammonium salts having an alkyl group and an aromatic ring, such as benzalkonium salts.
  • Examples of the alkyl group in the quaternary ammonium salt include an alkyl group having 1 to 20 carbon atoms.
  • Examples of the aromatic ring in the benzalkonium salt include an aromatic ring having 6 to 20 carbon atoms.
  • quaternary ammonium compounds include pyridine rings, quinoline rings, and morpholine rings such as alkylpyridinium salts, alkylisoquinolinium salts, and dialkylmorpholinium salts. Examples thereof include a quaternary ammonium salt having a nitrogen aromatic ring, a quaternary ammonium salt having an ether bond such as a benzeonium salt, and a quaternary ammonium salt having a polyoxyalkylene chain.
  • the polymer type quaternary ammonium salt include a quaternary amino polymer having a molecular weight of more than 1,000 and having a quaternary amino group in at least one of a main chain and a side chain.
  • the quaternary amino polymer examples include a quaternary amino group and a polymerizable agent. And a polymer obtained by homopolymerizing or copolymerizing a quaternary amino monomer which is a compound having a functional group.
  • quaternary amino monomer examples include N, N-dimethylaminoethyl (meth) acrylic acid salt, and zwitterionic N-methacryloyloxetyl-N, N-dimethylammonium ⁇ - Homopolymers and copolymers such as N-methylcarboxybetaine can be mentioned.
  • Examples of the salt of ⁇ , ⁇ -dimethylaminoethyl (meth) acrylic acid include hydrochloride and sulfate.
  • Examples of the monomer that can be copolymerized with the quaternary amino monomer include (meth) acrylic acid ester, styrene, vinylpyrrolidone, and (meth) acrylic acid.
  • Examples of the quaternary amino polymer are RAM Resin (trade name) and H.C. Polymer (trade name) manufactured by Osaka Organic Chemical Industry Co., Ltd., and Sanfloc (trade name) manufactured by Sanyo Chemical Industry Co., Ltd. (Product name) C-009P, Sanfloc C-1109P, Sanfloc C-0111P, and Sanfloc700.
  • polymer-type quaternary ammonium salt examples include a quaternized polyethyleneimine-based polymer obtained by quaternizing a polyethyleneimine-based polymer having a polyethyleneimine skeleton, and a cationic cellulose derivative. .
  • polyethyleneimine-based polymer examples include polyethyleneimine, a reaction product of polyethyleneimine with diisocyanate and Z or piperazine, and a copolymer of ethylenimine with a daricidyl compound having a glycidyl group.
  • Examples of the quaternized polyethyleneimine-based polymer include KA-170 (trade name), KA-160 (trade name), and KA-109 (trade name) manufactured by Nippon Kasei Co., Ltd. , KA-109 (trade name), KA-109 (trade name), and KA_1092 (trade name).
  • Examples of the cationic cellulose derivative include a cellulose derivative in which an organic group having a quaternary ammonium group is bonded to a hydroxyl group of cellulose. Specifically, O- [2-hydroxy-3 (trimethyl chloride) Ammonium) [Propyl] hydroxyethylcellulose.
  • Cationic cellulose derivatives include, for example, Katina manufactured by Toho Chemical Industry Co., Ltd.
  • Examples of the quaternary phosphonium compound include tetraalkyl phosphonium salts, tri (hydroxyalkyl) alkyl phosphonium salts, tri (alkyl) hydroxyalkyl phosphonium salts, and aromatic ring-containing phosphonium compounds having an aromatic ring. Salts and the like can be mentioned.
  • tetraalkylphosphonium salts examples include chlorides, bromides, and iodides of tetraalkylphosphonium compounds having an alkyl group having 1 to 20 carbon atoms.
  • the tri (hydroxyalkyl) alkyl phosphonium salt and the tri (alkyl) hydroxyalkyl phosphonium salt include, for example, a hydroxyalkyl group having 1 to 5 carbon atoms and a hydroxyalkyl group having 1 to 20 carbon atoms.
  • Tri (hydroxyalkyl) alkylphosphonium salts having a certain alkyl group can be mentioned. Specifically, tris (hydroxyethyl) alkylphosphonium salts and tris (3-hydroxypropyl) alkylphosphonium salts Salt, tri (alkyl) hydroxyethylphosphonium salt, and tri (alkyl) -3-hydroxypropylphosphonium salt.
  • aromatic ring-containing phosphonium compound examples include an alkyl group having 1 to 20 carbon atoms and an aromatic ring-containing phosphonium compound having an aromatic ring having 6 to 20 carbon atoms.
  • amidine base compound examples include an amidine compound having an amidine group and a salt thereof, and an amidine compound derivative derived from the amidine compound.
  • amidine-based compound and its salt examples include 4,4, -stilbendicalpoxamidine diisethionate (also referred to as stilbamidine isethionate), and N '-(4-chloro-2-methylphenyl). ) — N, N-dimethylmethanimide (also referred to as chlordimeform).
  • amidine-based compound derivative examples include an imidazoline compound having an imidazoline ring and a salt thereof, and more specifically, a 1-hydroxyethyl-12-alkylimidazoline quaternary salt. .
  • guanidine base compounds for example, 1,17-diguanidino-9-azaheptadecane (also referred to as guatatin), p- (clozen phenyldiguanide) hexane (also referred to as chlorhexidine) ), And p-benzoquinone amidinohydrazonethiosemicarbazone (also referred to as ambazone).
  • the organic base used in the antibacterial material of the present invention has a high ionic property, a strong antibacterial property, and a relatively low molecular weight, so that it easily penetrates into cell membranes of microorganisms and the like.
  • Low molecular weight quaternary ammonium compounds and quaternary phosphonium compounds are preferred because they have a particularly strong ionic bond with a sulfone group, and have little toxicity or skin irritation.
  • the organic bases used in the antistatic material of the present invention include those having high hydrophilicity, exhibiting a high antistatic effect over a long period of time, and hardly flowing out of the surface of the sulfonated polyester resin.
  • the polymer type quaternary ammonium compound and the amidine base compound are preferred.
  • the antibacterial and antistatic materials of the present invention can take the form of, for example, fibers and textile products.
  • the fibers and fiber products formed from the antibacterial material are also referred to as antibacterial polyester fibers and antibacterial polyester fiber products, respectively.
  • Fibers and fiber products formed from the antistatic material are also referred to as antistatic polyester fibers and antistatic polyester fiber products, respectively.
  • the antibacterial polyester fiber product and the antistatic polyester fiber product can be used for the same applications as the sulfonated polyester fiber product.
  • the antibacterial polyester fiber product can be further used for sanitary / medical materials and various filters.
  • Examples of the hygiene and medical materials include diapers, gauze, sterilizing gauze, masks, surgical gowns, and surgical aprons.
  • the various filters include an air filter.
  • the antimicrobial material of the present invention may further have the form of a sheet and a film.
  • the antibacterial sheet having the form of a sheet can be used, for example, for molded products such as trays, containers, and interior materials such as refrigerators.
  • the antibacterial film in the form of a film is used for packaging films, food storage bags, and the like.
  • Examples of the method for producing the antibacterial material and the antistatic material of the present invention include a method for treating the sulfonated polyester resin with an organic base.
  • Examples of the method of treating the sulfonated polyester resin with an organic base include, for example, adding an aqueous solution or suspension of the organic base to a sulfonated polyester fiber, a sulfonated polyester fiber product, and a sheet and a fill of the sulfonated polyester resin. Or a method of spraying an aqueous solution or suspension of the organic base onto any of sulfonated polyester fibers, sulfonated polyester fiber products, and sheets and films of sulfonated polyester resin. Can be mentioned.
  • the yarn may be produced by twisting an antibacterial polyester fiber obtained by treating a sulfonated polyester fiber with an organic base.
  • Woven fabrics, nonwoven fabrics, and knitted fabrics can be produced from antibacterial yarn obtained by twisting the antibacterial polyester fiber.
  • Cationic dye one of Basacryl Yellow FD-GFL 200% (yellow), Basacryl Blue X-3GL 200% (blue), and Basacryl Red FDX-GRL 200% (red)
  • the fabric after dyeing was measured for chromaticity (K / S), color clarity, and light fastness according to the following methods.
  • the spectral reflectance (R) of the dyed fabric was measured with a color analyzer (automatic recording spectrophotometer, manufactured by Hitachi, Ltd.), and the following Kuberka-Munk formula was used.
  • the dyed fabric was shown to ten panelists and subjected to a sensory evaluation for color clarity.
  • Each of the panelists rated 2 points for the fabric with extremely excellent clarity, 1 point for the fabric with excellent clarity, and 0 point for the fabric with poor clarity.
  • ⁇ for the cloth whose total score of the 10 panelists is 15 points or more
  • ⁇ for the cloth whose total point is 8 to 14 points
  • X for the cloth whose total point is 7 points or less. did.
  • JISL 0824 a brass lamp was produced using a carbon arc lamp manufactured by Shimadzu Corporation. Kkupaneru temperature 6 3, then irradiated with irradiation conditions of illuminance 1 5 O WZM 2, examine the discoloration of blue scale by a second exposure method according to JISL 0 8 2 4, the degree of light fastness after 2 0 h irradiation morphism showed that.
  • the hydrophilicity was evaluated according to JIS L1907. Five test pieces (20 O mm X 25 mm) were sampled for each fabric. The lower end of the test piece was immersed vertically in 20 ⁇ 2 water, and the height (mm) of water sucked up by capillary action after 10 minutes was measured. The average of the values was determined. The results are shown in Table 2 below.
  • a sensory test was conducted on the tension, waist, glossiness, and lightness by a pairwise comparison with the polyester woven fabric before sulfonation, and evaluated on a three-point scale.
  • the evaluation of the items of tension, waist, glossiness, and lightness was comprehensively judged, and as a result, the samples judged to be “excellent” were ⁇ , and the samples judged to be “excellent” As for (1), the sample judged as “slightly inferior” was rated as (2), and the sample judged as “poor” was evaluated as “X”.
  • a sulfonated polyester fabric was prepared according to the following procedure.
  • a polyester taffeta having a basis weight of 71.8 g Zm 2 made of polyester fiber (75 d X 36 d) was sufficiently dried, and was housed in an acid-resistant sealable container.
  • Sulfuric anhydride previously diluted 10 times with nitrogen gas is brought into contact with the polyester cloth stored in the container at a temperature of 20 to 40 for 10 seconds to 10 minutes, thereby obtaining the polyester cloth.
  • was sulfonated then washed with water and dried to produce a sulfonated polyester fabric.
  • the sulfonation temperature and sulfonation time are shown in Table 2 below.
  • the amount of sulfone groups added to the sulfonated polyester fabric was determined as follows.
  • the weight W of the washed and dried sulfonated polyester fabric was measured.
  • 1 O ml of 0.1 N KOH aqueous solution was added, and steam was added.
  • the aqueous solution was diluted with 10 Oml of distilled water, and the aqueous solution was stirred in a thermostat maintained at 60 for 1 hour.
  • additional amount I w (meq / g) 1 g of per potassium ion exchange capacity i.e. sulfone group of the sulfonated polyester fabric. Then, the additional amount 1 g of per sulfone group of the sulfonated polyester fabric (meqZg) to multiply the basis weight of said sulfonated polyester fabric, additional amount I a of lm 2 equivalents or sulfone group of the sulfonated polyester fabric (meq / m 2 ) was calculated. Since the basis weight of the sulfonated polyester fabric is considered to be substantially the same as the basis weight of the polyester cover, the basis weight of the sulfonated polyester fabric is used as the basis weight of the sulfonated polyester fabric. Was.
  • CD-PET cationic dyeing PET
  • Dyeability, hydrophilicity, and texture were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
  • the use of yarn of the circular knitted fabric, the knitting machine, the structure, etc. used are as follows.
  • Knitting machine 26 gauge, 30 inch diameter, 84 ports
  • Tissue smooth on both sides
  • a polyester woven fabric with a basis weight of 260 g Zm 2 was sufficiently dried and housed in an acid-resistant sealable container. Sulfuric anhydride, which was previously diluted 10-fold with dry nitrogen gas, was introduced into the container, and was brought into contact with the polyester woven fabric at room temperature for 10 seconds to 2 minutes to prepare Samples A to D. .
  • Samples A to D thus prepared were washed with water, neutralized with sulfonate groups with KOH or NaOH, and then dried.
  • the sulfone group densities of Samples A to D were determined as follows. First, the in the same manner as the actual Example 1 to obtain the potassium ion exchange capacity of the sample A ⁇ sample D, and sulfo down group density per lm 2 and multiplied by the basis weight of the polyester fabric to the potassium Umuion exchange amount I asked. Table 3 below shows the sulfonation conditions and the sulfone group density per 1 m 2 of Samples A to D.
  • Sample A and Sample B were immersed in a 2% aqueous solution of a quaternary ammonium compound, N, N-dimethyl-N, N-dimyristylammonium bromide, and the sulfone groups of Sample A and Sample B were It was reacted with N, N-dimethyl-N; N-dimyristylammonium bromide. After the reaction was completed, the samples A and B were washed with water and dried to produce an antibacterial material.
  • a quaternary ammonium compound N, N-dimethyl-N, N-dimyristylammonium bromide
  • Samples C and D were immersed in a 2% aqueous solution of quaternary phosphonium compound, triethyl octadecyl phosphonium bromide, and the sulfone groups in sample C and sample D and It was reacted with decylphosphonium bromide. After the reaction was completed, Sample C and Sample D were washed with water and dried to produce an antibacterial material.
  • polyester woven fabric used for preparing Samples A to D in Example 5 was directly subjected to evaluation of antibacterial properties and the like.
  • polyester woven fabric was immersed in a 2% aqueous solution of N, N-dimethyl-N, N-dimyristylammonium bromide, washed with ⁇ , dried, and evaluated for antibacterial properties and the like.
  • polyester woven fabric was immersed in a 2% aqueous solution of triethyl octadecyl phosphonium bromide, washed, dried and subjected to evaluation of antibacterial properties and the like.
  • Example 5 The antimicrobial materials according to Example 5, Comparative Examples 4 and 5, and the polyester woven fabric according to Comparative Example 3 were evaluated for antimicrobial properties, washing resistance, and dry cleaning resistance according to the following methods. evaluated. The results are also shown in Table 3 below.
  • a medium was prepared by mixing with 10 O ml of Soya agar. Next, 10 ml of the above medium was poured into a Petri dish to prepare a thin layer medium. A test piece having a size of 3 cm ⁇ 3 cm was placed on the thin layer medium, and the Petri dish was allowed to stand in an incubator held at 37 for 24 hours to culture Staphylococcus aureus, The growth status was observed 24 hours later.
  • Samples in which the growth inhibition zone of Staphylococcus aureus was clearly formed on the thin-layer medium were evaluated as ⁇ , and the growth inhibition zone of Staphylococcus aureus was formed on the thin-layer medium, but the area was quite opaque.
  • the sample in which was left was evaluated as ⁇ , and the sample in which the growth inhibition zone of S. aureus was not formed on the thin layer medium was evaluated as X.
  • the sample was dry-cleaned for 15 minutes at a room temperature with a bath ratio of 1:12 by using a rotary dry-cleaning machine and 3.7 l of Parkren.
  • the sample after the dry cleaning was drained and dried in a fume hood. This was defined as one dry cleaning.
  • the antimicrobial properties of the samples that had been subjected to dry cleaning five times were evaluated in the same manner as the samples before dry cleaning. Table 3
  • the non-sulfonated polyester woven fabric was treated with an aqueous solution of N, N-dimethyl-N, N-dimyristylammonium bromide to obtain the antibacterial material of Comparative Example 4, and the non-sulfonated polyester.
  • the antibacterial material of Comparative Example 5 in which the woven fabric was treated with an aqueous solution of triethyl octadecylphosphonium bromide showed some antibacterial properties at the beginning, but after washing five times, and performing dry cleaning 5 times. No antibacterial activity was observed after any of the rounds.
  • the antibacterial agent is merely mechanically held between the polyester fibers in the polyester woven fabric, and firmly adheres to the surface of the polyester fibers. It is considered that the antimicrobial agent was easily removed by washing and dry cleaning because it was not bound to the antibacterial agent.
  • Samples E and F were prepared by sulfonating the same polyester tough lid as the polyester toughness in Examples 1 to 4 in the same manner as in Example 2. Addition amount I a of lm 2 per sulfonic group specimen E and F were respectively 9. 8 meq / m 2 and 4. 5 meq / m 2. Samples E and F were treated with the following compound solutions to prepare antistatic polyester fabrics, Sample G, Sample H, Sample, and Sample J.
  • Sample G Sample E was prepared by treating with a 0.3% aqueous solution of Nissan cation AR4.
  • Sample H Sample F was prepared by treating with a 0.1% aqueous solution of Katinal HC-200.
  • Sample I Sample E was prepared by treating with a 0.3% aqueous solution of Nissan cation AR4.
  • Sample F was prepared by treating it with a 0.1% aqueous solution of HC-200.
  • the Nissan cation AR4 is a 1-hydroxyethyl-2-alkylimidazoline quaternary salt, and is therefore a kind of amidine base compound.
  • Catinal has a chemical structure represented by the structural name O- [2-hydroxy-3 (trimethylammonium) propyl] hydroxyethylcellulose, and is therefore a kind of polymer-type quaternary ammonium compound.
  • the N% was 1.78%
  • the pH (at 25) at a solid content of 2% by weight was 5.3
  • the solid content was 1%.
  • Aqueous Tenal HC-200 which had an aqueous solution viscosity (25 ° C.) of 1489 cp at% by weight, was used.
  • the triboelectric voltage (unit: V) was measured using cotton kanaquin as a friction cloth in accordance with the method B of JIS-L-1092, and in accordance with the method A of JIS-L-1092.
  • the half-life (seconds) was measured.
  • polyester tough resin was treated with a 0.1% aqueous solution of hydrogen chloride HC—200 without sulfonation to prepare a sample b.
  • Samples G to J according to Examples 6 and 7 had a value of 98 V to 110 V before washing, and a value of 110 V in the polyester lid of Comparative Example 6.
  • the friction band voltage was much lower than 5 V.
  • the half-life was extremely short, 0.3 seconds.
  • the sulfonated polyester resin provided by the present invention can take various forms such as fibers, fiber products, sheets, and films.
  • the sulfonated polyester fiber has good hydrophilicity and can be easily dyed with a cationic dye, it can be called an easily dyeable polyester fiber.
  • the easily dyeable polyester fiber has the same good texture as the conventional polyester fiber.
  • the easily dyeable polyester fiber is suitably used, for example, for various kinds of clothing, core materials such as ties, construction materials, and bedding.
  • the knitted fabric is used, for example, for socks, underwear, pants, jerseys, and the like.
  • the sulfonated polyester resin has excellent adhesiveness to a synthetic resin having a polar group such as a polyurethane resin and rubber, and is used for waterproof clothing coated with polyurethane or the like, and for automobiles and bicycles. It is suitable for tire power.
  • the antibacterial material and the antistatic material of the present invention have high antibacterial and antistatic properties that last for a long time because the organic base is strongly ion-bonded to the sulfone group formed at high density on the surface. Antibacterial agents and antistatic agents are not eluted to cause toxicity and irritation to the human body, and the texture is not impaired.
  • the antibacterial and antistatic materials of the present invention can take the form of, for example, fibers and textile products.
  • the antimicrobial material can further take the form of sheets and films.
  • the fiber product made of the antibacterial material and the antistatic material is preferably used for various kinds of clothing like the sulfonated polyester fiber product.
  • the antibacterial material can be further used for sanitary and medical devices, various filters, and the like.
  • the sheet and film formed from the antibacterial material are used, for example, for trays, containers, molded articles such as interior materials such as refrigerators, and bags for storing food.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

La présente invention concerne une résine polyester sulfonée ayant un groupe sulfo, une fibre polyester facile à teindre, une matière antibactérienne et une matière antistatique pouvant être utilisées pour différents types d'étoffes, de matériaux de constructions et analogues. On prépare la résine polyester sulfonée en traitant une résine polyester avec de l'acide sulfurique anhydre. Par ailleurs, la fibre polyester facile à teindre renferme la résine polyester sulfonée, la matière antibactérienne et la matière antistatique renfermant la résine polyester sulfonée et une base organique liée au groupe sulfo. La matière antibactérienne et la matière antistatique sont utilisées comme tissu, étoffe, article maillé, article cotonneux et analogues, la matière antibactérienne étant utilisée comme feuille, film ou analogues.
PCT/JP1999/000993 1998-03-17 1999-03-02 Resine polyester sulfonee, fibre polyester facile a teindre, matiere antistatique et procede de preparation associe WO1999047579A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP10/89229 1998-03-17
JP08922998A JP2002179503A (ja) 1998-03-17 1998-03-17 抗菌材料
JP17064298A JP2002180373A (ja) 1998-06-02 1998-06-02 改質されたポリエステル繊維
JP10/170642 1998-06-02

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT201700019556A1 (it) * 2017-02-21 2018-08-21 Golden Lady Co Spa Poliestere modificato con proprieta' anti-batteriche e suoi usi
WO2021212152A1 (fr) * 2020-04-17 2021-10-21 Kraton Polymers Llc Dispositif de filtre à air incorporant un milieu filtrant antimicrobien
WO2021212150A1 (fr) * 2020-04-17 2021-10-21 Kraton Polymers Llc Masque facial antimicrobien
CN114561034A (zh) * 2022-03-31 2022-05-31 中国科学院长春应用化学研究所 一种抗微生物改性磺化苯乙烯基聚合物复合物及其制备方法

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JPS5060597A (fr) * 1973-09-28 1975-05-24
JPS61136517A (ja) * 1984-12-05 1986-06-24 Nippon Ester Co Ltd 改質ポリエステルの製造法
JPS61136518A (ja) * 1984-12-07 1986-06-24 Nippon Ester Co Ltd 改質ポリエステルの製造法
JPH01165620A (ja) * 1987-12-22 1989-06-29 Nippon Ester Co Ltd 改質ポリエステルの製造法
JPH03263428A (ja) * 1990-01-25 1991-11-22 Toray Ind Inc 可染性液晶樹脂およびその製造法
JPH03273024A (ja) * 1990-02-26 1991-12-04 Toray Ind Inc 可染性液晶ポリエステル樹脂およびその製造法

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JPS5060597A (fr) * 1973-09-28 1975-05-24
JPS61136517A (ja) * 1984-12-05 1986-06-24 Nippon Ester Co Ltd 改質ポリエステルの製造法
JPS61136518A (ja) * 1984-12-07 1986-06-24 Nippon Ester Co Ltd 改質ポリエステルの製造法
JPH01165620A (ja) * 1987-12-22 1989-06-29 Nippon Ester Co Ltd 改質ポリエステルの製造法
JPH03263428A (ja) * 1990-01-25 1991-11-22 Toray Ind Inc 可染性液晶樹脂およびその製造法
JPH03273024A (ja) * 1990-02-26 1991-12-04 Toray Ind Inc 可染性液晶ポリエステル樹脂およびその製造法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT201700019556A1 (it) * 2017-02-21 2018-08-21 Golden Lady Co Spa Poliestere modificato con proprieta' anti-batteriche e suoi usi
WO2018154403A1 (fr) * 2017-02-21 2018-08-30 Golden Lady Company S.P.A. Polyester modifié ayant des propriétés antibactériennes et utilisation du polyester modifié
CN110312750A (zh) * 2017-02-21 2019-10-08 金莱迪公司 具有抗菌性的改性聚酯及其用途
US11427678B2 (en) 2017-02-21 2022-08-30 Golden Lady Company S.P.A. Modified polyester having antibacterial properties and use of the modified polyester
IL268769B1 (en) * 2017-02-21 2023-07-01 Golden Lady Co Spa Adapted polyester with antibacterial properties and use of the adapted polyester
WO2021212152A1 (fr) * 2020-04-17 2021-10-21 Kraton Polymers Llc Dispositif de filtre à air incorporant un milieu filtrant antimicrobien
WO2021212150A1 (fr) * 2020-04-17 2021-10-21 Kraton Polymers Llc Masque facial antimicrobien
CN114561034A (zh) * 2022-03-31 2022-05-31 中国科学院长春应用化学研究所 一种抗微生物改性磺化苯乙烯基聚合物复合物及其制备方法

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