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
  • D06M13/005—Compositions containing perfumes; Compositions containing deodorants
• • 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
  • D06M15/61—Polyamines polyimines
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
  • D06M2101/16—Synthetic fibres, other than mineral fibres
  • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
  • D06M2101/28—Acrylonitrile; Methacrylonitrile

Definitions

• the present invention relates to a so-called deodorant fiber having a function of removing malodor perceived by a sense of smell in a living environment space and a method for producing the same.
• the present invention also relates to a deodorant textile product capable of removing a wide variety of odors.
• Japanese Patent Application Laid-Open No. Hei 3146064 discloses an acrylic fiber woven fabric holding a deodorant which supports polyethylene and a nonionic hygroscopic organic substance. The product based on this proposal was not at a level that was sufficiently satisfactory in terms of washing durability and workability.
• Japanese Patent Application Laid-Open No. 57-16687 discloses a material for a filter for cigarette smoking, in which a reactive group is introduced into a cellulose molecule to react with polyethyleneimine.
• the publication discloses that a polyvinylamine, which is a polyamine compound, is chemically bonded to a metal polyphenylene.
• polyvinylamine and the metal form a complex and become water-insoluble, making it difficult to apply the fiber to the fiber in the form of an aqueous solution or the like. Only the complex will be attached. As a result, the dyeing durability of the processed fiber product is further reduced.
• Japanese Patent Publication No. 2-22673 discloses an air purifying filter in which a plurality of types of carriers impregnated with active ingredients for deodorizing different odors are combined. Impregnate or apply carrier with deodorant on textile surface Simply attaching the odor component gives the textile product a hard texture and easily removes the deodorant active component by washing, dyeing, and other treatments. Clothing that demands shock
• Laundry durability refers to the use of the mechanical action of water deposits on the fibers and the chemical action of the minimum amount of surfactant that does not cause discoloration or deterioration of physical properties of textiles. Performance retention when detached material is separated Laundry is a process that aims to remove extraneous matter due to a very weak bond, such as physical adsorption (a detailed washing test method is described in JIS-L-0217).
• the dyeing durability refers to the performance retention when the attached matter on the textile is separated by the strong thermodynamic action of heat. It also shows the shedding of the conjugate. Therefore, maintaining the deodorizing performance of the deodorant fibers against the malodorous substances after the dyeing process has been treated as a very difficult problem. Disclosure of the invention
• An object of the present invention is to provide, in the broadest sense, a deodorant fiber and a deodorant fiber product having a durable deodorizing effect.
• a specific object of the present invention is to cover ordinary textile products such as dyeing and washing. It is an object of the present invention to provide deodorant fibers and textile products having remarkable resistance to various kinds of treatments.
• an object of the present invention is to provide a textile material which does not lose its excellent deodorizing effect even when subjected to the above-mentioned daily treatment.
• Another object of the present invention is to provide a durable fiber product having an excellent deodorizing effect on a wide range of odors in the spectrum.
• the present invention relates to a fiber containing an acidic group in a fiber substrate at a rate of 0.01 to 2.5 mol Z kg fiber, and the fiber contains an amino group-containing chemical substance. At a rate of 0.03 to 3 mol / kg fiber as amino group, at least a part of the amino group is supported via a bond with the acidic group. Characteristic deodorant fiber.
• the acidic group is an acidic group contained in the substrate forming the fiber, for example, a carboxyl group or a sulfone group, which can react with an amino group-containing chemical substance.
• the fibers targeted by the present invention are organic fibers and include natural fibers, chemical fibers and synthetic fibers.
• natural fibers are cotton and wool.
• the chemical fibers include regenerated cellulose fibers such as viscose rayon and cupran monium rayon, and fibers formed through chemical modification of natural cellulose raw materials such as cellulose acetate.
• the synthetic fiber is a fiber-forming synthetic organic polymer fiber, and is typically a polyamide fiber, an acrylonitrile fiber, a polyester fiber, or the like. If these fibers do not inherently have acidic groups, a modifying compound having acidic groups is chemically added to the fiber substrate, or the fibers are treated with an appropriate modifier to remove acidic groups.
• a fiber which is introduced and contains a predetermined amount of an acidic group can be prepared and used as a substrate fiber.
• the fiber is a synthetic organic polymer fiber
• the acidic group is used when preparing the polymer.
• a predetermined amount of a copolymerizable comonomer having a copolymer of the following formula is introduced, and the resulting copolymer is subjected to a known spinning and drawing process to obtain an acid content of 0.01 to 2.5 mol / kg fiber per fiber.
• the fiber containing the group can be easily obtained.
• the acrylonitrile-based fiber can be used as the most suitable target fiber substrate in the present invention because a copolymer containing a predetermined amount of an acidic group can be easily prepared by the above-mentioned means. .
• an amino group is an amino group that is not salt-substituted, and is a polyamino compound having a molecular weight of 1,000 to 200.000 having two or more amino groups in a molecule. It is introduced by chemically bonding to the fiber and is firmly supported by the fiber.
• the salt-substituted amino group is neutralized with an acid such as, for example, aminosulfate or aminohydrochloride, so that the odor derived from a carbonyl group-containing compound or an acidic compound can be satisfied. Does not adsorb, and it is not possible to obtain textiles that are durable with respect to the deodorizing effect.
• the deodorant fiber of the present invention is firmly supported by chemically bonding the amino group to 50 mol% to 100 mol%, preferably 60 mol% or more of the acidic group contained in the fiber. You.
• the deodorant textile of the present invention has a sufficient amount of amino groups chemically bonded to the acidic groups in the textile substrate, and thus has a low acidity such as sulfides and aldehydes.
• the odor has a large deodorizing effect, and the deodorizing effect is a fiber that is resistant to chemical and physical actions such as dyeing and washing.
• the deodorizing fiber since the free amino groups exert a deodorizing effect, the amount of acidic groups in the fiber substrate is large and the amount of added amino groups is small. However, since the fiber does not exhibit a deodorizing effect, it is necessary to increase the amount of amino groups provided and to provide a fiber having free amino groups.
• the deodorant textile of the present invention is prepared by using a fiber containing the above-mentioned amount of acidic group in a textile substrate as a raw material, and adding water-soluble polyamine, particularly a molecular weight of 000 to The water-soluble polyamine-added fiber is applied by bringing it into contact with an aqueous solution containing a solution amount of 0.025 to 5 mol Z kg with respect to the molar amount of the acidic group of 200,000 water-soluble polyamine.
• it can be prepared by heat treatment at an ambient temperature of 100 ° C or more.
• the concentration of the water-soluble polyamine treatment bath may be any concentration as long as a predetermined amount of the water-soluble polyamine compound can be attached to the fiber, and the concentration to the textile may be sufficient.
• the amount applied can also be determined based on the squeezing rate and the like.
• the deodorant fiber of the present invention is an acrylonitrile-based fiber
• the acrylonitrile-based fiber is obtained by spinning or drawing by a wet or gear spinning wet spinning method.
• Dyeing and other treatments are performed by attaching a water-soluble polyamide compound to fibers that have been formed and have never been dried after stretching (hereinafter sometimes referred to as undried fibers).
• undried fibers The resistance of the deodorizing effect to the water can be further enhanced.
• the deodorant fiber of the present invention can be a long fiber or a short fiber.
• the fibers can be prepared in a tow state.
• the deodorant fiber of the present invention is processed into a woven, knitted or non-woven form as it is in the form of a thread and in many cases, and in the form of clothing or other secondary products. used.
• the deodorant fiber of the present invention is the above-mentioned fiber product, and all of the products can be composed of the deodorant fiber of the present invention.
• the deodorant fiber of the present invention can be mixed with other general-purpose fibers to prepare a secondary product.
• the deodorant fiber of the present invention has a basic odor of at least 5% by weight.
• the deodorizing fibers exhibiting deodorizing activity especially 0.2 to 10 equivalents based on the weight of the fiber, of the fibers containing 1 ⁇ fibers or 0 of the anionic functional groups.
• Deodorant fiber combined with transition metal of 1 to 5 equivalent / kg fiber or less At least 0.1% by weight in a textile product, it can be used in an atmosphere where acidic compound odors and basic compound odors are mixed, that is, in a wide range of deodorant spectra. It shows a high degree of deodorizing performance and is a textile product with excellent durability and deodorizing properties.
• the anionic functional group of the deodorant fiber which exhibits deodorant activity against a basic odor is a sulfone group or a carboxyl group, and is obtained by the same method as the above-mentioned acid group. Introduced into synthetic or synthetic fiber substrates.
• the transition metal is introduced into the fiber by subjecting the fiber containing the anionic functional group to contact treatment in the form of an aqueous solution of salts such as metal sulfates and nitrates.
• the mixed textile can be processed into a processed product such as a blended woven or knitted fabric, a twisted, a twisted knit, or a nonwoven fabric by applying a conventional processing method to general-purpose fibers.
• the acidic group contained in the deodorant textile of the present invention is preferably a carboxyl group or a sulfone group, particularly a sulfone group.
• the acidic group contained in the deodorant fiber of the present invention is O.Ol S.SmolZkg fiber, preferably 0.01 to! It is the ratio of .5mol / kg fiber. If the acidic group is less than 0.1 OlmolZkg fiber, the binding between the amino group-containing water-soluble polyamide compound and the acidic group becomes insufficient, and the amino group-containing water-soluble polyamine compound becomes insoluble. However, they are not used in the present invention because they easily fall off by washing and dyeing. Further, when the acidic group exceeds 2.5 molZkg fiber, the acidic group-containing polymer compound in the fiber is not preferable because it is easily removed by washing and dyeing.
• the acidic group contained in the fiber may be added to the fiber substrate by a known method such as graft polymerization by adding a chemical substance having an acidic group to the fiber substrate in a fiber which does not substantially contain an acidic group, Is changed by chemical treatment such as oxidation. Can be introduced by forming a predetermined amount of carboxyl group.
• a means for introducing an acidic group can be used as a method for preparing a fiber containing a predetermined amount of carboxylic acid group in wool, cotton, regenerated cellulose fiber, or cellulose acetate fiber. it can.
• a copolymer obtained by quantitatively copolymerizing a copolymer having an acidic group is prepared, and a known spin-drawing method suitable for practical use of the copolymer is prepared using the copolymer. By applying it, it is possible to easily introduce a fixed amount.
• Carboxyl groups or sulfone groups in condensation-type copolymers such as polyamide fibers and polyester fibers, and addition-type copolymers such as acrylonitrile-based fibers It is possible to prepare a fiber-forming copolymer having a predetermined amount of an acidic group by adding a copolymer monomer by a known method.
• the acrylonitrile-based arrowhead fiber is a fiber suitable for preparing a fiber having a carboxylic acid group or a sulfone group by applying a copolymerization method. Since the method for forming the fiber of the copolymer of a monomer having a certain amount of a carboxyl group or a sulfone group and the performance of the obtained fiber are substantially the same as those of general-purpose acrylonitrile fiber, It is convenient as a fiber substrate providing material of the deodorant fiber of the present invention.
• the acrylonitrile-based synthetic fiber constituting the deodorant acrylonitrile-based fiber of the present invention contains 30% by weight or more of acrylonitrile-based fiber, acrylic acid, and acrylic acid.
• Examples are copolymer fibers obtained by copolymerizing one or more vinyl monomers such as lilsulfonate.
• the acrylonitrile-based fibers particularly preferably used in the present invention are acrylonitrile of 80% by weight or more and acrylic acid, methyl acrylate, methyl acrylate. Obtained by copolymerizing one or more vinyl monomers such as methyl acrylate, acrylamide, vinyl acetate, vinylidene chloride, methyl sulfonate, and styrene sulfonate. It is a copolymer fiber.
• the amino group contained in the deodorant fiber of the present invention is preferably from 0.03 to 3. Omol / kg fiber, more preferably from 0.05 to 2 mol Z kg fiber, based on the fiber. There is.
• the amount is less than 0.03 mo i Z kg fiber, the adsorption performance of compounds containing acidic groups and acidic compounds against odor is low, and when the amount exceeds 3 nio no kg fiber, the texture of the fiber is remarkably reduced.
• the amino group is formed by binding to an acidic group of a polyamine compound having an amino group in the fiber, preferably a polyamine compound having a molecular weight of 1,000 to 200,000. Fixedly held.
• the polyamino compound into which an amino group is introduced is preferably a water-soluble polyamide compound having a bifunctional or higher functionality and not being substituted with a salt.
• the water-soluble polyamine compound include ethylenediamine, diaminopropylamine, 2,2'-azobis- (2-amidinopropane), carbohydrazine, and thiocarbohydra.
• the amino compound is converted into an aqueous solution during the treatment for applying to the fiber.
• it may be used as an emulsified dispersion.
• a water-soluble amine compound is preferably used. This is because not only the stability of the treatment bath when water is used as a medium but also a water-soluble solvent is required in order to obtain a strong bond between the acidic group and the amino group and a high bonding ratio according to the present invention. This is because amide compounds are preferred. If the amide compound is not water-soluble, the binding rate will be slightly lower.
• a water-soluble polyamine compound having a molecular weight of not less than 1.000 and not more than 200,000 is desirable.
• the molecular weight is less than 1,000, the ratio of bonds between the molecular chains constituting the acrylic synthetic fiber and the molecular chains constituting the water-soluble polyamine compound is reduced, and the bonds are easily formed by the dyeing treatment.
• the water-soluble polyamine compound is dropped off by cutting off, so that it is not used in the present invention.
• the molecular weight exceeds 200.000, the texture of the fiber is unfavorably reduced.
• the water-insoluble boron compound is not desirable because it hardly diffuses into the fiber and adheres to the surface, and the fiber sticks.
• polyethyleneimine, polyarylamine, and amino-modified acrylic polymer are desirably used.
• mixing the water-soluble polyamine compound with gold or metal ions forms a metal complex and becomes insoluble in water, so that the durability when applied to the fiber becomes extremely low. Not good.
• the binding ratio of the acidic group to the polyamide compound in the deodorant fiber of the present invention is desirably 50 to 100 mol%. Particularly preferably, it is 60 to 100 mol%.
• the bonding ratio of the acidic group is less than 50 mol%, the durability of the dyeing is low, and the durability of the deodorizing effect is inferior.
• the binding ratio of acidic groups is determined by measuring the total amount of acidic groups in the fiber and the amount of residual acidic groups not bound to functional groups of the polyamine compound (hereinafter simply referred to as “remaining acidic group amount”). It can be obtained from the formula.
• Acid group binding rate (mol%) (total amount of acidic groups-amount of remaining acidic groups) /
• the deodorant fiber of the present invention is prepared by bringing a fiber containing a predetermined amount of acidic group into contact with water-soluble polyamine, causing a predetermined amount of water-soluble polyamine to adhere to the fiber, and then performing a heat treatment.
• the amino group of the water-soluble polyamine is combined with 70 to 100% of the acidic group such as a carboxyl group or a sulfone group on the fiber substrate, and the polyamine residue having the amino group is bound. It is prepared by immobilizing a group on a fiber substrate and supporting it.
• the heat treatment can be performed in a dry heat atmosphere at a temperature of 100 ° C or higher. Dry heat treatment takes time. It is preferable to perform it under wet heat conditions.
• the moist heat conditions used here are that the fibers are treated with pressurized steam at a temperature of 100 ° C to 180 ° C, particularly preferably 105 ° C to 130 ° C for about 30 seconds to 10 minutes.
• the temperature of the pressurized steam is less than 100, the amino group-containing amide compound and the acidic group of the fiber do not sufficiently proceed to bind, and the amino group-containing amide compound is easily washed. Since they fall off, they are not used in the present invention. Further, when the water vapor temperature exceeds ⁇ 80 ° C., the texture of the fiber is remarkably reduced, so that it is not used in the present invention.
• the contact between the fiber containing an acidic group and the water-soluble amine compound can be performed by immersing the fiber in an aqueous solution of the water-soluble amine compound and squeezing the solution.
• concentration of the water-soluble amine compound in the aqueous solution at this time varies slightly depending on the operating conditions of immersion and squeezing, but it is an aqueous solution of about 0.01 to about 20% by weight. It is adjusted by squeezing or draining with a bracket, a center, etc., so that the concentration becomes 10% by weight.
• the temperature of the aqueous solution during immersion can be set arbitrarily without any problem.
• Heat treatment operation is subject to processing 5 Depending on the shape of the fiber, it can be performed using a heat treatment device commonly used in textile processing plants. For example, if the fiber is a continuous long piece such as tow, woven, knitted or non-woven cloth, it is possible to use a pad, then a steamer, a tow reactor, a spreading wet heat treatment machine, etc. It is convenient to apply it. If the fiber to be processed is a higher-processed fiber product such as a sweater, the heat treatment can be performed using a batch dryer, tumble dryer, or wet heat tumbler.
• the fibers after the heat treatment should be washed with water to remove excessively adhered water-soluble amine compounds.
• the fiber When the target fiber is polyacrylonitrile-based fiber, the fiber is wet-spun, formed through an appropriate drawing treatment, and has not been dried yet (a so-called “jet gel fiber”).
• a method of contacting a water-soluble polyamine compound with the water-soluble polyamine compound to impart a water-soluble polyamine to the textile is particularly preferable.
• acrylonitrile fiber that has never been dried is water swelling before the acrylonitrile fiber structure is irreversibly densified by drying.
• W is a weighing value (g) of a sample obtained by using a few g of fiber containing water that has never been dried and centrifuging at 25 ° C and 900 G for 5 minutes.
• W 2 represents the ⁇ value of the sample dried for 2 hours ago ⁇ fee at 1 05 ° C
• the amount of remaining acidic groups is reduced by performing a dry heat treatment, thereby improving the binding ratio of the acidic groups. .
• the amount of remaining acidic groups is further reduced, and the bonding ratio of acidic groups is improved.
• the ionic intermolecular cross-linking reaction between the acidic group and the amino group of the water-soluble polyamide compound in the cross section of the acrylonitrile synthetic fiber is promoted by the wet heat treatment. This is because It is thought that by promoting the intermolecular crosslinking reaction, washing durability and dyeing durability can be improved.
• the deodorant fiber of the present invention prepared as described above is a fiber exhibiting deodorant properties because it contains an amino group, and can be used alone or as another general-purpose textile material as a textile fiber material. Any form of advanced processed product can be produced by mixing with the fiber raw material and applying any processing method known in the textile industry.
• the deodorant fiber (hereinafter referred to as [A]) of the present invention is mixed with a deodorant fiber (hereinafter referred to as [B]) exhibiting an anionic functional group deodorant activity, so that a deodorant fiber can be obtained. It has a broad and high-level deodorizing function of the tram, and it is particularly preferable to use fibers selected from textiles that deodorize the odor of evening coconut deodorant fiber [A] and deodorant
• the method of combining and mixing with the conductive fiber [B] includes means such as blending, blending, twisting, twisting, and knitting. Applying these measures, high-processing textiles with a wide range of advanced deodorizing functions of deodorizing spectrum for various end uses in the form of yarn, woven, knitted and non-woven fabrics You can get the product.
• the fiber composition of these textiles is preferably at least 5% by weight or preferably 10% by weight of deodorant fiber [A] and at least 0.1% by weight of deodorant fiber [B].
• the mixing ratio is at least 1% by weight, and general-purpose fibers can be mixed as appropriate.
• the mixed high-order processed fiber product can remove odors derived from acidic compounds such as carbonyl compounds using the deodorant fiber [A] and also remove odors derived from basic compounds using the deodorant fiber [B].
• a durable composite odor can be deodorized.
• a processed fiber product having the deodorant fiber and the deodorant-mixed higher-order processed fiber of the present invention can be obtained.
• the anionic functional group of the deodorant fiber [B] is a carboxyl group or a sulfone group, and the content in the fiber is 0.2 to 10 equivalents / 1 ⁇ , and further, 0.4 to 5 equivalents Z kg or more 5 equivalents Z kg is preferred. If the amount of carboxyl groups is less than 0.2 equivalent Zkg, the deodorizing effect is small, and if it exceeds 10 equivalents Zkg, the moisture absorption and water absorption of the fiber itself become too high, and the form stability during washing and the durability are high. This is not preferred because it deteriorates and the texture after washing hardens.
• the carboxyl group and the sulfone group may be used alone or coexist. However, the carboxyl group is preferred because it is easier to introduce a large amount and the carboxyl group is superior in performance. New A transition metal may be added to the anionic functional group to increase the deodorizing species and enhance the deodorizing performance.
• An anionic functional group such as a carboxyl group
• a method in which acrylic acid or the like is subjected to graph polymerization using an amide group, an amino group, a hydroxyl group, or the like in a textile substrate examples include a method of hydrolyzing a lily fiber with an alcohol, a method of co-polymerizing a polymer having a carboxyl group such as acrylic acid, or a method of polymer blending. . Furthermore, it is introduced by a method such as wet spinning, immersion in an undried state in an aqueous solution of the polymer, and drying.
• transition metal is here, copper, refers zinc, iron, two Tsu Kell, click B beam, the cobalt and the like
• transition metal compounds include copper compounds (CuS0 4, Cu (N0 3 ) 2 , etc.), zinc compounds ( ZnS (K, Zn (N0 3 ) 2 , etc.), iron compounds (FeS0 4. Fe (N0 3 ) 2), Nickel compounds (NiS0 4, Ni (N0 3 ) 2 , etc.), chrome compounds (CrS0 4, Cr (N 0 3) 2 , etc.), using a cobalt compound (CoS0 4, Co (N0 3 ) 2 and the like) and the like) and the like
• the fiber is introduced into the fiber by impregnation of an aqueous solution.
• a copper compound and a zinc compound are preferably used because the deodorizing effect is remarkable.
• the content of the transition metal is preferably 0.2 to 10 equivalents of 71 ⁇ fiber, more preferably 0.2 to 3 equivalents / kg fiber.
• the amount is less than 0.2 equivalent Zkg fiber, the deodorizing effect is small, and when it exceeds 10 equivalents Zkg fiber, the content of anionic group becomes small, so that the deodorizing effect of vanmonia is small.
• Deodorant fiber [B] is a cellulosic fiber, acrylonitrile synthetic fiber, and polyamide fiber product can be mixed with known deodorant fiber and antibacterial fiber. Is not diminished.
• the test was performed according to the JIS-L-0217-103 method.
• Fiber 1 Add Og to 300 ml of 10 wt% sodium chloride aqueous solution, shake in a 40 ° C constant temperature bath for 30 hours, wash the sodium chloride adhered with purified water sufficiently, and wash with 80. After drying for 1 hour, the remaining acidic group sodium-substituted fiber was obtained. Next, the fiber was subjected to wet decomposition for 5 hours in a mixed solution of 5% of 96% by weight sulfuric acid, 40% of 62% by weight nitric acid and 2% of 70% by weight perchloric acid on an electric heater. The liquid obtained here is diluted 100 times with purified water and analyzed by flame spectrometry. Quantitative analysis of sodium was performed by using the method described above, and the amount of residual acidic groups was measured from the amount of sodium.
• the fiber is 3.0% owi with Kayanol Milling.
• Blue BW (trademark, manufactured by Nippon Kayaku Co., Ltd., acid dye L ACID BLUE 138), 1.0% owf with Micreger 2N as leveling agent, pH adjuster
• a 90% by weight aqueous solution of acetic acid was dyed with 0.2 cc / L at a bath ratio of 1:80 at 100 ° C for 60 minutes. Washing was performed. After washing with water, the dyed fiber was sufficiently dried and subjected to various tests.
• the test was performed according to the JIS-L-0217-103 method.
• acetoaldehyde 100 ppm as a compound containing a carbonyl group 1 g of textiles together with 600 liters of offensive odor components were placed in a 1 liter Tedlar bag, and the residual gas concentration after 60 minutes was measured with a Kitagawa gas detector tube.
• the initial concentrations of the malodorous components are as follows: acetoaldehyde 100 ppm as a compound containing a carbonyl group, 40 ppm of acetic acid and 25 ppm of hydrogen sulfide as an acidic compound, and 140 ppm of trimethylamine as a basic compound. pm and ammonia were set to 140 ppm.
• the touch evaluation of the product by the five panelists was evaluated based on the following criteria based on the total score of the five panelists.
• the deodorant properties of the tobacco odor of the fibers were measured by collecting a 10-second substream of the evening baco (Mild Seven manufactured by Nippon Tobacco Co., Ltd.) for 10 seconds in a 2-liter Meyer flask. 0.5 milliliters was poured into a 600 milliliter Meyer flask using a weighing machine, and 1 g of each sample fiber was put in the flask. After standing for 2 hours, the odor in the flask and the odor of the textile itself were measured by 16 persons. Panels were rated according to the following criteria, and the total score obtained by summing up the scores of all panels was evaluated.
• Example 1 1.3% by weight (Example 1), 2.5% by weight (Example 2), 3.8% by weight of the undried textile fiber in a polyethylene imide (manufactured by Nippon Shokubai Co., Ltd.) having a degree of polymerization of 1630 (molecular weight: about 70,000) % (Example 3), 6.3% by weight (Example 4) and 12.5% by weight (Example 5) in aqueous solution (20 ° C.) for 1 minute to dehydrate.
• the drawing ratio at this time was 80% by weight.
• the fiber was dried at 80 ° C for 1 hour, and was subjected to a wet heat treatment in an autoclave at 120 ° C for 5 minutes to obtain fibers of Examples 1 to 5.
• Example 1 As Comparative Example 1, the same treatment as in Example 2 was carried out using a polyethylenimine aqueous solution having a polymerization degree of 1630 (molecular weight: about 70.000) in which the polyethylenimine aqueous solution was subjected to phosphate substitution to pH 4 with phosphoric acid. was carried out to obtain a textile.
• the obtained fibers, the fibers obtained after washing the obtained fibers repeatedly 10 times, and the fibers obtained by dyeing the obtained fibers were subjected to a bad odor component adsorption test. See Table 1.
• Example 2 fibers obtained by omitting the wet heat treatment (Example 6) and fibers obtained by changing the wet heat treatment to a saturated steam at 190 ° C. for 5 minutes were obtained.
• Table 1 shows the binding ratio of acidic groups.
• Example 8 After dehydrating the undried fiber used in Example 1, drying at 80 ° C for 1 hour, and performing a wet heat treatment with saturated steam of 120 ° C for 5 minutes in an autoclave, a molecular weight of about 70,000 Was immersed in a 12.0% by weight aqueous solution of polyethyleneimine for 1 minute to dehydrate. The drawing ratio at this time was 17% by weight. Then, drying was performed at 80 ° C. for 1 hour to obtain the fiber of Example 8. The fiber obtained after washing the obtained fiber and the obtained textile for 10 times, and Table 1 shows the results of an odor component adsorption test performed on the fibers obtained by dyeing the obtained fibers and the binding ratio of acidic groups.
• the fibers after repeating the washing 10 times and the fibers subjected to the dyeing treatment had excellent deodorizing performance against acetate and hydrogen sulfide.
• the fiber of Comparative Example 1 in which the undried fiber was treated with the salt-substituted polyethylene imide had a lower acid group binding rate than the fiber of Example 2 having the same weight, and was 10 times less.
• the deodorizing performance of the fibers that had been repeatedly washed (and the dyed fiber) against acetaldehyde and hydrogen sulfide had a larger decrease rate than the fiber before the washing (and the dyeing processing).
• the fibers of Examples 6 and 8 were obtained by subjecting the fibers to a polyethyleneimine treatment followed by a heat treatment. Regardless of the heat treatment conditions, the fibers of these examples had much better deodorant washing resistance (dyeing treatment resistance) than the fibers of Comparative Example 1.
• Example 7 the fiber subjected to the steam treatment in 190 of Example 7 had severe adhesion.
• Example 2 The undried fiber used in Example 1 was added to an emulsion solution containing 6.3% by weight of polyethylene imide having a degree of polymerization of 1,630 (molecular weight: about 70,000) and 10% by weight of copper phthalocyanine at 20 ° C. For 1 minute to dehydrate. The drawing ratio at this time was 100% by weight. After dehydration, the fiber was dried at 80 ° C for 1 hour, and subjected to wet heat treatment with 120 ° C saturated steam in an autoclave for 5 minutes to obtain a fiber. Table 2 shows the results of the bad odor component absorption test and the acid group binding rate of the obtained fiber, the fiber obtained by repeatedly washing the obtained fiber 10 times, and the fiber obtained by dyeing the obtained fiber. Shown in
• Example 12 Chitosan (manufactured by Takamatsu Oil & Fat Co., Ltd.) was added to 0.35% by weight (Comparative Example 2), 5.0% by weight (Example 10), 10.0% by weight Example 11), 30.0 % By weight (Example 12)
• the sample was immersed in an aqueous solution at 20 ° C for 1 minute, and dehydrated to a squeezing ratio of 100%. After dehydration and drying at 120 ° C. for 15 minutes, wet heat treatment was performed for 3 minutes with saturated steam at 110 ° C. in an autoclave to obtain the fibers of Examples 10 to 12 and the fiber of Comparative Example 2.
• the obtained fibers, the fibers obtained by repeatedly washing the obtained textiles 10 times, and the fibers obtained by dyeing the obtained textiles were subjected to an odor component adsorption test. See Table 2.
• Water solubility of aminated ⁇ I S indicates water solubility, and I indicates water solubility.
• the fibers of Examples 9 to 12 having an amino group content of 0.3 to 1.89 mol / kg were contained in the fibers of Comparative Example 2 having an amino group content of 0.02 molZkg. Regardless of the type of amino group, the fiber and the fiber after 10 times of washing had good deodorizing performance against acetate and hydrogen sulfide.
• a polymer obtained by copolymerizing 79,0% by weight of acrylonitrile and 21.0% by weight of acrylic acid is dissolved in 75% by weight of nitric acid, and a stock solution for spinning having a polymer concentration of 16.0% by weight.
• This spinning solution is spun through a spinneret having a pore of 0.06 mm into a 25% by weight nitric acid-based coagulation bath maintained at 0 ° C, washed with water, stretched 8 times in boiling water to obtain undried fibers.
• the carboxyl group content of this undried fiber was measured, it was 2.72 molZkg fiber.
• the undried fiber was immersed in a 2% by weight ethanol solution of polyethyleneimine having a polymerization degree of 1,630 (molecular weight of about 70,000) at 20 ° C for 3 minutes to be dehydrated. The drawing ratio at this time was 150%. After dehydration, the fiber was dried at 60 ° C. for 1 hour to obtain a fiber of Comparative Example 8.
• Table 4 shows the results of the bad odor component adsorption test and the acid group binding rate of the obtained fiber, the fiber obtained by repeatedly washing the obtained fiber 10 times, and the fiber obtained by dyeing the obtained fiber. .
• the weight change rate of the fibers after washing was determined according to the following equation.
• Washing weight change rate (%) (W:-W 2 ) / W, X 100 where W, is the dry sample weight before washing and W 2 is the dry sample weight after washing
• the fiber of Comparative Example 3 containing a carboxyl group of 2.5 mol / kg fiber or more per fiber showed elution of the fiber after repeated washing, and after washing 10 times and after dyeing.
• the deodorizing performance against acetate was extremely low.
• a polymer obtained by copolymerizing 74.7% by weight of acrylonitrile, 25.0% by weight of vinylidene chloride, and 0.3% by weight of sodium metal sulfonate is dissolved in dimethylformamide to obtain a polymer.
• a spinning solution having a coalescing concentration of 18.0% by weight was prepared. This undiluted spinning solution is spun through a spinneret having 0.15 mm pores into a 75% by weight dimethylformamide-based coagulation bath maintained at 30 ° C, and 75% by weight maintained at 80 ° C. The film was stretched 5.0 times in a dimethylformamide stretching bath, washed with water and stretched 1.2 times in boiling water. The obtained undried fiber showed a swelling degree of 95.3% by weight. When the sulfon group content of this fiber was measured, it was found to be 0.1 OmolZkg fiber.
• the fibers were prepared by adding 0.03% by weight (Comparative Example 4), 0.15% by weight (Example 13), 0.5% by weight (Example 14), 3.0% by weight (Example 15) ), 5.0% by weight (Example 16), 10.0% by weight (Example 17), and 15.0% by weight (Comparative Example 5) were immersed at 25 ° C. for 1 minute to be dehydrated. The drawing ratio at this time was 100% by weight. The treated fiber was dehydrated and dried for 1 hour at 80 ° C. The fiber of Examples 13 to 17 and Comparative Examples 4 to 5 was subjected to wet heat treatment for 5 minutes at 120 ° C saturated steam in an autoclave.
• a polymer obtained by copolymerizing 94.6% by weight of acrylonitrile, 5.0% by weight of methyl acrylate, and 0.4% by weight of itaconic acid is dissolved in 70% by weight of nitric acid.
• a spinning stock solution having a polymer concentration of 16.0 weight was prepared. The undiluted spinning solution was spun through a spinneret having pores of 0.06 into a 35% by weight nitric acid-based coagulation bath kept at 0, washed with water and stretched 8 times in boiling water to obtain an undried fiber. When the content of the carboxyl group in this fiber was measured, it was 0.06 mol / kg fiber.
• This undried fiber is placed in a 1.3% by weight (Example 18), 2.5% by weight (Example 19), 3.8% by weight (Example 20) 20 ° C. aqueous solution of about 70,000 molecular weight for 1 minute. It was immersed and dehydrated (squeezing rate 80%). After dehydration, the fiber was dried at 80 ° C. for 1 hour, and was subjected to a wet heat treatment with saturated steam at 120 ° C. for 5 minutes in an autoclave to obtain fibers of Examples 18 to 20. Further, the fiber of Example 14 which was not subjected to the wet heat treatment was used as the fiber of Example 21.
• Table 5 shows the results of an odor component adsorption test and the acid group binding rate of the obtained fiber, the fiber obtained by repeatedly washing the obtained fiber 10 times, and the fiber obtained by dyeing the obtained textile. It was shown to. [Table 5] Water vapor fiber ⁇ 0 times
• Examples 18 to 20 were compared with the fibers of Example 21 which had not been subjected to the steam treatment, to the fibers obtained by repeating the washing 10 times and the aldehydes of the dyed fibers. And the deodorizing performance against hydrogen sulfide was further excellent.
• the molecular weight of polyethylene imine was about 300 (Example 22), the molecular weight was about 1,200 (Example 23), and the molecular weight was about 10,000 (Example 2) on the undried fiber drawn 9 times in boiling water used in Example 1.
• a molecular weight of about 70,000 (Example 25) was immersed in a 1.0 weight aqueous solution at 20 ° C for 1 minute, and dehydrated to a squeezing ratio of 100%. After dehydration, the fiber was dried at 120 ° C for 15 minutes, and then subjected to wet heat treatment with saturated steam at 120 ° C for 5 minutes in an autoclave to obtain fibers of Examples 22 to 25.
• Table 6 shows the results of the bad odor component adsorption test and the acid group binding rate of the obtained fibers, the fibers obtained by repeatedly washing the obtained fibers 10 times, and the fibers obtained by dyeing the obtained fibers. Shown in
• the fibers of Examples 24 to 27 having a molecular weight of 300 to 70,000 bound with polyethylene imide were the acetyl sulfide and sulfide of the fibers after 10 times of washing.
• the deodorizing performance against hydrogen was excellent.
• Examples 23 to 25 in which polyethyleneimine having a molecular weight of 1,200 to 70,000 was bound were dyed in comparison with the fibers in Example 22 in which polyethyleneimine was bound to a molecular weight of 300.
• the decrease in deodorizing performance with respect to acetate aldehyde and hydrogen sulfide was small.
• ordinary acrylic fiber Ciashmilon FK manufactured by Asahi Kasei Kogyo Co., Ltd.
• the obtained transition metal-containing fiber and ordinary acryl fiber (Cashmilon FK manufactured by Asahi Kasei Kogyo Co., Ltd.) were used in the same manner as in the example with a composition ratio of 3: 1: 6. Blended spun yarn was made into a woven fabric.
• the acryl fiber woven fabric containing sulfonic acid and 0.1 mol of OSmolZkg was immersed for 1 minute in a 12% by weight aqueous solution of polyethyleneimine with a molecular weight of 70,000 for 1 minute, and dehydrated. The drawing ratio at this time was 17% by weight. Next, drying was performed at 80 ° C. for 1 hour to obtain a fiber of Comparative Example 6.
• the deodorizing performance against various odors of the woven fabric of Example 26 was evaluated together with the performance after washing 10 times, and the evaluation results were evaluated according to Table 7 shown in Table 7. It can be seen that Sample No. 28 was good after 10 washes compared to Comparative Example 6. It can also be seen that Examples 28 and 29 were good in texture.
• Example 2 The fiber obtained in Example 2 and the undried fiber obtained in the middle of Example 2 were immersed in an aqueous solution of polyacrylic acid to reduce the carboxyl group content from 0.1 lmol / kg fiber. 1 5.
• the woven fabric was composed of spun yarn.
• Table 8 shows the evaluation results of the content of carboxyl groups of the fibers constituting each fabric and the deodorizing performance against malodor.
• the fiber having a carboxyl group content of 0.2 to 10 molZkg fiber (Examples 2'8 to 31) has excellent tobacco deodorizing performance.
• the deodorizing property of the fiber and the washing durability were good, and the texture after washing was also good.
• a polymer obtained by copolymerizing 74.7% by weight of acrylonitrile, 25.0% by weight of vinylidene chloride, and 0.3% by weight of sodium methyl sulfonate is dissolved in dimethylformamide to obtain a polymer.
• a spinning solution having a coalescing concentration of 18.0% by weight was prepared. This spinning solution is spun through a spinneret having 0.15 mm pores into a 75% by weight dimethylformamide-based coagulation bath maintained at 30 ° C, and 75% by weight maintained at 80 ° C. The film was stretched 5.0 times in a dimethylformamide stretching bath, washed with water and stretched 1.2 times in boiling water.
• the obtained undried fabric is immersed in an aqueous solution of 20% of 3.8% by weight of polyethyleneimine having a molecular weight of about 70,000 for 1 minute, dehydrated to a squeezing ratio of 80%, and dehydrated at 80 ° C for 1 hour.
• the amount of copper bound to the ruboxyl group of the fiber obtained by blending the copolymerized polymer and polyacrylonitrile at a ratio of 30:70 is 0.05 to 6.0 equivalents.
• the fabric is composed of a spun yarn obtained by blending the acrylic fiber changed in the above and the ordinary polyester fiber at a ratio of 3: 0.5: 6.5, and the evaluation of the deodorizing performance against the odor as in Example 20 is performed. went.
• Table 9 shows the evaluation results of the copper content of the fibers constituting each woven fabric and the deodorizing performance against odors. [Table 9] ⁇ gas desorption at quenching ⁇ (ppm)
• the woven fabric having a copper content of 0.1 to 5 equivalents / kg fiber deodorizes not only the carbonyl group-containing compound and the acidic compound but also the basic compound. It also has excellent tobacco deodorizing performance, indicating that the texture was good.
• a polymer obtained by copolymerizing 94.5% by weight of acrylonitrile, 5.0% by weight of methyl acrylate, and 0.5% by weight of sodium methyl sulfonate is dissolved in 70% by weight of nitric acid.
• a spinning dope having a polymer concentration of 15.5% by weight was prepared.
• the stock solution was spun through a spinneret having 0.06 pores into a 37% by weight nitric acid-based coagulation bath kept at 0, washed with water and stretched 9 times in boiling water to obtain undried fibers.
• This undried fiber is converted to a polyacrylamine pHIO aqueous solution with a molecular weight of about 30,000.
• a knitted fabric was formed from a spun yarn mixed with ordinary acrylic fiber (Cashmillon FK, manufactured by Asahi Kasei Kogyo Co., Ltd.) at different mixing ratios, and deodorant against the same bad odor as in Example 20 above. The performance was evaluated.
• Table 10 shows the evaluation results of the mixing ratio of the acrylic fiber containing polyacrylamide and the nylon fiber containing carboxyl group of the fibers constituting each knitted fabric, and the deodorizing performance against malodor. [Table 10] Free gas desorption at quenching ⁇ (ppm)
• woven fabrics using fibers in which the content of polyacrylamide-containing acrylic fibers is 5% by weight or more and the content of carboxyl group-containing nylon fibers is 0.1% or more are used. It can be seen that Examples 36 to 40) deodorize not only the carbonyl group-containing compound and the acidic compound but also the basic compound and are excellent in deodorizing performance of tobacco.
• a polymer obtained by copolymerizing 74.7% by weight of acrylonitrile, 25.0% by weight of vinylidene chloride and 0.3% by weight of sodium methyl sulfonate is dissolved in dimethylformamide to obtain a polymer.
• a spinning solution having a concentration of 18.0% by weight was prepared. This spinning solution was spun through a spinneret having 0.1 pores into a 75% by weight dimethylformamide-based coagulation bath maintained at 30 ° C. The film was stretched 5.0 times in a 75% by weight dimethylformamide stretching bath kept at C, washed with water and stretched 1.2 times in boiling water.
• the fiber is immersed in an aqueous solution of 5.0% by weight of polyarylamine having a molecular weight of about 30,000 at 25 ° C for 1 minute.
• the content of zinc bound to the carboxyl group of the fiber obtained by graph-polymerizing acrylic acid so that the carboxyl group contains 2.0 equivalent Zkg fiber is 0.2 equivalent / kg fiber.
• Fabrics are each composed of spun yarn obtained by blending acrylic fiber and the above-mentioned acrylic fiber (Casimilon FK) at a ratio of 3: 0.5: 6.5, respectively. The odor performance was evaluated.
• Table 11 shows the evaluation results of the mixing ratio of the acrylyl fibers containing acrylamide and the acryl fiber containing zinc and the deodorizing performance against the offensive odor. il) Yugas Fiber in ( ⁇ ) (ppm)
• the woven fabric using the fiber having a mixing ratio of the polyacrylamide-containing acryl fiber of 5% by weight or more and the zinc-containing acryl fiber of 0.1% by weight or more is shown. It can be seen that Examples 41 to 45 deodorize not only carbonyl group-containing compounds and acidic compounds but also basic compounds and are excellent in deodorizing performance of tobacco.
• a polymer obtained by copolymerizing 94.6% by weight of acrylonitrile, 5.0% by weight of methyl acrylate, and 0.4% by weight of itaconic acid was dissolved in 70% by weight of nitric acid, and the polymer concentration was 16.0%.
• a weight percent spinning dope was prepared. This undiluted spinning solution was spun through a spinneret having pores of 0.06 mm into a 35% by weight nitric acid-based coagulation bath maintained at 0 ° C, washed with water, stretched 8 times in boiling water to obtain an undried fiber. .
• This fiber is immersed in a 2.5% by weight polyethyleneimine solution with a molecular weight of about 70,000 at 20 ° C for 1 minute, dehydrated to a squeezing ratio of 80%, dried at 80 for 1 hour, and then dried.
• the fiber obtained by wet heat treatment with saturated steam at 120 ° C for 5 minutes in a crepe, and acrylinitrile and acrylic acid were copolymerized in a mixing ratio of 80:20 by weight.
• a woven fabric was constructed (Example 46).
• Example 12 As a comparative example, a woven fabric was formed in the same manner as in Example 46 except that the wet heat treatment was not performed, and Comparative Example 19 was performed. With respect to the examples and the comparative examples, the same evaluation of the deodorizing performance against malodor as in Example 2 and the evaluation of the deodorizing performance against malodor after washing 10 times and after dyeing were performed. Table 12 shows the results. [Table 12] Free gas desorption (ppm) deodorant value Deodorant value Subacetal torito sulphide Ammonia trimethyl sulfide by tobacco smoke Bonding rate Dehydrogen
• the deodorant fiber of this invention has the performance which adsorbs and removes the odor originating in acidic compounds, such as a carbonyl compound, and this odor removal performance falls by processing, such as dyeing, and many washings. There is nothing.
• the deodorant textile of the present invention is to be used as a textile material for textiles, and to provide products with a high deodorant effect on all textile high-order processed products such as clothing and bedding textile products. Can be.
• Higher-order fiber processing of a fabric or the like obtained by mixing the deodorant fiber of the present invention with a deodorant fiber having an odor removing activity derived from a basic compound or the like containing an anionic functional group in a textile substrate.
• the product can remove complex odors such as odors derived from acidic substances and odors derived from basic substances, and the removal performance is durable for washing and the like.
• the fiber advanced product in which the deodorant fiber according to the present invention is thus mixed has a deodorizing effect that lasts long for a complex odor such as a tobacco odor in which various odors are mixed.

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